Research Article Qualitative and Quantitative Analysis of

Research ArticleQualitative and Quantitative Analysis of the Major Constituentsin Chinese Medical Preparation Lianhua-Qingwen Capsule byUPLC-DAD-QTOF-MS

Weina Jia123 Chunhua Wang123 Yuefei Wang123 Guixiang Pan123 Miaomiao Jiang123

Zheng Li123 and Yan Zhu123

1 Tianjin Key Laboratory of Modern Chinese Medicine Tianjin University of Traditional Chinese Medicine Tianjin 300193 China2 Tianjin Key Laboratory of TCM Chemistry and Analysis Tianjin University of Traditional Chinese Medicine Tianjin 300193 China3 Research andDevelopmentCenter of Traditional ChineseMedicine Tianjin International JointAcademy of BiotechnologyampMedicineTianjin 300457 China

Correspondence should be addressed to Yan Zhu yanzhuharvardgmailcom

Received 7 July 2014 Revised 14 August 2014 Accepted 15 August 2014

Academic Editor Feng Sun

Copyright copy 2015 Weina Jia et alThis is an open access article distributed under the Creative CommonsAttribution License whichpermits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Lianhua-Qingwen capsule (LQC) is a commonly used Chinese medical preparation to treat viral influenza and especially played avery important role in the fight against severe acute respiratory syndrome (SARS) in 2002-2003 in China In this paper a rapidultraperformance liquid chromatography coupled with diode-array detector and quadrupole time-of-flight mass spectrometry(UPLC-DAD-QTOF-MS)methodwas established for qualitative and quantitative analysis of themajor constituents of LQC A totalof 61 compounds including flavonoids phenylpropanoids anthraquinones triterpenoids iridoids and other types of compoundswere unambiguously or tentatively identified by comparing the retention times and accurate mass measurement with referencecompounds or literature data Among them twelve representative compounds were further quantified as chemical markersin quantitative analysis including salidroside chlorogenic acid forsythoside E cryptochlorogenic acid amygdalin swerosidehyperin rutin forsythoside A phillyrin rhein and glycyrrhizic acid The UPLC-DAD method was evaluated with linearity limitof detection (LOD) limit of quantification (LOQ) precision stability repeatability and recovery tests The results showed that thedeveloped quantitative method was linear sensitive and precise for the quality control of LQC

1 Introduction

Lianhua-Qingwen capsule (LQC) developed from the twoclassical traditional Chinese medicine (TCM) formulaeMaxing-Shigan-Tang and Yinqiao-San which have a longhistory of clinical application in the treatment of influenza[1] is a commonly used Chinese medical preparation to treatviral influenza and especially played an important role in thefight against severe acute respiratory syndrome (SARS) in2002-2003 in China [2] LQC is composed of 11 herbs includ-ing Fructus Forsythiae (Lianqiao) Flos Lonicerae Japoni-cae (Jinyinhua) Herba Ephedrae (Mahuang) Semen Arme-niacae Amarum (Kuxingren) Radix Isatidis (Banlangen)Rhizoma Dryopteridis Crassirhizomatis (Mianmaguanzh-ong)Herba Houttuyniae (Yuxingcao) Herba Pogostemonis

(Guanghuoxiang) Radix et Rhizoma Rhei (Dahuang) Radixet Rhizoma Rhodiolae Crenulatae (Hongjingtian) and Radixet Rhizoma Glycyrrhizae (Gancao) along with menthol anda traditional Chinese mineral medicine Gypsum Fibrosum(Shigao) According to previous reports LQC has a goodclinical effect on influenza with the symptoms of high feveraversion to cold headache pharyngalgia cough sneezingmuscle ache and so on [3] Modern pharmacological studieshave shown that LQC also has the antiviral antibacterial andanti-inflammatory activities [4 5] Recently the study on itsbioactive ingredients andmolecularmechanism of action hasbeen gradually reported as well [6]

Although some preliminary analytical methods havebeen developed for the quality control for LQC includ-ing thin layer chromatography (TLC) [7] high performance

Hindawi Publishing Corporatione Scientific World JournalVolume 2015 Article ID 731765 19 pageshttpdxdoiorg1011552015731765

2 The Scientific World Journal

liquid chromatography (HPLC) [8 9] micellar electrokineticcapillary chromatography (MEKC) [10] and liquid chro-matography tandem mass spectrometry (LC-MSMS) [11]no systematical and comprehensive study on the chemicalprofiling and quality control method for LQC has beenreported so far For a classical and complex Chinese medicalpreparation the comprehensive quality evaluation methodshould be based on its multiple chemical constituentsThere-fore it is necessary to develop a rapid and sensitive methodto identify and quantify the chemical constituents in LQCwhich will be beneficial to investigate the effectiveness andevaluate the quality of LQC

In this study a reliable sensitive and simple ultraper-formance liquid chromatography coupled with diode-arraydetector and quadrupole time-of-flight mass spectrometry(UPLC-DAD-QTOF-MS) method which was more system-atical and comprehensive than the earlier ones was estab-lished for characterization and quantification of the majorchemical constituents of LQC A total of 61 compoundswere unambiguously or tentatively identified by comparingthe retention times exact molecular masses and MSMSspectral data with reference compounds or literature dataFurthermore twenty-seven compounds were confirmed bycomparing with the standards Among them twelve repre-sentative compounds were quantified as chemical markers inquantitative analysis including salidroside chlorogenic acidforsythoside E cryptochlorogenic acid amygdalin swero-side hyperin rutin forsythoside A phillyrin rhein andglycyrrhizic acid This is the first systematical and compre-hensive study on the qualitative and quantitative analysis ofLQC

2 Experimental

21 Reagents Chemicals and Materials Methanol and ace-tonitrile (HPLC grade) were purchased from Sigma Aldrich(St Louis MO USA) Formic acid (HPLC grade) waspurchased from Tianjin Damao chemical reagent factory(Tianjin China)Water (HPLC grade) for UPLC analysis wasproduced by theMilli-Qwater purification system (MilliporeUSA) Salidroside chlorogenic acid forsythoside E cryp-tochlorogenic acid amygdalin sweroside hyperin rutinforsythoside A phillyrin rhein and glycyrrhizic acid werepurchased from Sigma Aldrich (St Louis MO USA) Thepurity of standard substances was above 98 Ten batches ofLQC were provided by Shijiazhuang Yiling PharmaceuticalCo Ltd (Shijiazhuang China)

22 UPLC Analysis The UPLC analysis was performed on aWaters ACQUITY UPLC instrument (Waters CorporationMA USA) coupled with a binary pump a sample manageran autosampler a column compartment and diode-arraydetector (DAD)The separation of samples was performed ona Waters ACQUITY UPLC BEH C

18(100 times 21mm 17 120583m)

column with the column temperature at 50∘C The analysiswas completed in 30min with a gradient elution of 01formic acid aqueous solution (A) andmethanol (B) at the flowrate of 03mLmin The gradient program was designed as

follows 0ndash11min 5ndash35 B 11ndash18min 35ndash55 B 18ndash22min55ndash75 B 22ndash24min 75ndash90 B 24-25min 90ndash100 Band 25ndash30min 100 B The injection volume was 5120583L Thedetection wavelengths of DAD were set at 210 nm 225 nmand 254 nm

23 UPLC-DAD-QTOF-MSAnalysis TheWaters ACQUITYUPLC instrument (Waters MA USA) coupled with WatersSynapt HDMS G1 (Waters Manchester UK) via an elec-trospray ionization (ESI) interface The UPLC analyticalconditions were the same as the UPLC analysis describedabove The full scan mass spectra data were acquired inpositive and negative ion modes Acquisition parametersare as follows capillary voltage was 3000V for ESI (+)and 2600V for ESI (minus) cone voltage was 45V the ESIsource temperature was 100∘C the desolvation tempera-ture was 350∘C the nitrogen (N

2) was used as desolva-

tion gas at flow rates of 600 Lh for both ESI (+) andESI (minus) and the range of full scan was set at mz 150ndash1000Da The version of analysis software was Mass LynxV41

24 Sample and Standard Solutions Preparation The powderof LQC (04 g) was accurately weighed and extracted with60 methanol-water (vv) solution (20mL) in an ultrasonicwater bath for 30min at room temperature The supernatantsolution was diluted with the same amount of water andthen centrifuged for 10min at 14000 rmin All the obtainedsolutions were filtered through 022 120583m syringe filter beforethe UPLC analysis

Twelve standards were accurately weighed and dissolvedin methanol to obtain stock solutions respectively A mixedstock solution of standards was prepared by adding a suitablevolume of each stock solution to a 5mL flask and dilutedwith 30 methanol-water solution at the concentration of678 120583gmL for salidroside 10965 120583gmL for chlorogenicacid 7764 120583gmL for forsythoside E 10647 120583gmL for cryp-tochlorogenic acid 6257 120583gmL for amygdalin 3196 120583gmLfor sweroside 321 120583gmL for hyperin 85 120583gmL for rutin6734 120583gmL for forsythoside A 4571120583gmL for phillyrin5549 120583gmL for rhein and 8435 120583gmL for glycyrrhizicacid respectively The mixed stock solution was then seri-ally diluted with 30 methanol-water solution to obtainfive appropriate concentrations used for plotting standardcurves The lowest concentration of the mixture stocksolution was further diluted to give a series of differ-ent concentrations for investigating the limits of detection(LODs) and limits of quantification (LOQs) of the 12 chem-ical constituents All solutions were stored at 4∘C untilanalysis

25 Validation of the Quantitative Analysis TheUPLC-DADmethod was evaluated with linearity LOD LOQ precisionstability repeatability and recovery tests The calibrationcurves were constructed with five different concentrations ofchemical markers in triplicate The LODs and LOQs weremeasured under the UPLC analytical conditions at a signal-to-noise (SN) ratio of 3 and 10 respectively For intraday

The Scientific World Journal 3

Table 1 Quantitative results of 12 compounds in LQC extracted by different methods

Content (120583gg)

Methods30a 60 90 60 60 60 60 60 60

30minb 30min 30min 30min 30min 30min 15min 30min 45min1 100c 1 100 1 100 1 50 1 100 1 200 1 100 1 100 1 100

Salidroside 172628 170125 162202 152231 170125 165632 171154 170125 168854Chlorogenic acid 244497 249215 221689 228543 249215 228927 249262 249215 255217Forsythoside E 158393 162078 45191 146209 162078 140253 162701 162078 157963Cryptochlorogenic acid 186298 185164 66750 170305 185164 177179 183789 185164 185795Amygdalin 142411 145539 144256 126893 145539 129811 139597 145539 143138Sweroside 81619 81318 78932 74706 81318 77267 81251 81318 80824Hyperin 13510 15173 16726 14084 15173 14080 15272 15173 15767Rutin 12200 12117 11522 10611 12117 11667 11709 12117 11662Forsythoside A 248460 253634 266179 228576 253634 239635 254387 253634 252110Phillyrin 166026 152145 155159 141019 152145 139012 152301 152145 155152Rhein 80313 110206 137011 93763 110206 93205 95638 110206 105477Glycyrrhizic acid 153049 168043 159437 143740 168043 161999 167481 168043 166542aExtracting solvent 30 60 and 90 methanol-water solutionbUltrasonic time 15min 30min and 45mincExtraction solvent multiples 1 50 1 100 and 1 200 expressed 50 100 and 200 times per gram of sample

and interday precisions test the samples were analyzed bysix repetitive injections within one day and once a day forthree successive days respectively At room temperaturethe stability of sample solution was evaluated by replicateinjection at 0 1 2 4 6 8 10 14 24 and 48 h In order tocheck the repeatability six samples from the same sourcewereinvestigated Accurate amounts of the reference standardswere added to 020 g powder of sample in sextuplicate Theresultant sample solutions were then extracted and quantifiedwith the described method The relative standard deviation(RSD) was used to evaluate the results

3 Results and Discussion

31 Optimization of the Extraction and ChromatographicConditions A single-factor method was used to investigatethe extraction effect of the extraction solvent (30 60and 90 methanol-water solution) extraction solvent ratio(1 50 1 100 and 1 200 (wv)) and extraction time (15min30min and 45min) respectively By analyzing the extractionefficiency 60 methanol-water solution extraction solventratio at 1 100 and 30min of ultrasonic time were selected asthe eventual extraction conditions The results are describedin Table 1

Due to the existence of acidic constituents in samplesolutions formic acid was added into the mobile phasewhich could inhibit the ionization of these acidic ingredi-ents to improve the peak shape The mobile phase systems(methanol-formic acid aqueous solution and acetonitrile-formic acid aqueous solution) and column temperature (40∘Cand 50∘C) were investigated which showed that methanol-01 formic acid aqueous solution as mobile phase with

column temperature at 50∘C could obtain the best chro-matographic peak shape Because the maximum absorptionsof 12 reference compounds were different three detectionwavelengths were finally selected in order to achieve thegoal of high detection sensitivity and little interferenceForsythoside E (peak 7) cryptochlorogenic acid (peak 9)amygdalin (peak 33) and phillyrin (peak 39) had satisfactorysensitivity at 210 nm salidroside (peak 6) chlorogenic acid(peak 8) and rhein (peak 54) at 225 nm and sweroside(peak 13) hyperin (peak 26) rutin (peak 29) forsythosideA (peak 30) and glycyrrhizic acid (peak 57) at 254 nm Thechromatograms are presented in Figure 1

32 UPLC-DAD-QTOF-MS Analysis of Reference Compoundsand LQC Samples As shown in Table 2 a total of 61compounds were unambiguously or tentatively identifiedby comparing the retention times and accurate mass mea-surement with references or literature data These com-pounds were divided into six types according to their struc-tural characteristics including flavonoids phenylpropanoidsanthraquinones triterpenoids iridoids and other types Thestructures of identified compounds are listed in Figure 3Among them twenty-seven compounds were further con-firmed by comparing with standards The total ion chro-matograms are shown in Figure 2

321 Flavonoids Seventeen flavonoids (Figure 3(a)) in LQCincluding flavone aglycones and glycosides were identifiedThey were mainly obtained from Lianqiao Jinyinhua Gan-cao Hongjingtian and Mahuang Amongst them liquiritinapioside (22) ononin (25) hyperin (26) rutin (29) liquirit-igenin (35) isoliquiritin apioside (36) isoliquiritin (37) and


AU 0020406

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

minus06minus04minus02

687933

29

3039

(a)

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 30

AU 00204

0

minus02

6879

29

30

39

54 57

13

(b)

AU

0004008012016

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

6

8

7

9

3329

30

39 54

57

13

26

(c)

AU

0002004006008

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

minus002

(d)

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

AU

00204


minus1minus08

6

87933 29

30

39

57

26

(e)

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

AU 00204

minus04

minus02

6

8

79

33 29

30

39

54 57

(f)

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

AU

0004008012016

02

minus004

8

9

29

30

39

54

5713

26

(g)

Figure 1 UPLC-DAD chromatograms of standard solution of 210 nm (a) 225 nm (b) 254 nm (c) negative sample solution (d) and samplesolution of 210 nm (e) 225 nm (f) and 254 nm (g)

Time

()

0

100

()

0

100

2 4 6 8 10 12 14 16 18 20 22 24 26 28

Time2 4 6 8 10 12 14 16 18 20 22 24 26 28

1

2

34 5

67 8 9

101112

13

1415 16

1718

19

20

21

22

23

24

25

26

27

28

28

29

30

301317

31

32 33

34

35

3736

38

39

40

39

42

41

434445

46 47 484950

51

5253

54

5556

57

57

58

59

60

61

45

20130402-LHQW MSminus 1 TOF MS ESminusBPI

648e4

20130402-LHQW MS+1 TOF MS ES+

BPI813e4

Figure 2 UPLC-QTOF-MS chromatograms of sample solutionfrom negative ion mode and positive ion mode

formononetin (47) were unambiguously identified via thestandards

In negative and positive ion modes flavone aglyconesmainly gain fragment ions by the reverse Diels-Alder (RDA)reaction and the loss of CO (28Da) The characteris-tic fragmentation behavior of compound 35 is shown inFigure 4(a) with high abundant fragmentation [M+HndashVP (4-vinylphenol)]+ at mz 1370422 The abundance of fragmentions [M+HndashRL (resorcinol)]+ at mz 1470621 and [M+HndashRLndashCO]+ at mz 1190691 is relatively lower Compounds 2440 42 and 46were tentatively identified via comparing theirexact molecular masses MSMS spectra data and retentionbehaviors with literature data [13 26 39] Flavone glycosideshave the similar fragmentation pathways of simultaneous orsuccessive loss of glucose (162Da) rhamnose (146Da) orapiose (132Da) The fragmentation pathway of compound26 was exemplified in Figure 4(b) in negative ion modeCompounds 21 23 31 41 and 53 were tentatively identified


O

O

O

O

OH

OH

O

O

RO

HO

OR1

R1

R3

R2

R2

R4

R5R2OR1O

OR3

OR3

OCH3

21R1 = H R2 = H R3 = Glc 24 R1 = OH R2 = Rha (3rarr1) Glc R3 = OH R4 = H R5 = H 25 R = Glc22 R1 = H R2 = H R3 = Glc (2rarr4) Api 26 R1 = OGlc R2 = H R3 = H R4 = H R5 = OH 47 R = H35 R1 = H R2 = H R3 = H 29 R1 = OGlc (6rarr1) Rha R2 = H R3 = H R4 = OH R5 = H41R1 = Glc (6rarr1) Rha R2 = OH R3 = CH3 31R1 = OGlc (6rarr1) Rha R2 = H R3 = H R4 = H R5 = H

40 R1 = OH R2 = H R3 = H R4 = H R5 = OH42 R1 = OH R2 = H R3 = H R4 = H R5 = H53 R1 = H R2 = H R3 = H R4 = OCH3 R5 = OCH3

36 R1 = OH R2 = H R3 = Glc (2rarr4) Api37 R1 = H R2 = OH R3 = Glc46 R1 = H R2 = OH R3 = H

(a)

4 8 9 1618 R = OH

38

27 30 34

56

32 R1 = Glc R2 = H39 R1 = Glc R2 = CH3

O

O

O

O

O

O

O

O

O

OO O O

R

O

O

O

O

O

OO

O O O

OO

OO

O

O

O

O

OO

O

O

O

OO

OO

O

O

O

O

O

OH

OH

OHOH

OH

OHOH

OH

OH

OH

OH

OH

OHOH

OH

OHOH

OHOH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

HO

HO

HO

HO

HOHO

HOHO

HO

HO

HO

HOHO

HOHO

HO

HO

HO

HOHO

H3C

OR2

R1O

CH3

(b)

17R1 = Glc R2 = CH3 R3 = H R4 = H43 R1 = H R2 = CH3 R3 = H R4 = H45 R1 = H R2 = CH3 R3 = OH R4 = Glc49 R1 = H R2 = CH3 R3 = OCH3 R4 = Glc54 R1 = H R2 = COOH R3 = H R4 = H61R1 = H R2 = CH3 R3 = OH R4 = H

O

O

OR1

R3R2

OR4

(c)

Figure 3 Continued


6058 59

5550 52 R1 = GlcA (2rarr1) GlcA R2 = acetoxy57 R1 = GlcA (2rarr1) GlcA R2 = H

OO

OO

O

O

O

O

O

R2H

H

H

O

O

O

O

OO

O

O

O

O

OO

O

O

OO

O

O

O

OOO

OHOH

OH

OH

OH

OH

OH

OH OH

OHOH

OH

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

R1O

(d)

5 R1 = Glc R2 = H 13 2010R1 = Glc R2 = CH3

OH

HO

O O

O

HOO OO

OOH

H OO

OHOH

OHOH HO

HOHO

HOHOHO

OR1

OR2

(e)

1 2 3 6

15

7

11 33 51

O

O

O

O O

OO

OO

O O

OO

OOO

O

OO

N

OO

O

OHOH OH

OHOH

OH

OH

OH

OH

OHOHOH

OHOH

OH

OH

OH

OH

OH

OH

OHOH

OH

OHOH

HOHO

HO HOHO

HOHO

HO

HOHO

HOHOHO

HOHO

HOHO HO

HOHO

HOHOHO

HO

HO

H3C

(f)

Figure 3 Chemical structures of the compounds identified from LQC (except for the 7 isomers)

by comparing the molecular mass and MSMS data withliterature data [25 45]

322 Phenylpropanoids Fourteen phenylpropanoids (Figure3(b)) including phenylpropionic acids lignans and coum-arins were identified in LQC They were mainly obtainedfrom Lianqiao Jinyinhua and Gancao Neochlorogenic acid

(4) chlorogenic acid (8) cryptochlorogenic acid (9) 35-dicaffeoylquinic acid (27) forsythoside A (30) 34-dicaffe-oylquinic acid (34) and phillyrin (39) were unambiguouslycharacterized by comparing with standards

In negative ion mode phenylpropionic acids have thesimilar fragmentation pathways of simultaneous or succes-sive loss of H

2O (18Da) CO (28Da) and CO

2(44Da)


OHO

OH

O

OHO

O

OHH

mz 1470621

mz 1190691

+H

mz 2570659mz 2570659

mz 1370422

2570659

172999816301591319873 1941022

23914082651331

3011509

1370422

1190691

1199948

13800271470621

1650917 16902931810699 2112177

(MSMS)

100 120 140 160 180 200 220 240 260 280 300

()

0

100

()

0

100

mzmz

120 130 140 150 160 170 180 190 200 210

(MS+)

(a)

OHO

OHO

OH

O

OH

OOH

HOOH

OH

mz 3010464

3010464

1370281

3020746

3027005 4652560 62322138921294

4630905

43109651450305 2210378

46409055310850 7371886 11080997 13072520 14077662

(MSMS)

()

0

100(

)

0

100

mz

200 400 600 800 1000 1200 1400mz

200 400 600 800 1000 1200 1400

(MSminus)

(b)

OHHO

OHHOOC

OHOHHO

O

OHHO OH

COOminus

COOminus COOminus

Cminus

mz 1910733mz 1270486

mz 1730583 mz 1090409

mz 930425 mz 850426

minusCO2

minusCO2

minus2H2O minusC2H2

minusCO

Ominus

minusH

minusH2O minusH2O

minusH2O

1910733

8504261270486930425 1090409 1350577

1610264 1730583 19207421938051

3530878

1910558

3510719192060770718303540916

70516854510630 5031459 7081906

(MSMS)

()

0

100

()

0

100

mzmz

80 90 100 110 120 130 140 150 160 170 180 190 200200 250 300 350 400 450 500 550 600 650 700 750 800

(MSminus)

(c)

O OO

O

OH

OHOH

HO

HO

HO

HO

O

O OHOH

mz 4611920 mz 1610328

CH3

6232001

3112033 6211844

6242032

6252064 124749349575357 13186510

1610328

62325071620342 4611920

(MSMS)

()

0

100

()

0

100

200 400 600 800 1000 1200 1400mzmz

100 200 300 400 500 600 700 800 900 1000

(MSminus)

(d)

Figure 4 Continued


3561547

13599643083514

3711826

37218625161718

5792105

1129871 4310958

58021345812158 111342197973569 11814053

(MSMS)

O

O

O

OO

OO

OH

HOHO

OH

[MndashHndashGlc]minus[MndashHndashGlcndashCH3]minus

()

0

100

()

0

100

mz

150 200 250 300 350 400 450 500 550 600 650 700 750mz

200 400 600 800 1000 1200 1400

(MSminus)

mz 3561547

mz 3711826

(e)

2250723

18204771810753

18006601540552

19706952240626

2410669 2690634

2420626 2700607

2690462

1129890 27004855610872 8234322 9694360 14023499

O O

O

O

O O

(MSMS)

()

0

100(

)

0

100

mz

160 180 200 220 240 260 280mz

200 400 600 800 1000 1200 1400

(MSminus)

OH

OH

OHOH OH OH OH

OHOHOH

OH

minusCO2

minusCO2minusCO

minusCO

minusHminusHminusH

minusHminusH

minusH

H3CH3C

H3C H3C

mz 1970695mz 2410669

mz 2250723mz 2690462

mz 1820477mz 1540552

minusCH3minusCO

(f)

4310988

11692794321016

4990790 8632153 11946926 14410397

2690673

2250753

18204861710837

1970771 241071927007752710783 3110845

(MSMS)

O

O

O OH

OHO

HOHO

OH

HO

[MndashHndashGlc]minus[MndashHndashGlcndashCO]minus

[MndashHndashGlcndashCO2]minus

[MndashHndashGlcndashCOndashCO2]minus

[MndashHndashGlcndashCO2ndashCH3ndashCO]minus()

0

100

()

0

100

mz

200 400 600 800 1000 1200 1400mz

140 160 180 200 220 240 260 280 300 320

(MSminus)

mz 3711826mz 2690673

CH3

(g)

8214583

35108091130354

19305102890758

645410258340994693705 7594542

8224637

8234628

(MSMS)

H

HO

HO

OOH

O

O

HOOCHO

HOOHO

HOOH

HOOC

[MndashHndash2GlcA]minus[MndashHndashGlcA]minus

[2GlcAndashH]minus

()

0

100

mz

100 200 300 400 500 600 700 800

8213977

1169246 3111153 8203445

8224006

8434348125530939433099 13258577

()

0

100

mz

200 400 600 800 1000 1200 1400

mz 4693705mz 3510809mz 6454102

(MSminus)

(h)

Figure 4 Continued


3751302

21307733761332

75126674731059 8093751 10383667 13123422

1250712

1210637

930423

650486 950155 1260535 151087824011931740320 1999976 2505933

(MSMS)

OH

H

HO

OH

O

O

O

HO

OHOH

OH

[MndashHndashGlc]minus

[14FndashH2O]minus [MndashHndashGlcndash2CO2]minus

14F

minusH2O

()

0

100

()

0

100

mz

200 400 600 800 1000 1200 1400

mz

60 80 100 120 140 160 180 200 220 240 260

(MSminus)

minusCO2

minusCO2

[MndashHndashGlcndashCO2ndashH2O]minus

(i)

Figure 4TheMS spectra and fragmentation pathway of compound 35 (a) compound 26 (b) compound 8 (c) compound 30 (d) compound39 (e) compound 61 (f) compound 45 (g) compound 57 (h) and compound 5 (i)

The fragmentation pathway of compound 8 [18] as the rep-resentative of phenylpropionic acids is shown in Figure 4(c)Compound 30 produced [MndashHndashCa (caffeoyl)]minus at mz4611920 and [CaffeicndashHndashH

2O]minus atmz 1610328 as displayed

in Figure 4(d) Lignans primarily generated [M+HCOO]minusin negative ion mode and further elimination of glucose(162Da) produced aglycone As shown in Figure 4(e) com-pound 39 produced characteristic fragments at mz 3711826and mz 3561547 corresponding to [MndashHndashGlc (glucose)]minusand [MndashHndashGlcndashCH

3]minus respectively Compounds 16 18 19

28 32 38 and 56 were tentatively identified on the basisof the exact molecular formulae matching fragmentationinformation and retention behaviors as well as literature data[23 24 33 36 47]

323 Anthraquinones Eight anthraquinones (Figure 3(c)) inLQC were definitely or tentatively identified All of themwere derived from Dahuang Chrysophanol glucoside (17)emodin-8-O-glucoside (45) rhein (54) and emodin (61)were confirmed via comparing with standard substances

The characteristic fragmentation behavior of anthra-quinones was the loss of CO

2(44Da) CH

3(15Da) and

CO (28Da) in negative ion mode Typical compound 61was used to explain the fragmentation pathway of anth-raquinones presented in Figure 4(f) Compound 45 asshown in Figure 4(g) produced characteristic fragments atmz 2690673 mz 2410719 mz 2250753 mz 1970771andmz 1820486 which corresponded to [MndashHndashGlc]minus [MndashHndashGlcndashCO]minus [MndashHndashGlcndashCO

2]minus [MndashHndashCOndashCO

2]minus and

[MndashHndashCO2ndashCH3ndashCO]minus respectively Compounds 12 43

44 and 49 were tentatively identified by comparing theiraccurate molecular masses and MSMS fragment data withliterature data [21 40 41]

324 Triterpenoids Eight triterpenoids (Figure 3(d)) inLQC were unambiguously or tentatively identified All ofthem were derived from Gancao Glycyrrhizic acid (57) wasconfirmed by comparing with standards In negative ion

mode representative compound 57 yielded [MndashHndashH2Ondash

CO2]minus at mz 7594524 [MndashHndashGlcA (glucuronic acid)]minus

at mz 6454102 [MndashHndash2GlcA]minus at mz 4693705 [2GlcAndashH]minus at mz 3510809 and [2GlcAndashHndashH

2OndashCO

2]minus at mz

2890758 as shown in Figure 4(h) Compounds 48 50 5255 58 59 and 60 were tentatively identified by comparingtheir exact molecular masses and MSMS spectral data withthe literature data [51]

325 Iridoids Four iridoids (Figure 3(e)) in LQC includingiridoid glycosides and secoiridoid glycosides were identifiedAll of them were derived from Jinyinhua Loganic acid (5)sweroside (13) and secoxyloganin (20) were unambiguouslyidentified via the standards

The fragment 14F (fragment generated from the fractureof 14 bonds of iridoids) in the negative ion mode was identi-fied as the characteristic fragment ion of iridoid glycosidesMeanwhile iridoid glycosides would lose the functionalgroups such as H

2O (18Da) CO

2(44Da) and glucose

(162Da) Typical compound 5 gave [MndashHndashGlcndashCO2ndashH2O]minus

at mz 1510878 [MndashHndashGlcndash2CO2]minus at mz 1250712 and

[14FndashH2O]minus at mz 930423 [52] as presented in Figure 4(i)

Compound 10 was tentatively identified by comparing itsexact molecular mass and MSMS spectral data with theliterature data [19]

326 Other Types of Compounds Compounds 1 2 11 14 15and 51 were tentatively identified by comparing their exactmolecularmasses andMSMS spectral datawith the literaturedata except gallic acid (3) salidroside (6) forsythoside E (7)and amygdalin (33) which were identified via the standards(Figure 3(f)) [12 53]

33 Methodological Validation of the Quantitative AnalysisAs shown in Table 3 twelve standards were of good lin-earity with high correlation coefficient values over 09993The LODs and LOQs were 0051ndash171 120583gmL and 016ndash569 120583gmL independently Twelve analytes in sample solu-tion were stable at room temperature within 48 h with


Table2Ch

aracteriz

ationof

compo

unds

inLQ

Cby

UPL

C-DAD-Q

TOF-MS

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

10817

C 7H

12O

61910

555(minus05)

Quinica

cid

[12]

20982

223287

C 6H

8O7

1910

198(31)

17300

99[M

ndashHndashH

2O]minus

1110

088[M

ndashHndash2H

2OndashC

O2]minus

Citricacid

[13]

3a15

45216271

C 7H

6O5

1690

142(30)

1250241

[MndashH

ndashCO

2]minus

Gallic

acid

[14]

4a3010

325

C 16H

17O

9

3530878

(14)

3750695

[Mndash2H+

Na]minus70718

30[2MndashH

]minus

1910

497[M

ndashHndashC

a]minus

1790

312[C

affeica

cidndash

H]minus

1350359

[Caffeica

cidndash

HndashC

O2]minus

Neochlorogenic

acid

[13]

5a3639

254

C 16H

24O

103751302

(29)

7512

667[2MndashH

]minus

2130773

[MndashH

ndashGlc]minus

1510

878

[MndashH

ndashGlcndashC

O2ndashH

2O]minus

1250721

[MndashH

ndashGlcndash2CO

2]minus

Loganica

cid

[15]

6a404

8224

278

C 14H

20O

72991

133(07)

1790

447[M

ndashHndashC

8H8O

]minus

1190246[M

ndashHndashG

lcndashH

2O]minus

Salid

rosid

e[16]

7a4557

C 20H

30O

124611674(33)

3151348

[MndashH

ndashRha]minus

2971589[M

ndashHndashR

handashH

2O]minus

15306

44[M

ndashHndashR

handashG

lc]minus

1350573

[MndashH

ndashRhandashG

lcndashH

2O]minus

4631220

(minus43)

4851568

1370

599[M

+HndashR

handashG

lcndashH

2O]+

Forsytho

sideE

[17]

8a4749

327

C 16H

17O

93530880

(20)

1910

556[M

ndashHndashC

a]minus

1790

224[C

affeica

cidndash

H]minus

3551028

(minus03)

3770

857

Chlorogenica

cid

[18]

9a5281

325

C 16H

17O

93530880

(20)

1790

348[C

affeica

cidndash

H]minus

17304

61[Q

uinica

cidndash

HndashH

2O]minus

1910

417[M

ndashHndashC

a]minus

Cryptochlorogenic

acid

[18]

106435

270

C 17H

26O

103891

096(31)

3912

176

(minus08)

4131067

3952354

[M+

NandashH

2O]+

2290

835[M

+HndashG

lc]+

Loganin

[19]

116749

C 14H

23O

93350776

(27)

1730459

[MndashH

ndashGlc]minus

1610

373[G

lcndashHndashH

2O]minus

13304

08[G

lcndashH

ndashH2O

ndashCO]minus

3370

883

(53)

3590

686

1630

419[G

lc+

HndashH

2O]+

Reng

ynic

acid-11015840-O

-120573-D

-glucoside

[20]

1272

22C 2

1H20O

94151261

(51)

4391

207

2550879

[M+HndashG

lc]+

Isom

erof

chrysoph

anol

glucoside

[21]

13a

7428

245

C 16H22O9

3571208(62)4031263

[M

+HCO

O]minus

3930938

[M

+Cl]minus

3591

337

(minus14

)3811154

Sweroside

[15]

1478

59C 1

4H23O

93350871

(42)

1930506161037713304

233370

774

(09)

3590

225

1630

416[G

lc+

HndashH

2O]+

Isom

erof

reng

ynic

acid-11015840-O

-120573-D

-glucoside

158106

306

C 20H

22O

83891458(26)4351519

[M+HCO

O]minus

2270

943[M

ndashHndashG

lc]minus

Polydatin

[22]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

168222

C 29H

36O

166392

219(minus17

)4771894[M

ndashHndashG

lc]minus

1790

546[M

ndashRhandashC

17H

14O

6]minus

1610

328[G

lcndashHndashH

2O]minus

R-suspensasid

e[23]

17a

8320

C 21H

20O

94151253

(31)

2530542

[MndashH

ndashGlc]minus

4171394

(minus07)

4391

200

2550864

[M+HndashG

lc]+

Chrysoph

anol

glucoside

[21]

188874

C 29H

36O

166392

002(minus27)

1610

328[G

lcndashHndashH

2O]minus

1790

349[M

ndashRhandashC

17H

14O

6]minus

S-suspensasid

e[24]

1990

54C 2

9H36O

156231999

(minus12

)3112

176

6252137

(08)

6471942

4791

5624711479

32509251630394

Isom

erof

forsytho

sideA

20a

9470

235

C 17H

24O

114031261

(52)

4051331

(minus17

)4271203

2430871

[M+HndashG

lc]+

Secoxyloganin

[19]

2195

52276313

C 21H

22O

94171205(46)8352331

[2MndashH

]minus2550652

[MndashH

ndashGlc]minus

4411132

2570

811[M

+HndashG

lc]+

Liqu

iritin

[25]

22a

9886

277312

C 26H

30O

135491

627(35)

5512

823

(47)

5731737

2570

822[M

+HndashA

pindashG

lc]+

Liqu

iritin

apiosid

e[26]

2399

95C 2

6H30O

135491

629(38)

5513

403

(minus51)

5731735

2570

815[M

+HndashA

pindashG

lc]+

Isom

erof

liquiritin

apiosid

e[26]

2410088

C 27H

30O

1660

91844(minus18

)6331712

Rhod

iosin

[27]

25a

10384

250300

C 22H

22O

94291410(30)

453117

62690

974[M

+HndashG

lc]+

Ono

nin

[2829]

26a

10722

360

C 21H

20O

124630905

(28)

3010

464[M

ndashHndashG

lc]minus

4651033

(52)

4870

333

3030515

[M+HndashG

lc]+

Hyperin

[24]

27a

10819

326

C 25H

24O

125151205

(29)

3530751

[MndashH

ndashCa]minus

5171296

(17)

5391

156

4991

187[M

+HndashH

2O]+

1630

395[M

+HndashC

andashQuinica

cid]

+

35-Dicaffeoylqu

inic

acid

[30]

2810931

C 29H

36O

156231999

(minus19

)46113781610

185

6471941

47114973250925

1630

415

Isom

erof

forsytho

sideA

29a

1110

256354

C 27H

30O

1660

91465(15)

6111573

(33)

6331404

4650982

[M+HndashR

ha]+

3030495

[M+HndashR

ut]+

Rutin

[31]

30a

11220

280

C 29H

36O

156232001

(minus16

)4611920[M

ndashHndashC

a]minus

1610

328[C

affeica

cidndash

HndashH

2O]minus

6471927

1630386

[Caffeica

cid+

HndashH

2O]+

Forsytho

sideA

[32]

3111589

283

C 27H

30O

155931534

(minus13

)2850677

[MndashH

ndashRut]minus

5951694

(minus07)

2870

936[M

+HndashR

ut]+

Kaem

pferol-3-O

-rutin

oside

[13]

3211692

C 19H

35O

165191

884(35)5651953

[M+HCO

O]minus

3571366[M

ndashHndashG

lc]minus

5431855

3591454[M

+HndashG

lc]+

3411411[M

+HndashG

lcndashH

2O]+

(+)-Pino

resin

ol-120573-

D-glucosid

e[33]

33a

12213

210262

C 20H

27NO

114561523

(37)

4581641

(minus46)

2961124

[M+HndashG

lc]+

1620862

[M+

HndashG

lcndashH

CT]+

Amygdalin

[13]

12 The Scientific World JournalTa

ble2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

34a

12659

326

C 25H

24O

12515116

2(minus54)

3530786

[MndashH

ndashCa]minus

5171348

(04)

5391

193

4991

248[M

+HndashH

2O]+1630387[M

+HndashC

andashQuinica

cid]

+

34-

Dicaffeoylqu

inic

acid

[30]

35a

13082

276

C 15H

12O

42550654

(minus12

)2570

659

(minus08)

1470

621[M

+HndashR

L]+

1370

422[M

+HndashV

P]+

1190691[M

+HndashR

LndashCO

]+Liqu

iritig

enin

[34]

36a

13251

243372

C 26H

30O

135491

621(24)

5511725

(34)

5731563

4191

360[M

+HndashA

pi]+

2570

814[M

+HndashA

pindashG

lc]+

Isoliquiritin

apiosid

e[35]

37a

13300

242362

C 21H

22O

94171198(29)

2550518

[MndashH

ndashGlc]minus

4191

314

(minus67)

4411150

2570

823[M

+HndashG

lc]+

2291

357[M

+HndashG

lcndashC

O]+

Isoliquiritin

[26]

3813479

280

C 27H

34O

115792

103[M

+HCO

O]minus

5571987

5522463

[M+NH

4]+

3551516

[M+

HndashG

lcndashH

2O]+

Arctiin

[36]

39a

1416

1277

C 27H

34O

115792

106[M

+HCO

O]minus

3711826[M

ndashHndashG

lc]minus

3561547

[MndashH

ndashGlcndashH

2O]minus

5522444

[M

+NH

4]+5571991

3731563

[M+HndashG

lc]+

3551544

[M+

HndashG

lcndashH

2O]+

Phillyrin

[3738]

4014678

372255

C 15H

10O

73010

355(23)

1510

137[M

ndashHndashC

8H6O

3]minus

3030520

(49)

Quercetin

[39]

4115039

284

C 28H

34O

1560

91522(13)

3010

582[M

ndashHndashR

ut]minus

Hesperid

in[13]

4215402

265366

C 15H

10O

628504

06(25)

2870

721

(45)

15304

69[M

+HndashH

EP]+

Kaem

pferol

[13]

4316627

255

C 15H

10O

42530507

(24)

2250741

[MndashH

ndashCO]minus

2100494

[MndashH

ndashCOndashC

H3]minus

1820542

[MndashH

ndash2CO

ndashCH

3]minus

1540553

[MndashH

ndash3CO

ndashCH

3]minus

Chrysoph

anol

[40]

4417035

C 15H

10O

42530512

(43)

2250752210047418204

85

1540531

Isom

erof

chrysoph

anol

[40]

45a

17347

254

287426

C 21H

20O

104310

989(26)

2690

673[M

ndashHndashG

lc]minus

2410

719[M

ndashHndashG

lcndashC

O]minus

2250753

[MndashH

ndashGlcndashC

O2]minus

2100578

[MndashH

ndashGlcndashC

O2ndashCH

3]minus

1970

771[MndashH

ndashGlcndashC

OndashC

O2]minus

18204

86[M

ndashHndashG

lcndashC

O2ndashCH

3ndashCO

]minus

4551010

2710

715[M

+HndashG

lc]+

Emod

in-8-O

-glucoside

[41]

4617396

240

330395

C 15H

12O

42550639

(minus71)

2570

812

(minus08)

Isoliquiritigenin

[26]

47a

18385

250304

C 16H

12O

42670

653(minus15

)2690

827

(48)

2910

751

Form

onon

etin

[42]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

4818804

89540

82(28)

7193

849[M

ndashHndashG

lcA]minus

3510

630[2GlcAndash

H]minus

8974

107

(12)

9193

925

22120573-Acetoxy

licorices

apon

inB2

uralsa

poninF

[43]

491919

4271421

C 22H22O10

445116

8(minus56)

2830632

[MndashH

ndashGlc]minus

4691

128

2850775

[M+HndashG

lc]+

Physcion

-8-O

-120573-D

-glucop

yranoside

[41]

5019603

248

C 42H

60O

168193

843(06)

3510

699[2GlcAndash

H]minus

8213

994

(minus01)

8433996

6453612

[M+

HndashG

lcA]+

4693

302[M

+Hndash2GlcA]+

4513

211[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inE2

[35]

5119704

C 16H

24O

73272

180(28)

1649664

[MndashH

ndashGlc]minus

3512

133

Rhod

odendrol-41015840-

O-120573-D

-glucop

yranoside

[44]

5220000

254

C 44H

64O

188794

062(13)

3510

806[M

ndashHndash22A

G]minus

8814

170

(minus01)

7053897

[M+

HndashG

lcA]+

5293

588[M

+Hndash2GlcA]+

5113

395[M

+Hndash2GlcA

ndashH2O

]+

22-

Acetoxyglycyrrhizin

[42]

5320573

352

C 17H

14O

73292

341(39)

3532280

301144

3[M

+HndashC

H2O

]+

2872

002[M

+HndashC

O2]

+ 2591

248[M

+HndashC

O2ndashCO

]+

Tricin

[45]

54a

2119

9260

C 15H

8O6

2830262

(67)

2390

359[M

ndashHndashC

O2]minus

2850515

(minus130)

Rhein

[46]

5521540

253

8373977(12)

8194

404[M

ndashHndashH

2O]minus

6614

100[M

ndashHndashG

lcA]minus

3510

815[2GlcAndash

H]minus

2890

840

[2GlcAndash

HndashH

2OndashC

O2]minus

8394

061

(minus05)

8613

890

6633868

[M+

HndashG

lcA]+

4873395[M

+Hndash2GlcA]+

4693

286[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inG2

[42]

5621626

236

327370

384

C 21H

20O

63671208(71)

3091

566[M

ndashHndashC

OndashC

H2O

]minus

2650635

[MndashH

ndashCOndashC

H2O

ndashCO

2]minus

2210

221

[MndashH

ndashCOndashC

H2O

ndash2CO

2]minus

3691

369

(minus76

)3911176

Glycycoum

arin

[47]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

5722087

249

C 42H

62O

168213

977(17)

8034501

[MndashH

ndashH2O

]minus

7594

542[M

ndashHndashH

2OndashC

O2]minus

6454102

[MndashH

ndashGlcA]minus

6274

000[M

ndashHndashG

lcAndash

H2O

]minus

4693

705[M

ndashHndash2GlcA]minus

3510

809[2GlcAndash

H]minus

2890

758[2GlcAndash

HndashH

2OndashC

O2]minus

8234128

(15)

8454557

6473797[M

+HndashG

lcA]+

4713

480[M

+Hndash2GlcA]+

4533

365[M

+Hndash2GlcA

ndashH2O

]+

Glycyrrhizica

cid

[48]

582218

8252

C 42H

62O

168213

986(minus11)

3510

768[M

ndashHndashG

A]minus

8234134

(minus21)

8454127

6473

823[M

+HndashG

lcA]+

4713

365[M

+Hndash2GlcA]+

4533324

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inH2

[26]

5922389

248

C 42H

64O

158074

197(minus06)

74546

01[M

ndashHndashG

lc]minus

6314

210[M

ndashHndashG

lcA]minus

3510

699[M

ndashHndashG

A]minus

8094

410

(minus09)

8314

138

Licoric

esapon

inB2

[49]

6022623

252

C 42H

62O

168213

997(02)

3510

837[M

ndashHndashG

A]minus

8234105

(minus13

)8453900

6473

838[M

+HndashG

lcA]+

4713

288[M

+Hndash2GlcA]+

4533279

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inK2

[50]

61a

23230

288439

C 15H

10O

52690

462(45)

2410

669[M

ndashHndashC

O]minus

2250723

[MndashH

ndashCO

2]minus

21004

27[M

ndashHndashC

O2ndashCH

3]minus

1970

695[M

ndashHndashC

OndashC

O2]minus

1820477

[MndashH

ndashCO

2ndashCH

3ndashCO

]minus

1540552

[MndashH

ndashCO

2ndashCH

3ndash2C

O]minus

Emod

in[40]

a Com

paredwith

referencec

ompo

unds

b 22A

G2

2-acetoxyglycyrrhizin

ApiapioseC

acaffeoylGAg

lycyrrhetin

icacidG

lcg

lucoseG

lcAg

lucuronicacidH

CT4

-(hydroxym

ethyl)c

yclobu

tane-123-tr

iolHEP

4-(hydroxyethynyl)ph

enolR

ha

rham

noseR

LresorcinolR

utrutinoseVP

4-vinylpheno

l


Table3Linear

regressio

nLO

Dsa

ndLO

Qsintraday

andinterday

precision

srepeatabilitystabilityandrecovery

for12compo

unds

Com

poun

dRe

gressio

nequatio

na(119899=3)

1198772

Linear

range

(120583gmL)

LOD

b

(120583gmL)

LOQ

c

(120583gmL)

Intraday

(RSD

)

(119899=6)

Interday

(RSD

)

(119899=3)

Repeatability(119899=6)Stability

(RSD

)

Recovery

(119899=6)

Mean

(120583gg)

RSD

()

Orig

inal

(120583g)

Spiked

(120583g)

Detected

(120583g)

Recovery

()

RSD

()

Salid

rosid

e119910=

13980119909minus11265

09999

527ndash8

435

106

350

012

026177955plusmn

1092

061

138

35591

35420

7075

09928

124

Chlorogenica

cid

119910=

26510119909+36733

09998

685ndash10956

171

569

077

212247371plusmn

1274

051

254

49474

49385

9599

09419

242

Forsytho

sideE

119910=

11793119909+50168

09995

485ndash776

412

1404

067

225175403plusmn

1872

107

267

3518

13510

56772

69299

354

Cryptochlorogenic

acid

119910=

21498119909minus50189

09997

665ndash10647

166

553

110

163202949plusmn

2065

102

246

40590

40660

78400

9310

143

Amygdalin

119910=

10530119909minus34647

09998

391ndash6

257

098

326

079

093148538plusmn

2585

174

248

2970

829862

57639

9358

332

Sweroside

119910=

20593119909minus60034

09999

200ndash319

6025

080

011

033

79806plusmn

293

037

048

1596

11595

132543

10395

041

Hyperin

119910=

27773119909minus87941

09999

020ndash321

0051

016

078

062

9203plusmn

080

087

083

1841

1824

3707

10229

182

Rutin

119910=

30768119909minus37837

09993

053ndash850

0072

021

041

224

18415plusmn

306

166

157

3683

3681

7250

9690

234

Forsytho

sideA

119910=

85466119909minus60245

09999

421ndash6

734

030

105

020

292248499plusmn

1843

074

195

4970

049595

99733

10089

149

Phillyrin

119910=

30390119909+52828

09999

286ndash4

571

071

236

079

163157780plusmn

1011

064

276

31556

31672

62399

10025

160

Rhein

119910=

74736119909minus51727

09996

347ndash5549

087

288

040

028

68192plusmn

1632

239

097

13638

13627

27348

10061

161

Glycyrrhizica

cid

119910=

10296119909minus65313

09999

527ndash8

435

0092

033

034

209162275plusmn

1759

108

215

32455

323939

65216

1013

1327

a 119910isthep

eakarea119909

isthec

oncentratio

nof

stand

ardsolutio

ns

b LODrefersto

thelim

itsof

detection119878119873=3

c LOQrefersto

thelim

itsof

quantity119878119873=10


Table4Con

tentso

fthe

12compo

unds

in10

batches

Sample

Com

poun

d(m

eanplusmnSD

)(120583gg)

Total

RSD(

)Salid

rosid

eCh

lorogenic

acid

Forsytho

sideE

Cryptochlorogenic

acid

Amygdalin

Sweroside

Hyperin

Rutin

Forsytho

sideA

Phillyrin

Rhein

Glycyrrhizic

acid

Lot1174057plusmn3070215911plusmn1247188899plusmn795146488plusmn1022210985plusmn312783023plusmn8446706plusmn06815622plusmn111316384plusmn3314159920plusmn122957070plusmn223102845plusmn4211677910

1003











the RSD less than 276 The RSD values of intraday andinterday precisions were less than 110 and 292 res-pectively The RSD of repeatability was less than 239The average recovery rates of 12 compounds ranged from9299 to 10395 with the RSD less than 354 All theresults showed that the assay was satisfactory with highaccuracy good reproducibility and high sensitivity whichwere beneficial to the analytical investigation and qualitycontrol for LQC

34 Sample Analysis Twelve representative compounds in10 batches of LQC were quantified through the developedUPLC-DAD analytical method described above The resultsare summarized in Table 4 which showed that the totalconcentrations of 12 quantitative compounds in differentbatches of the LQC varied narrowly moreover the 12components differed greatly in their contents which may beaffected by the source of medicinal materials the quality ofthe plant material or the preparation technology Amongthem forsythoside A showed the highest amount (316455ndash208922120583gg) followed by amygdalin (259475ndash162314120583gg)and hyperin had the lowest amount at 10080ndash6256120583gg

4 Conclusion

LQC is a commonly used Chinese medical preparation totreat viral influenza To date there has not been a systematicaland comprehensive study on the chemical profiling andquality control method for LQC Therefore an accuratesensitive and reliable quality control procedure for LQC isin urgent need to be established In our study the chemicalprofile of LQC was thoroughly and systematically investi-gated by UPLC-DAD-QTOF-MS for the first time Sixty-onecompounds were unambiguously or tentatively identifiedBased on the qualitative analysis a UPLC-DAD method wasestablished for quantitative analysis of 12 representative com-pounds in LQC which has been demonstrated to be effectivefor the analysis of 10 batches of LQCThis developed methodcould be applied as an effective quality control procedure forLQC In addition this study would be a powerful referencefor the identification of similar compounds presented heresuch as flavonoids phenylpropanoids anthraquinones triter-penoids and iridoids by MS spectra

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Authorsrsquo Contribution

Weina Jia and Chunhua Wang contributed equally to thiswork

Acknowledgments

Financial support from Tianjin Applied Basic and Cutting-Edge Technology Research Programs (nos 13JCZDJC28600

and 13JCYBJC42000) Project of New Drug Discovery Plat-form (no 2012ZX09304007) and State Key DevelopmentProgram for Basic Research of China (ldquo973rdquo Program no2012CB723504) is gratefully acknowledged

References

[1] C Y Liu X Q Li and S Q Cai ldquoResearch progress onthe pharmacological and clinical study of Lianhua Qingwencapsulerdquo Pharmacology and Clinics of Chinese Materia Medicavol 26 no 6 pp 84ndash85 2010

[2] X Yi ldquoThe antiviral report of Lianhua Qingwen capsulerdquo TheChinese Health Care no 9 pp 13ndash14 2012

[3] Z-P Duan Z-H Jia J Zhang et al ldquoNatural herbal medicinelianhuaqingwen capsule anti-influenza a (H1N1) trial a ran-domized double blind positive controlled clinical trialrdquo Chi-nese Medical Journal vol 124 no 18 pp 2925ndash2933 2011

[4] H Kiyohara C Ichino Y Kawamura T Nagai N Sato and HYamada ldquoPatchouli alcohol in vitro direct anti-influenza virussesquiterpene in Pogostemon cablin Benthrdquo Journal of NaturalMedicines vol 66 no 1 pp 55ndash61 2012

[5] L Dong J-W Xia Y Gong et al ldquoEffect of Lianhuaqingwencapsules on airway inflammation in patients with acute exac-erbation of chronic obstructive pulmonary diseaserdquo Evidence-Based Complementary and Alternative Medicine vol 2014Article ID 637969 11 pages 2014

[6] G Chen H M Guang L Li et al ldquoBiological network analysisonmechanism of LianhuaQingwen granulescapsules forH1N1influenzaArdquo Journal of Traditional ChineseMedicine vol 55 no8 pp 703ndash707 2014

[7] S H Zhao H H Xu X Y Li et al ldquoTLC and quantitativedetermination by HPLC for Lianhua Qingwen capsulerdquo DrugStandards of China vol 8 no 1 pp 55ndash59 2007

[8] Q F Qin ldquoDetermination of chlorogenic acid forsythin rheinemodin and chrysophanol in Lianhua Qingwen capsules byHPLCrdquo Chinese Journal of Modern Applied Pharmacy vol 31no 2 pp 210ndash213 2014

[9] Y Ling Y Y Wang G T Chen and X Y Wang ldquoSimultaneousdetermination of five components from radixet rhizoma rhei inLianhua Qingwen capsule by HPLCrdquo China Journal of ChineseMedicine vol 27 no 172 pp 1157ndash1158 2012

[10] P Huo S Qin L H Huang and Y J Xu ldquoSimultaneousdetermination of six effective components in Lianhuaqingwencapsule by micellar electrokinetic capillary chromatographyrdquoJournal of Instrumental Analysis vol 30 no 4 pp 396ndash4002011

[11] R Shi W J Jiang S Qiao M Y Liu and Q Wang ldquoDeter-mination of nine constituents in Lianhua Qingwen capsules byLC-MSMS combined with ion switching technologyrdquo ChineseJournal of Pharmaceuticals vol 42 no 10 pp 777ndash780 2011

[12] Y Ogawa M Kawai A Kinoshita and T Konishi ldquoNitrogen-containing compounds from Hemerocallis fulva var semper-virensrdquoChemistry of Natural Compounds vol 49 no 6 pp 991ndash995 2014

[13] L Zhang L Zhu YWang et al ldquoCharacterization and quantifi-cation of major constituents of Xue Fu Zhu Yu by UPLC-DAD-MSMSrdquo Journal of Pharmaceutical and Biomedical Analysisvol 62 pp 203ndash209 2012

[14] W Lan L Bian X Zhao et al ldquoLiquid chromatogra-phyquadrupole time-of-flight mass spectrometry for identi-fication of in vitro and in vivo metabolites of bornyl gallate


in ratsrdquo Journal of Analytical Methods in Chemistry vol 2013Article ID 473649 10 pages 2013

[15] S Deng B J West and C J Jensen ldquoUPLC-TOF-MS char-acterization and identification of bioactive iridoids in Cornusmas fruitrdquo Journal of Analytical Methods in Chemistry vol 2013Article ID 710972 7 pages 2013

[16] N Guo ZW Hu X X Fan et al ldquoSimultaneous determinationof Salidroside and its aglycone metabolite p-tyrosol in ratplasma by liquid chromatography-tandem mass spectrometryrdquoMolecules vol 17 no 4 pp 4733ndash4754 2012

[17] L H Jian Q Hu J Q Zhong Q Meng K Wang and S JildquoDetermination of forsythoside E in Tanreqing injection by LC-MSMSrdquoChinese Journal of Pharmaceutical Analysis vol 33 no3 pp 435ndash438 2013

[18] Y-J Li J Chen and P Li ldquoIdentification and quantification offree radical scavengers in the flower buds of Lonicera species byonline HPLC-DPPH assay coupled with electrospray ionizationquadrupole time-of-flight tandemmass spectrometryrdquoBiomed-ical Chromatography vol 26 no 4 pp 449ndash457 2012

[19] Z-M Qian H-J Li P Li M-T Ren and D Tang ldquoSimul-taneous qualitation and quantification of thirteen bioactivecompounds in Flos Lonicerae by high-performance liquid chro-matography with diode array detector and mass spectrometryrdquoChemical and Pharmaceutical Bulletin vol 55 no 7 pp 1073ndash1076 2007

[20] Y Liu Studies on the Chemical Constituents of the Extractwith Water from Forsythia Suspensa (Thunb) Vahl ShenyangPharmaceutical University Shenyang China 2003

[21] H Q Jiang R Rong and Q H Lv ldquoIdentification of chemicalcomposition in Rhubarb by high performance liquid chro-matography with mass spectrometryrdquo Lishizhen Medicine andMateria Medica Research vol 22 no 7 pp 1075ndash1076 2011

[22] G Qian S-Y Leung L U Guanghua and K S-Y LeungldquoDifferentiation of Rhizoma et Radix Polygoni Cuspidati fromclosely related herbs by HPLC fingerprintingrdquo Chemical andPharmaceutical Bulletin vol 54 no 8 pp 1179ndash1186 2006

[23] H Guo A-H Liu L Li and D-A Guo ldquoSimultaneousdetermination of 12 major constituents in Forsythia suspensaby high performance liquid chromatography-DAD methodrdquoJournal of Pharmaceutical and Biomedical Analysis vol 43 no3 pp 1000ndash1006 2007

[24] Y Cui Q Wang X Shi X Zhang X Sheng and L ZhangldquoSimultaneous quantification of 14 bioactive constituents inForsythia suspensa by liquid chromatography-electrosprayionisation-mass spectrometryrdquo Phytochemical Analysis vol 21no 3 pp 253ndash260 2010

[25] H Liu J Su X Liang et al ldquoIdentification and determinationof the major constituents in traditional Chinese medicineLongdan Xiegan Pill by HPLC-DAD-ESI-MSrdquo Journal of Phar-maceutical Analysis vol 1 no 1 pp 1ndash7 2011

[26] Q W Yin P Wang A H Zhang H Sun X H Wu andXWang ldquoUltra-performance LC-ESIquadrupole-TOFMS forrapid analysis of chemical constituents of Shaoyao-Gancaodecoctionrdquo Journal of Separation Science vol 36 no 7 pp 1238ndash1246 2013

[27] J L Huo J H Wang Z J Wu and G L Zhang ldquoAnalysisof chemical constituents of Rhodiola crenulata using high per-formance liquid chromatography-mass spectrometryrdquo NaturalProduct Research and Development vol 24 pp 1405ndash1407 2012

[28] J Dong Y Zhu X Gao Y Chang M Wang and P ZhangldquoQualitative and quantitative analysis of the major constituents

in Chinese medicinal preparation Dan-Lou tablet by ultrahigh performance liquid chromatographydiode-array detec-torquadrupole time-of-flight tandem mass spectrometryrdquoJournal of Pharmaceutical and Biomedical Analysis vol 80 pp50ndash62 2013

[29] M I Kusaikin A M Zakharenko S P Ermakova et al ldquoDeg-lycosylation of isoflavonoid glycosides fromMaackia amurensiscell culture by 120573-D-glucosidase from Littorina sitkana hep-atopancreaserdquo Chemistry of Natural Compounds vol 47 no 2pp 197ndash200 2011

[30] C P Wan Y Y Yu S R Zhou S G Tian and S WCao ldquoIsolation and identification of phenolic compounds fromGynura divaricata leavesrdquo Pharmacognosy Magazine vol 7 no26 pp 101ndash108 2011

[31] X Yao G S Zhou Y P Tang et al ldquoA UPLC-MSMS methodfor qualification of quercetin-3-O-120573-D- glucopyranoside -(4 rarr 1)-120572-L- rhamnoside in rat plasma and application topharmacokinetic studiesrdquo Molecules vol 18 no 3 pp 3050ndash3059 2013

[32] H Guo A-H Liu M Ye M Yang and D-A Guo ldquoChar-acterization of phenolic compounds in the fruits of Forsythiasuspensa by high-performance liquid chromatography coupledwith electrospray ionization tandemmass spectrometryrdquo RapidCommunications in Mass Spectrometry vol 21 no 5 pp 715ndash729 2007

[33] G L Yan A H Zhang H Sun et al ldquoAn effective methodfor determining the ingredients of Shuanghuanglian for-mula in blood samples using high-resolution LC-MS coupledwith background subtraction and a multiple data processingapproachrdquo Journal of Separation Science vol 36 no 19 pp 3191ndash3199 2013

[34] M Ye W Z Yang K D Liu et al ldquoCharacterizationof flavonoids in Millettia nitida var hirsutissima byHPLCDADESI-MS119899rdquo Journal of Pharmaceutical Analysis vol2 no 1 pp 35ndash42 2012

[35] W-J Miao Q Wang T Bo et al ldquoRapid characteri-zation of chemical constituents and rats metabolites ofthe traditional Chinese patent medicine Gegen-Qinlian-Wanby UHPLCDADqTOF-MSrdquo Journal of Pharmaceutical andBiomedical Analysis vol 72 pp 99ndash108 2013

[36] F He D-Q Dou Y Sun L Zhu H-B Xiao and T-G KangldquoPlasma pharmacokinetics and tissue distribution of arctiin andits main metabolite in rats by HPLC-UV and LC-MSrdquo PlantaMedica vol 78 no 8 pp 800ndash806 2012

[37] Q Su Q-F Liu Y Wang K-S Bi and G-A Luo ldquoRapid andsensitive assay of the main components in Shuanghuanglianpreparations by UPLC-TOF-MSrdquo Chemical Research in ChineseUniversities vol 25 no 1 pp 122ndash124 2009

[38] QWuM-H Bang J-G Cho et al ldquoPhenolic compounds fromthe roots of Brassica rapa ssp campestrisrdquo Chemistry of NaturalCompounds vol 49 no 5 pp 852ndash856 2013

[39] N Li C H Liu S Q Mi et al ldquoSimultaneous determinationof oleanolic acid p-coumaric acid ferulic acid kaemperol andquercetin in rat plasma by LC-MS-MS and application to apharmacokinetic study of oldenlandia diffusa extract in ratsrdquoJournal of Chromatographic Science vol 50 no 10 pp 885ndash8922012

[40] J Z Zhang W Y Gao Z Liu and Z D Zhang ldquoIdentificationand simultaneous determination of twelve active components inthe methanol extract of traditional medicine Weichangrsquoan pillby HPLC-DAD-ESI-MSMSrdquo Iranian Journal of Pharmaceuti-cal Research vol 12 no 1 pp 15ndash24 2013


[41] Z T Liang H B Chen Z L Yu and Z Z Zhao ldquoComparisonof raw and processed Radix Polygoni Multiflori (Heshouwu) byhigh performance liquid chromatography and mass spectrom-etryrdquo Chinese Medicine vol 5 article 29 2010

[42] W-WHuangM-YWang H-M Shi et al ldquoComparative studyof bioactive constituents in crude and processed Glycyrrhizaeradix and their respective metabolic profiles in gastrointestinaltract in vitro by HPLC-DAD and HPLC-ESIMS analysesrdquoArchives of Pharmacal Research vol 35 no 11 pp 1945ndash19522012

[43] W W Tao J A Duan J M Guo et al ldquoSimultaneous deter-mination of triterpenoid saponins in dog plasma by a validatedUPLC-MSMS and its application to a pharmacokinetic studyafter administration of total saponin of licoricerdquo Journal ofPharmaceutical and Biomedical Analysis vol 75 pp 248ndash2552013

[44] W Zhao Studies on the Chemical Constituents of Ephedra sinicaPeking Union Medical College Beijing China 2009

[45] J Sun Y D Yue F Tang X F Guo and J Wang ldquoFlavonoidsfrom the leaves ofNeosinocalamus affinisrdquo Chemistry of NaturalCompounds vol 49 pp 822ndash825 2013

[46] M L Hou L W Chang C H Lin L C Lin and T H TsaildquoDetermination of bioactive components in Chinese herbalformulae and pharmacokinetics of rhein in rats by UPLC-MSMSrdquoMolecules vol 19 pp 4058ndash4075 2014

[47] L Zhou Y-P Tang L Gao X-S Fan C-M Liu and D-KWu ldquoSeparation characterization and dose-effect relationshipof the PPAR120574-activating bio-active constituents in the chineseherb formulation lsquoSan-ao decoctionrsquordquo Molecules vol 14 no 10pp 3942ndash3951 2009

[48] S Tsuruda T Sakamoto and K Akaki ldquoSimultaneous deter-mination of twelve sweeteners and nine preservatives in foodsby solid-phase extraction and LC-MSMSrdquo Shokuhin EiseigakuZasshi vol 54 no 3 pp 204ndash212 2013

[49] I KitagawaKHori T Taniyama J-L Zhou andMYoshikawaldquoSaponin and sapogenol XLVIIOn the constituents of the rootsof Glycyrrhiza uralensis Fisher from Northeastern China (1)Licorice-saponins A3 B2 and C2rdquo Chemical and Pharmaceu-tical Bulletin vol 41 no 1 pp 43ndash49 1993

[50] I Kitagawa K Hori M Sakagami J-L Zhou and MYoshikawa ldquoSaponin and sapogenol XLVIII On the con-stituents of the roots of Glycyrrhiza uralensis FISCHER fromNortheastern China (2) Licorice-saponins D3 E2 F3 G2 H2J2 and K2rdquo Chemical and Pharmaceutical Bulletin vol 41 no8 pp 1337ndash1345 1993

[51] X-D Yang X-Y Tang and L Sang ldquoRapid identificationof micro-constituents in monoammonium glycyrrhizinate rawmaterials by high-pressure solid phase extraction-high per-formance liquid chromatography-mass spectrometryrdquo ChinaJournal of ChineseMateriaMedica vol 37 no 22 pp 3416ndash34212012

[52] C-M Li X-M Liang and X-Y Xue ldquoElectrospray ionizationquadrupole time-of-flight tandemmass spectrometry of iridoidglucosides in positive ion moderdquo Chemical Journal of ChineseUniversities vol 34 no 3 pp 567ndash572 2013

[53] F Wang J Y Zhang Q Wang Y Liu Z J Wang and J QLu ldquoIdentification of phenolic acids from Kudiezi injection byHPLC-HR-MSsimnrdquo Central South Pharmacy vol 11 no 8 pp561ndash565 2013

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


liquid chromatography (HPLC) [8 9] micellar electrokineticcapillary chromatography (MEKC) [10] and liquid chro-matography tandem mass spectrometry (LC-MSMS) [11]no systematical and comprehensive study on the chemicalprofiling and quality control method for LQC has beenreported so far For a classical and complex Chinese medicalpreparation the comprehensive quality evaluation methodshould be based on its multiple chemical constituentsThere-fore it is necessary to develop a rapid and sensitive methodto identify and quantify the chemical constituents in LQCwhich will be beneficial to investigate the effectiveness andevaluate the quality of LQC

In this study a reliable sensitive and simple ultraper-formance liquid chromatography coupled with diode-arraydetector and quadrupole time-of-flight mass spectrometry(UPLC-DAD-QTOF-MS) method which was more system-atical and comprehensive than the earlier ones was estab-lished for characterization and quantification of the majorchemical constituents of LQC A total of 61 compoundswere unambiguously or tentatively identified by comparingthe retention times exact molecular masses and MSMSspectral data with reference compounds or literature dataFurthermore twenty-seven compounds were confirmed bycomparing with the standards Among them twelve repre-sentative compounds were quantified as chemical markers inquantitative analysis including salidroside chlorogenic acidforsythoside E cryptochlorogenic acid amygdalin swero-side hyperin rutin forsythoside A phillyrin rhein andglycyrrhizic acid This is the first systematical and compre-hensive study on the qualitative and quantitative analysis ofLQC

2 Experimental

21 Reagents Chemicals and Materials Methanol and ace-tonitrile (HPLC grade) were purchased from Sigma Aldrich(St Louis MO USA) Formic acid (HPLC grade) waspurchased from Tianjin Damao chemical reagent factory(Tianjin China)Water (HPLC grade) for UPLC analysis wasproduced by theMilli-Qwater purification system (MilliporeUSA) Salidroside chlorogenic acid forsythoside E cryp-tochlorogenic acid amygdalin sweroside hyperin rutinforsythoside A phillyrin rhein and glycyrrhizic acid werepurchased from Sigma Aldrich (St Louis MO USA) Thepurity of standard substances was above 98 Ten batches ofLQC were provided by Shijiazhuang Yiling PharmaceuticalCo Ltd (Shijiazhuang China)

22 UPLC Analysis The UPLC analysis was performed on aWaters ACQUITY UPLC instrument (Waters CorporationMA USA) coupled with a binary pump a sample manageran autosampler a column compartment and diode-arraydetector (DAD)The separation of samples was performed ona Waters ACQUITY UPLC BEH C

18(100 times 21mm 17 120583m)

column with the column temperature at 50∘C The analysiswas completed in 30min with a gradient elution of 01formic acid aqueous solution (A) andmethanol (B) at the flowrate of 03mLmin The gradient program was designed as

follows 0ndash11min 5ndash35 B 11ndash18min 35ndash55 B 18ndash22min55ndash75 B 22ndash24min 75ndash90 B 24-25min 90ndash100 Band 25ndash30min 100 B The injection volume was 5120583L Thedetection wavelengths of DAD were set at 210 nm 225 nmand 254 nm

23 UPLC-DAD-QTOF-MSAnalysis TheWaters ACQUITYUPLC instrument (Waters MA USA) coupled with WatersSynapt HDMS G1 (Waters Manchester UK) via an elec-trospray ionization (ESI) interface The UPLC analyticalconditions were the same as the UPLC analysis describedabove The full scan mass spectra data were acquired inpositive and negative ion modes Acquisition parametersare as follows capillary voltage was 3000V for ESI (+)and 2600V for ESI (minus) cone voltage was 45V the ESIsource temperature was 100∘C the desolvation tempera-ture was 350∘C the nitrogen (N

2) was used as desolva-

tion gas at flow rates of 600 Lh for both ESI (+) andESI (minus) and the range of full scan was set at mz 150ndash1000Da The version of analysis software was Mass LynxV41

24 Sample and Standard Solutions Preparation The powderof LQC (04 g) was accurately weighed and extracted with60 methanol-water (vv) solution (20mL) in an ultrasonicwater bath for 30min at room temperature The supernatantsolution was diluted with the same amount of water andthen centrifuged for 10min at 14000 rmin All the obtainedsolutions were filtered through 022 120583m syringe filter beforethe UPLC analysis

Twelve standards were accurately weighed and dissolvedin methanol to obtain stock solutions respectively A mixedstock solution of standards was prepared by adding a suitablevolume of each stock solution to a 5mL flask and dilutedwith 30 methanol-water solution at the concentration of678 120583gmL for salidroside 10965 120583gmL for chlorogenicacid 7764 120583gmL for forsythoside E 10647 120583gmL for cryp-tochlorogenic acid 6257 120583gmL for amygdalin 3196 120583gmLfor sweroside 321 120583gmL for hyperin 85 120583gmL for rutin6734 120583gmL for forsythoside A 4571120583gmL for phillyrin5549 120583gmL for rhein and 8435 120583gmL for glycyrrhizicacid respectively The mixed stock solution was then seri-ally diluted with 30 methanol-water solution to obtainfive appropriate concentrations used for plotting standardcurves The lowest concentration of the mixture stocksolution was further diluted to give a series of differ-ent concentrations for investigating the limits of detection(LODs) and limits of quantification (LOQs) of the 12 chem-ical constituents All solutions were stored at 4∘C untilanalysis

25 Validation of the Quantitative Analysis TheUPLC-DADmethod was evaluated with linearity LOD LOQ precisionstability repeatability and recovery tests The calibrationcurves were constructed with five different concentrations ofchemical markers in triplicate The LODs and LOQs weremeasured under the UPLC analytical conditions at a signal-to-noise (SN) ratio of 3 and 10 respectively For intraday



Content (120583gg)

Methods30a 60 90 60 60 60 60 60 60











AU 0020406

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300


687933

29

3039

(a)

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 30

AU 00204

0

minus02

6879

29

30

39

54 57

13

(b)

AU

0004008012016

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

6

8

7

9

3329

30

39 54

57

13

26

(c)

AU

0002004006008

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

minus002

(d)

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

AU

00204


minus1minus08

6

87933 29

30

39

57

26

(e)

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

AU 00204

minus04

minus02

6

8

79

33 29

30

39

54 57

(f)

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

AU

0004008012016

02

minus004

8

9

29

30

39

54

5713

26

(g)


Time

()

0

100

()

0

100

2 4 6 8 10 12 14 16 18 20 22 24 26 28

Time2 4 6 8 10 12 14 16 18 20 22 24 26 28

1

2

34 5

67 8 9

101112

13

1415 16

1718

19

20

21

22

23

24

25

26

27

28

28

29

30

301317

31

32 33

34

35

3736

38

39

40

39

42

41

434445

46 47 484950

51

5253

54

5556

57

57

58

59

60

61

45


648e4


BPI813e4





O

O

O

O

OH

OH

O

O

RO

HO

OR1

R1

R3

R2

R2

R4

R5R2OR1O

OR3

OR3

OCH3




(a)

4 8 9 1618 R = OH

38

27 30 34

56

32 R1 = Glc R2 = H39 R1 = Glc R2 = CH3

O

O

O

O

O

O

O

O

O

OO O O

R

O

O

O

O

O

OO

O O O

OO

OO

O

O

O

O

OO

O

O

O

OO

OO

O

O

O

O

O

OH

OH

OHOH

OH

OHOH

OH

OH

OH

OH

OH

OHOH

OH

OHOH

OHOH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

HO

HO

HO

HO

HOHO

HOHO

HO

HO

HO

HOHO

HOHO

HO

HO

HO

HOHO

H3C

OR2

R1O

CH3

(b)


O

O

OR1

R3R2

OR4

(c)

Figure 3 Continued


6058 59


OO

OO

O

O

O

O

O

R2H

H

H

O

O

O

O

OO

O

O

O

O

OO

O

O

OO

O

O

O

OOO

OHOH

OH

OH

OH

OH

OH

OH OH

OHOH

OH

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

R1O

(d)

5 R1 = Glc R2 = H 13 2010R1 = Glc R2 = CH3

OH

HO

O O

O

HOO OO

OOH

H OO

OHOH

OHOH HO

HOHO

HOHOHO

OR1

OR2

(e)

1 2 3 6

15

7

11 33 51

O

O

O

O O

OO

OO

O O

OO

OOO

O

OO

N

OO

O

OHOH OH

OHOH

OH

OH

OH

OH

OHOHOH

OHOH

OH

OH

OH

OH

OH

OH

OHOH

OH

OHOH

HOHO

HO HOHO

HOHO

HO

HOHO

HOHOHO

HOHO

HOHO HO

HOHO

HOHOHO

HO

HO

H3C

(f)







2(44Da)


OHO

OH

O

OHO

O

OHH

mz 1470621

mz 1190691

+H

mz 2570659mz 2570659

mz 1370422

2570659

172999816301591319873 1941022

23914082651331

3011509

1370422

1190691

1199948

13800271470621

1650917 16902931810699 2112177

(MSMS)

100 120 140 160 180 200 220 240 260 280 300

()

0

100

()

0

100

mzmz

120 130 140 150 160 170 180 190 200 210

(MS+)

(a)

OHO

OHO

OH

O

OH

OOH

HOOH

OH

mz 3010464

3010464

1370281

3020746

3027005 4652560 62322138921294

4630905

43109651450305 2210378

46409055310850 7371886 11080997 13072520 14077662

(MSMS)

()

0

100(

)

0

100

mz

200 400 600 800 1000 1200 1400mz

200 400 600 800 1000 1200 1400

(MSminus)

(b)

OHHO

OHHOOC

OHOHHO

O

OHHO OH

COOminus

COOminus COOminus

Cminus

mz 1910733mz 1270486

mz 1730583 mz 1090409

mz 930425 mz 850426

minusCO2

minusCO2

minus2H2O minusC2H2

minusCO

Ominus

minusH

minusH2O minusH2O

minusH2O

1910733

8504261270486930425 1090409 1350577

1610264 1730583 19207421938051

3530878

1910558

3510719192060770718303540916

70516854510630 5031459 7081906

(MSMS)

()

0

100

()

0

100

mzmz

80 90 100 110 120 130 140 150 160 170 180 190 200200 250 300 350 400 450 500 550 600 650 700 750 800

(MSminus)

(c)

O OO

O

OH

OHOH

HO

HO

HO

HO

O

O OHOH

mz 4611920 mz 1610328

CH3

6232001

3112033 6211844

6242032

6252064 124749349575357 13186510

1610328

62325071620342 4611920

(MSMS)

()

0

100

()

0

100

200 400 600 800 1000 1200 1400mzmz

100 200 300 400 500 600 700 800 900 1000

(MSminus)

(d)

Figure 4 Continued


3561547

13599643083514

3711826

37218625161718

5792105

1129871 4310958

58021345812158 111342197973569 11814053

(MSMS)

O

O

O

OO

OO

OH

HOHO

OH


()

0

100

()

0

100

mz

150 200 250 300 350 400 450 500 550 600 650 700 750mz

200 400 600 800 1000 1200 1400

(MSminus)

mz 3561547

mz 3711826

(e)

2250723

18204771810753

18006601540552

19706952240626

2410669 2690634

2420626 2700607

2690462

1129890 27004855610872 8234322 9694360 14023499

O O

O

O

O O

(MSMS)

()

0

100(

)

0

100

mz

160 180 200 220 240 260 280mz

200 400 600 800 1000 1200 1400

(MSminus)

OH

OH

OHOH OH OH OH

OHOHOH

OH

minusCO2

minusCO2minusCO

minusCO

minusHminusHminusH

minusHminusH

minusH

H3CH3C

H3C H3C

mz 1970695mz 2410669

mz 2250723mz 2690462

mz 1820477mz 1540552

minusCH3minusCO

(f)

4310988

11692794321016

4990790 8632153 11946926 14410397

2690673

2250753

18204861710837

1970771 241071927007752710783 3110845

(MSMS)

O

O

O OH

OHO

HOHO

OH

HO





0

100

()

0

100

mz

200 400 600 800 1000 1200 1400mz

140 160 180 200 220 240 260 280 300 320

(MSminus)

mz 3711826mz 2690673

CH3

(g)

8214583

35108091130354

19305102890758

645410258340994693705 7594542

8224637

8234628

(MSMS)

H

HO

HO

OOH

O

O

HOOCHO

HOOHO

HOOH

HOOC


[2GlcAndashH]minus

()

0

100

mz

100 200 300 400 500 600 700 800

8213977

1169246 3111153 8203445

8224006

8434348125530939433099 13258577

()

0

100

mz

200 400 600 800 1000 1200 1400

mz 4693705mz 3510809mz 6454102

(MSminus)

(h)

Figure 4 Continued


3751302

21307733761332

75126674731059 8093751 10383667 13123422

1250712

1210637

930423

650486 950155 1260535 151087824011931740320 1999976 2505933

(MSMS)

OH

H

HO

OH

O

O

O

HO

OHOH

OH



14F

minusH2O

()

0

100

()

0

100

mz

200 400 600 800 1000 1200 1400

mz

60 80 100 120 140 160 180 200 220 240 260

(MSminus)

minusCO2

minusCO2


(i)









2(44Da) CH

3(15Da) and



2]minus and







2OndashCO

2]minus at mz




2O (18Da) CO

2(44Da) and glucose








Table2Ch

aracteriz

ationof

compo

unds

inLQ

Cby

UPL

C-DAD-Q

TOF-MS

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

10817

C 7H

12O

61910

555(minus05)

Quinica

cid

[12]

20982

223287

C 6H

8O7

1910

198(31)

17300

99[M

ndashHndashH

2O]minus

1110

088[M

ndashHndash2H

2OndashC

O2]minus

Citricacid

[13]

3a15

45216271

C 7H

6O5

1690

142(30)

1250241

[MndashH

ndashCO

2]minus

Gallic

acid

[14]

4a3010

325

C 16H

17O

9

3530878

(14)

3750695

[Mndash2H+

Na]minus70718

30[2MndashH

]minus

1910

497[M

ndashHndashC

a]minus

1790

312[C

affeica

cidndash

H]minus

1350359

[Caffeica

cidndash

HndashC

O2]minus

Neochlorogenic

acid

[13]

5a3639

254

C 16H

24O

103751302

(29)

7512

667[2MndashH

]minus

2130773

[MndashH

ndashGlc]minus

1510

878

[MndashH

ndashGlcndashC

O2ndashH

2O]minus

1250721

[MndashH

ndashGlcndash2CO

2]minus

Loganica

cid

[15]

6a404

8224

278

C 14H

20O

72991

133(07)

1790

447[M

ndashHndashC

8H8O

]minus

1190246[M

ndashHndashG

lcndashH

2O]minus

Salid

rosid

e[16]

7a4557

C 20H

30O

124611674(33)

3151348

[MndashH

ndashRha]minus

2971589[M

ndashHndashR

handashH

2O]minus

15306

44[M

ndashHndashR

handashG

lc]minus

1350573

[MndashH

ndashRhandashG

lcndashH

2O]minus

4631220

(minus43)

4851568

1370

599[M

+HndashR

handashG

lcndashH

2O]+

Forsytho

sideE

[17]

8a4749

327

C 16H

17O

93530880

(20)

1910

556[M

ndashHndashC

a]minus

1790

224[C

affeica

cidndash

H]minus

3551028

(minus03)

3770

857

Chlorogenica

cid

[18]

9a5281

325

C 16H

17O

93530880

(20)

1790

348[C

affeica

cidndash

H]minus

17304

61[Q

uinica

cidndash

HndashH

2O]minus

1910

417[M

ndashHndashC

a]minus

Cryptochlorogenic

acid

[18]

106435

270

C 17H

26O

103891

096(31)

3912

176

(minus08)

4131067

3952354

[M+

NandashH

2O]+

2290

835[M

+HndashG

lc]+

Loganin

[19]

116749

C 14H

23O

93350776

(27)

1730459

[MndashH

ndashGlc]minus

1610

373[G

lcndashHndashH

2O]minus

13304

08[G

lcndashH

ndashH2O

ndashCO]minus

3370

883

(53)

3590

686

1630

419[G

lc+

HndashH

2O]+

Reng

ynic

acid-11015840-O

-120573-D

-glucoside

[20]

1272

22C 2

1H20O

94151261

(51)

4391

207

2550879

[M+HndashG

lc]+

Isom

erof

chrysoph

anol

glucoside

[21]

13a

7428

245

C 16H22O9

3571208(62)4031263

[M

+HCO

O]minus

3930938

[M

+Cl]minus

3591

337

(minus14

)3811154

Sweroside

[15]

1478

59C 1

4H23O

93350871

(42)

1930506161037713304

233370

774

(09)

3590

225

1630

416[G

lc+

HndashH

2O]+

Isom

erof

reng

ynic

acid-11015840-O

-120573-D

-glucoside

158106

306

C 20H

22O

83891458(26)4351519

[M+HCO

O]minus

2270

943[M

ndashHndashG

lc]minus

Polydatin

[22]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

168222

C 29H

36O

166392

219(minus17

)4771894[M

ndashHndashG

lc]minus

1790

546[M

ndashRhandashC

17H

14O

6]minus

1610

328[G

lcndashHndashH

2O]minus

R-suspensasid

e[23]

17a

8320

C 21H

20O

94151253

(31)

2530542

[MndashH

ndashGlc]minus

4171394

(minus07)

4391

200

2550864

[M+HndashG

lc]+

Chrysoph

anol

glucoside

[21]

188874

C 29H

36O

166392

002(minus27)

1610

328[G

lcndashHndashH

2O]minus

1790

349[M

ndashRhandashC

17H

14O

6]minus

S-suspensasid

e[24]

1990

54C 2

9H36O

156231999

(minus12

)3112

176

6252137

(08)

6471942

4791

5624711479

32509251630394

Isom

erof

forsytho

sideA

20a

9470

235

C 17H

24O

114031261

(52)

4051331

(minus17

)4271203

2430871

[M+HndashG

lc]+

Secoxyloganin

[19]

2195

52276313

C 21H

22O

94171205(46)8352331

[2MndashH

]minus2550652

[MndashH

ndashGlc]minus

4411132

2570

811[M

+HndashG

lc]+

Liqu

iritin

[25]

22a

9886

277312

C 26H

30O

135491

627(35)

5512

823

(47)

5731737

2570

822[M

+HndashA

pindashG

lc]+

Liqu

iritin

apiosid

e[26]

2399

95C 2

6H30O

135491

629(38)

5513

403

(minus51)

5731735

2570

815[M

+HndashA

pindashG

lc]+

Isom

erof

liquiritin

apiosid

e[26]

2410088

C 27H

30O

1660

91844(minus18

)6331712

Rhod

iosin

[27]

25a

10384

250300

C 22H

22O

94291410(30)

453117

62690

974[M

+HndashG

lc]+

Ono

nin

[2829]

26a

10722

360

C 21H

20O

124630905

(28)

3010

464[M

ndashHndashG

lc]minus

4651033

(52)

4870

333

3030515

[M+HndashG

lc]+

Hyperin

[24]

27a

10819

326

C 25H

24O

125151205

(29)

3530751

[MndashH

ndashCa]minus

5171296

(17)

5391

156

4991

187[M

+HndashH

2O]+

1630

395[M

+HndashC

andashQuinica

cid]

+

35-Dicaffeoylqu

inic

acid

[30]

2810931

C 29H

36O

156231999

(minus19

)46113781610

185

6471941

47114973250925

1630

415

Isom

erof

forsytho

sideA

29a

1110

256354

C 27H

30O

1660

91465(15)

6111573

(33)

6331404

4650982

[M+HndashR

ha]+

3030495

[M+HndashR

ut]+

Rutin

[31]

30a

11220

280

C 29H

36O

156232001

(minus16

)4611920[M

ndashHndashC

a]minus

1610

328[C

affeica

cidndash

HndashH

2O]minus

6471927

1630386

[Caffeica

cid+

HndashH

2O]+

Forsytho

sideA

[32]

3111589

283

C 27H

30O

155931534

(minus13

)2850677

[MndashH

ndashRut]minus

5951694

(minus07)

2870

936[M

+HndashR

ut]+

Kaem

pferol-3-O

-rutin

oside

[13]

3211692

C 19H

35O

165191

884(35)5651953

[M+HCO

O]minus

3571366[M

ndashHndashG

lc]minus

5431855

3591454[M

+HndashG

lc]+

3411411[M

+HndashG

lcndashH

2O]+

(+)-Pino

resin

ol-120573-

D-glucosid

e[33]

33a

12213

210262

C 20H

27NO

114561523

(37)

4581641

(minus46)

2961124

[M+HndashG

lc]+

1620862

[M+

HndashG

lcndashH

CT]+

Amygdalin

[13]


ble2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

34a

12659

326

C 25H

24O

12515116

2(minus54)

3530786

[MndashH

ndashCa]minus

5171348

(04)

5391

193

4991

248[M

+HndashH

2O]+1630387[M

+HndashC

andashQuinica

cid]

+

34-

Dicaffeoylqu

inic

acid

[30]

35a

13082

276

C 15H

12O

42550654

(minus12

)2570

659

(minus08)

1470

621[M

+HndashR

L]+

1370

422[M

+HndashV

P]+

1190691[M

+HndashR

LndashCO

]+Liqu

iritig

enin

[34]

36a

13251

243372

C 26H

30O

135491

621(24)

5511725

(34)

5731563

4191

360[M

+HndashA

pi]+

2570

814[M

+HndashA

pindashG

lc]+

Isoliquiritin

apiosid

e[35]

37a

13300

242362

C 21H

22O

94171198(29)

2550518

[MndashH

ndashGlc]minus

4191

314

(minus67)

4411150

2570

823[M

+HndashG

lc]+

2291

357[M

+HndashG

lcndashC

O]+

Isoliquiritin

[26]

3813479

280

C 27H

34O

115792

103[M

+HCO

O]minus

5571987

5522463

[M+NH

4]+

3551516

[M+

HndashG

lcndashH

2O]+

Arctiin

[36]

39a

1416

1277

C 27H

34O

115792

106[M

+HCO

O]minus

3711826[M

ndashHndashG

lc]minus

3561547

[MndashH

ndashGlcndashH

2O]minus

5522444

[M

+NH

4]+5571991

3731563

[M+HndashG

lc]+

3551544

[M+

HndashG

lcndashH

2O]+

Phillyrin

[3738]

4014678

372255

C 15H

10O

73010

355(23)

1510

137[M

ndashHndashC

8H6O

3]minus

3030520

(49)

Quercetin

[39]

4115039

284

C 28H

34O

1560

91522(13)

3010

582[M

ndashHndashR

ut]minus

Hesperid

in[13]

4215402

265366

C 15H

10O

628504

06(25)

2870

721

(45)

15304

69[M

+HndashH

EP]+

Kaem

pferol

[13]

4316627

255

C 15H

10O

42530507

(24)

2250741

[MndashH

ndashCO]minus

2100494

[MndashH

ndashCOndashC

H3]minus

1820542

[MndashH

ndash2CO

ndashCH

3]minus

1540553

[MndashH

ndash3CO

ndashCH

3]minus

Chrysoph

anol

[40]

4417035

C 15H

10O

42530512

(43)

2250752210047418204

85

1540531

Isom

erof

chrysoph

anol

[40]

45a

17347

254

287426

C 21H

20O

104310

989(26)

2690

673[M

ndashHndashG

lc]minus

2410

719[M

ndashHndashG

lcndashC

O]minus

2250753

[MndashH

ndashGlcndashC

O2]minus

2100578

[MndashH

ndashGlcndashC

O2ndashCH

3]minus

1970

771[MndashH

ndashGlcndashC

OndashC

O2]minus

18204

86[M

ndashHndashG

lcndashC

O2ndashCH

3ndashCO

]minus

4551010

2710

715[M

+HndashG

lc]+

Emod

in-8-O

-glucoside

[41]

4617396

240

330395

C 15H

12O

42550639

(minus71)

2570

812

(minus08)

Isoliquiritigenin

[26]

47a

18385

250304

C 16H

12O

42670

653(minus15

)2690

827

(48)

2910

751

Form

onon

etin

[42]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

4818804

89540

82(28)

7193

849[M

ndashHndashG

lcA]minus

3510

630[2GlcAndash

H]minus

8974

107

(12)

9193

925

22120573-Acetoxy

licorices

apon

inB2

uralsa

poninF

[43]

491919

4271421

C 22H22O10

445116

8(minus56)

2830632

[MndashH

ndashGlc]minus

4691

128

2850775

[M+HndashG

lc]+

Physcion

-8-O

-120573-D

-glucop

yranoside

[41]

5019603

248

C 42H

60O

168193

843(06)

3510

699[2GlcAndash

H]minus

8213

994

(minus01)

8433996

6453612

[M+

HndashG

lcA]+

4693

302[M

+Hndash2GlcA]+

4513

211[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inE2

[35]

5119704

C 16H

24O

73272

180(28)

1649664

[MndashH

ndashGlc]minus

3512

133

Rhod

odendrol-41015840-

O-120573-D

-glucop

yranoside

[44]

5220000

254

C 44H

64O

188794

062(13)

3510

806[M

ndashHndash22A

G]minus

8814

170

(minus01)

7053897

[M+

HndashG

lcA]+

5293

588[M

+Hndash2GlcA]+

5113

395[M

+Hndash2GlcA

ndashH2O

]+

22-

Acetoxyglycyrrhizin

[42]

5320573

352

C 17H

14O

73292

341(39)

3532280

301144

3[M

+HndashC

H2O

]+

2872

002[M

+HndashC

O2]

+ 2591

248[M

+HndashC

O2ndashCO

]+

Tricin

[45]

54a

2119

9260

C 15H

8O6

2830262

(67)

2390

359[M

ndashHndashC

O2]minus

2850515

(minus130)

Rhein

[46]

5521540

253

8373977(12)

8194

404[M

ndashHndashH

2O]minus

6614

100[M

ndashHndashG

lcA]minus

3510

815[2GlcAndash

H]minus

2890

840

[2GlcAndash

HndashH

2OndashC

O2]minus

8394

061

(minus05)

8613

890

6633868

[M+

HndashG

lcA]+

4873395[M

+Hndash2GlcA]+

4693

286[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inG2

[42]

5621626

236

327370

384

C 21H

20O

63671208(71)

3091

566[M

ndashHndashC

OndashC

H2O

]minus

2650635

[MndashH

ndashCOndashC

H2O

ndashCO

2]minus

2210

221

[MndashH

ndashCOndashC

H2O

ndash2CO

2]minus

3691

369

(minus76

)3911176

Glycycoum

arin

[47]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

5722087

249

C 42H

62O

168213

977(17)

8034501

[MndashH

ndashH2O

]minus

7594

542[M

ndashHndashH

2OndashC

O2]minus

6454102

[MndashH

ndashGlcA]minus

6274

000[M

ndashHndashG

lcAndash

H2O

]minus

4693

705[M


3510

809[2GlcAndash

H]minus

2890

758[2GlcAndash

HndashH

2OndashC

O2]minus

8234128

(15)

8454557

6473797[M

+HndashG

lcA]+

4713

480[M

+Hndash2GlcA]+

4533

365[M

+Hndash2GlcA

ndashH2O

]+

Glycyrrhizica

cid

[48]

582218

8252

C 42H

62O

168213

986(minus11)

3510

768[M

ndashHndashG

A]minus

8234134

(minus21)

8454127

6473

823[M

+HndashG

lcA]+

4713

365[M

+Hndash2GlcA]+

4533324

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inH2

[26]

5922389

248

C 42H

64O

158074

197(minus06)

74546

01[M

ndashHndashG

lc]minus

6314

210[M

ndashHndashG

lcA]minus

3510

699[M

ndashHndashG

A]minus

8094

410

(minus09)

8314

138

Licoric

esapon

inB2

[49]

6022623

252

C 42H

62O

168213

997(02)

3510

837[M

ndashHndashG

A]minus

8234105

(minus13

)8453900

6473

838[M

+HndashG

lcA]+

4713

288[M

+Hndash2GlcA]+

4533279

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inK2

[50]

61a

23230

288439

C 15H

10O

52690

462(45)

2410

669[M

ndashHndashC

O]minus

2250723

[MndashH

ndashCO

2]minus

21004

27[M

ndashHndashC

O2ndashCH

3]minus

1970

695[M

ndashHndashC

OndashC

O2]minus

1820477

[MndashH

ndashCO

2ndashCH

3ndashCO

]minus

1540552

[MndashH

ndashCO

2ndashCH

3ndash2C

O]minus

Emod

in[40]

a Com

paredwith

referencec

ompo

unds

b 22A

G2


ApiapioseC

acaffeoylGAg

lycyrrhetin

icacidG

lcg

lucoseG

lcAg

lucuronicacidH

CT4

-(hydroxym

ethyl)c

yclobu

tane-123-tr

iolHEP


enolR

ha

rham

noseR

LresorcinolR

utrutinoseVP

4-vinylpheno

l


Table3Linear

regressio

nLO

Dsa

ndLO

Qsintraday

andinterday

precision


for12compo

unds

Com

poun

dRe

gressio

nequatio

na(119899=3)

1198772

Linear

range

(120583gmL)

LOD

b

(120583gmL)

LOQ

c

(120583gmL)

Intraday

(RSD

)

(119899=6)

Interday

(RSD

)

(119899=3)


(RSD

)

Recovery

(119899=6)

Mean

(120583gg)

RSD

()

Orig

inal

(120583g)

Spiked

(120583g)

Detected

(120583g)

Recovery

()

RSD

()

Salid

rosid

e119910=

13980119909minus11265

09999

527ndash8

435

106

350

012

026177955plusmn

1092

061

138

35591

35420

7075

09928

124

Chlorogenica

cid

119910=

26510119909+36733

09998

685ndash10956

171

569

077

212247371plusmn

1274

051

254

49474

49385

9599

09419

242

Forsytho

sideE

119910=

11793119909+50168

09995

485ndash776

412

1404

067

225175403plusmn

1872

107

267

3518

13510

56772

69299

354

Cryptochlorogenic

acid

119910=

21498119909minus50189

09997

665ndash10647

166

553

110

163202949plusmn

2065

102

246

40590

40660

78400

9310

143

Amygdalin

119910=

10530119909minus34647

09998

391ndash6

257

098

326

079

093148538plusmn

2585

174

248

2970

829862

57639

9358

332

Sweroside

119910=

20593119909minus60034

09999

200ndash319

6025

080

011

033

79806plusmn

293

037

048

1596

11595

132543

10395

041

Hyperin

119910=

27773119909minus87941

09999

020ndash321

0051

016

078

062

9203plusmn

080

087

083

1841

1824

3707

10229

182

Rutin

119910=

30768119909minus37837

09993

053ndash850

0072

021

041

224

18415plusmn

306

166

157

3683

3681

7250

9690

234

Forsytho

sideA

119910=

85466119909minus60245

09999

421ndash6

734

030

105

020

292248499plusmn

1843

074

195

4970

049595

99733

10089

149

Phillyrin

119910=

30390119909+52828

09999

286ndash4

571

071

236

079

163157780plusmn

1011

064

276

31556

31672

62399

10025

160

Rhein

119910=

74736119909minus51727

09996

347ndash5549

087

288

040

028

68192plusmn

1632

239

097

13638

13627

27348

10061

161

Glycyrrhizica

cid

119910=

10296119909minus65313

09999

527ndash8

435

0092

033

034

209162275plusmn

1759

108

215

32455

323939

65216

1013

1327

a 119910isthep

eakarea119909

isthec

oncentratio

nof

stand

ardsolutio

ns

b LODrefersto

thelim

itsof

detection119878119873=3

c LOQrefersto

thelim

itsof

quantity119878119873=10


Table4Con

tentso

fthe

12compo

unds

in10

batches

Sample

Com

poun

d(m

eanplusmnSD

)(120583gg)

Total

RSD(

)Salid

rosid

eCh

lorogenic

acid

Forsytho

sideE

Cryptochlorogenic

acid

Amygdalin

Sweroside

Hyperin

Rutin

Forsytho

sideA

Phillyrin

Rhein

Glycyrrhizic

acid


1003













4 Conclusion






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



Content (120583gg)

Methods30a 60 90 60 60 60 60 60 60











AU 0020406

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300


687933

29

3039

(a)

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 30

AU 00204

0

minus02

6879

29

30

39

54 57

13

(b)

AU

0004008012016

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

6

8

7

9

3329

30

39 54

57

13

26

(c)

AU

0002004006008

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

minus002

(d)

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

AU

00204


minus1minus08

6

87933 29

30

39

57

26

(e)

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

AU 00204

minus04

minus02

6

8

79

33 29

30

39

54 57

(f)

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

AU

0004008012016

02

minus004

8

9

29

30

39

54

5713

26

(g)


Time

()

0

100

()

0

100

2 4 6 8 10 12 14 16 18 20 22 24 26 28

Time2 4 6 8 10 12 14 16 18 20 22 24 26 28

1

2

34 5

67 8 9

101112

13

1415 16

1718

19

20

21

22

23

24

25

26

27

28

28

29

30

301317

31

32 33

34

35

3736

38

39

40

39

42

41

434445

46 47 484950

51

5253

54

5556

57

57

58

59

60

61

45


648e4


BPI813e4





O

O

O

O

OH

OH

O

O

RO

HO

OR1

R1

R3

R2

R2

R4

R5R2OR1O

OR3

OR3

OCH3




(a)

4 8 9 1618 R = OH

38

27 30 34

56

32 R1 = Glc R2 = H39 R1 = Glc R2 = CH3

O

O

O

O

O

O

O

O

O

OO O O

R

O

O

O

O

O

OO

O O O

OO

OO

O

O

O

O

OO

O

O

O

OO

OO

O

O

O

O

O

OH

OH

OHOH

OH

OHOH

OH

OH

OH

OH

OH

OHOH

OH

OHOH

OHOH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

HO

HO

HO

HO

HOHO

HOHO

HO

HO

HO

HOHO

HOHO

HO

HO

HO

HOHO

H3C

OR2

R1O

CH3

(b)


O

O

OR1

R3R2

OR4

(c)

Figure 3 Continued


6058 59


OO

OO

O

O

O

O

O

R2H

H

H

O

O

O

O

OO

O

O

O

O

OO

O

O

OO

O

O

O

OOO

OHOH

OH

OH

OH

OH

OH

OH OH

OHOH

OH

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

R1O

(d)

5 R1 = Glc R2 = H 13 2010R1 = Glc R2 = CH3

OH

HO

O O

O

HOO OO

OOH

H OO

OHOH

OHOH HO

HOHO

HOHOHO

OR1

OR2

(e)

1 2 3 6

15

7

11 33 51

O

O

O

O O

OO

OO

O O

OO

OOO

O

OO

N

OO

O

OHOH OH

OHOH

OH

OH

OH

OH

OHOHOH

OHOH

OH

OH

OH

OH

OH

OH

OHOH

OH

OHOH

HOHO

HO HOHO

HOHO

HO

HOHO

HOHOHO

HOHO

HOHO HO

HOHO

HOHOHO

HO

HO

H3C

(f)







2(44Da)


OHO

OH

O

OHO

O

OHH

mz 1470621

mz 1190691

+H

mz 2570659mz 2570659

mz 1370422

2570659

172999816301591319873 1941022

23914082651331

3011509

1370422

1190691

1199948

13800271470621

1650917 16902931810699 2112177

(MSMS)

100 120 140 160 180 200 220 240 260 280 300

()

0

100

()

0

100

mzmz

120 130 140 150 160 170 180 190 200 210

(MS+)

(a)

OHO

OHO

OH

O

OH

OOH

HOOH

OH

mz 3010464

3010464

1370281

3020746

3027005 4652560 62322138921294

4630905

43109651450305 2210378

46409055310850 7371886 11080997 13072520 14077662

(MSMS)

()

0

100(

)

0

100

mz

200 400 600 800 1000 1200 1400mz

200 400 600 800 1000 1200 1400

(MSminus)

(b)

OHHO

OHHOOC

OHOHHO

O

OHHO OH

COOminus

COOminus COOminus

Cminus

mz 1910733mz 1270486

mz 1730583 mz 1090409

mz 930425 mz 850426

minusCO2

minusCO2

minus2H2O minusC2H2

minusCO

Ominus

minusH

minusH2O minusH2O

minusH2O

1910733

8504261270486930425 1090409 1350577

1610264 1730583 19207421938051

3530878

1910558

3510719192060770718303540916

70516854510630 5031459 7081906

(MSMS)

()

0

100

()

0

100

mzmz

80 90 100 110 120 130 140 150 160 170 180 190 200200 250 300 350 400 450 500 550 600 650 700 750 800

(MSminus)

(c)

O OO

O

OH

OHOH

HO

HO

HO

HO

O

O OHOH

mz 4611920 mz 1610328

CH3

6232001

3112033 6211844

6242032

6252064 124749349575357 13186510

1610328

62325071620342 4611920

(MSMS)

()

0

100

()

0

100

200 400 600 800 1000 1200 1400mzmz

100 200 300 400 500 600 700 800 900 1000

(MSminus)

(d)

Figure 4 Continued


3561547

13599643083514

3711826

37218625161718

5792105

1129871 4310958

58021345812158 111342197973569 11814053

(MSMS)

O

O

O

OO

OO

OH

HOHO

OH


()

0

100

()

0

100

mz

150 200 250 300 350 400 450 500 550 600 650 700 750mz

200 400 600 800 1000 1200 1400

(MSminus)

mz 3561547

mz 3711826

(e)

2250723

18204771810753

18006601540552

19706952240626

2410669 2690634

2420626 2700607

2690462

1129890 27004855610872 8234322 9694360 14023499

O O

O

O

O O

(MSMS)

()

0

100(

)

0

100

mz

160 180 200 220 240 260 280mz

200 400 600 800 1000 1200 1400

(MSminus)

OH

OH

OHOH OH OH OH

OHOHOH

OH

minusCO2

minusCO2minusCO

minusCO

minusHminusHminusH

minusHminusH

minusH

H3CH3C

H3C H3C

mz 1970695mz 2410669

mz 2250723mz 2690462

mz 1820477mz 1540552

minusCH3minusCO

(f)

4310988

11692794321016

4990790 8632153 11946926 14410397

2690673

2250753

18204861710837

1970771 241071927007752710783 3110845

(MSMS)

O

O

O OH

OHO

HOHO

OH

HO





0

100

()

0

100

mz

200 400 600 800 1000 1200 1400mz

140 160 180 200 220 240 260 280 300 320

(MSminus)

mz 3711826mz 2690673

CH3

(g)

8214583

35108091130354

19305102890758

645410258340994693705 7594542

8224637

8234628

(MSMS)

H

HO

HO

OOH

O

O

HOOCHO

HOOHO

HOOH

HOOC


[2GlcAndashH]minus

()

0

100

mz

100 200 300 400 500 600 700 800

8213977

1169246 3111153 8203445

8224006

8434348125530939433099 13258577

()

0

100

mz

200 400 600 800 1000 1200 1400

mz 4693705mz 3510809mz 6454102

(MSminus)

(h)

Figure 4 Continued


3751302

21307733761332

75126674731059 8093751 10383667 13123422

1250712

1210637

930423

650486 950155 1260535 151087824011931740320 1999976 2505933

(MSMS)

OH

H

HO

OH

O

O

O

HO

OHOH

OH



14F

minusH2O

()

0

100

()

0

100

mz

200 400 600 800 1000 1200 1400

mz

60 80 100 120 140 160 180 200 220 240 260

(MSminus)

minusCO2

minusCO2


(i)









2(44Da) CH

3(15Da) and



2]minus and







2OndashCO

2]minus at mz




2O (18Da) CO

2(44Da) and glucose








Table2Ch

aracteriz

ationof

compo

unds

inLQ

Cby

UPL

C-DAD-Q

TOF-MS

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

10817

C 7H

12O

61910

555(minus05)

Quinica

cid

[12]

20982

223287

C 6H

8O7

1910

198(31)

17300

99[M

ndashHndashH

2O]minus

1110

088[M

ndashHndash2H

2OndashC

O2]minus

Citricacid

[13]

3a15

45216271

C 7H

6O5

1690

142(30)

1250241

[MndashH

ndashCO

2]minus

Gallic

acid

[14]

4a3010

325

C 16H

17O

9

3530878

(14)

3750695

[Mndash2H+

Na]minus70718

30[2MndashH

]minus

1910

497[M

ndashHndashC

a]minus

1790

312[C

affeica

cidndash

H]minus

1350359

[Caffeica

cidndash

HndashC

O2]minus

Neochlorogenic

acid

[13]

5a3639

254

C 16H

24O

103751302

(29)

7512

667[2MndashH

]minus

2130773

[MndashH

ndashGlc]minus

1510

878

[MndashH

ndashGlcndashC

O2ndashH

2O]minus

1250721

[MndashH

ndashGlcndash2CO

2]minus

Loganica

cid

[15]

6a404

8224

278

C 14H

20O

72991

133(07)

1790

447[M

ndashHndashC

8H8O

]minus

1190246[M

ndashHndashG

lcndashH

2O]minus

Salid

rosid

e[16]

7a4557

C 20H

30O

124611674(33)

3151348

[MndashH

ndashRha]minus

2971589[M

ndashHndashR

handashH

2O]minus

15306

44[M

ndashHndashR

handashG

lc]minus

1350573

[MndashH

ndashRhandashG

lcndashH

2O]minus

4631220

(minus43)

4851568

1370

599[M

+HndashR

handashG

lcndashH

2O]+

Forsytho

sideE

[17]

8a4749

327

C 16H

17O

93530880

(20)

1910

556[M

ndashHndashC

a]minus

1790

224[C

affeica

cidndash

H]minus

3551028

(minus03)

3770

857

Chlorogenica

cid

[18]

9a5281

325

C 16H

17O

93530880

(20)

1790

348[C

affeica

cidndash

H]minus

17304

61[Q

uinica

cidndash

HndashH

2O]minus

1910

417[M

ndashHndashC

a]minus

Cryptochlorogenic

acid

[18]

106435

270

C 17H

26O

103891

096(31)

3912

176

(minus08)

4131067

3952354

[M+

NandashH

2O]+

2290

835[M

+HndashG

lc]+

Loganin

[19]

116749

C 14H

23O

93350776

(27)

1730459

[MndashH

ndashGlc]minus

1610

373[G

lcndashHndashH

2O]minus

13304

08[G

lcndashH

ndashH2O

ndashCO]minus

3370

883

(53)

3590

686

1630

419[G

lc+

HndashH

2O]+

Reng

ynic

acid-11015840-O

-120573-D

-glucoside

[20]

1272

22C 2

1H20O

94151261

(51)

4391

207

2550879

[M+HndashG

lc]+

Isom

erof

chrysoph

anol

glucoside

[21]

13a

7428

245

C 16H22O9

3571208(62)4031263

[M

+HCO

O]minus

3930938

[M

+Cl]minus

3591

337

(minus14

)3811154

Sweroside

[15]

1478

59C 1

4H23O

93350871

(42)

1930506161037713304

233370

774

(09)

3590

225

1630

416[G

lc+

HndashH

2O]+

Isom

erof

reng

ynic

acid-11015840-O

-120573-D

-glucoside

158106

306

C 20H

22O

83891458(26)4351519

[M+HCO

O]minus

2270

943[M

ndashHndashG

lc]minus

Polydatin

[22]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

168222

C 29H

36O

166392

219(minus17

)4771894[M

ndashHndashG

lc]minus

1790

546[M

ndashRhandashC

17H

14O

6]minus

1610

328[G

lcndashHndashH

2O]minus

R-suspensasid

e[23]

17a

8320

C 21H

20O

94151253

(31)

2530542

[MndashH

ndashGlc]minus

4171394

(minus07)

4391

200

2550864

[M+HndashG

lc]+

Chrysoph

anol

glucoside

[21]

188874

C 29H

36O

166392

002(minus27)

1610

328[G

lcndashHndashH

2O]minus

1790

349[M

ndashRhandashC

17H

14O

6]minus

S-suspensasid

e[24]

1990

54C 2

9H36O

156231999

(minus12

)3112

176

6252137

(08)

6471942

4791

5624711479

32509251630394

Isom

erof

forsytho

sideA

20a

9470

235

C 17H

24O

114031261

(52)

4051331

(minus17

)4271203

2430871

[M+HndashG

lc]+

Secoxyloganin

[19]

2195

52276313

C 21H

22O

94171205(46)8352331

[2MndashH

]minus2550652

[MndashH

ndashGlc]minus

4411132

2570

811[M

+HndashG

lc]+

Liqu

iritin

[25]

22a

9886

277312

C 26H

30O

135491

627(35)

5512

823

(47)

5731737

2570

822[M

+HndashA

pindashG

lc]+

Liqu

iritin

apiosid

e[26]

2399

95C 2

6H30O

135491

629(38)

5513

403

(minus51)

5731735

2570

815[M

+HndashA

pindashG

lc]+

Isom

erof

liquiritin

apiosid

e[26]

2410088

C 27H

30O

1660

91844(minus18

)6331712

Rhod

iosin

[27]

25a

10384

250300

C 22H

22O

94291410(30)

453117

62690

974[M

+HndashG

lc]+

Ono

nin

[2829]

26a

10722

360

C 21H

20O

124630905

(28)

3010

464[M

ndashHndashG

lc]minus

4651033

(52)

4870

333

3030515

[M+HndashG

lc]+

Hyperin

[24]

27a

10819

326

C 25H

24O

125151205

(29)

3530751

[MndashH

ndashCa]minus

5171296

(17)

5391

156

4991

187[M

+HndashH

2O]+

1630

395[M

+HndashC

andashQuinica

cid]

+

35-Dicaffeoylqu

inic

acid

[30]

2810931

C 29H

36O

156231999

(minus19

)46113781610

185

6471941

47114973250925

1630

415

Isom

erof

forsytho

sideA

29a

1110

256354

C 27H

30O

1660

91465(15)

6111573

(33)

6331404

4650982

[M+HndashR

ha]+

3030495

[M+HndashR

ut]+

Rutin

[31]

30a

11220

280

C 29H

36O

156232001

(minus16

)4611920[M

ndashHndashC

a]minus

1610

328[C

affeica

cidndash

HndashH

2O]minus

6471927

1630386

[Caffeica

cid+

HndashH

2O]+

Forsytho

sideA

[32]

3111589

283

C 27H

30O

155931534

(minus13

)2850677

[MndashH

ndashRut]minus

5951694

(minus07)

2870

936[M

+HndashR

ut]+

Kaem

pferol-3-O

-rutin

oside

[13]

3211692

C 19H

35O

165191

884(35)5651953

[M+HCO

O]minus

3571366[M

ndashHndashG

lc]minus

5431855

3591454[M

+HndashG

lc]+

3411411[M

+HndashG

lcndashH

2O]+

(+)-Pino

resin

ol-120573-

D-glucosid

e[33]

33a

12213

210262

C 20H

27NO

114561523

(37)

4581641

(minus46)

2961124

[M+HndashG

lc]+

1620862

[M+

HndashG

lcndashH

CT]+

Amygdalin

[13]


ble2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

34a

12659

326

C 25H

24O

12515116

2(minus54)

3530786

[MndashH

ndashCa]minus

5171348

(04)

5391

193

4991

248[M

+HndashH

2O]+1630387[M

+HndashC

andashQuinica

cid]

+

34-

Dicaffeoylqu

inic

acid

[30]

35a

13082

276

C 15H

12O

42550654

(minus12

)2570

659

(minus08)

1470

621[M

+HndashR

L]+

1370

422[M

+HndashV

P]+

1190691[M

+HndashR

LndashCO

]+Liqu

iritig

enin

[34]

36a

13251

243372

C 26H

30O

135491

621(24)

5511725

(34)

5731563

4191

360[M

+HndashA

pi]+

2570

814[M

+HndashA

pindashG

lc]+

Isoliquiritin

apiosid

e[35]

37a

13300

242362

C 21H

22O

94171198(29)

2550518

[MndashH

ndashGlc]minus

4191

314

(minus67)

4411150

2570

823[M

+HndashG

lc]+

2291

357[M

+HndashG

lcndashC

O]+

Isoliquiritin

[26]

3813479

280

C 27H

34O

115792

103[M

+HCO

O]minus

5571987

5522463

[M+NH

4]+

3551516

[M+

HndashG

lcndashH

2O]+

Arctiin

[36]

39a

1416

1277

C 27H

34O

115792

106[M

+HCO

O]minus

3711826[M

ndashHndashG

lc]minus

3561547

[MndashH

ndashGlcndashH

2O]minus

5522444

[M

+NH

4]+5571991

3731563

[M+HndashG

lc]+

3551544

[M+

HndashG

lcndashH

2O]+

Phillyrin

[3738]

4014678

372255

C 15H

10O

73010

355(23)

1510

137[M

ndashHndashC

8H6O

3]minus

3030520

(49)

Quercetin

[39]

4115039

284

C 28H

34O

1560

91522(13)

3010

582[M

ndashHndashR

ut]minus

Hesperid

in[13]

4215402

265366

C 15H

10O

628504

06(25)

2870

721

(45)

15304

69[M

+HndashH

EP]+

Kaem

pferol

[13]

4316627

255

C 15H

10O

42530507

(24)

2250741

[MndashH

ndashCO]minus

2100494

[MndashH

ndashCOndashC

H3]minus

1820542

[MndashH

ndash2CO

ndashCH

3]minus

1540553

[MndashH

ndash3CO

ndashCH

3]minus

Chrysoph

anol

[40]

4417035

C 15H

10O

42530512

(43)

2250752210047418204

85

1540531

Isom

erof

chrysoph

anol

[40]

45a

17347

254

287426

C 21H

20O

104310

989(26)

2690

673[M

ndashHndashG

lc]minus

2410

719[M

ndashHndashG

lcndashC

O]minus

2250753

[MndashH

ndashGlcndashC

O2]minus

2100578

[MndashH

ndashGlcndashC

O2ndashCH

3]minus

1970

771[MndashH

ndashGlcndashC

OndashC

O2]minus

18204

86[M

ndashHndashG

lcndashC

O2ndashCH

3ndashCO

]minus

4551010

2710

715[M

+HndashG

lc]+

Emod

in-8-O

-glucoside

[41]

4617396

240

330395

C 15H

12O

42550639

(minus71)

2570

812

(minus08)

Isoliquiritigenin

[26]

47a

18385

250304

C 16H

12O

42670

653(minus15

)2690

827

(48)

2910

751

Form

onon

etin

[42]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

4818804

89540

82(28)

7193

849[M

ndashHndashG

lcA]minus

3510

630[2GlcAndash

H]minus

8974

107

(12)

9193

925

22120573-Acetoxy

licorices

apon

inB2

uralsa

poninF

[43]

491919

4271421

C 22H22O10

445116

8(minus56)

2830632

[MndashH

ndashGlc]minus

4691

128

2850775

[M+HndashG

lc]+

Physcion

-8-O

-120573-D

-glucop

yranoside

[41]

5019603

248

C 42H

60O

168193

843(06)

3510

699[2GlcAndash

H]minus

8213

994

(minus01)

8433996

6453612

[M+

HndashG

lcA]+

4693

302[M

+Hndash2GlcA]+

4513

211[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inE2

[35]

5119704

C 16H

24O

73272

180(28)

1649664

[MndashH

ndashGlc]minus

3512

133

Rhod

odendrol-41015840-

O-120573-D

-glucop

yranoside

[44]

5220000

254

C 44H

64O

188794

062(13)

3510

806[M

ndashHndash22A

G]minus

8814

170

(minus01)

7053897

[M+

HndashG

lcA]+

5293

588[M

+Hndash2GlcA]+

5113

395[M

+Hndash2GlcA

ndashH2O

]+

22-

Acetoxyglycyrrhizin

[42]

5320573

352

C 17H

14O

73292

341(39)

3532280

301144

3[M

+HndashC

H2O

]+

2872

002[M

+HndashC

O2]

+ 2591

248[M

+HndashC

O2ndashCO

]+

Tricin

[45]

54a

2119

9260

C 15H

8O6

2830262

(67)

2390

359[M

ndashHndashC

O2]minus

2850515

(minus130)

Rhein

[46]

5521540

253

8373977(12)

8194

404[M

ndashHndashH

2O]minus

6614

100[M

ndashHndashG

lcA]minus

3510

815[2GlcAndash

H]minus

2890

840

[2GlcAndash

HndashH

2OndashC

O2]minus

8394

061

(minus05)

8613

890

6633868

[M+

HndashG

lcA]+

4873395[M

+Hndash2GlcA]+

4693

286[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inG2

[42]

5621626

236

327370

384

C 21H

20O

63671208(71)

3091

566[M

ndashHndashC

OndashC

H2O

]minus

2650635

[MndashH

ndashCOndashC

H2O

ndashCO

2]minus

2210

221

[MndashH

ndashCOndashC

H2O

ndash2CO

2]minus

3691

369

(minus76

)3911176

Glycycoum

arin

[47]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

5722087

249

C 42H

62O

168213

977(17)

8034501

[MndashH

ndashH2O

]minus

7594

542[M

ndashHndashH

2OndashC

O2]minus

6454102

[MndashH

ndashGlcA]minus

6274

000[M

ndashHndashG

lcAndash

H2O

]minus

4693

705[M


3510

809[2GlcAndash

H]minus

2890

758[2GlcAndash

HndashH

2OndashC

O2]minus

8234128

(15)

8454557

6473797[M

+HndashG

lcA]+

4713

480[M

+Hndash2GlcA]+

4533

365[M

+Hndash2GlcA

ndashH2O

]+

Glycyrrhizica

cid

[48]

582218

8252

C 42H

62O

168213

986(minus11)

3510

768[M

ndashHndashG

A]minus

8234134

(minus21)

8454127

6473

823[M

+HndashG

lcA]+

4713

365[M

+Hndash2GlcA]+

4533324

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inH2

[26]

5922389

248

C 42H

64O

158074

197(minus06)

74546

01[M

ndashHndashG

lc]minus

6314

210[M

ndashHndashG

lcA]minus

3510

699[M

ndashHndashG

A]minus

8094

410

(minus09)

8314

138

Licoric

esapon

inB2

[49]

6022623

252

C 42H

62O

168213

997(02)

3510

837[M

ndashHndashG

A]minus

8234105

(minus13

)8453900

6473

838[M

+HndashG

lcA]+

4713

288[M

+Hndash2GlcA]+

4533279

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inK2

[50]

61a

23230

288439

C 15H

10O

52690

462(45)

2410

669[M

ndashHndashC

O]minus

2250723

[MndashH

ndashCO

2]minus

21004

27[M

ndashHndashC

O2ndashCH

3]minus

1970

695[M

ndashHndashC

OndashC

O2]minus

1820477

[MndashH

ndashCO

2ndashCH

3ndashCO

]minus

1540552

[MndashH

ndashCO

2ndashCH

3ndash2C

O]minus

Emod

in[40]

a Com

paredwith

referencec

ompo

unds

b 22A

G2


ApiapioseC

acaffeoylGAg

lycyrrhetin

icacidG

lcg

lucoseG

lcAg

lucuronicacidH

CT4

-(hydroxym

ethyl)c

yclobu

tane-123-tr

iolHEP


enolR

ha

rham

noseR

LresorcinolR

utrutinoseVP

4-vinylpheno

l


Table3Linear

regressio

nLO

Dsa

ndLO

Qsintraday

andinterday

precision


for12compo

unds

Com

poun

dRe

gressio

nequatio

na(119899=3)

1198772

Linear

range

(120583gmL)

LOD

b

(120583gmL)

LOQ

c

(120583gmL)

Intraday

(RSD

)

(119899=6)

Interday

(RSD

)

(119899=3)


(RSD

)

Recovery

(119899=6)

Mean

(120583gg)

RSD

()

Orig

inal

(120583g)

Spiked

(120583g)

Detected

(120583g)

Recovery

()

RSD

()

Salid

rosid

e119910=

13980119909minus11265

09999

527ndash8

435

106

350

012

026177955plusmn

1092

061

138

35591

35420

7075

09928

124

Chlorogenica

cid

119910=

26510119909+36733

09998

685ndash10956

171

569

077

212247371plusmn

1274

051

254

49474

49385

9599

09419

242

Forsytho

sideE

119910=

11793119909+50168

09995

485ndash776

412

1404

067

225175403plusmn

1872

107

267

3518

13510

56772

69299

354

Cryptochlorogenic

acid

119910=

21498119909minus50189

09997

665ndash10647

166

553

110

163202949plusmn

2065

102

246

40590

40660

78400

9310

143

Amygdalin

119910=

10530119909minus34647

09998

391ndash6

257

098

326

079

093148538plusmn

2585

174

248

2970

829862

57639

9358

332

Sweroside

119910=

20593119909minus60034

09999

200ndash319

6025

080

011

033

79806plusmn

293

037

048

1596

11595

132543

10395

041

Hyperin

119910=

27773119909minus87941

09999

020ndash321

0051

016

078

062

9203plusmn

080

087

083

1841

1824

3707

10229

182

Rutin

119910=

30768119909minus37837

09993

053ndash850

0072

021

041

224

18415plusmn

306

166

157

3683

3681

7250

9690

234

Forsytho

sideA

119910=

85466119909minus60245

09999

421ndash6

734

030

105

020

292248499plusmn

1843

074

195

4970

049595

99733

10089

149

Phillyrin

119910=

30390119909+52828

09999

286ndash4

571

071

236

079

163157780plusmn

1011

064

276

31556

31672

62399

10025

160

Rhein

119910=

74736119909minus51727

09996

347ndash5549

087

288

040

028

68192plusmn

1632

239

097

13638

13627

27348

10061

161

Glycyrrhizica

cid

119910=

10296119909minus65313

09999

527ndash8

435

0092

033

034

209162275plusmn

1759

108

215

32455

323939

65216

1013

1327

a 119910isthep

eakarea119909

isthec

oncentratio

nof

stand

ardsolutio

ns

b LODrefersto

thelim

itsof

detection119878119873=3

c LOQrefersto

thelim

itsof

quantity119878119873=10


Table4Con

tentso

fthe

12compo

unds

in10

batches

Sample

Com

poun

d(m

eanplusmnSD

)(120583gg)

Total

RSD(

)Salid

rosid

eCh

lorogenic

acid

Forsytho

sideE

Cryptochlorogenic

acid

Amygdalin

Sweroside

Hyperin

Rutin

Forsytho

sideA

Phillyrin

Rhein

Glycyrrhizic

acid


1003













4 Conclusion






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


AU 0020406

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300


687933

29

3039

(a)

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 30

AU 00204

0

minus02

6879

29

30

39

54 57

13

(b)

AU

0004008012016

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

6

8

7

9

3329

30

39 54

57

13

26

(c)

AU

0002004006008

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

minus002

(d)

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

AU

00204


minus1minus08

6

87933 29

30

39

57

26

(e)

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

AU 00204

minus04

minus02

6

8

79

33 29

30

39

54 57

(f)

(min)2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

AU

0004008012016

02

minus004

8

9

29

30

39

54

5713

26

(g)


Time

()

0

100

()

0

100

2 4 6 8 10 12 14 16 18 20 22 24 26 28

Time2 4 6 8 10 12 14 16 18 20 22 24 26 28

1

2

34 5

67 8 9

101112

13

1415 16

1718

19

20

21

22

23

24

25

26

27

28

28

29

30

301317

31

32 33

34

35

3736

38

39

40

39

42

41

434445

46 47 484950

51

5253

54

5556

57

57

58

59

60

61

45


648e4


BPI813e4





O

O

O

O

OH

OH

O

O

RO

HO

OR1

R1

R3

R2

R2

R4

R5R2OR1O

OR3

OR3

OCH3




(a)

4 8 9 1618 R = OH

38

27 30 34

56

32 R1 = Glc R2 = H39 R1 = Glc R2 = CH3

O

O

O

O

O

O

O

O

O

OO O O

R

O

O

O

O

O

OO

O O O

OO

OO

O

O

O

O

OO

O

O

O

OO

OO

O

O

O

O

O

OH

OH

OHOH

OH

OHOH

OH

OH

OH

OH

OH

OHOH

OH

OHOH

OHOH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

HO

HO

HO

HO

HOHO

HOHO

HO

HO

HO

HOHO

HOHO

HO

HO

HO

HOHO

H3C

OR2

R1O

CH3

(b)


O

O

OR1

R3R2

OR4

(c)

Figure 3 Continued


6058 59


OO

OO

O

O

O

O

O

R2H

H

H

O

O

O

O

OO

O

O

O

O

OO

O

O

OO

O

O

O

OOO

OHOH

OH

OH

OH

OH

OH

OH OH

OHOH

OH

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

R1O

(d)

5 R1 = Glc R2 = H 13 2010R1 = Glc R2 = CH3

OH

HO

O O

O

HOO OO

OOH

H OO

OHOH

OHOH HO

HOHO

HOHOHO

OR1

OR2

(e)

1 2 3 6

15

7

11 33 51

O

O

O

O O

OO

OO

O O

OO

OOO

O

OO

N

OO

O

OHOH OH

OHOH

OH

OH

OH

OH

OHOHOH

OHOH

OH

OH

OH

OH

OH

OH

OHOH

OH

OHOH

HOHO

HO HOHO

HOHO

HO

HOHO

HOHOHO

HOHO

HOHO HO

HOHO

HOHOHO

HO

HO

H3C

(f)







2(44Da)


OHO

OH

O

OHO

O

OHH

mz 1470621

mz 1190691

+H

mz 2570659mz 2570659

mz 1370422

2570659

172999816301591319873 1941022

23914082651331

3011509

1370422

1190691

1199948

13800271470621

1650917 16902931810699 2112177

(MSMS)

100 120 140 160 180 200 220 240 260 280 300

()

0

100

()

0

100

mzmz

120 130 140 150 160 170 180 190 200 210

(MS+)

(a)

OHO

OHO

OH

O

OH

OOH

HOOH

OH

mz 3010464

3010464

1370281

3020746

3027005 4652560 62322138921294

4630905

43109651450305 2210378

46409055310850 7371886 11080997 13072520 14077662

(MSMS)

()

0

100(

)

0

100

mz

200 400 600 800 1000 1200 1400mz

200 400 600 800 1000 1200 1400

(MSminus)

(b)

OHHO

OHHOOC

OHOHHO

O

OHHO OH

COOminus

COOminus COOminus

Cminus

mz 1910733mz 1270486

mz 1730583 mz 1090409

mz 930425 mz 850426

minusCO2

minusCO2

minus2H2O minusC2H2

minusCO

Ominus

minusH

minusH2O minusH2O

minusH2O

1910733

8504261270486930425 1090409 1350577

1610264 1730583 19207421938051

3530878

1910558

3510719192060770718303540916

70516854510630 5031459 7081906

(MSMS)

()

0

100

()

0

100

mzmz

80 90 100 110 120 130 140 150 160 170 180 190 200200 250 300 350 400 450 500 550 600 650 700 750 800

(MSminus)

(c)

O OO

O

OH

OHOH

HO

HO

HO

HO

O

O OHOH

mz 4611920 mz 1610328

CH3

6232001

3112033 6211844

6242032

6252064 124749349575357 13186510

1610328

62325071620342 4611920

(MSMS)

()

0

100

()

0

100

200 400 600 800 1000 1200 1400mzmz

100 200 300 400 500 600 700 800 900 1000

(MSminus)

(d)

Figure 4 Continued


3561547

13599643083514

3711826

37218625161718

5792105

1129871 4310958

58021345812158 111342197973569 11814053

(MSMS)

O

O

O

OO

OO

OH

HOHO

OH


()

0

100

()

0

100

mz

150 200 250 300 350 400 450 500 550 600 650 700 750mz

200 400 600 800 1000 1200 1400

(MSminus)

mz 3561547

mz 3711826

(e)

2250723

18204771810753

18006601540552

19706952240626

2410669 2690634

2420626 2700607

2690462

1129890 27004855610872 8234322 9694360 14023499

O O

O

O

O O

(MSMS)

()

0

100(

)

0

100

mz

160 180 200 220 240 260 280mz

200 400 600 800 1000 1200 1400

(MSminus)

OH

OH

OHOH OH OH OH

OHOHOH

OH

minusCO2

minusCO2minusCO

minusCO

minusHminusHminusH

minusHminusH

minusH

H3CH3C

H3C H3C

mz 1970695mz 2410669

mz 2250723mz 2690462

mz 1820477mz 1540552

minusCH3minusCO

(f)

4310988

11692794321016

4990790 8632153 11946926 14410397

2690673

2250753

18204861710837

1970771 241071927007752710783 3110845

(MSMS)

O

O

O OH

OHO

HOHO

OH

HO





0

100

()

0

100

mz

200 400 600 800 1000 1200 1400mz

140 160 180 200 220 240 260 280 300 320

(MSminus)

mz 3711826mz 2690673

CH3

(g)

8214583

35108091130354

19305102890758

645410258340994693705 7594542

8224637

8234628

(MSMS)

H

HO

HO

OOH

O

O

HOOCHO

HOOHO

HOOH

HOOC


[2GlcAndashH]minus

()

0

100

mz

100 200 300 400 500 600 700 800

8213977

1169246 3111153 8203445

8224006

8434348125530939433099 13258577

()

0

100

mz

200 400 600 800 1000 1200 1400

mz 4693705mz 3510809mz 6454102

(MSminus)

(h)

Figure 4 Continued


3751302

21307733761332

75126674731059 8093751 10383667 13123422

1250712

1210637

930423

650486 950155 1260535 151087824011931740320 1999976 2505933

(MSMS)

OH

H

HO

OH

O

O

O

HO

OHOH

OH



14F

minusH2O

()

0

100

()

0

100

mz

200 400 600 800 1000 1200 1400

mz

60 80 100 120 140 160 180 200 220 240 260

(MSminus)

minusCO2

minusCO2


(i)









2(44Da) CH

3(15Da) and



2]minus and







2OndashCO

2]minus at mz




2O (18Da) CO

2(44Da) and glucose








Table2Ch

aracteriz

ationof

compo

unds

inLQ

Cby

UPL

C-DAD-Q

TOF-MS

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

10817

C 7H

12O

61910

555(minus05)

Quinica

cid

[12]

20982

223287

C 6H

8O7

1910

198(31)

17300

99[M

ndashHndashH

2O]minus

1110

088[M

ndashHndash2H

2OndashC

O2]minus

Citricacid

[13]

3a15

45216271

C 7H

6O5

1690

142(30)

1250241

[MndashH

ndashCO

2]minus

Gallic

acid

[14]

4a3010

325

C 16H

17O

9

3530878

(14)

3750695

[Mndash2H+

Na]minus70718

30[2MndashH

]minus

1910

497[M

ndashHndashC

a]minus

1790

312[C

affeica

cidndash

H]minus

1350359

[Caffeica

cidndash

HndashC

O2]minus

Neochlorogenic

acid

[13]

5a3639

254

C 16H

24O

103751302

(29)

7512

667[2MndashH

]minus

2130773

[MndashH

ndashGlc]minus

1510

878

[MndashH

ndashGlcndashC

O2ndashH

2O]minus

1250721

[MndashH

ndashGlcndash2CO

2]minus

Loganica

cid

[15]

6a404

8224

278

C 14H

20O

72991

133(07)

1790

447[M

ndashHndashC

8H8O

]minus

1190246[M

ndashHndashG

lcndashH

2O]minus

Salid

rosid

e[16]

7a4557

C 20H

30O

124611674(33)

3151348

[MndashH

ndashRha]minus

2971589[M

ndashHndashR

handashH

2O]minus

15306

44[M

ndashHndashR

handashG

lc]minus

1350573

[MndashH

ndashRhandashG

lcndashH

2O]minus

4631220

(minus43)

4851568

1370

599[M

+HndashR

handashG

lcndashH

2O]+

Forsytho

sideE

[17]

8a4749

327

C 16H

17O

93530880

(20)

1910

556[M

ndashHndashC

a]minus

1790

224[C

affeica

cidndash

H]minus

3551028

(minus03)

3770

857

Chlorogenica

cid

[18]

9a5281

325

C 16H

17O

93530880

(20)

1790

348[C

affeica

cidndash

H]minus

17304

61[Q

uinica

cidndash

HndashH

2O]minus

1910

417[M

ndashHndashC

a]minus

Cryptochlorogenic

acid

[18]

106435

270

C 17H

26O

103891

096(31)

3912

176

(minus08)

4131067

3952354

[M+

NandashH

2O]+

2290

835[M

+HndashG

lc]+

Loganin

[19]

116749

C 14H

23O

93350776

(27)

1730459

[MndashH

ndashGlc]minus

1610

373[G

lcndashHndashH

2O]minus

13304

08[G

lcndashH

ndashH2O

ndashCO]minus

3370

883

(53)

3590

686

1630

419[G

lc+

HndashH

2O]+

Reng

ynic

acid-11015840-O

-120573-D

-glucoside

[20]

1272

22C 2

1H20O

94151261

(51)

4391

207

2550879

[M+HndashG

lc]+

Isom

erof

chrysoph

anol

glucoside

[21]

13a

7428

245

C 16H22O9

3571208(62)4031263

[M

+HCO

O]minus

3930938

[M

+Cl]minus

3591

337

(minus14

)3811154

Sweroside

[15]

1478

59C 1

4H23O

93350871

(42)

1930506161037713304

233370

774

(09)

3590

225

1630

416[G

lc+

HndashH

2O]+

Isom

erof

reng

ynic

acid-11015840-O

-120573-D

-glucoside

158106

306

C 20H

22O

83891458(26)4351519

[M+HCO

O]minus

2270

943[M

ndashHndashG

lc]minus

Polydatin

[22]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

168222

C 29H

36O

166392

219(minus17

)4771894[M

ndashHndashG

lc]minus

1790

546[M

ndashRhandashC

17H

14O

6]minus

1610

328[G

lcndashHndashH

2O]minus

R-suspensasid

e[23]

17a

8320

C 21H

20O

94151253

(31)

2530542

[MndashH

ndashGlc]minus

4171394

(minus07)

4391

200

2550864

[M+HndashG

lc]+

Chrysoph

anol

glucoside

[21]

188874

C 29H

36O

166392

002(minus27)

1610

328[G

lcndashHndashH

2O]minus

1790

349[M

ndashRhandashC

17H

14O

6]minus

S-suspensasid

e[24]

1990

54C 2

9H36O

156231999

(minus12

)3112

176

6252137

(08)

6471942

4791

5624711479

32509251630394

Isom

erof

forsytho

sideA

20a

9470

235

C 17H

24O

114031261

(52)

4051331

(minus17

)4271203

2430871

[M+HndashG

lc]+

Secoxyloganin

[19]

2195

52276313

C 21H

22O

94171205(46)8352331

[2MndashH

]minus2550652

[MndashH

ndashGlc]minus

4411132

2570

811[M

+HndashG

lc]+

Liqu

iritin

[25]

22a

9886

277312

C 26H

30O

135491

627(35)

5512

823

(47)

5731737

2570

822[M

+HndashA

pindashG

lc]+

Liqu

iritin

apiosid

e[26]

2399

95C 2

6H30O

135491

629(38)

5513

403

(minus51)

5731735

2570

815[M

+HndashA

pindashG

lc]+

Isom

erof

liquiritin

apiosid

e[26]

2410088

C 27H

30O

1660

91844(minus18

)6331712

Rhod

iosin

[27]

25a

10384

250300

C 22H

22O

94291410(30)

453117

62690

974[M

+HndashG

lc]+

Ono

nin

[2829]

26a

10722

360

C 21H

20O

124630905

(28)

3010

464[M

ndashHndashG

lc]minus

4651033

(52)

4870

333

3030515

[M+HndashG

lc]+

Hyperin

[24]

27a

10819

326

C 25H

24O

125151205

(29)

3530751

[MndashH

ndashCa]minus

5171296

(17)

5391

156

4991

187[M

+HndashH

2O]+

1630

395[M

+HndashC

andashQuinica

cid]

+

35-Dicaffeoylqu

inic

acid

[30]

2810931

C 29H

36O

156231999

(minus19

)46113781610

185

6471941

47114973250925

1630

415

Isom

erof

forsytho

sideA

29a

1110

256354

C 27H

30O

1660

91465(15)

6111573

(33)

6331404

4650982

[M+HndashR

ha]+

3030495

[M+HndashR

ut]+

Rutin

[31]

30a

11220

280

C 29H

36O

156232001

(minus16

)4611920[M

ndashHndashC

a]minus

1610

328[C

affeica

cidndash

HndashH

2O]minus

6471927

1630386

[Caffeica

cid+

HndashH

2O]+

Forsytho

sideA

[32]

3111589

283

C 27H

30O

155931534

(minus13

)2850677

[MndashH

ndashRut]minus

5951694

(minus07)

2870

936[M

+HndashR

ut]+

Kaem

pferol-3-O

-rutin

oside

[13]

3211692

C 19H

35O

165191

884(35)5651953

[M+HCO

O]minus

3571366[M

ndashHndashG

lc]minus

5431855

3591454[M

+HndashG

lc]+

3411411[M

+HndashG

lcndashH

2O]+

(+)-Pino

resin

ol-120573-

D-glucosid

e[33]

33a

12213

210262

C 20H

27NO

114561523

(37)

4581641

(minus46)

2961124

[M+HndashG

lc]+

1620862

[M+

HndashG

lcndashH

CT]+

Amygdalin

[13]


ble2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

34a

12659

326

C 25H

24O

12515116

2(minus54)

3530786

[MndashH

ndashCa]minus

5171348

(04)

5391

193

4991

248[M

+HndashH

2O]+1630387[M

+HndashC

andashQuinica

cid]

+

34-

Dicaffeoylqu

inic

acid

[30]

35a

13082

276

C 15H

12O

42550654

(minus12

)2570

659

(minus08)

1470

621[M

+HndashR

L]+

1370

422[M

+HndashV

P]+

1190691[M

+HndashR

LndashCO

]+Liqu

iritig

enin

[34]

36a

13251

243372

C 26H

30O

135491

621(24)

5511725

(34)

5731563

4191

360[M

+HndashA

pi]+

2570

814[M

+HndashA

pindashG

lc]+

Isoliquiritin

apiosid

e[35]

37a

13300

242362

C 21H

22O

94171198(29)

2550518

[MndashH

ndashGlc]minus

4191

314

(minus67)

4411150

2570

823[M

+HndashG

lc]+

2291

357[M

+HndashG

lcndashC

O]+

Isoliquiritin

[26]

3813479

280

C 27H

34O

115792

103[M

+HCO

O]minus

5571987

5522463

[M+NH

4]+

3551516

[M+

HndashG

lcndashH

2O]+

Arctiin

[36]

39a

1416

1277

C 27H

34O

115792

106[M

+HCO

O]minus

3711826[M

ndashHndashG

lc]minus

3561547

[MndashH

ndashGlcndashH

2O]minus

5522444

[M

+NH

4]+5571991

3731563

[M+HndashG

lc]+

3551544

[M+

HndashG

lcndashH

2O]+

Phillyrin

[3738]

4014678

372255

C 15H

10O

73010

355(23)

1510

137[M

ndashHndashC

8H6O

3]minus

3030520

(49)

Quercetin

[39]

4115039

284

C 28H

34O

1560

91522(13)

3010

582[M

ndashHndashR

ut]minus

Hesperid

in[13]

4215402

265366

C 15H

10O

628504

06(25)

2870

721

(45)

15304

69[M

+HndashH

EP]+

Kaem

pferol

[13]

4316627

255

C 15H

10O

42530507

(24)

2250741

[MndashH

ndashCO]minus

2100494

[MndashH

ndashCOndashC

H3]minus

1820542

[MndashH

ndash2CO

ndashCH

3]minus

1540553

[MndashH

ndash3CO

ndashCH

3]minus

Chrysoph

anol

[40]

4417035

C 15H

10O

42530512

(43)

2250752210047418204

85

1540531

Isom

erof

chrysoph

anol

[40]

45a

17347

254

287426

C 21H

20O

104310

989(26)

2690

673[M

ndashHndashG

lc]minus

2410

719[M

ndashHndashG

lcndashC

O]minus

2250753

[MndashH

ndashGlcndashC

O2]minus

2100578

[MndashH

ndashGlcndashC

O2ndashCH

3]minus

1970

771[MndashH

ndashGlcndashC

OndashC

O2]minus

18204

86[M

ndashHndashG

lcndashC

O2ndashCH

3ndashCO

]minus

4551010

2710

715[M

+HndashG

lc]+

Emod

in-8-O

-glucoside

[41]

4617396

240

330395

C 15H

12O

42550639

(minus71)

2570

812

(minus08)

Isoliquiritigenin

[26]

47a

18385

250304

C 16H

12O

42670

653(minus15

)2690

827

(48)

2910

751

Form

onon

etin

[42]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

4818804

89540

82(28)

7193

849[M

ndashHndashG

lcA]minus

3510

630[2GlcAndash

H]minus

8974

107

(12)

9193

925

22120573-Acetoxy

licorices

apon

inB2

uralsa

poninF

[43]

491919

4271421

C 22H22O10

445116

8(minus56)

2830632

[MndashH

ndashGlc]minus

4691

128

2850775

[M+HndashG

lc]+

Physcion

-8-O

-120573-D

-glucop

yranoside

[41]

5019603

248

C 42H

60O

168193

843(06)

3510

699[2GlcAndash

H]minus

8213

994

(minus01)

8433996

6453612

[M+

HndashG

lcA]+

4693

302[M

+Hndash2GlcA]+

4513

211[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inE2

[35]

5119704

C 16H

24O

73272

180(28)

1649664

[MndashH

ndashGlc]minus

3512

133

Rhod

odendrol-41015840-

O-120573-D

-glucop

yranoside

[44]

5220000

254

C 44H

64O

188794

062(13)

3510

806[M

ndashHndash22A

G]minus

8814

170

(minus01)

7053897

[M+

HndashG

lcA]+

5293

588[M

+Hndash2GlcA]+

5113

395[M

+Hndash2GlcA

ndashH2O

]+

22-

Acetoxyglycyrrhizin

[42]

5320573

352

C 17H

14O

73292

341(39)

3532280

301144

3[M

+HndashC

H2O

]+

2872

002[M

+HndashC

O2]

+ 2591

248[M

+HndashC

O2ndashCO

]+

Tricin

[45]

54a

2119

9260

C 15H

8O6

2830262

(67)

2390

359[M

ndashHndashC

O2]minus

2850515

(minus130)

Rhein

[46]

5521540

253

8373977(12)

8194

404[M

ndashHndashH

2O]minus

6614

100[M

ndashHndashG

lcA]minus

3510

815[2GlcAndash

H]minus

2890

840

[2GlcAndash

HndashH

2OndashC

O2]minus

8394

061

(minus05)

8613

890

6633868

[M+

HndashG

lcA]+

4873395[M

+Hndash2GlcA]+

4693

286[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inG2

[42]

5621626

236

327370

384

C 21H

20O

63671208(71)

3091

566[M

ndashHndashC

OndashC

H2O

]minus

2650635

[MndashH

ndashCOndashC

H2O

ndashCO

2]minus

2210

221

[MndashH

ndashCOndashC

H2O

ndash2CO

2]minus

3691

369

(minus76

)3911176

Glycycoum

arin

[47]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

5722087

249

C 42H

62O

168213

977(17)

8034501

[MndashH

ndashH2O

]minus

7594

542[M

ndashHndashH

2OndashC

O2]minus

6454102

[MndashH

ndashGlcA]minus

6274

000[M

ndashHndashG

lcAndash

H2O

]minus

4693

705[M


3510

809[2GlcAndash

H]minus

2890

758[2GlcAndash

HndashH

2OndashC

O2]minus

8234128

(15)

8454557

6473797[M

+HndashG

lcA]+

4713

480[M

+Hndash2GlcA]+

4533

365[M

+Hndash2GlcA

ndashH2O

]+

Glycyrrhizica

cid

[48]

582218

8252

C 42H

62O

168213

986(minus11)

3510

768[M

ndashHndashG

A]minus

8234134

(minus21)

8454127

6473

823[M

+HndashG

lcA]+

4713

365[M

+Hndash2GlcA]+

4533324

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inH2

[26]

5922389

248

C 42H

64O

158074

197(minus06)

74546

01[M

ndashHndashG

lc]minus

6314

210[M

ndashHndashG

lcA]minus

3510

699[M

ndashHndashG

A]minus

8094

410

(minus09)

8314

138

Licoric

esapon

inB2

[49]

6022623

252

C 42H

62O

168213

997(02)

3510

837[M

ndashHndashG

A]minus

8234105

(minus13

)8453900

6473

838[M

+HndashG

lcA]+

4713

288[M

+Hndash2GlcA]+

4533279

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inK2

[50]

61a

23230

288439

C 15H

10O

52690

462(45)

2410

669[M

ndashHndashC

O]minus

2250723

[MndashH

ndashCO

2]minus

21004

27[M

ndashHndashC

O2ndashCH

3]minus

1970

695[M

ndashHndashC

OndashC

O2]minus

1820477

[MndashH

ndashCO

2ndashCH

3ndashCO

]minus

1540552

[MndashH

ndashCO

2ndashCH

3ndash2C

O]minus

Emod

in[40]

a Com

paredwith

referencec

ompo

unds

b 22A

G2


ApiapioseC

acaffeoylGAg

lycyrrhetin

icacidG

lcg

lucoseG

lcAg

lucuronicacidH

CT4

-(hydroxym

ethyl)c

yclobu

tane-123-tr

iolHEP


enolR

ha

rham

noseR

LresorcinolR

utrutinoseVP

4-vinylpheno

l


Table3Linear

regressio

nLO

Dsa

ndLO

Qsintraday

andinterday

precision


for12compo

unds

Com

poun

dRe

gressio

nequatio

na(119899=3)

1198772

Linear

range

(120583gmL)

LOD

b

(120583gmL)

LOQ

c

(120583gmL)

Intraday

(RSD

)

(119899=6)

Interday

(RSD

)

(119899=3)


(RSD

)

Recovery

(119899=6)

Mean

(120583gg)

RSD

()

Orig

inal

(120583g)

Spiked

(120583g)

Detected

(120583g)

Recovery

()

RSD

()

Salid

rosid

e119910=

13980119909minus11265

09999

527ndash8

435

106

350

012

026177955plusmn

1092

061

138

35591

35420

7075

09928

124

Chlorogenica

cid

119910=

26510119909+36733

09998

685ndash10956

171

569

077

212247371plusmn

1274

051

254

49474

49385

9599

09419

242

Forsytho

sideE

119910=

11793119909+50168

09995

485ndash776

412

1404

067

225175403plusmn

1872

107

267

3518

13510

56772

69299

354

Cryptochlorogenic

acid

119910=

21498119909minus50189

09997

665ndash10647

166

553

110

163202949plusmn

2065

102

246

40590

40660

78400

9310

143

Amygdalin

119910=

10530119909minus34647

09998

391ndash6

257

098

326

079

093148538plusmn

2585

174

248

2970

829862

57639

9358

332

Sweroside

119910=

20593119909minus60034

09999

200ndash319

6025

080

011

033

79806plusmn

293

037

048

1596

11595

132543

10395

041

Hyperin

119910=

27773119909minus87941

09999

020ndash321

0051

016

078

062

9203plusmn

080

087

083

1841

1824

3707

10229

182

Rutin

119910=

30768119909minus37837

09993

053ndash850

0072

021

041

224

18415plusmn

306

166

157

3683

3681

7250

9690

234

Forsytho

sideA

119910=

85466119909minus60245

09999

421ndash6

734

030

105

020

292248499plusmn

1843

074

195

4970

049595

99733

10089

149

Phillyrin

119910=

30390119909+52828

09999

286ndash4

571

071

236

079

163157780plusmn

1011

064

276

31556

31672

62399

10025

160

Rhein

119910=

74736119909minus51727

09996

347ndash5549

087

288

040

028

68192plusmn

1632

239

097

13638

13627

27348

10061

161

Glycyrrhizica

cid

119910=

10296119909minus65313

09999

527ndash8

435

0092

033

034

209162275plusmn

1759

108

215

32455

323939

65216

1013

1327

a 119910isthep

eakarea119909

isthec

oncentratio

nof

stand

ardsolutio

ns

b LODrefersto

thelim

itsof

detection119878119873=3

c LOQrefersto

thelim

itsof

quantity119878119873=10


Table4Con

tentso

fthe

12compo

unds

in10

batches

Sample

Com

poun

d(m

eanplusmnSD

)(120583gg)

Total

RSD(

)Salid

rosid

eCh

lorogenic

acid

Forsytho

sideE

Cryptochlorogenic

acid

Amygdalin

Sweroside

Hyperin

Rutin

Forsytho

sideA

Phillyrin

Rhein

Glycyrrhizic

acid


1003













4 Conclusion






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


O

O

O

O

OH

OH

O

O

RO

HO

OR1

R1

R3

R2

R2

R4

R5R2OR1O

OR3

OR3

OCH3




(a)

4 8 9 1618 R = OH

38

27 30 34

56

32 R1 = Glc R2 = H39 R1 = Glc R2 = CH3

O

O

O

O

O

O

O

O

O

OO O O

R

O

O

O

O

O

OO

O O O

OO

OO

O

O

O

O

OO

O

O

O

OO

OO

O

O

O

O

O

OH

OH

OHOH

OH

OHOH

OH

OH

OH

OH

OH

OHOH

OH

OHOH

OHOH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

HO

HO

HO

HO

HOHO

HOHO

HO

HO

HO

HOHO

HOHO

HO

HO

HO

HOHO

H3C

OR2

R1O

CH3

(b)


O

O

OR1

R3R2

OR4

(c)

Figure 3 Continued


6058 59


OO

OO

O

O

O

O

O

R2H

H

H

O

O

O

O

OO

O

O

O

O

OO

O

O

OO

O

O

O

OOO

OHOH

OH

OH

OH

OH

OH

OH OH

OHOH

OH

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

R1O

(d)

5 R1 = Glc R2 = H 13 2010R1 = Glc R2 = CH3

OH

HO

O O

O

HOO OO

OOH

H OO

OHOH

OHOH HO

HOHO

HOHOHO

OR1

OR2

(e)

1 2 3 6

15

7

11 33 51

O

O

O

O O

OO

OO

O O

OO

OOO

O

OO

N

OO

O

OHOH OH

OHOH

OH

OH

OH

OH

OHOHOH

OHOH

OH

OH

OH

OH

OH

OH

OHOH

OH

OHOH

HOHO

HO HOHO

HOHO

HO

HOHO

HOHOHO

HOHO

HOHO HO

HOHO

HOHOHO

HO

HO

H3C

(f)







2(44Da)


OHO

OH

O

OHO

O

OHH

mz 1470621

mz 1190691

+H

mz 2570659mz 2570659

mz 1370422

2570659

172999816301591319873 1941022

23914082651331

3011509

1370422

1190691

1199948

13800271470621

1650917 16902931810699 2112177

(MSMS)

100 120 140 160 180 200 220 240 260 280 300

()

0

100

()

0

100

mzmz

120 130 140 150 160 170 180 190 200 210

(MS+)

(a)

OHO

OHO

OH

O

OH

OOH

HOOH

OH

mz 3010464

3010464

1370281

3020746

3027005 4652560 62322138921294

4630905

43109651450305 2210378

46409055310850 7371886 11080997 13072520 14077662

(MSMS)

()

0

100(

)

0

100

mz

200 400 600 800 1000 1200 1400mz

200 400 600 800 1000 1200 1400

(MSminus)

(b)

OHHO

OHHOOC

OHOHHO

O

OHHO OH

COOminus

COOminus COOminus

Cminus

mz 1910733mz 1270486

mz 1730583 mz 1090409

mz 930425 mz 850426

minusCO2

minusCO2

minus2H2O minusC2H2

minusCO

Ominus

minusH

minusH2O minusH2O

minusH2O

1910733

8504261270486930425 1090409 1350577

1610264 1730583 19207421938051

3530878

1910558

3510719192060770718303540916

70516854510630 5031459 7081906

(MSMS)

()

0

100

()

0

100

mzmz

80 90 100 110 120 130 140 150 160 170 180 190 200200 250 300 350 400 450 500 550 600 650 700 750 800

(MSminus)

(c)

O OO

O

OH

OHOH

HO

HO

HO

HO

O

O OHOH

mz 4611920 mz 1610328

CH3

6232001

3112033 6211844

6242032

6252064 124749349575357 13186510

1610328

62325071620342 4611920

(MSMS)

()

0

100

()

0

100

200 400 600 800 1000 1200 1400mzmz

100 200 300 400 500 600 700 800 900 1000

(MSminus)

(d)

Figure 4 Continued


3561547

13599643083514

3711826

37218625161718

5792105

1129871 4310958

58021345812158 111342197973569 11814053

(MSMS)

O

O

O

OO

OO

OH

HOHO

OH


()

0

100

()

0

100

mz

150 200 250 300 350 400 450 500 550 600 650 700 750mz

200 400 600 800 1000 1200 1400

(MSminus)

mz 3561547

mz 3711826

(e)

2250723

18204771810753

18006601540552

19706952240626

2410669 2690634

2420626 2700607

2690462

1129890 27004855610872 8234322 9694360 14023499

O O

O

O

O O

(MSMS)

()

0

100(

)

0

100

mz

160 180 200 220 240 260 280mz

200 400 600 800 1000 1200 1400

(MSminus)

OH

OH

OHOH OH OH OH

OHOHOH

OH

minusCO2

minusCO2minusCO

minusCO

minusHminusHminusH

minusHminusH

minusH

H3CH3C

H3C H3C

mz 1970695mz 2410669

mz 2250723mz 2690462

mz 1820477mz 1540552

minusCH3minusCO

(f)

4310988

11692794321016

4990790 8632153 11946926 14410397

2690673

2250753

18204861710837

1970771 241071927007752710783 3110845

(MSMS)

O

O

O OH

OHO

HOHO

OH

HO





0

100

()

0

100

mz

200 400 600 800 1000 1200 1400mz

140 160 180 200 220 240 260 280 300 320

(MSminus)

mz 3711826mz 2690673

CH3

(g)

8214583

35108091130354

19305102890758

645410258340994693705 7594542

8224637

8234628

(MSMS)

H

HO

HO

OOH

O

O

HOOCHO

HOOHO

HOOH

HOOC


[2GlcAndashH]minus

()

0

100

mz

100 200 300 400 500 600 700 800

8213977

1169246 3111153 8203445

8224006

8434348125530939433099 13258577

()

0

100

mz

200 400 600 800 1000 1200 1400

mz 4693705mz 3510809mz 6454102

(MSminus)

(h)

Figure 4 Continued


3751302

21307733761332

75126674731059 8093751 10383667 13123422

1250712

1210637

930423

650486 950155 1260535 151087824011931740320 1999976 2505933

(MSMS)

OH

H

HO

OH

O

O

O

HO

OHOH

OH



14F

minusH2O

()

0

100

()

0

100

mz

200 400 600 800 1000 1200 1400

mz

60 80 100 120 140 160 180 200 220 240 260

(MSminus)

minusCO2

minusCO2


(i)









2(44Da) CH

3(15Da) and



2]minus and







2OndashCO

2]minus at mz




2O (18Da) CO

2(44Da) and glucose








Table2Ch

aracteriz

ationof

compo

unds

inLQ

Cby

UPL

C-DAD-Q

TOF-MS

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

10817

C 7H

12O

61910

555(minus05)

Quinica

cid

[12]

20982

223287

C 6H

8O7

1910

198(31)

17300

99[M

ndashHndashH

2O]minus

1110

088[M

ndashHndash2H

2OndashC

O2]minus

Citricacid

[13]

3a15

45216271

C 7H

6O5

1690

142(30)

1250241

[MndashH

ndashCO

2]minus

Gallic

acid

[14]

4a3010

325

C 16H

17O

9

3530878

(14)

3750695

[Mndash2H+

Na]minus70718

30[2MndashH

]minus

1910

497[M

ndashHndashC

a]minus

1790

312[C

affeica

cidndash

H]minus

1350359

[Caffeica

cidndash

HndashC

O2]minus

Neochlorogenic

acid

[13]

5a3639

254

C 16H

24O

103751302

(29)

7512

667[2MndashH

]minus

2130773

[MndashH

ndashGlc]minus

1510

878

[MndashH

ndashGlcndashC

O2ndashH

2O]minus

1250721

[MndashH

ndashGlcndash2CO

2]minus

Loganica

cid

[15]

6a404

8224

278

C 14H

20O

72991

133(07)

1790

447[M

ndashHndashC

8H8O

]minus

1190246[M

ndashHndashG

lcndashH

2O]minus

Salid

rosid

e[16]

7a4557

C 20H

30O

124611674(33)

3151348

[MndashH

ndashRha]minus

2971589[M

ndashHndashR

handashH

2O]minus

15306

44[M

ndashHndashR

handashG

lc]minus

1350573

[MndashH

ndashRhandashG

lcndashH

2O]minus

4631220

(minus43)

4851568

1370

599[M

+HndashR

handashG

lcndashH

2O]+

Forsytho

sideE

[17]

8a4749

327

C 16H

17O

93530880

(20)

1910

556[M

ndashHndashC

a]minus

1790

224[C

affeica

cidndash

H]minus

3551028

(minus03)

3770

857

Chlorogenica

cid

[18]

9a5281

325

C 16H

17O

93530880

(20)

1790

348[C

affeica

cidndash

H]minus

17304

61[Q

uinica

cidndash

HndashH

2O]minus

1910

417[M

ndashHndashC

a]minus

Cryptochlorogenic

acid

[18]

106435

270

C 17H

26O

103891

096(31)

3912

176

(minus08)

4131067

3952354

[M+

NandashH

2O]+

2290

835[M

+HndashG

lc]+

Loganin

[19]

116749

C 14H

23O

93350776

(27)

1730459

[MndashH

ndashGlc]minus

1610

373[G

lcndashHndashH

2O]minus

13304

08[G

lcndashH

ndashH2O

ndashCO]minus

3370

883

(53)

3590

686

1630

419[G

lc+

HndashH

2O]+

Reng

ynic

acid-11015840-O

-120573-D

-glucoside

[20]

1272

22C 2

1H20O

94151261

(51)

4391

207

2550879

[M+HndashG

lc]+

Isom

erof

chrysoph

anol

glucoside

[21]

13a

7428

245

C 16H22O9

3571208(62)4031263

[M

+HCO

O]minus

3930938

[M

+Cl]minus

3591

337

(minus14

)3811154

Sweroside

[15]

1478

59C 1

4H23O

93350871

(42)

1930506161037713304

233370

774

(09)

3590

225

1630

416[G

lc+

HndashH

2O]+

Isom

erof

reng

ynic

acid-11015840-O

-120573-D

-glucoside

158106

306

C 20H

22O

83891458(26)4351519

[M+HCO

O]minus

2270

943[M

ndashHndashG

lc]minus

Polydatin

[22]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

168222

C 29H

36O

166392

219(minus17

)4771894[M

ndashHndashG

lc]minus

1790

546[M

ndashRhandashC

17H

14O

6]minus

1610

328[G

lcndashHndashH

2O]minus

R-suspensasid

e[23]

17a

8320

C 21H

20O

94151253

(31)

2530542

[MndashH

ndashGlc]minus

4171394

(minus07)

4391

200

2550864

[M+HndashG

lc]+

Chrysoph

anol

glucoside

[21]

188874

C 29H

36O

166392

002(minus27)

1610

328[G

lcndashHndashH

2O]minus

1790

349[M

ndashRhandashC

17H

14O

6]minus

S-suspensasid

e[24]

1990

54C 2

9H36O

156231999

(minus12

)3112

176

6252137

(08)

6471942

4791

5624711479

32509251630394

Isom

erof

forsytho

sideA

20a

9470

235

C 17H

24O

114031261

(52)

4051331

(minus17

)4271203

2430871

[M+HndashG

lc]+

Secoxyloganin

[19]

2195

52276313

C 21H

22O

94171205(46)8352331

[2MndashH

]minus2550652

[MndashH

ndashGlc]minus

4411132

2570

811[M

+HndashG

lc]+

Liqu

iritin

[25]

22a

9886

277312

C 26H

30O

135491

627(35)

5512

823

(47)

5731737

2570

822[M

+HndashA

pindashG

lc]+

Liqu

iritin

apiosid

e[26]

2399

95C 2

6H30O

135491

629(38)

5513

403

(minus51)

5731735

2570

815[M

+HndashA

pindashG

lc]+

Isom

erof

liquiritin

apiosid

e[26]

2410088

C 27H

30O

1660

91844(minus18

)6331712

Rhod

iosin

[27]

25a

10384

250300

C 22H

22O

94291410(30)

453117

62690

974[M

+HndashG

lc]+

Ono

nin

[2829]

26a

10722

360

C 21H

20O

124630905

(28)

3010

464[M

ndashHndashG

lc]minus

4651033

(52)

4870

333

3030515

[M+HndashG

lc]+

Hyperin

[24]

27a

10819

326

C 25H

24O

125151205

(29)

3530751

[MndashH

ndashCa]minus

5171296

(17)

5391

156

4991

187[M

+HndashH

2O]+

1630

395[M

+HndashC

andashQuinica

cid]

+

35-Dicaffeoylqu

inic

acid

[30]

2810931

C 29H

36O

156231999

(minus19

)46113781610

185

6471941

47114973250925

1630

415

Isom

erof

forsytho

sideA

29a

1110

256354

C 27H

30O

1660

91465(15)

6111573

(33)

6331404

4650982

[M+HndashR

ha]+

3030495

[M+HndashR

ut]+

Rutin

[31]

30a

11220

280

C 29H

36O

156232001

(minus16

)4611920[M

ndashHndashC

a]minus

1610

328[C

affeica

cidndash

HndashH

2O]minus

6471927

1630386

[Caffeica

cid+

HndashH

2O]+

Forsytho

sideA

[32]

3111589

283

C 27H

30O

155931534

(minus13

)2850677

[MndashH

ndashRut]minus

5951694

(minus07)

2870

936[M

+HndashR

ut]+

Kaem

pferol-3-O

-rutin

oside

[13]

3211692

C 19H

35O

165191

884(35)5651953

[M+HCO

O]minus

3571366[M

ndashHndashG

lc]minus

5431855

3591454[M

+HndashG

lc]+

3411411[M

+HndashG

lcndashH

2O]+

(+)-Pino

resin

ol-120573-

D-glucosid

e[33]

33a

12213

210262

C 20H

27NO

114561523

(37)

4581641

(minus46)

2961124

[M+HndashG

lc]+

1620862

[M+

HndashG

lcndashH

CT]+

Amygdalin

[13]


ble2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

34a

12659

326

C 25H

24O

12515116

2(minus54)

3530786

[MndashH

ndashCa]minus

5171348

(04)

5391

193

4991

248[M

+HndashH

2O]+1630387[M

+HndashC

andashQuinica

cid]

+

34-

Dicaffeoylqu

inic

acid

[30]

35a

13082

276

C 15H

12O

42550654

(minus12

)2570

659

(minus08)

1470

621[M

+HndashR

L]+

1370

422[M

+HndashV

P]+

1190691[M

+HndashR

LndashCO

]+Liqu

iritig

enin

[34]

36a

13251

243372

C 26H

30O

135491

621(24)

5511725

(34)

5731563

4191

360[M

+HndashA

pi]+

2570

814[M

+HndashA

pindashG

lc]+

Isoliquiritin

apiosid

e[35]

37a

13300

242362

C 21H

22O

94171198(29)

2550518

[MndashH

ndashGlc]minus

4191

314

(minus67)

4411150

2570

823[M

+HndashG

lc]+

2291

357[M

+HndashG

lcndashC

O]+

Isoliquiritin

[26]

3813479

280

C 27H

34O

115792

103[M

+HCO

O]minus

5571987

5522463

[M+NH

4]+

3551516

[M+

HndashG

lcndashH

2O]+

Arctiin

[36]

39a

1416

1277

C 27H

34O

115792

106[M

+HCO

O]minus

3711826[M

ndashHndashG

lc]minus

3561547

[MndashH

ndashGlcndashH

2O]minus

5522444

[M

+NH

4]+5571991

3731563

[M+HndashG

lc]+

3551544

[M+

HndashG

lcndashH

2O]+

Phillyrin

[3738]

4014678

372255

C 15H

10O

73010

355(23)

1510

137[M

ndashHndashC

8H6O

3]minus

3030520

(49)

Quercetin

[39]

4115039

284

C 28H

34O

1560

91522(13)

3010

582[M

ndashHndashR

ut]minus

Hesperid

in[13]

4215402

265366

C 15H

10O

628504

06(25)

2870

721

(45)

15304

69[M

+HndashH

EP]+

Kaem

pferol

[13]

4316627

255

C 15H

10O

42530507

(24)

2250741

[MndashH

ndashCO]minus

2100494

[MndashH

ndashCOndashC

H3]minus

1820542

[MndashH

ndash2CO

ndashCH

3]minus

1540553

[MndashH

ndash3CO

ndashCH

3]minus

Chrysoph

anol

[40]

4417035

C 15H

10O

42530512

(43)

2250752210047418204

85

1540531

Isom

erof

chrysoph

anol

[40]

45a

17347

254

287426

C 21H

20O

104310

989(26)

2690

673[M

ndashHndashG

lc]minus

2410

719[M

ndashHndashG

lcndashC

O]minus

2250753

[MndashH

ndashGlcndashC

O2]minus

2100578

[MndashH

ndashGlcndashC

O2ndashCH

3]minus

1970

771[MndashH

ndashGlcndashC

OndashC

O2]minus

18204

86[M

ndashHndashG

lcndashC

O2ndashCH

3ndashCO

]minus

4551010

2710

715[M

+HndashG

lc]+

Emod

in-8-O

-glucoside

[41]

4617396

240

330395

C 15H

12O

42550639

(minus71)

2570

812

(minus08)

Isoliquiritigenin

[26]

47a

18385

250304

C 16H

12O

42670

653(minus15

)2690

827

(48)

2910

751

Form

onon

etin

[42]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

4818804

89540

82(28)

7193

849[M

ndashHndashG

lcA]minus

3510

630[2GlcAndash

H]minus

8974

107

(12)

9193

925

22120573-Acetoxy

licorices

apon

inB2

uralsa

poninF

[43]

491919

4271421

C 22H22O10

445116

8(minus56)

2830632

[MndashH

ndashGlc]minus

4691

128

2850775

[M+HndashG

lc]+

Physcion

-8-O

-120573-D

-glucop

yranoside

[41]

5019603

248

C 42H

60O

168193

843(06)

3510

699[2GlcAndash

H]minus

8213

994

(minus01)

8433996

6453612

[M+

HndashG

lcA]+

4693

302[M

+Hndash2GlcA]+

4513

211[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inE2

[35]

5119704

C 16H

24O

73272

180(28)

1649664

[MndashH

ndashGlc]minus

3512

133

Rhod

odendrol-41015840-

O-120573-D

-glucop

yranoside

[44]

5220000

254

C 44H

64O

188794

062(13)

3510

806[M

ndashHndash22A

G]minus

8814

170

(minus01)

7053897

[M+

HndashG

lcA]+

5293

588[M

+Hndash2GlcA]+

5113

395[M

+Hndash2GlcA

ndashH2O

]+

22-

Acetoxyglycyrrhizin

[42]

5320573

352

C 17H

14O

73292

341(39)

3532280

301144

3[M

+HndashC

H2O

]+

2872

002[M

+HndashC

O2]

+ 2591

248[M

+HndashC

O2ndashCO

]+

Tricin

[45]

54a

2119

9260

C 15H

8O6

2830262

(67)

2390

359[M

ndashHndashC

O2]minus

2850515

(minus130)

Rhein

[46]

5521540

253

8373977(12)

8194

404[M

ndashHndashH

2O]minus

6614

100[M

ndashHndashG

lcA]minus

3510

815[2GlcAndash

H]minus

2890

840

[2GlcAndash

HndashH

2OndashC

O2]minus

8394

061

(minus05)

8613

890

6633868

[M+

HndashG

lcA]+

4873395[M

+Hndash2GlcA]+

4693

286[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inG2

[42]

5621626

236

327370

384

C 21H

20O

63671208(71)

3091

566[M

ndashHndashC

OndashC

H2O

]minus

2650635

[MndashH

ndashCOndashC

H2O

ndashCO

2]minus

2210

221

[MndashH

ndashCOndashC

H2O

ndash2CO

2]minus

3691

369

(minus76

)3911176

Glycycoum

arin

[47]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

5722087

249

C 42H

62O

168213

977(17)

8034501

[MndashH

ndashH2O

]minus

7594

542[M

ndashHndashH

2OndashC

O2]minus

6454102

[MndashH

ndashGlcA]minus

6274

000[M

ndashHndashG

lcAndash

H2O

]minus

4693

705[M


3510

809[2GlcAndash

H]minus

2890

758[2GlcAndash

HndashH

2OndashC

O2]minus

8234128

(15)

8454557

6473797[M

+HndashG

lcA]+

4713

480[M

+Hndash2GlcA]+

4533

365[M

+Hndash2GlcA

ndashH2O

]+

Glycyrrhizica

cid

[48]

582218

8252

C 42H

62O

168213

986(minus11)

3510

768[M

ndashHndashG

A]minus

8234134

(minus21)

8454127

6473

823[M

+HndashG

lcA]+

4713

365[M

+Hndash2GlcA]+

4533324

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inH2

[26]

5922389

248

C 42H

64O

158074

197(minus06)

74546

01[M

ndashHndashG

lc]minus

6314

210[M

ndashHndashG

lcA]minus

3510

699[M

ndashHndashG

A]minus

8094

410

(minus09)

8314

138

Licoric

esapon

inB2

[49]

6022623

252

C 42H

62O

168213

997(02)

3510

837[M

ndashHndashG

A]minus

8234105

(minus13

)8453900

6473

838[M

+HndashG

lcA]+

4713

288[M

+Hndash2GlcA]+

4533279

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inK2

[50]

61a

23230

288439

C 15H

10O

52690

462(45)

2410

669[M

ndashHndashC

O]minus

2250723

[MndashH

ndashCO

2]minus

21004

27[M

ndashHndashC

O2ndashCH

3]minus

1970

695[M

ndashHndashC

OndashC

O2]minus

1820477

[MndashH

ndashCO

2ndashCH

3ndashCO

]minus

1540552

[MndashH

ndashCO

2ndashCH

3ndash2C

O]minus

Emod

in[40]

a Com

paredwith

referencec

ompo

unds

b 22A

G2


ApiapioseC

acaffeoylGAg

lycyrrhetin

icacidG

lcg

lucoseG

lcAg

lucuronicacidH

CT4

-(hydroxym

ethyl)c

yclobu

tane-123-tr

iolHEP


enolR

ha

rham

noseR

LresorcinolR

utrutinoseVP

4-vinylpheno

l


Table3Linear

regressio

nLO

Dsa

ndLO

Qsintraday

andinterday

precision


for12compo

unds

Com

poun

dRe

gressio

nequatio

na(119899=3)

1198772

Linear

range

(120583gmL)

LOD

b

(120583gmL)

LOQ

c

(120583gmL)

Intraday

(RSD

)

(119899=6)

Interday

(RSD

)

(119899=3)


(RSD

)

Recovery

(119899=6)

Mean

(120583gg)

RSD

()

Orig

inal

(120583g)

Spiked

(120583g)

Detected

(120583g)

Recovery

()

RSD

()

Salid

rosid

e119910=

13980119909minus11265

09999

527ndash8

435

106

350

012

026177955plusmn

1092

061

138

35591

35420

7075

09928

124

Chlorogenica

cid

119910=

26510119909+36733

09998

685ndash10956

171

569

077

212247371plusmn

1274

051

254

49474

49385

9599

09419

242

Forsytho

sideE

119910=

11793119909+50168

09995

485ndash776

412

1404

067

225175403plusmn

1872

107

267

3518

13510

56772

69299

354

Cryptochlorogenic

acid

119910=

21498119909minus50189

09997

665ndash10647

166

553

110

163202949plusmn

2065

102

246

40590

40660

78400

9310

143

Amygdalin

119910=

10530119909minus34647

09998

391ndash6

257

098

326

079

093148538plusmn

2585

174

248

2970

829862

57639

9358

332

Sweroside

119910=

20593119909minus60034

09999

200ndash319

6025

080

011

033

79806plusmn

293

037

048

1596

11595

132543

10395

041

Hyperin

119910=

27773119909minus87941

09999

020ndash321

0051

016

078

062

9203plusmn

080

087

083

1841

1824

3707

10229

182

Rutin

119910=

30768119909minus37837

09993

053ndash850

0072

021

041

224

18415plusmn

306

166

157

3683

3681

7250

9690

234

Forsytho

sideA

119910=

85466119909minus60245

09999

421ndash6

734

030

105

020

292248499plusmn

1843

074

195

4970

049595

99733

10089

149

Phillyrin

119910=

30390119909+52828

09999

286ndash4

571

071

236

079

163157780plusmn

1011

064

276

31556

31672

62399

10025

160

Rhein

119910=

74736119909minus51727

09996

347ndash5549

087

288

040

028

68192plusmn

1632

239

097

13638

13627

27348

10061

161

Glycyrrhizica

cid

119910=

10296119909minus65313

09999

527ndash8

435

0092

033

034

209162275plusmn

1759

108

215

32455

323939

65216

1013

1327

a 119910isthep

eakarea119909

isthec

oncentratio

nof

stand

ardsolutio

ns

b LODrefersto

thelim

itsof

detection119878119873=3

c LOQrefersto

thelim

itsof

quantity119878119873=10


Table4Con

tentso

fthe

12compo

unds

in10

batches

Sample

Com

poun

d(m

eanplusmnSD

)(120583gg)

Total

RSD(

)Salid

rosid

eCh

lorogenic

acid

Forsytho

sideE

Cryptochlorogenic

acid

Amygdalin

Sweroside

Hyperin

Rutin

Forsytho

sideA

Phillyrin

Rhein

Glycyrrhizic

acid


1003













4 Conclusion






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


6058 59


OO

OO

O

O

O

O

O

R2H

H

H

O

O

O

O

OO

O

O

O

O

OO

O

O

OO

O

O

O

OOO

OHOH

OH

OH

OH

OH

OH

OH OH

OHOH

OH

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOHO

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

HOOC

R1O

(d)

5 R1 = Glc R2 = H 13 2010R1 = Glc R2 = CH3

OH

HO

O O

O

HOO OO

OOH

H OO

OHOH

OHOH HO

HOHO

HOHOHO

OR1

OR2

(e)

1 2 3 6

15

7

11 33 51

O

O

O

O O

OO

OO

O O

OO

OOO

O

OO

N

OO

O

OHOH OH

OHOH

OH

OH

OH

OH

OHOHOH

OHOH

OH

OH

OH

OH

OH

OH

OHOH

OH

OHOH

HOHO

HO HOHO

HOHO

HO

HOHO

HOHOHO

HOHO

HOHO HO

HOHO

HOHOHO

HO

HO

H3C

(f)







2(44Da)


OHO

OH

O

OHO

O

OHH

mz 1470621

mz 1190691

+H

mz 2570659mz 2570659

mz 1370422

2570659

172999816301591319873 1941022

23914082651331

3011509

1370422

1190691

1199948

13800271470621

1650917 16902931810699 2112177

(MSMS)

100 120 140 160 180 200 220 240 260 280 300

()

0

100

()

0

100

mzmz

120 130 140 150 160 170 180 190 200 210

(MS+)

(a)

OHO

OHO

OH

O

OH

OOH

HOOH

OH

mz 3010464

3010464

1370281

3020746

3027005 4652560 62322138921294

4630905

43109651450305 2210378

46409055310850 7371886 11080997 13072520 14077662

(MSMS)

()

0

100(

)

0

100

mz

200 400 600 800 1000 1200 1400mz

200 400 600 800 1000 1200 1400

(MSminus)

(b)

OHHO

OHHOOC

OHOHHO

O

OHHO OH

COOminus

COOminus COOminus

Cminus

mz 1910733mz 1270486

mz 1730583 mz 1090409

mz 930425 mz 850426

minusCO2

minusCO2

minus2H2O minusC2H2

minusCO

Ominus

minusH

minusH2O minusH2O

minusH2O

1910733

8504261270486930425 1090409 1350577

1610264 1730583 19207421938051

3530878

1910558

3510719192060770718303540916

70516854510630 5031459 7081906

(MSMS)

()

0

100

()

0

100

mzmz

80 90 100 110 120 130 140 150 160 170 180 190 200200 250 300 350 400 450 500 550 600 650 700 750 800

(MSminus)

(c)

O OO

O

OH

OHOH

HO

HO

HO

HO

O

O OHOH

mz 4611920 mz 1610328

CH3

6232001

3112033 6211844

6242032

6252064 124749349575357 13186510

1610328

62325071620342 4611920

(MSMS)

()

0

100

()

0

100

200 400 600 800 1000 1200 1400mzmz

100 200 300 400 500 600 700 800 900 1000

(MSminus)

(d)

Figure 4 Continued


3561547

13599643083514

3711826

37218625161718

5792105

1129871 4310958

58021345812158 111342197973569 11814053

(MSMS)

O

O

O

OO

OO

OH

HOHO

OH


()

0

100

()

0

100

mz

150 200 250 300 350 400 450 500 550 600 650 700 750mz

200 400 600 800 1000 1200 1400

(MSminus)

mz 3561547

mz 3711826

(e)

2250723

18204771810753

18006601540552

19706952240626

2410669 2690634

2420626 2700607

2690462

1129890 27004855610872 8234322 9694360 14023499

O O

O

O

O O

(MSMS)

()

0

100(

)

0

100

mz

160 180 200 220 240 260 280mz

200 400 600 800 1000 1200 1400

(MSminus)

OH

OH

OHOH OH OH OH

OHOHOH

OH

minusCO2

minusCO2minusCO

minusCO

minusHminusHminusH

minusHminusH

minusH

H3CH3C

H3C H3C

mz 1970695mz 2410669

mz 2250723mz 2690462

mz 1820477mz 1540552

minusCH3minusCO

(f)

4310988

11692794321016

4990790 8632153 11946926 14410397

2690673

2250753

18204861710837

1970771 241071927007752710783 3110845

(MSMS)

O

O

O OH

OHO

HOHO

OH

HO





0

100

()

0

100

mz

200 400 600 800 1000 1200 1400mz

140 160 180 200 220 240 260 280 300 320

(MSminus)

mz 3711826mz 2690673

CH3

(g)

8214583

35108091130354

19305102890758

645410258340994693705 7594542

8224637

8234628

(MSMS)

H

HO

HO

OOH

O

O

HOOCHO

HOOHO

HOOH

HOOC


[2GlcAndashH]minus

()

0

100

mz

100 200 300 400 500 600 700 800

8213977

1169246 3111153 8203445

8224006

8434348125530939433099 13258577

()

0

100

mz

200 400 600 800 1000 1200 1400

mz 4693705mz 3510809mz 6454102

(MSminus)

(h)

Figure 4 Continued


3751302

21307733761332

75126674731059 8093751 10383667 13123422

1250712

1210637

930423

650486 950155 1260535 151087824011931740320 1999976 2505933

(MSMS)

OH

H

HO

OH

O

O

O

HO

OHOH

OH



14F

minusH2O

()

0

100

()

0

100

mz

200 400 600 800 1000 1200 1400

mz

60 80 100 120 140 160 180 200 220 240 260

(MSminus)

minusCO2

minusCO2


(i)









2(44Da) CH

3(15Da) and



2]minus and







2OndashCO

2]minus at mz




2O (18Da) CO

2(44Da) and glucose








Table2Ch

aracteriz

ationof

compo

unds

inLQ

Cby

UPL

C-DAD-Q

TOF-MS

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

10817

C 7H

12O

61910

555(minus05)

Quinica

cid

[12]

20982

223287

C 6H

8O7

1910

198(31)

17300

99[M

ndashHndashH

2O]minus

1110

088[M

ndashHndash2H

2OndashC

O2]minus

Citricacid

[13]

3a15

45216271

C 7H

6O5

1690

142(30)

1250241

[MndashH

ndashCO

2]minus

Gallic

acid

[14]

4a3010

325

C 16H

17O

9

3530878

(14)

3750695

[Mndash2H+

Na]minus70718

30[2MndashH

]minus

1910

497[M

ndashHndashC

a]minus

1790

312[C

affeica

cidndash

H]minus

1350359

[Caffeica

cidndash

HndashC

O2]minus

Neochlorogenic

acid

[13]

5a3639

254

C 16H

24O

103751302

(29)

7512

667[2MndashH

]minus

2130773

[MndashH

ndashGlc]minus

1510

878

[MndashH

ndashGlcndashC

O2ndashH

2O]minus

1250721

[MndashH

ndashGlcndash2CO

2]minus

Loganica

cid

[15]

6a404

8224

278

C 14H

20O

72991

133(07)

1790

447[M

ndashHndashC

8H8O

]minus

1190246[M

ndashHndashG

lcndashH

2O]minus

Salid

rosid

e[16]

7a4557

C 20H

30O

124611674(33)

3151348

[MndashH

ndashRha]minus

2971589[M

ndashHndashR

handashH

2O]minus

15306

44[M

ndashHndashR

handashG

lc]minus

1350573

[MndashH

ndashRhandashG

lcndashH

2O]minus

4631220

(minus43)

4851568

1370

599[M

+HndashR

handashG

lcndashH

2O]+

Forsytho

sideE

[17]

8a4749

327

C 16H

17O

93530880

(20)

1910

556[M

ndashHndashC

a]minus

1790

224[C

affeica

cidndash

H]minus

3551028

(minus03)

3770

857

Chlorogenica

cid

[18]

9a5281

325

C 16H

17O

93530880

(20)

1790

348[C

affeica

cidndash

H]minus

17304

61[Q

uinica

cidndash

HndashH

2O]minus

1910

417[M

ndashHndashC

a]minus

Cryptochlorogenic

acid

[18]

106435

270

C 17H

26O

103891

096(31)

3912

176

(minus08)

4131067

3952354

[M+

NandashH

2O]+

2290

835[M

+HndashG

lc]+

Loganin

[19]

116749

C 14H

23O

93350776

(27)

1730459

[MndashH

ndashGlc]minus

1610

373[G

lcndashHndashH

2O]minus

13304

08[G

lcndashH

ndashH2O

ndashCO]minus

3370

883

(53)

3590

686

1630

419[G

lc+

HndashH

2O]+

Reng

ynic

acid-11015840-O

-120573-D

-glucoside

[20]

1272

22C 2

1H20O

94151261

(51)

4391

207

2550879

[M+HndashG

lc]+

Isom

erof

chrysoph

anol

glucoside

[21]

13a

7428

245

C 16H22O9

3571208(62)4031263

[M

+HCO

O]minus

3930938

[M

+Cl]minus

3591

337

(minus14

)3811154

Sweroside

[15]

1478

59C 1

4H23O

93350871

(42)

1930506161037713304

233370

774

(09)

3590

225

1630

416[G

lc+

HndashH

2O]+

Isom

erof

reng

ynic

acid-11015840-O

-120573-D

-glucoside

158106

306

C 20H

22O

83891458(26)4351519

[M+HCO

O]minus

2270

943[M

ndashHndashG

lc]minus

Polydatin

[22]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

168222

C 29H

36O

166392

219(minus17

)4771894[M

ndashHndashG

lc]minus

1790

546[M

ndashRhandashC

17H

14O

6]minus

1610

328[G

lcndashHndashH

2O]minus

R-suspensasid

e[23]

17a

8320

C 21H

20O

94151253

(31)

2530542

[MndashH

ndashGlc]minus

4171394

(minus07)

4391

200

2550864

[M+HndashG

lc]+

Chrysoph

anol

glucoside

[21]

188874

C 29H

36O

166392

002(minus27)

1610

328[G

lcndashHndashH

2O]minus

1790

349[M

ndashRhandashC

17H

14O

6]minus

S-suspensasid

e[24]

1990

54C 2

9H36O

156231999

(minus12

)3112

176

6252137

(08)

6471942

4791

5624711479

32509251630394

Isom

erof

forsytho

sideA

20a

9470

235

C 17H

24O

114031261

(52)

4051331

(minus17

)4271203

2430871

[M+HndashG

lc]+

Secoxyloganin

[19]

2195

52276313

C 21H

22O

94171205(46)8352331

[2MndashH

]minus2550652

[MndashH

ndashGlc]minus

4411132

2570

811[M

+HndashG

lc]+

Liqu

iritin

[25]

22a

9886

277312

C 26H

30O

135491

627(35)

5512

823

(47)

5731737

2570

822[M

+HndashA

pindashG

lc]+

Liqu

iritin

apiosid

e[26]

2399

95C 2

6H30O

135491

629(38)

5513

403

(minus51)

5731735

2570

815[M

+HndashA

pindashG

lc]+

Isom

erof

liquiritin

apiosid

e[26]

2410088

C 27H

30O

1660

91844(minus18

)6331712

Rhod

iosin

[27]

25a

10384

250300

C 22H

22O

94291410(30)

453117

62690

974[M

+HndashG

lc]+

Ono

nin

[2829]

26a

10722

360

C 21H

20O

124630905

(28)

3010

464[M

ndashHndashG

lc]minus

4651033

(52)

4870

333

3030515

[M+HndashG

lc]+

Hyperin

[24]

27a

10819

326

C 25H

24O

125151205

(29)

3530751

[MndashH

ndashCa]minus

5171296

(17)

5391

156

4991

187[M

+HndashH

2O]+

1630

395[M

+HndashC

andashQuinica

cid]

+

35-Dicaffeoylqu

inic

acid

[30]

2810931

C 29H

36O

156231999

(minus19

)46113781610

185

6471941

47114973250925

1630

415

Isom

erof

forsytho

sideA

29a

1110

256354

C 27H

30O

1660

91465(15)

6111573

(33)

6331404

4650982

[M+HndashR

ha]+

3030495

[M+HndashR

ut]+

Rutin

[31]

30a

11220

280

C 29H

36O

156232001

(minus16

)4611920[M

ndashHndashC

a]minus

1610

328[C

affeica

cidndash

HndashH

2O]minus

6471927

1630386

[Caffeica

cid+

HndashH

2O]+

Forsytho

sideA

[32]

3111589

283

C 27H

30O

155931534

(minus13

)2850677

[MndashH

ndashRut]minus

5951694

(minus07)

2870

936[M

+HndashR

ut]+

Kaem

pferol-3-O

-rutin

oside

[13]

3211692

C 19H

35O

165191

884(35)5651953

[M+HCO

O]minus

3571366[M

ndashHndashG

lc]minus

5431855

3591454[M

+HndashG

lc]+

3411411[M

+HndashG

lcndashH

2O]+

(+)-Pino

resin

ol-120573-

D-glucosid

e[33]

33a

12213

210262

C 20H

27NO

114561523

(37)

4581641

(minus46)

2961124

[M+HndashG

lc]+

1620862

[M+

HndashG

lcndashH

CT]+

Amygdalin

[13]


ble2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

34a

12659

326

C 25H

24O

12515116

2(minus54)

3530786

[MndashH

ndashCa]minus

5171348

(04)

5391

193

4991

248[M

+HndashH

2O]+1630387[M

+HndashC

andashQuinica

cid]

+

34-

Dicaffeoylqu

inic

acid

[30]

35a

13082

276

C 15H

12O

42550654

(minus12

)2570

659

(minus08)

1470

621[M

+HndashR

L]+

1370

422[M

+HndashV

P]+

1190691[M

+HndashR

LndashCO

]+Liqu

iritig

enin

[34]

36a

13251

243372

C 26H

30O

135491

621(24)

5511725

(34)

5731563

4191

360[M

+HndashA

pi]+

2570

814[M

+HndashA

pindashG

lc]+

Isoliquiritin

apiosid

e[35]

37a

13300

242362

C 21H

22O

94171198(29)

2550518

[MndashH

ndashGlc]minus

4191

314

(minus67)

4411150

2570

823[M

+HndashG

lc]+

2291

357[M

+HndashG

lcndashC

O]+

Isoliquiritin

[26]

3813479

280

C 27H

34O

115792

103[M

+HCO

O]minus

5571987

5522463

[M+NH

4]+

3551516

[M+

HndashG

lcndashH

2O]+

Arctiin

[36]

39a

1416

1277

C 27H

34O

115792

106[M

+HCO

O]minus

3711826[M

ndashHndashG

lc]minus

3561547

[MndashH

ndashGlcndashH

2O]minus

5522444

[M

+NH

4]+5571991

3731563

[M+HndashG

lc]+

3551544

[M+

HndashG

lcndashH

2O]+

Phillyrin

[3738]

4014678

372255

C 15H

10O

73010

355(23)

1510

137[M

ndashHndashC

8H6O

3]minus

3030520

(49)

Quercetin

[39]

4115039

284

C 28H

34O

1560

91522(13)

3010

582[M

ndashHndashR

ut]minus

Hesperid

in[13]

4215402

265366

C 15H

10O

628504

06(25)

2870

721

(45)

15304

69[M

+HndashH

EP]+

Kaem

pferol

[13]

4316627

255

C 15H

10O

42530507

(24)

2250741

[MndashH

ndashCO]minus

2100494

[MndashH

ndashCOndashC

H3]minus

1820542

[MndashH

ndash2CO

ndashCH

3]minus

1540553

[MndashH

ndash3CO

ndashCH

3]minus

Chrysoph

anol

[40]

4417035

C 15H

10O

42530512

(43)

2250752210047418204

85

1540531

Isom

erof

chrysoph

anol

[40]

45a

17347

254

287426

C 21H

20O

104310

989(26)

2690

673[M

ndashHndashG

lc]minus

2410

719[M

ndashHndashG

lcndashC

O]minus

2250753

[MndashH

ndashGlcndashC

O2]minus

2100578

[MndashH

ndashGlcndashC

O2ndashCH

3]minus

1970

771[MndashH

ndashGlcndashC

OndashC

O2]minus

18204

86[M

ndashHndashG

lcndashC

O2ndashCH

3ndashCO

]minus

4551010

2710

715[M

+HndashG

lc]+

Emod

in-8-O

-glucoside

[41]

4617396

240

330395

C 15H

12O

42550639

(minus71)

2570

812

(minus08)

Isoliquiritigenin

[26]

47a

18385

250304

C 16H

12O

42670

653(minus15

)2690

827

(48)

2910

751

Form

onon

etin

[42]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

4818804

89540

82(28)

7193

849[M

ndashHndashG

lcA]minus

3510

630[2GlcAndash

H]minus

8974

107

(12)

9193

925

22120573-Acetoxy

licorices

apon

inB2

uralsa

poninF

[43]

491919

4271421

C 22H22O10

445116

8(minus56)

2830632

[MndashH

ndashGlc]minus

4691

128

2850775

[M+HndashG

lc]+

Physcion

-8-O

-120573-D

-glucop

yranoside

[41]

5019603

248

C 42H

60O

168193

843(06)

3510

699[2GlcAndash

H]minus

8213

994

(minus01)

8433996

6453612

[M+

HndashG

lcA]+

4693

302[M

+Hndash2GlcA]+

4513

211[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inE2

[35]

5119704

C 16H

24O

73272

180(28)

1649664

[MndashH

ndashGlc]minus

3512

133

Rhod

odendrol-41015840-

O-120573-D

-glucop

yranoside

[44]

5220000

254

C 44H

64O

188794

062(13)

3510

806[M

ndashHndash22A

G]minus

8814

170

(minus01)

7053897

[M+

HndashG

lcA]+

5293

588[M

+Hndash2GlcA]+

5113

395[M

+Hndash2GlcA

ndashH2O

]+

22-

Acetoxyglycyrrhizin

[42]

5320573

352

C 17H

14O

73292

341(39)

3532280

301144

3[M

+HndashC

H2O

]+

2872

002[M

+HndashC

O2]

+ 2591

248[M

+HndashC

O2ndashCO

]+

Tricin

[45]

54a

2119

9260

C 15H

8O6

2830262

(67)

2390

359[M

ndashHndashC

O2]minus

2850515

(minus130)

Rhein

[46]

5521540

253

8373977(12)

8194

404[M

ndashHndashH

2O]minus

6614

100[M

ndashHndashG

lcA]minus

3510

815[2GlcAndash

H]minus

2890

840

[2GlcAndash

HndashH

2OndashC

O2]minus

8394

061

(minus05)

8613

890

6633868

[M+

HndashG

lcA]+

4873395[M

+Hndash2GlcA]+

4693

286[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inG2

[42]

5621626

236

327370

384

C 21H

20O

63671208(71)

3091

566[M

ndashHndashC

OndashC

H2O

]minus

2650635

[MndashH

ndashCOndashC

H2O

ndashCO

2]minus

2210

221

[MndashH

ndashCOndashC

H2O

ndash2CO

2]minus

3691

369

(minus76

)3911176

Glycycoum

arin

[47]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

5722087

249

C 42H

62O

168213

977(17)

8034501

[MndashH

ndashH2O

]minus

7594

542[M

ndashHndashH

2OndashC

O2]minus

6454102

[MndashH

ndashGlcA]minus

6274

000[M

ndashHndashG

lcAndash

H2O

]minus

4693

705[M


3510

809[2GlcAndash

H]minus

2890

758[2GlcAndash

HndashH

2OndashC

O2]minus

8234128

(15)

8454557

6473797[M

+HndashG

lcA]+

4713

480[M

+Hndash2GlcA]+

4533

365[M

+Hndash2GlcA

ndashH2O

]+

Glycyrrhizica

cid

[48]

582218

8252

C 42H

62O

168213

986(minus11)

3510

768[M

ndashHndashG

A]minus

8234134

(minus21)

8454127

6473

823[M

+HndashG

lcA]+

4713

365[M

+Hndash2GlcA]+

4533324

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inH2

[26]

5922389

248

C 42H

64O

158074

197(minus06)

74546

01[M

ndashHndashG

lc]minus

6314

210[M

ndashHndashG

lcA]minus

3510

699[M

ndashHndashG

A]minus

8094

410

(minus09)

8314

138

Licoric

esapon

inB2

[49]

6022623

252

C 42H

62O

168213

997(02)

3510

837[M

ndashHndashG

A]minus

8234105

(minus13

)8453900

6473

838[M

+HndashG

lcA]+

4713

288[M

+Hndash2GlcA]+

4533279

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inK2

[50]

61a

23230

288439

C 15H

10O

52690

462(45)

2410

669[M

ndashHndashC

O]minus

2250723

[MndashH

ndashCO

2]minus

21004

27[M

ndashHndashC

O2ndashCH

3]minus

1970

695[M

ndashHndashC

OndashC

O2]minus

1820477

[MndashH

ndashCO

2ndashCH

3ndashCO

]minus

1540552

[MndashH

ndashCO

2ndashCH

3ndash2C

O]minus

Emod

in[40]

a Com

paredwith

referencec

ompo

unds

b 22A

G2


ApiapioseC

acaffeoylGAg

lycyrrhetin

icacidG

lcg

lucoseG

lcAg

lucuronicacidH

CT4

-(hydroxym

ethyl)c

yclobu

tane-123-tr

iolHEP


enolR

ha

rham

noseR

LresorcinolR

utrutinoseVP

4-vinylpheno

l


Table3Linear

regressio

nLO

Dsa

ndLO

Qsintraday

andinterday

precision


for12compo

unds

Com

poun

dRe

gressio

nequatio

na(119899=3)

1198772

Linear

range

(120583gmL)

LOD

b

(120583gmL)

LOQ

c

(120583gmL)

Intraday

(RSD

)

(119899=6)

Interday

(RSD

)

(119899=3)


(RSD

)

Recovery

(119899=6)

Mean

(120583gg)

RSD

()

Orig

inal

(120583g)

Spiked

(120583g)

Detected

(120583g)

Recovery

()

RSD

()

Salid

rosid

e119910=

13980119909minus11265

09999

527ndash8

435

106

350

012

026177955plusmn

1092

061

138

35591

35420

7075

09928

124

Chlorogenica

cid

119910=

26510119909+36733

09998

685ndash10956

171

569

077

212247371plusmn

1274

051

254

49474

49385

9599

09419

242

Forsytho

sideE

119910=

11793119909+50168

09995

485ndash776

412

1404

067

225175403plusmn

1872

107

267

3518

13510

56772

69299

354

Cryptochlorogenic

acid

119910=

21498119909minus50189

09997

665ndash10647

166

553

110

163202949plusmn

2065

102

246

40590

40660

78400

9310

143

Amygdalin

119910=

10530119909minus34647

09998

391ndash6

257

098

326

079

093148538plusmn

2585

174

248

2970

829862

57639

9358

332

Sweroside

119910=

20593119909minus60034

09999

200ndash319

6025

080

011

033

79806plusmn

293

037

048

1596

11595

132543

10395

041

Hyperin

119910=

27773119909minus87941

09999

020ndash321

0051

016

078

062

9203plusmn

080

087

083

1841

1824

3707

10229

182

Rutin

119910=

30768119909minus37837

09993

053ndash850

0072

021

041

224

18415plusmn

306

166

157

3683

3681

7250

9690

234

Forsytho

sideA

119910=

85466119909minus60245

09999

421ndash6

734

030

105

020

292248499plusmn

1843

074

195

4970

049595

99733

10089

149

Phillyrin

119910=

30390119909+52828

09999

286ndash4

571

071

236

079

163157780plusmn

1011

064

276

31556

31672

62399

10025

160

Rhein

119910=

74736119909minus51727

09996

347ndash5549

087

288

040

028

68192plusmn

1632

239

097

13638

13627

27348

10061

161

Glycyrrhizica

cid

119910=

10296119909minus65313

09999

527ndash8

435

0092

033

034

209162275plusmn

1759

108

215

32455

323939

65216

1013

1327

a 119910isthep

eakarea119909

isthec

oncentratio

nof

stand

ardsolutio

ns

b LODrefersto

thelim

itsof

detection119878119873=3

c LOQrefersto

thelim

itsof

quantity119878119873=10


Table4Con

tentso

fthe

12compo

unds

in10

batches

Sample

Com

poun

d(m

eanplusmnSD

)(120583gg)

Total

RSD(

)Salid

rosid

eCh

lorogenic

acid

Forsytho

sideE

Cryptochlorogenic

acid

Amygdalin

Sweroside

Hyperin

Rutin

Forsytho

sideA

Phillyrin

Rhein

Glycyrrhizic

acid


1003













4 Conclusion






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


OHO

OH

O

OHO

O

OHH

mz 1470621

mz 1190691

+H

mz 2570659mz 2570659

mz 1370422

2570659

172999816301591319873 1941022

23914082651331

3011509

1370422

1190691

1199948

13800271470621

1650917 16902931810699 2112177

(MSMS)

100 120 140 160 180 200 220 240 260 280 300

()

0

100

()

0

100

mzmz

120 130 140 150 160 170 180 190 200 210

(MS+)

(a)

OHO

OHO

OH

O

OH

OOH

HOOH

OH

mz 3010464

3010464

1370281

3020746

3027005 4652560 62322138921294

4630905

43109651450305 2210378

46409055310850 7371886 11080997 13072520 14077662

(MSMS)

()

0

100(

)

0

100

mz

200 400 600 800 1000 1200 1400mz

200 400 600 800 1000 1200 1400

(MSminus)

(b)

OHHO

OHHOOC

OHOHHO

O

OHHO OH

COOminus

COOminus COOminus

Cminus

mz 1910733mz 1270486

mz 1730583 mz 1090409

mz 930425 mz 850426

minusCO2

minusCO2

minus2H2O minusC2H2

minusCO

Ominus

minusH

minusH2O minusH2O

minusH2O

1910733

8504261270486930425 1090409 1350577

1610264 1730583 19207421938051

3530878

1910558

3510719192060770718303540916

70516854510630 5031459 7081906

(MSMS)

()

0

100

()

0

100

mzmz

80 90 100 110 120 130 140 150 160 170 180 190 200200 250 300 350 400 450 500 550 600 650 700 750 800

(MSminus)

(c)

O OO

O

OH

OHOH

HO

HO

HO

HO

O

O OHOH

mz 4611920 mz 1610328

CH3

6232001

3112033 6211844

6242032

6252064 124749349575357 13186510

1610328

62325071620342 4611920

(MSMS)

()

0

100

()

0

100

200 400 600 800 1000 1200 1400mzmz

100 200 300 400 500 600 700 800 900 1000

(MSminus)

(d)

Figure 4 Continued


3561547

13599643083514

3711826

37218625161718

5792105

1129871 4310958

58021345812158 111342197973569 11814053

(MSMS)

O

O

O

OO

OO

OH

HOHO

OH


()

0

100

()

0

100

mz

150 200 250 300 350 400 450 500 550 600 650 700 750mz

200 400 600 800 1000 1200 1400

(MSminus)

mz 3561547

mz 3711826

(e)

2250723

18204771810753

18006601540552

19706952240626

2410669 2690634

2420626 2700607

2690462

1129890 27004855610872 8234322 9694360 14023499

O O

O

O

O O

(MSMS)

()

0

100(

)

0

100

mz

160 180 200 220 240 260 280mz

200 400 600 800 1000 1200 1400

(MSminus)

OH

OH

OHOH OH OH OH

OHOHOH

OH

minusCO2

minusCO2minusCO

minusCO

minusHminusHminusH

minusHminusH

minusH

H3CH3C

H3C H3C

mz 1970695mz 2410669

mz 2250723mz 2690462

mz 1820477mz 1540552

minusCH3minusCO

(f)

4310988

11692794321016

4990790 8632153 11946926 14410397

2690673

2250753

18204861710837

1970771 241071927007752710783 3110845

(MSMS)

O

O

O OH

OHO

HOHO

OH

HO





0

100

()

0

100

mz

200 400 600 800 1000 1200 1400mz

140 160 180 200 220 240 260 280 300 320

(MSminus)

mz 3711826mz 2690673

CH3

(g)

8214583

35108091130354

19305102890758

645410258340994693705 7594542

8224637

8234628

(MSMS)

H

HO

HO

OOH

O

O

HOOCHO

HOOHO

HOOH

HOOC


[2GlcAndashH]minus

()

0

100

mz

100 200 300 400 500 600 700 800

8213977

1169246 3111153 8203445

8224006

8434348125530939433099 13258577

()

0

100

mz

200 400 600 800 1000 1200 1400

mz 4693705mz 3510809mz 6454102

(MSminus)

(h)

Figure 4 Continued


3751302

21307733761332

75126674731059 8093751 10383667 13123422

1250712

1210637

930423

650486 950155 1260535 151087824011931740320 1999976 2505933

(MSMS)

OH

H

HO

OH

O

O

O

HO

OHOH

OH



14F

minusH2O

()

0

100

()

0

100

mz

200 400 600 800 1000 1200 1400

mz

60 80 100 120 140 160 180 200 220 240 260

(MSminus)

minusCO2

minusCO2


(i)









2(44Da) CH

3(15Da) and



2]minus and







2OndashCO

2]minus at mz




2O (18Da) CO

2(44Da) and glucose








Table2Ch

aracteriz

ationof

compo

unds

inLQ

Cby

UPL

C-DAD-Q

TOF-MS

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

10817

C 7H

12O

61910

555(minus05)

Quinica

cid

[12]

20982

223287

C 6H

8O7

1910

198(31)

17300

99[M

ndashHndashH

2O]minus

1110

088[M

ndashHndash2H

2OndashC

O2]minus

Citricacid

[13]

3a15

45216271

C 7H

6O5

1690

142(30)

1250241

[MndashH

ndashCO

2]minus

Gallic

acid

[14]

4a3010

325

C 16H

17O

9

3530878

(14)

3750695

[Mndash2H+

Na]minus70718

30[2MndashH

]minus

1910

497[M

ndashHndashC

a]minus

1790

312[C

affeica

cidndash

H]minus

1350359

[Caffeica

cidndash

HndashC

O2]minus

Neochlorogenic

acid

[13]

5a3639

254

C 16H

24O

103751302

(29)

7512

667[2MndashH

]minus

2130773

[MndashH

ndashGlc]minus

1510

878

[MndashH

ndashGlcndashC

O2ndashH

2O]minus

1250721

[MndashH

ndashGlcndash2CO

2]minus

Loganica

cid

[15]

6a404

8224

278

C 14H

20O

72991

133(07)

1790

447[M

ndashHndashC

8H8O

]minus

1190246[M

ndashHndashG

lcndashH

2O]minus

Salid

rosid

e[16]

7a4557

C 20H

30O

124611674(33)

3151348

[MndashH

ndashRha]minus

2971589[M

ndashHndashR

handashH

2O]minus

15306

44[M

ndashHndashR

handashG

lc]minus

1350573

[MndashH

ndashRhandashG

lcndashH

2O]minus

4631220

(minus43)

4851568

1370

599[M

+HndashR

handashG

lcndashH

2O]+

Forsytho

sideE

[17]

8a4749

327

C 16H

17O

93530880

(20)

1910

556[M

ndashHndashC

a]minus

1790

224[C

affeica

cidndash

H]minus

3551028

(minus03)

3770

857

Chlorogenica

cid

[18]

9a5281

325

C 16H

17O

93530880

(20)

1790

348[C

affeica

cidndash

H]minus

17304

61[Q

uinica

cidndash

HndashH

2O]minus

1910

417[M

ndashHndashC

a]minus

Cryptochlorogenic

acid

[18]

106435

270

C 17H

26O

103891

096(31)

3912

176

(minus08)

4131067

3952354

[M+

NandashH

2O]+

2290

835[M

+HndashG

lc]+

Loganin

[19]

116749

C 14H

23O

93350776

(27)

1730459

[MndashH

ndashGlc]minus

1610

373[G

lcndashHndashH

2O]minus

13304

08[G

lcndashH

ndashH2O

ndashCO]minus

3370

883

(53)

3590

686

1630

419[G

lc+

HndashH

2O]+

Reng

ynic

acid-11015840-O

-120573-D

-glucoside

[20]

1272

22C 2

1H20O

94151261

(51)

4391

207

2550879

[M+HndashG

lc]+

Isom

erof

chrysoph

anol

glucoside

[21]

13a

7428

245

C 16H22O9

3571208(62)4031263

[M

+HCO

O]minus

3930938

[M

+Cl]minus

3591

337

(minus14

)3811154

Sweroside

[15]

1478

59C 1

4H23O

93350871

(42)

1930506161037713304

233370

774

(09)

3590

225

1630

416[G

lc+

HndashH

2O]+

Isom

erof

reng

ynic

acid-11015840-O

-120573-D

-glucoside

158106

306

C 20H

22O

83891458(26)4351519

[M+HCO

O]minus

2270

943[M

ndashHndashG

lc]minus

Polydatin

[22]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

168222

C 29H

36O

166392

219(minus17

)4771894[M

ndashHndashG

lc]minus

1790

546[M

ndashRhandashC

17H

14O

6]minus

1610

328[G

lcndashHndashH

2O]minus

R-suspensasid

e[23]

17a

8320

C 21H

20O

94151253

(31)

2530542

[MndashH

ndashGlc]minus

4171394

(minus07)

4391

200

2550864

[M+HndashG

lc]+

Chrysoph

anol

glucoside

[21]

188874

C 29H

36O

166392

002(minus27)

1610

328[G

lcndashHndashH

2O]minus

1790

349[M

ndashRhandashC

17H

14O

6]minus

S-suspensasid

e[24]

1990

54C 2

9H36O

156231999

(minus12

)3112

176

6252137

(08)

6471942

4791

5624711479

32509251630394

Isom

erof

forsytho

sideA

20a

9470

235

C 17H

24O

114031261

(52)

4051331

(minus17

)4271203

2430871

[M+HndashG

lc]+

Secoxyloganin

[19]

2195

52276313

C 21H

22O

94171205(46)8352331

[2MndashH

]minus2550652

[MndashH

ndashGlc]minus

4411132

2570

811[M

+HndashG

lc]+

Liqu

iritin

[25]

22a

9886

277312

C 26H

30O

135491

627(35)

5512

823

(47)

5731737

2570

822[M

+HndashA

pindashG

lc]+

Liqu

iritin

apiosid

e[26]

2399

95C 2

6H30O

135491

629(38)

5513

403

(minus51)

5731735

2570

815[M

+HndashA

pindashG

lc]+

Isom

erof

liquiritin

apiosid

e[26]

2410088

C 27H

30O

1660

91844(minus18

)6331712

Rhod

iosin

[27]

25a

10384

250300

C 22H

22O

94291410(30)

453117

62690

974[M

+HndashG

lc]+

Ono

nin

[2829]

26a

10722

360

C 21H

20O

124630905

(28)

3010

464[M

ndashHndashG

lc]minus

4651033

(52)

4870

333

3030515

[M+HndashG

lc]+

Hyperin

[24]

27a

10819

326

C 25H

24O

125151205

(29)

3530751

[MndashH

ndashCa]minus

5171296

(17)

5391

156

4991

187[M

+HndashH

2O]+

1630

395[M

+HndashC

andashQuinica

cid]

+

35-Dicaffeoylqu

inic

acid

[30]

2810931

C 29H

36O

156231999

(minus19

)46113781610

185

6471941

47114973250925

1630

415

Isom

erof

forsytho

sideA

29a

1110

256354

C 27H

30O

1660

91465(15)

6111573

(33)

6331404

4650982

[M+HndashR

ha]+

3030495

[M+HndashR

ut]+

Rutin

[31]

30a

11220

280

C 29H

36O

156232001

(minus16

)4611920[M

ndashHndashC

a]minus

1610

328[C

affeica

cidndash

HndashH

2O]minus

6471927

1630386

[Caffeica

cid+

HndashH

2O]+

Forsytho

sideA

[32]

3111589

283

C 27H

30O

155931534

(minus13

)2850677

[MndashH

ndashRut]minus

5951694

(minus07)

2870

936[M

+HndashR

ut]+

Kaem

pferol-3-O

-rutin

oside

[13]

3211692

C 19H

35O

165191

884(35)5651953

[M+HCO

O]minus

3571366[M

ndashHndashG

lc]minus

5431855

3591454[M

+HndashG

lc]+

3411411[M

+HndashG

lcndashH

2O]+

(+)-Pino

resin

ol-120573-

D-glucosid

e[33]

33a

12213

210262

C 20H

27NO

114561523

(37)

4581641

(minus46)

2961124

[M+HndashG

lc]+

1620862

[M+

HndashG

lcndashH

CT]+

Amygdalin

[13]


ble2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

34a

12659

326

C 25H

24O

12515116

2(minus54)

3530786

[MndashH

ndashCa]minus

5171348

(04)

5391

193

4991

248[M

+HndashH

2O]+1630387[M

+HndashC

andashQuinica

cid]

+

34-

Dicaffeoylqu

inic

acid

[30]

35a

13082

276

C 15H

12O

42550654

(minus12

)2570

659

(minus08)

1470

621[M

+HndashR

L]+

1370

422[M

+HndashV

P]+

1190691[M

+HndashR

LndashCO

]+Liqu

iritig

enin

[34]

36a

13251

243372

C 26H

30O

135491

621(24)

5511725

(34)

5731563

4191

360[M

+HndashA

pi]+

2570

814[M

+HndashA

pindashG

lc]+

Isoliquiritin

apiosid

e[35]

37a

13300

242362

C 21H

22O

94171198(29)

2550518

[MndashH

ndashGlc]minus

4191

314

(minus67)

4411150

2570

823[M

+HndashG

lc]+

2291

357[M

+HndashG

lcndashC

O]+

Isoliquiritin

[26]

3813479

280

C 27H

34O

115792

103[M

+HCO

O]minus

5571987

5522463

[M+NH

4]+

3551516

[M+

HndashG

lcndashH

2O]+

Arctiin

[36]

39a

1416

1277

C 27H

34O

115792

106[M

+HCO

O]minus

3711826[M

ndashHndashG

lc]minus

3561547

[MndashH

ndashGlcndashH

2O]minus

5522444

[M

+NH

4]+5571991

3731563

[M+HndashG

lc]+

3551544

[M+

HndashG

lcndashH

2O]+

Phillyrin

[3738]

4014678

372255

C 15H

10O

73010

355(23)

1510

137[M

ndashHndashC

8H6O

3]minus

3030520

(49)

Quercetin

[39]

4115039

284

C 28H

34O

1560

91522(13)

3010

582[M

ndashHndashR

ut]minus

Hesperid

in[13]

4215402

265366

C 15H

10O

628504

06(25)

2870

721

(45)

15304

69[M

+HndashH

EP]+

Kaem

pferol

[13]

4316627

255

C 15H

10O

42530507

(24)

2250741

[MndashH

ndashCO]minus

2100494

[MndashH

ndashCOndashC

H3]minus

1820542

[MndashH

ndash2CO

ndashCH

3]minus

1540553

[MndashH

ndash3CO

ndashCH

3]minus

Chrysoph

anol

[40]

4417035

C 15H

10O

42530512

(43)

2250752210047418204

85

1540531

Isom

erof

chrysoph

anol

[40]

45a

17347

254

287426

C 21H

20O

104310

989(26)

2690

673[M

ndashHndashG

lc]minus

2410

719[M

ndashHndashG

lcndashC

O]minus

2250753

[MndashH

ndashGlcndashC

O2]minus

2100578

[MndashH

ndashGlcndashC

O2ndashCH

3]minus

1970

771[MndashH

ndashGlcndashC

OndashC

O2]minus

18204

86[M

ndashHndashG

lcndashC

O2ndashCH

3ndashCO

]minus

4551010

2710

715[M

+HndashG

lc]+

Emod

in-8-O

-glucoside

[41]

4617396

240

330395

C 15H

12O

42550639

(minus71)

2570

812

(minus08)

Isoliquiritigenin

[26]

47a

18385

250304

C 16H

12O

42670

653(minus15

)2690

827

(48)

2910

751

Form

onon

etin

[42]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

4818804

89540

82(28)

7193

849[M

ndashHndashG

lcA]minus

3510

630[2GlcAndash

H]minus

8974

107

(12)

9193

925

22120573-Acetoxy

licorices

apon

inB2

uralsa

poninF

[43]

491919

4271421

C 22H22O10

445116

8(minus56)

2830632

[MndashH

ndashGlc]minus

4691

128

2850775

[M+HndashG

lc]+

Physcion

-8-O

-120573-D

-glucop

yranoside

[41]

5019603

248

C 42H

60O

168193

843(06)

3510

699[2GlcAndash

H]minus

8213

994

(minus01)

8433996

6453612

[M+

HndashG

lcA]+

4693

302[M

+Hndash2GlcA]+

4513

211[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inE2

[35]

5119704

C 16H

24O

73272

180(28)

1649664

[MndashH

ndashGlc]minus

3512

133

Rhod

odendrol-41015840-

O-120573-D

-glucop

yranoside

[44]

5220000

254

C 44H

64O

188794

062(13)

3510

806[M

ndashHndash22A

G]minus

8814

170

(minus01)

7053897

[M+

HndashG

lcA]+

5293

588[M

+Hndash2GlcA]+

5113

395[M

+Hndash2GlcA

ndashH2O

]+

22-

Acetoxyglycyrrhizin

[42]

5320573

352

C 17H

14O

73292

341(39)

3532280

301144

3[M

+HndashC

H2O

]+

2872

002[M

+HndashC

O2]

+ 2591

248[M

+HndashC

O2ndashCO

]+

Tricin

[45]

54a

2119

9260

C 15H

8O6

2830262

(67)

2390

359[M

ndashHndashC

O2]minus

2850515

(minus130)

Rhein

[46]

5521540

253

8373977(12)

8194

404[M

ndashHndashH

2O]minus

6614

100[M

ndashHndashG

lcA]minus

3510

815[2GlcAndash

H]minus

2890

840

[2GlcAndash

HndashH

2OndashC

O2]minus

8394

061

(minus05)

8613

890

6633868

[M+

HndashG

lcA]+

4873395[M

+Hndash2GlcA]+

4693

286[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inG2

[42]

5621626

236

327370

384

C 21H

20O

63671208(71)

3091

566[M

ndashHndashC

OndashC

H2O

]minus

2650635

[MndashH

ndashCOndashC

H2O

ndashCO

2]minus

2210

221

[MndashH

ndashCOndashC

H2O

ndash2CO

2]minus

3691

369

(minus76

)3911176

Glycycoum

arin

[47]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

5722087

249

C 42H

62O

168213

977(17)

8034501

[MndashH

ndashH2O

]minus

7594

542[M

ndashHndashH

2OndashC

O2]minus

6454102

[MndashH

ndashGlcA]minus

6274

000[M

ndashHndashG

lcAndash

H2O

]minus

4693

705[M


3510

809[2GlcAndash

H]minus

2890

758[2GlcAndash

HndashH

2OndashC

O2]minus

8234128

(15)

8454557

6473797[M

+HndashG

lcA]+

4713

480[M

+Hndash2GlcA]+

4533

365[M

+Hndash2GlcA

ndashH2O

]+

Glycyrrhizica

cid

[48]

582218

8252

C 42H

62O

168213

986(minus11)

3510

768[M

ndashHndashG

A]minus

8234134

(minus21)

8454127

6473

823[M

+HndashG

lcA]+

4713

365[M

+Hndash2GlcA]+

4533324

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inH2

[26]

5922389

248

C 42H

64O

158074

197(minus06)

74546

01[M

ndashHndashG

lc]minus

6314

210[M

ndashHndashG

lcA]minus

3510

699[M

ndashHndashG

A]minus

8094

410

(minus09)

8314

138

Licoric

esapon

inB2

[49]

6022623

252

C 42H

62O

168213

997(02)

3510

837[M

ndashHndashG

A]minus

8234105

(minus13

)8453900

6473

838[M

+HndashG

lcA]+

4713

288[M

+Hndash2GlcA]+

4533279

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inK2

[50]

61a

23230

288439

C 15H

10O

52690

462(45)

2410

669[M

ndashHndashC

O]minus

2250723

[MndashH

ndashCO

2]minus

21004

27[M

ndashHndashC

O2ndashCH

3]minus

1970

695[M

ndashHndashC

OndashC

O2]minus

1820477

[MndashH

ndashCO

2ndashCH

3ndashCO

]minus

1540552

[MndashH

ndashCO

2ndashCH

3ndash2C

O]minus

Emod

in[40]

a Com

paredwith

referencec

ompo

unds

b 22A

G2


ApiapioseC

acaffeoylGAg

lycyrrhetin

icacidG

lcg

lucoseG

lcAg

lucuronicacidH

CT4

-(hydroxym

ethyl)c

yclobu

tane-123-tr

iolHEP


enolR

ha

rham

noseR

LresorcinolR

utrutinoseVP

4-vinylpheno

l


Table3Linear

regressio

nLO

Dsa

ndLO

Qsintraday

andinterday

precision


for12compo

unds

Com

poun

dRe

gressio

nequatio

na(119899=3)

1198772

Linear

range

(120583gmL)

LOD

b

(120583gmL)

LOQ

c

(120583gmL)

Intraday

(RSD

)

(119899=6)

Interday

(RSD

)

(119899=3)


(RSD

)

Recovery

(119899=6)

Mean

(120583gg)

RSD

()

Orig

inal

(120583g)

Spiked

(120583g)

Detected

(120583g)

Recovery

()

RSD

()

Salid

rosid

e119910=

13980119909minus11265

09999

527ndash8

435

106

350

012

026177955plusmn

1092

061

138

35591

35420

7075

09928

124

Chlorogenica

cid

119910=

26510119909+36733

09998

685ndash10956

171

569

077

212247371plusmn

1274

051

254

49474

49385

9599

09419

242

Forsytho

sideE

119910=

11793119909+50168

09995

485ndash776

412

1404

067

225175403plusmn

1872

107

267

3518

13510

56772

69299

354

Cryptochlorogenic

acid

119910=

21498119909minus50189

09997

665ndash10647

166

553

110

163202949plusmn

2065

102

246

40590

40660

78400

9310

143

Amygdalin

119910=

10530119909minus34647

09998

391ndash6

257

098

326

079

093148538plusmn

2585

174

248

2970

829862

57639

9358

332

Sweroside

119910=

20593119909minus60034

09999

200ndash319

6025

080

011

033

79806plusmn

293

037

048

1596

11595

132543

10395

041

Hyperin

119910=

27773119909minus87941

09999

020ndash321

0051

016

078

062

9203plusmn

080

087

083

1841

1824

3707

10229

182

Rutin

119910=

30768119909minus37837

09993

053ndash850

0072

021

041

224

18415plusmn

306

166

157

3683

3681

7250

9690

234

Forsytho

sideA

119910=

85466119909minus60245

09999

421ndash6

734

030

105

020

292248499plusmn

1843

074

195

4970

049595

99733

10089

149

Phillyrin

119910=

30390119909+52828

09999

286ndash4

571

071

236

079

163157780plusmn

1011

064

276

31556

31672

62399

10025

160

Rhein

119910=

74736119909minus51727

09996

347ndash5549

087

288

040

028

68192plusmn

1632

239

097

13638

13627

27348

10061

161

Glycyrrhizica

cid

119910=

10296119909minus65313

09999

527ndash8

435

0092

033

034

209162275plusmn

1759

108

215

32455

323939

65216

1013

1327

a 119910isthep

eakarea119909

isthec

oncentratio

nof

stand

ardsolutio

ns

b LODrefersto

thelim

itsof

detection119878119873=3

c LOQrefersto

thelim

itsof

quantity119878119873=10


Table4Con

tentso

fthe

12compo

unds

in10

batches

Sample

Com

poun

d(m

eanplusmnSD

)(120583gg)

Total

RSD(

)Salid

rosid

eCh

lorogenic

acid

Forsytho

sideE

Cryptochlorogenic

acid

Amygdalin

Sweroside

Hyperin

Rutin

Forsytho

sideA

Phillyrin

Rhein

Glycyrrhizic

acid


1003













4 Conclusion






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


3561547

13599643083514

3711826

37218625161718

5792105

1129871 4310958

58021345812158 111342197973569 11814053

(MSMS)

O

O

O

OO

OO

OH

HOHO

OH


()

0

100

()

0

100

mz

150 200 250 300 350 400 450 500 550 600 650 700 750mz

200 400 600 800 1000 1200 1400

(MSminus)

mz 3561547

mz 3711826

(e)

2250723

18204771810753

18006601540552

19706952240626

2410669 2690634

2420626 2700607

2690462

1129890 27004855610872 8234322 9694360 14023499

O O

O

O

O O

(MSMS)

()

0

100(

)

0

100

mz

160 180 200 220 240 260 280mz

200 400 600 800 1000 1200 1400

(MSminus)

OH

OH

OHOH OH OH OH

OHOHOH

OH

minusCO2

minusCO2minusCO

minusCO

minusHminusHminusH

minusHminusH

minusH

H3CH3C

H3C H3C

mz 1970695mz 2410669

mz 2250723mz 2690462

mz 1820477mz 1540552

minusCH3minusCO

(f)

4310988

11692794321016

4990790 8632153 11946926 14410397

2690673

2250753

18204861710837

1970771 241071927007752710783 3110845

(MSMS)

O

O

O OH

OHO

HOHO

OH

HO





0

100

()

0

100

mz

200 400 600 800 1000 1200 1400mz

140 160 180 200 220 240 260 280 300 320

(MSminus)

mz 3711826mz 2690673

CH3

(g)

8214583

35108091130354

19305102890758

645410258340994693705 7594542

8224637

8234628

(MSMS)

H

HO

HO

OOH

O

O

HOOCHO

HOOHO

HOOH

HOOC


[2GlcAndashH]minus

()

0

100

mz

100 200 300 400 500 600 700 800

8213977

1169246 3111153 8203445

8224006

8434348125530939433099 13258577

()

0

100

mz

200 400 600 800 1000 1200 1400

mz 4693705mz 3510809mz 6454102

(MSminus)

(h)

Figure 4 Continued


3751302

21307733761332

75126674731059 8093751 10383667 13123422

1250712

1210637

930423

650486 950155 1260535 151087824011931740320 1999976 2505933

(MSMS)

OH

H

HO

OH

O

O

O

HO

OHOH

OH



14F

minusH2O

()

0

100

()

0

100

mz

200 400 600 800 1000 1200 1400

mz

60 80 100 120 140 160 180 200 220 240 260

(MSminus)

minusCO2

minusCO2


(i)









2(44Da) CH

3(15Da) and



2]minus and







2OndashCO

2]minus at mz




2O (18Da) CO

2(44Da) and glucose








Table2Ch

aracteriz

ationof

compo

unds

inLQ

Cby

UPL

C-DAD-Q

TOF-MS

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

10817

C 7H

12O

61910

555(minus05)

Quinica

cid

[12]

20982

223287

C 6H

8O7

1910

198(31)

17300

99[M

ndashHndashH

2O]minus

1110

088[M

ndashHndash2H

2OndashC

O2]minus

Citricacid

[13]

3a15

45216271

C 7H

6O5

1690

142(30)

1250241

[MndashH

ndashCO

2]minus

Gallic

acid

[14]

4a3010

325

C 16H

17O

9

3530878

(14)

3750695

[Mndash2H+

Na]minus70718

30[2MndashH

]minus

1910

497[M

ndashHndashC

a]minus

1790

312[C

affeica

cidndash

H]minus

1350359

[Caffeica

cidndash

HndashC

O2]minus

Neochlorogenic

acid

[13]

5a3639

254

C 16H

24O

103751302

(29)

7512

667[2MndashH

]minus

2130773

[MndashH

ndashGlc]minus

1510

878

[MndashH

ndashGlcndashC

O2ndashH

2O]minus

1250721

[MndashH

ndashGlcndash2CO

2]minus

Loganica

cid

[15]

6a404

8224

278

C 14H

20O

72991

133(07)

1790

447[M

ndashHndashC

8H8O

]minus

1190246[M

ndashHndashG

lcndashH

2O]minus

Salid

rosid

e[16]

7a4557

C 20H

30O

124611674(33)

3151348

[MndashH

ndashRha]minus

2971589[M

ndashHndashR

handashH

2O]minus

15306

44[M

ndashHndashR

handashG

lc]minus

1350573

[MndashH

ndashRhandashG

lcndashH

2O]minus

4631220

(minus43)

4851568

1370

599[M

+HndashR

handashG

lcndashH

2O]+

Forsytho

sideE

[17]

8a4749

327

C 16H

17O

93530880

(20)

1910

556[M

ndashHndashC

a]minus

1790

224[C

affeica

cidndash

H]minus

3551028

(minus03)

3770

857

Chlorogenica

cid

[18]

9a5281

325

C 16H

17O

93530880

(20)

1790

348[C

affeica

cidndash

H]minus

17304

61[Q

uinica

cidndash

HndashH

2O]minus

1910

417[M

ndashHndashC

a]minus

Cryptochlorogenic

acid

[18]

106435

270

C 17H

26O

103891

096(31)

3912

176

(minus08)

4131067

3952354

[M+

NandashH

2O]+

2290

835[M

+HndashG

lc]+

Loganin

[19]

116749

C 14H

23O

93350776

(27)

1730459

[MndashH

ndashGlc]minus

1610

373[G

lcndashHndashH

2O]minus

13304

08[G

lcndashH

ndashH2O

ndashCO]minus

3370

883

(53)

3590

686

1630

419[G

lc+

HndashH

2O]+

Reng

ynic

acid-11015840-O

-120573-D

-glucoside

[20]

1272

22C 2

1H20O

94151261

(51)

4391

207

2550879

[M+HndashG

lc]+

Isom

erof

chrysoph

anol

glucoside

[21]

13a

7428

245

C 16H22O9

3571208(62)4031263

[M

+HCO

O]minus

3930938

[M

+Cl]minus

3591

337

(minus14

)3811154

Sweroside

[15]

1478

59C 1

4H23O

93350871

(42)

1930506161037713304

233370

774

(09)

3590

225

1630

416[G

lc+

HndashH

2O]+

Isom

erof

reng

ynic

acid-11015840-O

-120573-D

-glucoside

158106

306

C 20H

22O

83891458(26)4351519

[M+HCO

O]minus

2270

943[M

ndashHndashG

lc]minus

Polydatin

[22]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

168222

C 29H

36O

166392

219(minus17

)4771894[M

ndashHndashG

lc]minus

1790

546[M

ndashRhandashC

17H

14O

6]minus

1610

328[G

lcndashHndashH

2O]minus

R-suspensasid

e[23]

17a

8320

C 21H

20O

94151253

(31)

2530542

[MndashH

ndashGlc]minus

4171394

(minus07)

4391

200

2550864

[M+HndashG

lc]+

Chrysoph

anol

glucoside

[21]

188874

C 29H

36O

166392

002(minus27)

1610

328[G

lcndashHndashH

2O]minus

1790

349[M

ndashRhandashC

17H

14O

6]minus

S-suspensasid

e[24]

1990

54C 2

9H36O

156231999

(minus12

)3112

176

6252137

(08)

6471942

4791

5624711479

32509251630394

Isom

erof

forsytho

sideA

20a

9470

235

C 17H

24O

114031261

(52)

4051331

(minus17

)4271203

2430871

[M+HndashG

lc]+

Secoxyloganin

[19]

2195

52276313

C 21H

22O

94171205(46)8352331

[2MndashH

]minus2550652

[MndashH

ndashGlc]minus

4411132

2570

811[M

+HndashG

lc]+

Liqu

iritin

[25]

22a

9886

277312

C 26H

30O

135491

627(35)

5512

823

(47)

5731737

2570

822[M

+HndashA

pindashG

lc]+

Liqu

iritin

apiosid

e[26]

2399

95C 2

6H30O

135491

629(38)

5513

403

(minus51)

5731735

2570

815[M

+HndashA

pindashG

lc]+

Isom

erof

liquiritin

apiosid

e[26]

2410088

C 27H

30O

1660

91844(minus18

)6331712

Rhod

iosin

[27]

25a

10384

250300

C 22H

22O

94291410(30)

453117

62690

974[M

+HndashG

lc]+

Ono

nin

[2829]

26a

10722

360

C 21H

20O

124630905

(28)

3010

464[M

ndashHndashG

lc]minus

4651033

(52)

4870

333

3030515

[M+HndashG

lc]+

Hyperin

[24]

27a

10819

326

C 25H

24O

125151205

(29)

3530751

[MndashH

ndashCa]minus

5171296

(17)

5391

156

4991

187[M

+HndashH

2O]+

1630

395[M

+HndashC

andashQuinica

cid]

+

35-Dicaffeoylqu

inic

acid

[30]

2810931

C 29H

36O

156231999

(minus19

)46113781610

185

6471941

47114973250925

1630

415

Isom

erof

forsytho

sideA

29a

1110

256354

C 27H

30O

1660

91465(15)

6111573

(33)

6331404

4650982

[M+HndashR

ha]+

3030495

[M+HndashR

ut]+

Rutin

[31]

30a

11220

280

C 29H

36O

156232001

(minus16

)4611920[M

ndashHndashC

a]minus

1610

328[C

affeica

cidndash

HndashH

2O]minus

6471927

1630386

[Caffeica

cid+

HndashH

2O]+

Forsytho

sideA

[32]

3111589

283

C 27H

30O

155931534

(minus13

)2850677

[MndashH

ndashRut]minus

5951694

(minus07)

2870

936[M

+HndashR

ut]+

Kaem

pferol-3-O

-rutin

oside

[13]

3211692

C 19H

35O

165191

884(35)5651953

[M+HCO

O]minus

3571366[M

ndashHndashG

lc]minus

5431855

3591454[M

+HndashG

lc]+

3411411[M

+HndashG

lcndashH

2O]+

(+)-Pino

resin

ol-120573-

D-glucosid

e[33]

33a

12213

210262

C 20H

27NO

114561523

(37)

4581641

(minus46)

2961124

[M+HndashG

lc]+

1620862

[M+

HndashG

lcndashH

CT]+

Amygdalin

[13]


ble2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

34a

12659

326

C 25H

24O

12515116

2(minus54)

3530786

[MndashH

ndashCa]minus

5171348

(04)

5391

193

4991

248[M

+HndashH

2O]+1630387[M

+HndashC

andashQuinica

cid]

+

34-

Dicaffeoylqu

inic

acid

[30]

35a

13082

276

C 15H

12O

42550654

(minus12

)2570

659

(minus08)

1470

621[M

+HndashR

L]+

1370

422[M

+HndashV

P]+

1190691[M

+HndashR

LndashCO

]+Liqu

iritig

enin

[34]

36a

13251

243372

C 26H

30O

135491

621(24)

5511725

(34)

5731563

4191

360[M

+HndashA

pi]+

2570

814[M

+HndashA

pindashG

lc]+

Isoliquiritin

apiosid

e[35]

37a

13300

242362

C 21H

22O

94171198(29)

2550518

[MndashH

ndashGlc]minus

4191

314

(minus67)

4411150

2570

823[M

+HndashG

lc]+

2291

357[M

+HndashG

lcndashC

O]+

Isoliquiritin

[26]

3813479

280

C 27H

34O

115792

103[M

+HCO

O]minus

5571987

5522463

[M+NH

4]+

3551516

[M+

HndashG

lcndashH

2O]+

Arctiin

[36]

39a

1416

1277

C 27H

34O

115792

106[M

+HCO

O]minus

3711826[M

ndashHndashG

lc]minus

3561547

[MndashH

ndashGlcndashH

2O]minus

5522444

[M

+NH

4]+5571991

3731563

[M+HndashG

lc]+

3551544

[M+

HndashG

lcndashH

2O]+

Phillyrin

[3738]

4014678

372255

C 15H

10O

73010

355(23)

1510

137[M

ndashHndashC

8H6O

3]minus

3030520

(49)

Quercetin

[39]

4115039

284

C 28H

34O

1560

91522(13)

3010

582[M

ndashHndashR

ut]minus

Hesperid

in[13]

4215402

265366

C 15H

10O

628504

06(25)

2870

721

(45)

15304

69[M

+HndashH

EP]+

Kaem

pferol

[13]

4316627

255

C 15H

10O

42530507

(24)

2250741

[MndashH

ndashCO]minus

2100494

[MndashH

ndashCOndashC

H3]minus

1820542

[MndashH

ndash2CO

ndashCH

3]minus

1540553

[MndashH

ndash3CO

ndashCH

3]minus

Chrysoph

anol

[40]

4417035

C 15H

10O

42530512

(43)

2250752210047418204

85

1540531

Isom

erof

chrysoph

anol

[40]

45a

17347

254

287426

C 21H

20O

104310

989(26)

2690

673[M

ndashHndashG

lc]minus

2410

719[M

ndashHndashG

lcndashC

O]minus

2250753

[MndashH

ndashGlcndashC

O2]minus

2100578

[MndashH

ndashGlcndashC

O2ndashCH

3]minus

1970

771[MndashH

ndashGlcndashC

OndashC

O2]minus

18204

86[M

ndashHndashG

lcndashC

O2ndashCH

3ndashCO

]minus

4551010

2710

715[M

+HndashG

lc]+

Emod

in-8-O

-glucoside

[41]

4617396

240

330395

C 15H

12O

42550639

(minus71)

2570

812

(minus08)

Isoliquiritigenin

[26]

47a

18385

250304

C 16H

12O

42670

653(minus15

)2690

827

(48)

2910

751

Form

onon

etin

[42]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

4818804

89540

82(28)

7193

849[M

ndashHndashG

lcA]minus

3510

630[2GlcAndash

H]minus

8974

107

(12)

9193

925

22120573-Acetoxy

licorices

apon

inB2

uralsa

poninF

[43]

491919

4271421

C 22H22O10

445116

8(minus56)

2830632

[MndashH

ndashGlc]minus

4691

128

2850775

[M+HndashG

lc]+

Physcion

-8-O

-120573-D

-glucop

yranoside

[41]

5019603

248

C 42H

60O

168193

843(06)

3510

699[2GlcAndash

H]minus

8213

994

(minus01)

8433996

6453612

[M+

HndashG

lcA]+

4693

302[M

+Hndash2GlcA]+

4513

211[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inE2

[35]

5119704

C 16H

24O

73272

180(28)

1649664

[MndashH

ndashGlc]minus

3512

133

Rhod

odendrol-41015840-

O-120573-D

-glucop

yranoside

[44]

5220000

254

C 44H

64O

188794

062(13)

3510

806[M

ndashHndash22A

G]minus

8814

170

(minus01)

7053897

[M+

HndashG

lcA]+

5293

588[M

+Hndash2GlcA]+

5113

395[M

+Hndash2GlcA

ndashH2O

]+

22-

Acetoxyglycyrrhizin

[42]

5320573

352

C 17H

14O

73292

341(39)

3532280

301144

3[M

+HndashC

H2O

]+

2872

002[M

+HndashC

O2]

+ 2591

248[M

+HndashC

O2ndashCO

]+

Tricin

[45]

54a

2119

9260

C 15H

8O6

2830262

(67)

2390

359[M

ndashHndashC

O2]minus

2850515

(minus130)

Rhein

[46]

5521540

253

8373977(12)

8194

404[M

ndashHndashH

2O]minus

6614

100[M

ndashHndashG

lcA]minus

3510

815[2GlcAndash

H]minus

2890

840

[2GlcAndash

HndashH

2OndashC

O2]minus

8394

061

(minus05)

8613

890

6633868

[M+

HndashG

lcA]+

4873395[M

+Hndash2GlcA]+

4693

286[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inG2

[42]

5621626

236

327370

384

C 21H

20O

63671208(71)

3091

566[M

ndashHndashC

OndashC

H2O

]minus

2650635

[MndashH

ndashCOndashC

H2O

ndashCO

2]minus

2210

221

[MndashH

ndashCOndashC

H2O

ndash2CO

2]minus

3691

369

(minus76

)3911176

Glycycoum

arin

[47]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

5722087

249

C 42H

62O

168213

977(17)

8034501

[MndashH

ndashH2O

]minus

7594

542[M

ndashHndashH

2OndashC

O2]minus

6454102

[MndashH

ndashGlcA]minus

6274

000[M

ndashHndashG

lcAndash

H2O

]minus

4693

705[M


3510

809[2GlcAndash

H]minus

2890

758[2GlcAndash

HndashH

2OndashC

O2]minus

8234128

(15)

8454557

6473797[M

+HndashG

lcA]+

4713

480[M

+Hndash2GlcA]+

4533

365[M

+Hndash2GlcA

ndashH2O

]+

Glycyrrhizica

cid

[48]

582218

8252

C 42H

62O

168213

986(minus11)

3510

768[M

ndashHndashG

A]minus

8234134

(minus21)

8454127

6473

823[M

+HndashG

lcA]+

4713

365[M

+Hndash2GlcA]+

4533324

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inH2

[26]

5922389

248

C 42H

64O

158074

197(minus06)

74546

01[M

ndashHndashG

lc]minus

6314

210[M

ndashHndashG

lcA]minus

3510

699[M

ndashHndashG

A]minus

8094

410

(minus09)

8314

138

Licoric

esapon

inB2

[49]

6022623

252

C 42H

62O

168213

997(02)

3510

837[M

ndashHndashG

A]minus

8234105

(minus13

)8453900

6473

838[M

+HndashG

lcA]+

4713

288[M

+Hndash2GlcA]+

4533279

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inK2

[50]

61a

23230

288439

C 15H

10O

52690

462(45)

2410

669[M

ndashHndashC

O]minus

2250723

[MndashH

ndashCO

2]minus

21004

27[M

ndashHndashC

O2ndashCH

3]minus

1970

695[M

ndashHndashC

OndashC

O2]minus

1820477

[MndashH

ndashCO

2ndashCH

3ndashCO

]minus

1540552

[MndashH

ndashCO

2ndashCH

3ndash2C

O]minus

Emod

in[40]

a Com

paredwith

referencec

ompo

unds

b 22A

G2


ApiapioseC

acaffeoylGAg

lycyrrhetin

icacidG

lcg

lucoseG

lcAg

lucuronicacidH

CT4

-(hydroxym

ethyl)c

yclobu

tane-123-tr

iolHEP


enolR

ha

rham

noseR

LresorcinolR

utrutinoseVP

4-vinylpheno

l


Table3Linear

regressio

nLO

Dsa

ndLO

Qsintraday

andinterday

precision


for12compo

unds

Com

poun

dRe

gressio

nequatio

na(119899=3)

1198772

Linear

range

(120583gmL)

LOD

b

(120583gmL)

LOQ

c

(120583gmL)

Intraday

(RSD

)

(119899=6)

Interday

(RSD

)

(119899=3)


(RSD

)

Recovery

(119899=6)

Mean

(120583gg)

RSD

()

Orig

inal

(120583g)

Spiked

(120583g)

Detected

(120583g)

Recovery

()

RSD

()

Salid

rosid

e119910=

13980119909minus11265

09999

527ndash8

435

106

350

012

026177955plusmn

1092

061

138

35591

35420

7075

09928

124

Chlorogenica

cid

119910=

26510119909+36733

09998

685ndash10956

171

569

077

212247371plusmn

1274

051

254

49474

49385

9599

09419

242

Forsytho

sideE

119910=

11793119909+50168

09995

485ndash776

412

1404

067

225175403plusmn

1872

107

267

3518

13510

56772

69299

354

Cryptochlorogenic

acid

119910=

21498119909minus50189

09997

665ndash10647

166

553

110

163202949plusmn

2065

102

246

40590

40660

78400

9310

143

Amygdalin

119910=

10530119909minus34647

09998

391ndash6

257

098

326

079

093148538plusmn

2585

174

248

2970

829862

57639

9358

332

Sweroside

119910=

20593119909minus60034

09999

200ndash319

6025

080

011

033

79806plusmn

293

037

048

1596

11595

132543

10395

041

Hyperin

119910=

27773119909minus87941

09999

020ndash321

0051

016

078

062

9203plusmn

080

087

083

1841

1824

3707

10229

182

Rutin

119910=

30768119909minus37837

09993

053ndash850

0072

021

041

224

18415plusmn

306

166

157

3683

3681

7250

9690

234

Forsytho

sideA

119910=

85466119909minus60245

09999

421ndash6

734

030

105

020

292248499plusmn

1843

074

195

4970

049595

99733

10089

149

Phillyrin

119910=

30390119909+52828

09999

286ndash4

571

071

236

079

163157780plusmn

1011

064

276

31556

31672

62399

10025

160

Rhein

119910=

74736119909minus51727

09996

347ndash5549

087

288

040

028

68192plusmn

1632

239

097

13638

13627

27348

10061

161

Glycyrrhizica

cid

119910=

10296119909minus65313

09999

527ndash8

435

0092

033

034

209162275plusmn

1759

108

215

32455

323939

65216

1013

1327

a 119910isthep

eakarea119909

isthec

oncentratio

nof

stand

ardsolutio

ns

b LODrefersto

thelim

itsof

detection119878119873=3

c LOQrefersto

thelim

itsof

quantity119878119873=10


Table4Con

tentso

fthe

12compo

unds

in10

batches

Sample

Com

poun

d(m

eanplusmnSD

)(120583gg)

Total

RSD(

)Salid

rosid

eCh

lorogenic

acid

Forsytho

sideE

Cryptochlorogenic

acid

Amygdalin

Sweroside

Hyperin

Rutin

Forsytho

sideA

Phillyrin

Rhein

Glycyrrhizic

acid


1003













4 Conclusion






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


3751302

21307733761332

75126674731059 8093751 10383667 13123422

1250712

1210637

930423

650486 950155 1260535 151087824011931740320 1999976 2505933

(MSMS)

OH

H

HO

OH

O

O

O

HO

OHOH

OH



14F

minusH2O

()

0

100

()

0

100

mz

200 400 600 800 1000 1200 1400

mz

60 80 100 120 140 160 180 200 220 240 260

(MSminus)

minusCO2

minusCO2


(i)









2(44Da) CH

3(15Da) and



2]minus and







2OndashCO

2]minus at mz




2O (18Da) CO

2(44Da) and glucose








Table2Ch

aracteriz

ationof

compo

unds

inLQ

Cby

UPL

C-DAD-Q

TOF-MS

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

10817

C 7H

12O

61910

555(minus05)

Quinica

cid

[12]

20982

223287

C 6H

8O7

1910

198(31)

17300

99[M

ndashHndashH

2O]minus

1110

088[M

ndashHndash2H

2OndashC

O2]minus

Citricacid

[13]

3a15

45216271

C 7H

6O5

1690

142(30)

1250241

[MndashH

ndashCO

2]minus

Gallic

acid

[14]

4a3010

325

C 16H

17O

9

3530878

(14)

3750695

[Mndash2H+

Na]minus70718

30[2MndashH

]minus

1910

497[M

ndashHndashC

a]minus

1790

312[C

affeica

cidndash

H]minus

1350359

[Caffeica

cidndash

HndashC

O2]minus

Neochlorogenic

acid

[13]

5a3639

254

C 16H

24O

103751302

(29)

7512

667[2MndashH

]minus

2130773

[MndashH

ndashGlc]minus

1510

878

[MndashH

ndashGlcndashC

O2ndashH

2O]minus

1250721

[MndashH

ndashGlcndash2CO

2]minus

Loganica

cid

[15]

6a404

8224

278

C 14H

20O

72991

133(07)

1790

447[M

ndashHndashC

8H8O

]minus

1190246[M

ndashHndashG

lcndashH

2O]minus

Salid

rosid

e[16]

7a4557

C 20H

30O

124611674(33)

3151348

[MndashH

ndashRha]minus

2971589[M

ndashHndashR

handashH

2O]minus

15306

44[M

ndashHndashR

handashG

lc]minus

1350573

[MndashH

ndashRhandashG

lcndashH

2O]minus

4631220

(minus43)

4851568

1370

599[M

+HndashR

handashG

lcndashH

2O]+

Forsytho

sideE

[17]

8a4749

327

C 16H

17O

93530880

(20)

1910

556[M

ndashHndashC

a]minus

1790

224[C

affeica

cidndash

H]minus

3551028

(minus03)

3770

857

Chlorogenica

cid

[18]

9a5281

325

C 16H

17O

93530880

(20)

1790

348[C

affeica

cidndash

H]minus

17304

61[Q

uinica

cidndash

HndashH

2O]minus

1910

417[M

ndashHndashC

a]minus

Cryptochlorogenic

acid

[18]

106435

270

C 17H

26O

103891

096(31)

3912

176

(minus08)

4131067

3952354

[M+

NandashH

2O]+

2290

835[M

+HndashG

lc]+

Loganin

[19]

116749

C 14H

23O

93350776

(27)

1730459

[MndashH

ndashGlc]minus

1610

373[G

lcndashHndashH

2O]minus

13304

08[G

lcndashH

ndashH2O

ndashCO]minus

3370

883

(53)

3590

686

1630

419[G

lc+

HndashH

2O]+

Reng

ynic

acid-11015840-O

-120573-D

-glucoside

[20]

1272

22C 2

1H20O

94151261

(51)

4391

207

2550879

[M+HndashG

lc]+

Isom

erof

chrysoph

anol

glucoside

[21]

13a

7428

245

C 16H22O9

3571208(62)4031263

[M

+HCO

O]minus

3930938

[M

+Cl]minus

3591

337

(minus14

)3811154

Sweroside

[15]

1478

59C 1

4H23O

93350871

(42)

1930506161037713304

233370

774

(09)

3590

225

1630

416[G

lc+

HndashH

2O]+

Isom

erof

reng

ynic

acid-11015840-O

-120573-D

-glucoside

158106

306

C 20H

22O

83891458(26)4351519

[M+HCO

O]minus

2270

943[M

ndashHndashG

lc]minus

Polydatin

[22]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

168222

C 29H

36O

166392

219(minus17

)4771894[M

ndashHndashG

lc]minus

1790

546[M

ndashRhandashC

17H

14O

6]minus

1610

328[G

lcndashHndashH

2O]minus

R-suspensasid

e[23]

17a

8320

C 21H

20O

94151253

(31)

2530542

[MndashH

ndashGlc]minus

4171394

(minus07)

4391

200

2550864

[M+HndashG

lc]+

Chrysoph

anol

glucoside

[21]

188874

C 29H

36O

166392

002(minus27)

1610

328[G

lcndashHndashH

2O]minus

1790

349[M

ndashRhandashC

17H

14O

6]minus

S-suspensasid

e[24]

1990

54C 2

9H36O

156231999

(minus12

)3112

176

6252137

(08)

6471942

4791

5624711479

32509251630394

Isom

erof

forsytho

sideA

20a

9470

235

C 17H

24O

114031261

(52)

4051331

(minus17

)4271203

2430871

[M+HndashG

lc]+

Secoxyloganin

[19]

2195

52276313

C 21H

22O

94171205(46)8352331

[2MndashH

]minus2550652

[MndashH

ndashGlc]minus

4411132

2570

811[M

+HndashG

lc]+

Liqu

iritin

[25]

22a

9886

277312

C 26H

30O

135491

627(35)

5512

823

(47)

5731737

2570

822[M

+HndashA

pindashG

lc]+

Liqu

iritin

apiosid

e[26]

2399

95C 2

6H30O

135491

629(38)

5513

403

(minus51)

5731735

2570

815[M

+HndashA

pindashG

lc]+

Isom

erof

liquiritin

apiosid

e[26]

2410088

C 27H

30O

1660

91844(minus18

)6331712

Rhod

iosin

[27]

25a

10384

250300

C 22H

22O

94291410(30)

453117

62690

974[M

+HndashG

lc]+

Ono

nin

[2829]

26a

10722

360

C 21H

20O

124630905

(28)

3010

464[M

ndashHndashG

lc]minus

4651033

(52)

4870

333

3030515

[M+HndashG

lc]+

Hyperin

[24]

27a

10819

326

C 25H

24O

125151205

(29)

3530751

[MndashH

ndashCa]minus

5171296

(17)

5391

156

4991

187[M

+HndashH

2O]+

1630

395[M

+HndashC

andashQuinica

cid]

+

35-Dicaffeoylqu

inic

acid

[30]

2810931

C 29H

36O

156231999

(minus19

)46113781610

185

6471941

47114973250925

1630

415

Isom

erof

forsytho

sideA

29a

1110

256354

C 27H

30O

1660

91465(15)

6111573

(33)

6331404

4650982

[M+HndashR

ha]+

3030495

[M+HndashR

ut]+

Rutin

[31]

30a

11220

280

C 29H

36O

156232001

(minus16

)4611920[M

ndashHndashC

a]minus

1610

328[C

affeica

cidndash

HndashH

2O]minus

6471927

1630386

[Caffeica

cid+

HndashH

2O]+

Forsytho

sideA

[32]

3111589

283

C 27H

30O

155931534

(minus13

)2850677

[MndashH

ndashRut]minus

5951694

(minus07)

2870

936[M

+HndashR

ut]+

Kaem

pferol-3-O

-rutin

oside

[13]

3211692

C 19H

35O

165191

884(35)5651953

[M+HCO

O]minus

3571366[M

ndashHndashG

lc]minus

5431855

3591454[M

+HndashG

lc]+

3411411[M

+HndashG

lcndashH

2O]+

(+)-Pino

resin

ol-120573-

D-glucosid

e[33]

33a

12213

210262

C 20H

27NO

114561523

(37)

4581641

(minus46)

2961124

[M+HndashG

lc]+

1620862

[M+

HndashG

lcndashH

CT]+

Amygdalin

[13]


ble2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

34a

12659

326

C 25H

24O

12515116

2(minus54)

3530786

[MndashH

ndashCa]minus

5171348

(04)

5391

193

4991

248[M

+HndashH

2O]+1630387[M

+HndashC

andashQuinica

cid]

+

34-

Dicaffeoylqu

inic

acid

[30]

35a

13082

276

C 15H

12O

42550654

(minus12

)2570

659

(minus08)

1470

621[M

+HndashR

L]+

1370

422[M

+HndashV

P]+

1190691[M

+HndashR

LndashCO

]+Liqu

iritig

enin

[34]

36a

13251

243372

C 26H

30O

135491

621(24)

5511725

(34)

5731563

4191

360[M

+HndashA

pi]+

2570

814[M

+HndashA

pindashG

lc]+

Isoliquiritin

apiosid

e[35]

37a

13300

242362

C 21H

22O

94171198(29)

2550518

[MndashH

ndashGlc]minus

4191

314

(minus67)

4411150

2570

823[M

+HndashG

lc]+

2291

357[M

+HndashG

lcndashC

O]+

Isoliquiritin

[26]

3813479

280

C 27H

34O

115792

103[M

+HCO

O]minus

5571987

5522463

[M+NH

4]+

3551516

[M+

HndashG

lcndashH

2O]+

Arctiin

[36]

39a

1416

1277

C 27H

34O

115792

106[M

+HCO

O]minus

3711826[M

ndashHndashG

lc]minus

3561547

[MndashH

ndashGlcndashH

2O]minus

5522444

[M

+NH

4]+5571991

3731563

[M+HndashG

lc]+

3551544

[M+

HndashG

lcndashH

2O]+

Phillyrin

[3738]

4014678

372255

C 15H

10O

73010

355(23)

1510

137[M

ndashHndashC

8H6O

3]minus

3030520

(49)

Quercetin

[39]

4115039

284

C 28H

34O

1560

91522(13)

3010

582[M

ndashHndashR

ut]minus

Hesperid

in[13]

4215402

265366

C 15H

10O

628504

06(25)

2870

721

(45)

15304

69[M

+HndashH

EP]+

Kaem

pferol

[13]

4316627

255

C 15H

10O

42530507

(24)

2250741

[MndashH

ndashCO]minus

2100494

[MndashH

ndashCOndashC

H3]minus

1820542

[MndashH

ndash2CO

ndashCH

3]minus

1540553

[MndashH

ndash3CO

ndashCH

3]minus

Chrysoph

anol

[40]

4417035

C 15H

10O

42530512

(43)

2250752210047418204

85

1540531

Isom

erof

chrysoph

anol

[40]

45a

17347

254

287426

C 21H

20O

104310

989(26)

2690

673[M

ndashHndashG

lc]minus

2410

719[M

ndashHndashG

lcndashC

O]minus

2250753

[MndashH

ndashGlcndashC

O2]minus

2100578

[MndashH

ndashGlcndashC

O2ndashCH

3]minus

1970

771[MndashH

ndashGlcndashC

OndashC

O2]minus

18204

86[M

ndashHndashG

lcndashC

O2ndashCH

3ndashCO

]minus

4551010

2710

715[M

+HndashG

lc]+

Emod

in-8-O

-glucoside

[41]

4617396

240

330395

C 15H

12O

42550639

(minus71)

2570

812

(minus08)

Isoliquiritigenin

[26]

47a

18385

250304

C 16H

12O

42670

653(minus15

)2690

827

(48)

2910

751

Form

onon

etin

[42]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

4818804

89540

82(28)

7193

849[M

ndashHndashG

lcA]minus

3510

630[2GlcAndash

H]minus

8974

107

(12)

9193

925

22120573-Acetoxy

licorices

apon

inB2

uralsa

poninF

[43]

491919

4271421

C 22H22O10

445116

8(minus56)

2830632

[MndashH

ndashGlc]minus

4691

128

2850775

[M+HndashG

lc]+

Physcion

-8-O

-120573-D

-glucop

yranoside

[41]

5019603

248

C 42H

60O

168193

843(06)

3510

699[2GlcAndash

H]minus

8213

994

(minus01)

8433996

6453612

[M+

HndashG

lcA]+

4693

302[M

+Hndash2GlcA]+

4513

211[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inE2

[35]

5119704

C 16H

24O

73272

180(28)

1649664

[MndashH

ndashGlc]minus

3512

133

Rhod

odendrol-41015840-

O-120573-D

-glucop

yranoside

[44]

5220000

254

C 44H

64O

188794

062(13)

3510

806[M

ndashHndash22A

G]minus

8814

170

(minus01)

7053897

[M+

HndashG

lcA]+

5293

588[M

+Hndash2GlcA]+

5113

395[M

+Hndash2GlcA

ndashH2O

]+

22-

Acetoxyglycyrrhizin

[42]

5320573

352

C 17H

14O

73292

341(39)

3532280

301144

3[M

+HndashC

H2O

]+

2872

002[M

+HndashC

O2]

+ 2591

248[M

+HndashC

O2ndashCO

]+

Tricin

[45]

54a

2119

9260

C 15H

8O6

2830262

(67)

2390

359[M

ndashHndashC

O2]minus

2850515

(minus130)

Rhein

[46]

5521540

253

8373977(12)

8194

404[M

ndashHndashH

2O]minus

6614

100[M

ndashHndashG

lcA]minus

3510

815[2GlcAndash

H]minus

2890

840

[2GlcAndash

HndashH

2OndashC

O2]minus

8394

061

(minus05)

8613

890

6633868

[M+

HndashG

lcA]+

4873395[M

+Hndash2GlcA]+

4693

286[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inG2

[42]

5621626

236

327370

384

C 21H

20O

63671208(71)

3091

566[M

ndashHndashC

OndashC

H2O

]minus

2650635

[MndashH

ndashCOndashC

H2O

ndashCO

2]minus

2210

221

[MndashH

ndashCOndashC

H2O

ndash2CO

2]minus

3691

369

(minus76

)3911176

Glycycoum

arin

[47]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

5722087

249

C 42H

62O

168213

977(17)

8034501

[MndashH

ndashH2O

]minus

7594

542[M

ndashHndashH

2OndashC

O2]minus

6454102

[MndashH

ndashGlcA]minus

6274

000[M

ndashHndashG

lcAndash

H2O

]minus

4693

705[M


3510

809[2GlcAndash

H]minus

2890

758[2GlcAndash

HndashH

2OndashC

O2]minus

8234128

(15)

8454557

6473797[M

+HndashG

lcA]+

4713

480[M

+Hndash2GlcA]+

4533

365[M

+Hndash2GlcA

ndashH2O

]+

Glycyrrhizica

cid

[48]

582218

8252

C 42H

62O

168213

986(minus11)

3510

768[M

ndashHndashG

A]minus

8234134

(minus21)

8454127

6473

823[M

+HndashG

lcA]+

4713

365[M

+Hndash2GlcA]+

4533324

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inH2

[26]

5922389

248

C 42H

64O

158074

197(minus06)

74546

01[M

ndashHndashG

lc]minus

6314

210[M

ndashHndashG

lcA]minus

3510

699[M

ndashHndashG

A]minus

8094

410

(minus09)

8314

138

Licoric

esapon

inB2

[49]

6022623

252

C 42H

62O

168213

997(02)

3510

837[M

ndashHndashG

A]minus

8234105

(minus13

)8453900

6473

838[M

+HndashG

lcA]+

4713

288[M

+Hndash2GlcA]+

4533279

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inK2

[50]

61a

23230

288439

C 15H

10O

52690

462(45)

2410

669[M

ndashHndashC

O]minus

2250723

[MndashH

ndashCO

2]minus

21004

27[M

ndashHndashC

O2ndashCH

3]minus

1970

695[M

ndashHndashC

OndashC

O2]minus

1820477

[MndashH

ndashCO

2ndashCH

3ndashCO

]minus

1540552

[MndashH

ndashCO

2ndashCH

3ndash2C

O]minus

Emod

in[40]

a Com

paredwith

referencec

ompo

unds

b 22A

G2


ApiapioseC

acaffeoylGAg

lycyrrhetin

icacidG

lcg

lucoseG

lcAg

lucuronicacidH

CT4

-(hydroxym

ethyl)c

yclobu

tane-123-tr

iolHEP


enolR

ha

rham

noseR

LresorcinolR

utrutinoseVP

4-vinylpheno

l


Table3Linear

regressio

nLO

Dsa

ndLO

Qsintraday

andinterday

precision


for12compo

unds

Com

poun

dRe

gressio

nequatio

na(119899=3)

1198772

Linear

range

(120583gmL)

LOD

b

(120583gmL)

LOQ

c

(120583gmL)

Intraday

(RSD

)

(119899=6)

Interday

(RSD

)

(119899=3)


(RSD

)

Recovery

(119899=6)

Mean

(120583gg)

RSD

()

Orig

inal

(120583g)

Spiked

(120583g)

Detected

(120583g)

Recovery

()

RSD

()

Salid

rosid

e119910=

13980119909minus11265

09999

527ndash8

435

106

350

012

026177955plusmn

1092

061

138

35591

35420

7075

09928

124

Chlorogenica

cid

119910=

26510119909+36733

09998

685ndash10956

171

569

077

212247371plusmn

1274

051

254

49474

49385

9599

09419

242

Forsytho

sideE

119910=

11793119909+50168

09995

485ndash776

412

1404

067

225175403plusmn

1872

107

267

3518

13510

56772

69299

354

Cryptochlorogenic

acid

119910=

21498119909minus50189

09997

665ndash10647

166

553

110

163202949plusmn

2065

102

246

40590

40660

78400

9310

143

Amygdalin

119910=

10530119909minus34647

09998

391ndash6

257

098

326

079

093148538plusmn

2585

174

248

2970

829862

57639

9358

332

Sweroside

119910=

20593119909minus60034

09999

200ndash319

6025

080

011

033

79806plusmn

293

037

048

1596

11595

132543

10395

041

Hyperin

119910=

27773119909minus87941

09999

020ndash321

0051

016

078

062

9203plusmn

080

087

083

1841

1824

3707

10229

182

Rutin

119910=

30768119909minus37837

09993

053ndash850

0072

021

041

224

18415plusmn

306

166

157

3683

3681

7250

9690

234

Forsytho

sideA

119910=

85466119909minus60245

09999

421ndash6

734

030

105

020

292248499plusmn

1843

074

195

4970

049595

99733

10089

149

Phillyrin

119910=

30390119909+52828

09999

286ndash4

571

071

236

079

163157780plusmn

1011

064

276

31556

31672

62399

10025

160

Rhein

119910=

74736119909minus51727

09996

347ndash5549

087

288

040

028

68192plusmn

1632

239

097

13638

13627

27348

10061

161

Glycyrrhizica

cid

119910=

10296119909minus65313

09999

527ndash8

435

0092

033

034

209162275plusmn

1759

108

215

32455

323939

65216

1013

1327

a 119910isthep

eakarea119909

isthec

oncentratio

nof

stand

ardsolutio

ns

b LODrefersto

thelim

itsof

detection119878119873=3

c LOQrefersto

thelim

itsof

quantity119878119873=10


Table4Con

tentso

fthe

12compo

unds

in10

batches

Sample

Com

poun

d(m

eanplusmnSD

)(120583gg)

Total

RSD(

)Salid

rosid

eCh

lorogenic

acid

Forsytho

sideE

Cryptochlorogenic

acid

Amygdalin

Sweroside

Hyperin

Rutin

Forsytho

sideA

Phillyrin

Rhein

Glycyrrhizic

acid


1003













4 Conclusion






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Table2Ch

aracteriz

ationof

compo

unds

inLQ

Cby

UPL

C-DAD-Q

TOF-MS

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

10817

C 7H

12O

61910

555(minus05)

Quinica

cid

[12]

20982

223287

C 6H

8O7

1910

198(31)

17300

99[M

ndashHndashH

2O]minus

1110

088[M

ndashHndash2H

2OndashC

O2]minus

Citricacid

[13]

3a15

45216271

C 7H

6O5

1690

142(30)

1250241

[MndashH

ndashCO

2]minus

Gallic

acid

[14]

4a3010

325

C 16H

17O

9

3530878

(14)

3750695

[Mndash2H+

Na]minus70718

30[2MndashH

]minus

1910

497[M

ndashHndashC

a]minus

1790

312[C

affeica

cidndash

H]minus

1350359

[Caffeica

cidndash

HndashC

O2]minus

Neochlorogenic

acid

[13]

5a3639

254

C 16H

24O

103751302

(29)

7512

667[2MndashH

]minus

2130773

[MndashH

ndashGlc]minus

1510

878

[MndashH

ndashGlcndashC

O2ndashH

2O]minus

1250721

[MndashH

ndashGlcndash2CO

2]minus

Loganica

cid

[15]

6a404

8224

278

C 14H

20O

72991

133(07)

1790

447[M

ndashHndashC

8H8O

]minus

1190246[M

ndashHndashG

lcndashH

2O]minus

Salid

rosid

e[16]

7a4557

C 20H

30O

124611674(33)

3151348

[MndashH

ndashRha]minus

2971589[M

ndashHndashR

handashH

2O]minus

15306

44[M

ndashHndashR

handashG

lc]minus

1350573

[MndashH

ndashRhandashG

lcndashH

2O]minus

4631220

(minus43)

4851568

1370

599[M

+HndashR

handashG

lcndashH

2O]+

Forsytho

sideE

[17]

8a4749

327

C 16H

17O

93530880

(20)

1910

556[M

ndashHndashC

a]minus

1790

224[C

affeica

cidndash

H]minus

3551028

(minus03)

3770

857

Chlorogenica

cid

[18]

9a5281

325

C 16H

17O

93530880

(20)

1790

348[C

affeica

cidndash

H]minus

17304

61[Q

uinica

cidndash

HndashH

2O]minus

1910

417[M

ndashHndashC

a]minus

Cryptochlorogenic

acid

[18]

106435

270

C 17H

26O

103891

096(31)

3912

176

(minus08)

4131067

3952354

[M+

NandashH

2O]+

2290

835[M

+HndashG

lc]+

Loganin

[19]

116749

C 14H

23O

93350776

(27)

1730459

[MndashH

ndashGlc]minus

1610

373[G

lcndashHndashH

2O]minus

13304

08[G

lcndashH

ndashH2O

ndashCO]minus

3370

883

(53)

3590

686

1630

419[G

lc+

HndashH

2O]+

Reng

ynic

acid-11015840-O

-120573-D

-glucoside

[20]

1272

22C 2

1H20O

94151261

(51)

4391

207

2550879

[M+HndashG

lc]+

Isom

erof

chrysoph

anol

glucoside

[21]

13a

7428

245

C 16H22O9

3571208(62)4031263

[M

+HCO

O]minus

3930938

[M

+Cl]minus

3591

337

(minus14

)3811154

Sweroside

[15]

1478

59C 1

4H23O

93350871

(42)

1930506161037713304

233370

774

(09)

3590

225

1630

416[G

lc+

HndashH

2O]+

Isom

erof

reng

ynic

acid-11015840-O

-120573-D

-glucoside

158106

306

C 20H

22O

83891458(26)4351519

[M+HCO

O]minus

2270

943[M

ndashHndashG

lc]minus

Polydatin

[22]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

168222

C 29H

36O

166392

219(minus17

)4771894[M

ndashHndashG

lc]minus

1790

546[M

ndashRhandashC

17H

14O

6]minus

1610

328[G

lcndashHndashH

2O]minus

R-suspensasid

e[23]

17a

8320

C 21H

20O

94151253

(31)

2530542

[MndashH

ndashGlc]minus

4171394

(minus07)

4391

200

2550864

[M+HndashG

lc]+

Chrysoph

anol

glucoside

[21]

188874

C 29H

36O

166392

002(minus27)

1610

328[G

lcndashHndashH

2O]minus

1790

349[M

ndashRhandashC

17H

14O

6]minus

S-suspensasid

e[24]

1990

54C 2

9H36O

156231999

(minus12

)3112

176

6252137

(08)

6471942

4791

5624711479

32509251630394

Isom

erof

forsytho

sideA

20a

9470

235

C 17H

24O

114031261

(52)

4051331

(minus17

)4271203

2430871

[M+HndashG

lc]+

Secoxyloganin

[19]

2195

52276313

C 21H

22O

94171205(46)8352331

[2MndashH

]minus2550652

[MndashH

ndashGlc]minus

4411132

2570

811[M

+HndashG

lc]+

Liqu

iritin

[25]

22a

9886

277312

C 26H

30O

135491

627(35)

5512

823

(47)

5731737

2570

822[M

+HndashA

pindashG

lc]+

Liqu

iritin

apiosid

e[26]

2399

95C 2

6H30O

135491

629(38)

5513

403

(minus51)

5731735

2570

815[M

+HndashA

pindashG

lc]+

Isom

erof

liquiritin

apiosid

e[26]

2410088

C 27H

30O

1660

91844(minus18

)6331712

Rhod

iosin

[27]

25a

10384

250300

C 22H

22O

94291410(30)

453117

62690

974[M

+HndashG

lc]+

Ono

nin

[2829]

26a

10722

360

C 21H

20O

124630905

(28)

3010

464[M

ndashHndashG

lc]minus

4651033

(52)

4870

333

3030515

[M+HndashG

lc]+

Hyperin

[24]

27a

10819

326

C 25H

24O

125151205

(29)

3530751

[MndashH

ndashCa]minus

5171296

(17)

5391

156

4991

187[M

+HndashH

2O]+

1630

395[M

+HndashC

andashQuinica

cid]

+

35-Dicaffeoylqu

inic

acid

[30]

2810931

C 29H

36O

156231999

(minus19

)46113781610

185

6471941

47114973250925

1630

415

Isom

erof

forsytho

sideA

29a

1110

256354

C 27H

30O

1660

91465(15)

6111573

(33)

6331404

4650982

[M+HndashR

ha]+

3030495

[M+HndashR

ut]+

Rutin

[31]

30a

11220

280

C 29H

36O

156232001

(minus16

)4611920[M

ndashHndashC

a]minus

1610

328[C

affeica

cidndash

HndashH

2O]minus

6471927

1630386

[Caffeica

cid+

HndashH

2O]+

Forsytho

sideA

[32]

3111589

283

C 27H

30O

155931534

(minus13

)2850677

[MndashH

ndashRut]minus

5951694

(minus07)

2870

936[M

+HndashR

ut]+

Kaem

pferol-3-O

-rutin

oside

[13]

3211692

C 19H

35O

165191

884(35)5651953

[M+HCO

O]minus

3571366[M

ndashHndashG

lc]minus

5431855

3591454[M

+HndashG

lc]+

3411411[M

+HndashG

lcndashH

2O]+

(+)-Pino

resin

ol-120573-

D-glucosid

e[33]

33a

12213

210262

C 20H

27NO

114561523

(37)

4581641

(minus46)

2961124

[M+HndashG

lc]+

1620862

[M+

HndashG

lcndashH

CT]+

Amygdalin

[13]


ble2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

34a

12659

326

C 25H

24O

12515116

2(minus54)

3530786

[MndashH

ndashCa]minus

5171348

(04)

5391

193

4991

248[M

+HndashH

2O]+1630387[M

+HndashC

andashQuinica

cid]

+

34-

Dicaffeoylqu

inic

acid

[30]

35a

13082

276

C 15H

12O

42550654

(minus12

)2570

659

(minus08)

1470

621[M

+HndashR

L]+

1370

422[M

+HndashV

P]+

1190691[M

+HndashR

LndashCO

]+Liqu

iritig

enin

[34]

36a

13251

243372

C 26H

30O

135491

621(24)

5511725

(34)

5731563

4191

360[M

+HndashA

pi]+

2570

814[M

+HndashA

pindashG

lc]+

Isoliquiritin

apiosid

e[35]

37a

13300

242362

C 21H

22O

94171198(29)

2550518

[MndashH

ndashGlc]minus

4191

314

(minus67)

4411150

2570

823[M

+HndashG

lc]+

2291

357[M

+HndashG

lcndashC

O]+

Isoliquiritin

[26]

3813479

280

C 27H

34O

115792

103[M

+HCO

O]minus

5571987

5522463

[M+NH

4]+

3551516

[M+

HndashG

lcndashH

2O]+

Arctiin

[36]

39a

1416

1277

C 27H

34O

115792

106[M

+HCO

O]minus

3711826[M

ndashHndashG

lc]minus

3561547

[MndashH

ndashGlcndashH

2O]minus

5522444

[M

+NH

4]+5571991

3731563

[M+HndashG

lc]+

3551544

[M+

HndashG

lcndashH

2O]+

Phillyrin

[3738]

4014678

372255

C 15H

10O

73010

355(23)

1510

137[M

ndashHndashC

8H6O

3]minus

3030520

(49)

Quercetin

[39]

4115039

284

C 28H

34O

1560

91522(13)

3010

582[M

ndashHndashR

ut]minus

Hesperid

in[13]

4215402

265366

C 15H

10O

628504

06(25)

2870

721

(45)

15304

69[M

+HndashH

EP]+

Kaem

pferol

[13]

4316627

255

C 15H

10O

42530507

(24)

2250741

[MndashH

ndashCO]minus

2100494

[MndashH

ndashCOndashC

H3]minus

1820542

[MndashH

ndash2CO

ndashCH

3]minus

1540553

[MndashH

ndash3CO

ndashCH

3]minus

Chrysoph

anol

[40]

4417035

C 15H

10O

42530512

(43)

2250752210047418204

85

1540531

Isom

erof

chrysoph

anol

[40]

45a

17347

254

287426

C 21H

20O

104310

989(26)

2690

673[M

ndashHndashG

lc]minus

2410

719[M

ndashHndashG

lcndashC

O]minus

2250753

[MndashH

ndashGlcndashC

O2]minus

2100578

[MndashH

ndashGlcndashC

O2ndashCH

3]minus

1970

771[MndashH

ndashGlcndashC

OndashC

O2]minus

18204

86[M

ndashHndashG

lcndashC

O2ndashCH

3ndashCO

]minus

4551010

2710

715[M

+HndashG

lc]+

Emod

in-8-O

-glucoside

[41]

4617396

240

330395

C 15H

12O

42550639

(minus71)

2570

812

(minus08)

Isoliquiritigenin

[26]

47a

18385

250304

C 16H

12O

42670

653(minus15

)2690

827

(48)

2910

751

Form

onon

etin

[42]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

4818804

89540

82(28)

7193

849[M

ndashHndashG

lcA]minus

3510

630[2GlcAndash

H]minus

8974

107

(12)

9193

925

22120573-Acetoxy

licorices

apon

inB2

uralsa

poninF

[43]

491919

4271421

C 22H22O10

445116

8(minus56)

2830632

[MndashH

ndashGlc]minus

4691

128

2850775

[M+HndashG

lc]+

Physcion

-8-O

-120573-D

-glucop

yranoside

[41]

5019603

248

C 42H

60O

168193

843(06)

3510

699[2GlcAndash

H]minus

8213

994

(minus01)

8433996

6453612

[M+

HndashG

lcA]+

4693

302[M

+Hndash2GlcA]+

4513

211[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inE2

[35]

5119704

C 16H

24O

73272

180(28)

1649664

[MndashH

ndashGlc]minus

3512

133

Rhod

odendrol-41015840-

O-120573-D

-glucop

yranoside

[44]

5220000

254

C 44H

64O

188794

062(13)

3510

806[M

ndashHndash22A

G]minus

8814

170

(minus01)

7053897

[M+

HndashG

lcA]+

5293

588[M

+Hndash2GlcA]+

5113

395[M

+Hndash2GlcA

ndashH2O

]+

22-

Acetoxyglycyrrhizin

[42]

5320573

352

C 17H

14O

73292

341(39)

3532280

301144

3[M

+HndashC

H2O

]+

2872

002[M

+HndashC

O2]

+ 2591

248[M

+HndashC

O2ndashCO

]+

Tricin

[45]

54a

2119

9260

C 15H

8O6

2830262

(67)

2390

359[M

ndashHndashC

O2]minus

2850515

(minus130)

Rhein

[46]

5521540

253

8373977(12)

8194

404[M

ndashHndashH

2O]minus

6614

100[M

ndashHndashG

lcA]minus

3510

815[2GlcAndash

H]minus

2890

840

[2GlcAndash

HndashH

2OndashC

O2]minus

8394

061

(minus05)

8613

890

6633868

[M+

HndashG

lcA]+

4873395[M

+Hndash2GlcA]+

4693

286[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inG2

[42]

5621626

236

327370

384

C 21H

20O

63671208(71)

3091

566[M

ndashHndashC

OndashC

H2O

]minus

2650635

[MndashH

ndashCOndashC

H2O

ndashCO

2]minus

2210

221

[MndashH

ndashCOndashC

H2O

ndash2CO

2]minus

3691

369

(minus76

)3911176

Glycycoum

arin

[47]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

5722087

249

C 42H

62O

168213

977(17)

8034501

[MndashH

ndashH2O

]minus

7594

542[M

ndashHndashH

2OndashC

O2]minus

6454102

[MndashH

ndashGlcA]minus

6274

000[M

ndashHndashG

lcAndash

H2O

]minus

4693

705[M


3510

809[2GlcAndash

H]minus

2890

758[2GlcAndash

HndashH

2OndashC

O2]minus

8234128

(15)

8454557

6473797[M

+HndashG

lcA]+

4713

480[M

+Hndash2GlcA]+

4533

365[M

+Hndash2GlcA

ndashH2O

]+

Glycyrrhizica

cid

[48]

582218

8252

C 42H

62O

168213

986(minus11)

3510

768[M

ndashHndashG

A]minus

8234134

(minus21)

8454127

6473

823[M

+HndashG

lcA]+

4713

365[M

+Hndash2GlcA]+

4533324

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inH2

[26]

5922389

248

C 42H

64O

158074

197(minus06)

74546

01[M

ndashHndashG

lc]minus

6314

210[M

ndashHndashG

lcA]minus

3510

699[M

ndashHndashG

A]minus

8094

410

(minus09)

8314

138

Licoric

esapon

inB2

[49]

6022623

252

C 42H

62O

168213

997(02)

3510

837[M

ndashHndashG

A]minus

8234105

(minus13

)8453900

6473

838[M

+HndashG

lcA]+

4713

288[M

+Hndash2GlcA]+

4533279

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inK2

[50]

61a

23230

288439

C 15H

10O

52690

462(45)

2410

669[M

ndashHndashC

O]minus

2250723

[MndashH

ndashCO

2]minus

21004

27[M

ndashHndashC

O2ndashCH

3]minus

1970

695[M

ndashHndashC

OndashC

O2]minus

1820477

[MndashH

ndashCO

2ndashCH

3ndashCO

]minus

1540552

[MndashH

ndashCO

2ndashCH

3ndash2C

O]minus

Emod

in[40]

a Com

paredwith

referencec

ompo

unds

b 22A

G2


ApiapioseC

acaffeoylGAg

lycyrrhetin

icacidG

lcg

lucoseG

lcAg

lucuronicacidH

CT4

-(hydroxym

ethyl)c

yclobu

tane-123-tr

iolHEP


enolR

ha

rham

noseR

LresorcinolR

utrutinoseVP

4-vinylpheno

l


Table3Linear

regressio

nLO

Dsa

ndLO

Qsintraday

andinterday

precision


for12compo

unds

Com

poun

dRe

gressio

nequatio

na(119899=3)

1198772

Linear

range

(120583gmL)

LOD

b

(120583gmL)

LOQ

c

(120583gmL)

Intraday

(RSD

)

(119899=6)

Interday

(RSD

)

(119899=3)


(RSD

)

Recovery

(119899=6)

Mean

(120583gg)

RSD

()

Orig

inal

(120583g)

Spiked

(120583g)

Detected

(120583g)

Recovery

()

RSD

()

Salid

rosid

e119910=

13980119909minus11265

09999

527ndash8

435

106

350

012

026177955plusmn

1092

061

138

35591

35420

7075

09928

124

Chlorogenica

cid

119910=

26510119909+36733

09998

685ndash10956

171

569

077

212247371plusmn

1274

051

254

49474

49385

9599

09419

242

Forsytho

sideE

119910=

11793119909+50168

09995

485ndash776

412

1404

067

225175403plusmn

1872

107

267

3518

13510

56772

69299

354

Cryptochlorogenic

acid

119910=

21498119909minus50189

09997

665ndash10647

166

553

110

163202949plusmn

2065

102

246

40590

40660

78400

9310

143

Amygdalin

119910=

10530119909minus34647

09998

391ndash6

257

098

326

079

093148538plusmn

2585

174

248

2970

829862

57639

9358

332

Sweroside

119910=

20593119909minus60034

09999

200ndash319

6025

080

011

033

79806plusmn

293

037

048

1596

11595

132543

10395

041

Hyperin

119910=

27773119909minus87941

09999

020ndash321

0051

016

078

062

9203plusmn

080

087

083

1841

1824

3707

10229

182

Rutin

119910=

30768119909minus37837

09993

053ndash850

0072

021

041

224

18415plusmn

306

166

157

3683

3681

7250

9690

234

Forsytho

sideA

119910=

85466119909minus60245

09999

421ndash6

734

030

105

020

292248499plusmn

1843

074

195

4970

049595

99733

10089

149

Phillyrin

119910=

30390119909+52828

09999

286ndash4

571

071

236

079

163157780plusmn

1011

064

276

31556

31672

62399

10025

160

Rhein

119910=

74736119909minus51727

09996

347ndash5549

087

288

040

028

68192plusmn

1632

239

097

13638

13627

27348

10061

161

Glycyrrhizica

cid

119910=

10296119909minus65313

09999

527ndash8

435

0092

033

034

209162275plusmn

1759

108

215

32455

323939

65216

1013

1327

a 119910isthep

eakarea119909

isthec

oncentratio

nof

stand

ardsolutio

ns

b LODrefersto

thelim

itsof

detection119878119873=3

c LOQrefersto

thelim

itsof

quantity119878119873=10


Table4Con

tentso

fthe

12compo

unds

in10

batches

Sample

Com

poun

d(m

eanplusmnSD

)(120583gg)

Total

RSD(

)Salid

rosid

eCh

lorogenic

acid

Forsytho

sideE

Cryptochlorogenic

acid

Amygdalin

Sweroside

Hyperin

Rutin

Forsytho

sideA

Phillyrin

Rhein

Glycyrrhizic

acid


1003













4 Conclusion






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

168222

C 29H

36O

166392

219(minus17

)4771894[M

ndashHndashG

lc]minus

1790

546[M

ndashRhandashC

17H

14O

6]minus

1610

328[G

lcndashHndashH

2O]minus

R-suspensasid

e[23]

17a

8320

C 21H

20O

94151253

(31)

2530542

[MndashH

ndashGlc]minus

4171394

(minus07)

4391

200

2550864

[M+HndashG

lc]+

Chrysoph

anol

glucoside

[21]

188874

C 29H

36O

166392

002(minus27)

1610

328[G

lcndashHndashH

2O]minus

1790

349[M

ndashRhandashC

17H

14O

6]minus

S-suspensasid

e[24]

1990

54C 2

9H36O

156231999

(minus12

)3112

176

6252137

(08)

6471942

4791

5624711479

32509251630394

Isom

erof

forsytho

sideA

20a

9470

235

C 17H

24O

114031261

(52)

4051331

(minus17

)4271203

2430871

[M+HndashG

lc]+

Secoxyloganin

[19]

2195

52276313

C 21H

22O

94171205(46)8352331

[2MndashH

]minus2550652

[MndashH

ndashGlc]minus

4411132

2570

811[M

+HndashG

lc]+

Liqu

iritin

[25]

22a

9886

277312

C 26H

30O

135491

627(35)

5512

823

(47)

5731737

2570

822[M

+HndashA

pindashG

lc]+

Liqu

iritin

apiosid

e[26]

2399

95C 2

6H30O

135491

629(38)

5513

403

(minus51)

5731735

2570

815[M

+HndashA

pindashG

lc]+

Isom

erof

liquiritin

apiosid

e[26]

2410088

C 27H

30O

1660

91844(minus18

)6331712

Rhod

iosin

[27]

25a

10384

250300

C 22H

22O

94291410(30)

453117

62690

974[M

+HndashG

lc]+

Ono

nin

[2829]

26a

10722

360

C 21H

20O

124630905

(28)

3010

464[M

ndashHndashG

lc]minus

4651033

(52)

4870

333

3030515

[M+HndashG

lc]+

Hyperin

[24]

27a

10819

326

C 25H

24O

125151205

(29)

3530751

[MndashH

ndashCa]minus

5171296

(17)

5391

156

4991

187[M

+HndashH

2O]+

1630

395[M

+HndashC

andashQuinica

cid]

+

35-Dicaffeoylqu

inic

acid

[30]

2810931

C 29H

36O

156231999

(minus19

)46113781610

185

6471941

47114973250925

1630

415

Isom

erof

forsytho

sideA

29a

1110

256354

C 27H

30O

1660

91465(15)

6111573

(33)

6331404

4650982

[M+HndashR

ha]+

3030495

[M+HndashR

ut]+

Rutin

[31]

30a

11220

280

C 29H

36O

156232001

(minus16

)4611920[M

ndashHndashC

a]minus

1610

328[C

affeica

cidndash

HndashH

2O]minus

6471927

1630386

[Caffeica

cid+

HndashH

2O]+

Forsytho

sideA

[32]

3111589

283

C 27H

30O

155931534

(minus13

)2850677

[MndashH

ndashRut]minus

5951694

(minus07)

2870

936[M

+HndashR

ut]+

Kaem

pferol-3-O

-rutin

oside

[13]

3211692

C 19H

35O

165191

884(35)5651953

[M+HCO

O]minus

3571366[M

ndashHndashG

lc]minus

5431855

3591454[M

+HndashG

lc]+

3411411[M

+HndashG

lcndashH

2O]+

(+)-Pino

resin

ol-120573-

D-glucosid

e[33]

33a

12213

210262

C 20H

27NO

114561523

(37)

4581641

(minus46)

2961124

[M+HndashG

lc]+

1620862

[M+

HndashG

lcndashH

CT]+

Amygdalin

[13]


ble2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

34a

12659

326

C 25H

24O

12515116

2(minus54)

3530786

[MndashH

ndashCa]minus

5171348

(04)

5391

193

4991

248[M

+HndashH

2O]+1630387[M

+HndashC

andashQuinica

cid]

+

34-

Dicaffeoylqu

inic

acid

[30]

35a

13082

276

C 15H

12O

42550654

(minus12

)2570

659

(minus08)

1470

621[M

+HndashR

L]+

1370

422[M

+HndashV

P]+

1190691[M

+HndashR

LndashCO

]+Liqu

iritig

enin

[34]

36a

13251

243372

C 26H

30O

135491

621(24)

5511725

(34)

5731563

4191

360[M

+HndashA

pi]+

2570

814[M

+HndashA

pindashG

lc]+

Isoliquiritin

apiosid

e[35]

37a

13300

242362

C 21H

22O

94171198(29)

2550518

[MndashH

ndashGlc]minus

4191

314

(minus67)

4411150

2570

823[M

+HndashG

lc]+

2291

357[M

+HndashG

lcndashC

O]+

Isoliquiritin

[26]

3813479

280

C 27H

34O

115792

103[M

+HCO

O]minus

5571987

5522463

[M+NH

4]+

3551516

[M+

HndashG

lcndashH

2O]+

Arctiin

[36]

39a

1416

1277

C 27H

34O

115792

106[M

+HCO

O]minus

3711826[M

ndashHndashG

lc]minus

3561547

[MndashH

ndashGlcndashH

2O]minus

5522444

[M

+NH

4]+5571991

3731563

[M+HndashG

lc]+

3551544

[M+

HndashG

lcndashH

2O]+

Phillyrin

[3738]

4014678

372255

C 15H

10O

73010

355(23)

1510

137[M

ndashHndashC

8H6O

3]minus

3030520

(49)

Quercetin

[39]

4115039

284

C 28H

34O

1560

91522(13)

3010

582[M

ndashHndashR

ut]minus

Hesperid

in[13]

4215402

265366

C 15H

10O

628504

06(25)

2870

721

(45)

15304

69[M

+HndashH

EP]+

Kaem

pferol

[13]

4316627

255

C 15H

10O

42530507

(24)

2250741

[MndashH

ndashCO]minus

2100494

[MndashH

ndashCOndashC

H3]minus

1820542

[MndashH

ndash2CO

ndashCH

3]minus

1540553

[MndashH

ndash3CO

ndashCH

3]minus

Chrysoph

anol

[40]

4417035

C 15H

10O

42530512

(43)

2250752210047418204

85

1540531

Isom

erof

chrysoph

anol

[40]

45a

17347

254

287426

C 21H

20O

104310

989(26)

2690

673[M

ndashHndashG

lc]minus

2410

719[M

ndashHndashG

lcndashC

O]minus

2250753

[MndashH

ndashGlcndashC

O2]minus

2100578

[MndashH

ndashGlcndashC

O2ndashCH

3]minus

1970

771[MndashH

ndashGlcndashC

OndashC

O2]minus

18204

86[M

ndashHndashG

lcndashC

O2ndashCH

3ndashCO

]minus

4551010

2710

715[M

+HndashG

lc]+

Emod

in-8-O

-glucoside

[41]

4617396

240

330395

C 15H

12O

42550639

(minus71)

2570

812

(minus08)

Isoliquiritigenin

[26]

47a

18385

250304

C 16H

12O

42670

653(minus15

)2690

827

(48)

2910

751

Form

onon

etin

[42]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

4818804

89540

82(28)

7193

849[M

ndashHndashG

lcA]minus

3510

630[2GlcAndash

H]minus

8974

107

(12)

9193

925

22120573-Acetoxy

licorices

apon

inB2

uralsa

poninF

[43]

491919

4271421

C 22H22O10

445116

8(minus56)

2830632

[MndashH

ndashGlc]minus

4691

128

2850775

[M+HndashG

lc]+

Physcion

-8-O

-120573-D

-glucop

yranoside

[41]

5019603

248

C 42H

60O

168193

843(06)

3510

699[2GlcAndash

H]minus

8213

994

(minus01)

8433996

6453612

[M+

HndashG

lcA]+

4693

302[M

+Hndash2GlcA]+

4513

211[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inE2

[35]

5119704

C 16H

24O

73272

180(28)

1649664

[MndashH

ndashGlc]minus

3512

133

Rhod

odendrol-41015840-

O-120573-D

-glucop

yranoside

[44]

5220000

254

C 44H

64O

188794

062(13)

3510

806[M

ndashHndash22A

G]minus

8814

170

(minus01)

7053897

[M+

HndashG

lcA]+

5293

588[M

+Hndash2GlcA]+

5113

395[M

+Hndash2GlcA

ndashH2O

]+

22-

Acetoxyglycyrrhizin

[42]

5320573

352

C 17H

14O

73292

341(39)

3532280

301144

3[M

+HndashC

H2O

]+

2872

002[M

+HndashC

O2]

+ 2591

248[M

+HndashC

O2ndashCO

]+

Tricin

[45]

54a

2119

9260

C 15H

8O6

2830262

(67)

2390

359[M

ndashHndashC

O2]minus

2850515

(minus130)

Rhein

[46]

5521540

253

8373977(12)

8194

404[M

ndashHndashH

2O]minus

6614

100[M

ndashHndashG

lcA]minus

3510

815[2GlcAndash

H]minus

2890

840

[2GlcAndash

HndashH

2OndashC

O2]minus

8394

061

(minus05)

8613

890

6633868

[M+

HndashG

lcA]+

4873395[M

+Hndash2GlcA]+

4693

286[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inG2

[42]

5621626

236

327370

384

C 21H

20O

63671208(71)

3091

566[M

ndashHndashC

OndashC

H2O

]minus

2650635

[MndashH

ndashCOndashC

H2O

ndashCO

2]minus

2210

221

[MndashH

ndashCOndashC

H2O

ndash2CO

2]minus

3691

369

(minus76

)3911176

Glycycoum

arin

[47]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

5722087

249

C 42H

62O

168213

977(17)

8034501

[MndashH

ndashH2O

]minus

7594

542[M

ndashHndashH

2OndashC

O2]minus

6454102

[MndashH

ndashGlcA]minus

6274

000[M

ndashHndashG

lcAndash

H2O

]minus

4693

705[M


3510

809[2GlcAndash

H]minus

2890

758[2GlcAndash

HndashH

2OndashC

O2]minus

8234128

(15)

8454557

6473797[M

+HndashG

lcA]+

4713

480[M

+Hndash2GlcA]+

4533

365[M

+Hndash2GlcA

ndashH2O

]+

Glycyrrhizica

cid

[48]

582218

8252

C 42H

62O

168213

986(minus11)

3510

768[M

ndashHndashG

A]minus

8234134

(minus21)

8454127

6473

823[M

+HndashG

lcA]+

4713

365[M

+Hndash2GlcA]+

4533324

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inH2

[26]

5922389

248

C 42H

64O

158074

197(minus06)

74546

01[M

ndashHndashG

lc]minus

6314

210[M

ndashHndashG

lcA]minus

3510

699[M

ndashHndashG

A]minus

8094

410

(minus09)

8314

138

Licoric

esapon

inB2

[49]

6022623

252

C 42H

62O

168213

997(02)

3510

837[M

ndashHndashG

A]minus

8234105

(minus13

)8453900

6473

838[M

+HndashG

lcA]+

4713

288[M

+Hndash2GlcA]+

4533279

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inK2

[50]

61a

23230

288439

C 15H

10O

52690

462(45)

2410

669[M

ndashHndashC

O]minus

2250723

[MndashH

ndashCO

2]minus

21004

27[M

ndashHndashC

O2ndashCH

3]minus

1970

695[M

ndashHndashC

OndashC

O2]minus

1820477

[MndashH

ndashCO

2ndashCH

3ndashCO

]minus

1540552

[MndashH

ndashCO

2ndashCH

3ndash2C

O]minus

Emod

in[40]

a Com

paredwith

referencec

ompo

unds

b 22A

G2


ApiapioseC

acaffeoylGAg

lycyrrhetin

icacidG

lcg

lucoseG

lcAg

lucuronicacidH

CT4

-(hydroxym

ethyl)c

yclobu

tane-123-tr

iolHEP


enolR

ha

rham

noseR

LresorcinolR

utrutinoseVP

4-vinylpheno

l


Table3Linear

regressio

nLO

Dsa

ndLO

Qsintraday

andinterday

precision


for12compo

unds

Com

poun

dRe

gressio

nequatio

na(119899=3)

1198772

Linear

range

(120583gmL)

LOD

b

(120583gmL)

LOQ

c

(120583gmL)

Intraday

(RSD

)

(119899=6)

Interday

(RSD

)

(119899=3)


(RSD

)

Recovery

(119899=6)

Mean

(120583gg)

RSD

()

Orig

inal

(120583g)

Spiked

(120583g)

Detected

(120583g)

Recovery

()

RSD

()

Salid

rosid

e119910=

13980119909minus11265

09999

527ndash8

435

106

350

012

026177955plusmn

1092

061

138

35591

35420

7075

09928

124

Chlorogenica

cid

119910=

26510119909+36733

09998

685ndash10956

171

569

077

212247371plusmn

1274

051

254

49474

49385

9599

09419

242

Forsytho

sideE

119910=

11793119909+50168

09995

485ndash776

412

1404

067

225175403plusmn

1872

107

267

3518

13510

56772

69299

354

Cryptochlorogenic

acid

119910=

21498119909minus50189

09997

665ndash10647

166

553

110

163202949plusmn

2065

102

246

40590

40660

78400

9310

143

Amygdalin

119910=

10530119909minus34647

09998

391ndash6

257

098

326

079

093148538plusmn

2585

174

248

2970

829862

57639

9358

332

Sweroside

119910=

20593119909minus60034

09999

200ndash319

6025

080

011

033

79806plusmn

293

037

048

1596

11595

132543

10395

041

Hyperin

119910=

27773119909minus87941

09999

020ndash321

0051

016

078

062

9203plusmn

080

087

083

1841

1824

3707

10229

182

Rutin

119910=

30768119909minus37837

09993

053ndash850

0072

021

041

224

18415plusmn

306

166

157

3683

3681

7250

9690

234

Forsytho

sideA

119910=

85466119909minus60245

09999

421ndash6

734

030

105

020

292248499plusmn

1843

074

195

4970

049595

99733

10089

149

Phillyrin

119910=

30390119909+52828

09999

286ndash4

571

071

236

079

163157780plusmn

1011

064

276

31556

31672

62399

10025

160

Rhein

119910=

74736119909minus51727

09996

347ndash5549

087

288

040

028

68192plusmn

1632

239

097

13638

13627

27348

10061

161

Glycyrrhizica

cid

119910=

10296119909minus65313

09999

527ndash8

435

0092

033

034

209162275plusmn

1759

108

215

32455

323939

65216

1013

1327

a 119910isthep

eakarea119909

isthec

oncentratio

nof

stand

ardsolutio

ns

b LODrefersto

thelim

itsof

detection119878119873=3

c LOQrefersto

thelim

itsof

quantity119878119873=10


Table4Con

tentso

fthe

12compo

unds

in10

batches

Sample

Com

poun

d(m

eanplusmnSD

)(120583gg)

Total

RSD(

)Salid

rosid

eCh

lorogenic

acid

Forsytho

sideE

Cryptochlorogenic

acid

Amygdalin

Sweroside

Hyperin

Rutin

Forsytho

sideA

Phillyrin

Rhein

Glycyrrhizic

acid


1003













4 Conclusion






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


ble2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

34a

12659

326

C 25H

24O

12515116

2(minus54)

3530786

[MndashH

ndashCa]minus

5171348

(04)

5391

193

4991

248[M

+HndashH

2O]+1630387[M

+HndashC

andashQuinica

cid]

+

34-

Dicaffeoylqu

inic

acid

[30]

35a

13082

276

C 15H

12O

42550654

(minus12

)2570

659

(minus08)

1470

621[M

+HndashR

L]+

1370

422[M

+HndashV

P]+

1190691[M

+HndashR

LndashCO

]+Liqu

iritig

enin

[34]

36a

13251

243372

C 26H

30O

135491

621(24)

5511725

(34)

5731563

4191

360[M

+HndashA

pi]+

2570

814[M

+HndashA

pindashG

lc]+

Isoliquiritin

apiosid

e[35]

37a

13300

242362

C 21H

22O

94171198(29)

2550518

[MndashH

ndashGlc]minus

4191

314

(minus67)

4411150

2570

823[M

+HndashG

lc]+

2291

357[M

+HndashG

lcndashC

O]+

Isoliquiritin

[26]

3813479

280

C 27H

34O

115792

103[M

+HCO

O]minus

5571987

5522463

[M+NH

4]+

3551516

[M+

HndashG

lcndashH

2O]+

Arctiin

[36]

39a

1416

1277

C 27H

34O

115792

106[M

+HCO

O]minus

3711826[M

ndashHndashG

lc]minus

3561547

[MndashH

ndashGlcndashH

2O]minus

5522444

[M

+NH

4]+5571991

3731563

[M+HndashG

lc]+

3551544

[M+

HndashG

lcndashH

2O]+

Phillyrin

[3738]

4014678

372255

C 15H

10O

73010

355(23)

1510

137[M

ndashHndashC

8H6O

3]minus

3030520

(49)

Quercetin

[39]

4115039

284

C 28H

34O

1560

91522(13)

3010

582[M

ndashHndashR

ut]minus

Hesperid

in[13]

4215402

265366

C 15H

10O

628504

06(25)

2870

721

(45)

15304

69[M

+HndashH

EP]+

Kaem

pferol

[13]

4316627

255

C 15H

10O

42530507

(24)

2250741

[MndashH

ndashCO]minus

2100494

[MndashH

ndashCOndashC

H3]minus

1820542

[MndashH

ndash2CO

ndashCH

3]minus

1540553

[MndashH

ndash3CO

ndashCH

3]minus

Chrysoph

anol

[40]

4417035

C 15H

10O

42530512

(43)

2250752210047418204

85

1540531

Isom

erof

chrysoph

anol

[40]

45a

17347

254

287426

C 21H

20O

104310

989(26)

2690

673[M

ndashHndashG

lc]minus

2410

719[M

ndashHndashG

lcndashC

O]minus

2250753

[MndashH

ndashGlcndashC

O2]minus

2100578

[MndashH

ndashGlcndashC

O2ndashCH

3]minus

1970

771[MndashH

ndashGlcndashC

OndashC

O2]minus

18204

86[M

ndashHndashG

lcndashC

O2ndashCH

3ndashCO

]minus

4551010

2710

715[M

+HndashG

lc]+

Emod

in-8-O

-glucoside

[41]

4617396

240

330395

C 15H

12O

42550639

(minus71)

2570

812

(minus08)

Isoliquiritigenin

[26]

47a

18385

250304

C 16H

12O

42670

653(minus15

)2690

827

(48)

2910

751

Form

onon

etin

[42]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

4818804

89540

82(28)

7193

849[M

ndashHndashG

lcA]minus

3510

630[2GlcAndash

H]minus

8974

107

(12)

9193

925

22120573-Acetoxy

licorices

apon

inB2

uralsa

poninF

[43]

491919

4271421

C 22H22O10

445116

8(minus56)

2830632

[MndashH

ndashGlc]minus

4691

128

2850775

[M+HndashG

lc]+

Physcion

-8-O

-120573-D

-glucop

yranoside

[41]

5019603

248

C 42H

60O

168193

843(06)

3510

699[2GlcAndash

H]minus

8213

994

(minus01)

8433996

6453612

[M+

HndashG

lcA]+

4693

302[M

+Hndash2GlcA]+

4513

211[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inE2

[35]

5119704

C 16H

24O

73272

180(28)

1649664

[MndashH

ndashGlc]minus

3512

133

Rhod

odendrol-41015840-

O-120573-D

-glucop

yranoside

[44]

5220000

254

C 44H

64O

188794

062(13)

3510

806[M

ndashHndash22A

G]minus

8814

170

(minus01)

7053897

[M+

HndashG

lcA]+

5293

588[M

+Hndash2GlcA]+

5113

395[M

+Hndash2GlcA

ndashH2O

]+

22-

Acetoxyglycyrrhizin

[42]

5320573

352

C 17H

14O

73292

341(39)

3532280

301144

3[M

+HndashC

H2O

]+

2872

002[M

+HndashC

O2]

+ 2591

248[M

+HndashC

O2ndashCO

]+

Tricin

[45]

54a

2119

9260

C 15H

8O6

2830262

(67)

2390

359[M

ndashHndashC

O2]minus

2850515

(minus130)

Rhein

[46]

5521540

253

8373977(12)

8194

404[M

ndashHndashH

2O]minus

6614

100[M

ndashHndashG

lcA]minus

3510

815[2GlcAndash

H]minus

2890

840

[2GlcAndash

HndashH

2OndashC

O2]minus

8394

061

(minus05)

8613

890

6633868

[M+

HndashG

lcA]+

4873395[M

+Hndash2GlcA]+

4693

286[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inG2

[42]

5621626

236

327370

384

C 21H

20O

63671208(71)

3091

566[M

ndashHndashC

OndashC

H2O

]minus

2650635

[MndashH

ndashCOndashC

H2O

ndashCO

2]minus

2210

221

[MndashH

ndashCOndashC

H2O

ndash2CO

2]minus

3691

369

(minus76

)3911176

Glycycoum

arin

[47]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

5722087

249

C 42H

62O

168213

977(17)

8034501

[MndashH

ndashH2O

]minus

7594

542[M

ndashHndashH

2OndashC

O2]minus

6454102

[MndashH

ndashGlcA]minus

6274

000[M

ndashHndashG

lcAndash

H2O

]minus

4693

705[M


3510

809[2GlcAndash

H]minus

2890

758[2GlcAndash

HndashH

2OndashC

O2]minus

8234128

(15)

8454557

6473797[M

+HndashG

lcA]+

4713

480[M

+Hndash2GlcA]+

4533

365[M

+Hndash2GlcA

ndashH2O

]+

Glycyrrhizica

cid

[48]

582218

8252

C 42H

62O

168213

986(minus11)

3510

768[M

ndashHndashG

A]minus

8234134

(minus21)

8454127

6473

823[M

+HndashG

lcA]+

4713

365[M

+Hndash2GlcA]+

4533324

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inH2

[26]

5922389

248

C 42H

64O

158074

197(minus06)

74546

01[M

ndashHndashG

lc]minus

6314

210[M

ndashHndashG

lcA]minus

3510

699[M

ndashHndashG

A]minus

8094

410

(minus09)

8314

138

Licoric

esapon

inB2

[49]

6022623

252

C 42H

62O

168213

997(02)

3510

837[M

ndashHndashG

A]minus

8234105

(minus13

)8453900

6473

838[M

+HndashG

lcA]+

4713

288[M

+Hndash2GlcA]+

4533279

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inK2

[50]

61a

23230

288439

C 15H

10O

52690

462(45)

2410

669[M

ndashHndashC

O]minus

2250723

[MndashH

ndashCO

2]minus

21004

27[M

ndashHndashC

O2ndashCH

3]minus

1970

695[M

ndashHndashC

OndashC

O2]minus

1820477

[MndashH

ndashCO

2ndashCH

3ndashCO

]minus

1540552

[MndashH

ndashCO

2ndashCH

3ndash2C

O]minus

Emod

in[40]

a Com

paredwith

referencec

ompo

unds

b 22A

G2


ApiapioseC

acaffeoylGAg

lycyrrhetin

icacidG

lcg

lucoseG

lcAg

lucuronicacidH

CT4

-(hydroxym

ethyl)c

yclobu

tane-123-tr

iolHEP


enolR

ha

rham

noseR

LresorcinolR

utrutinoseVP

4-vinylpheno

l


Table3Linear

regressio

nLO

Dsa

ndLO

Qsintraday

andinterday

precision


for12compo

unds

Com

poun

dRe

gressio

nequatio

na(119899=3)

1198772

Linear

range

(120583gmL)

LOD

b

(120583gmL)

LOQ

c

(120583gmL)

Intraday

(RSD

)

(119899=6)

Interday

(RSD

)

(119899=3)


(RSD

)

Recovery

(119899=6)

Mean

(120583gg)

RSD

()

Orig

inal

(120583g)

Spiked

(120583g)

Detected

(120583g)

Recovery

()

RSD

()

Salid

rosid

e119910=

13980119909minus11265

09999

527ndash8

435

106

350

012

026177955plusmn

1092

061

138

35591

35420

7075

09928

124

Chlorogenica

cid

119910=

26510119909+36733

09998

685ndash10956

171

569

077

212247371plusmn

1274

051

254

49474

49385

9599

09419

242

Forsytho

sideE

119910=

11793119909+50168

09995

485ndash776

412

1404

067

225175403plusmn

1872

107

267

3518

13510

56772

69299

354

Cryptochlorogenic

acid

119910=

21498119909minus50189

09997

665ndash10647

166

553

110

163202949plusmn

2065

102

246

40590

40660

78400

9310

143

Amygdalin

119910=

10530119909minus34647

09998

391ndash6

257

098

326

079

093148538plusmn

2585

174

248

2970

829862

57639

9358

332

Sweroside

119910=

20593119909minus60034

09999

200ndash319

6025

080

011

033

79806plusmn

293

037

048

1596

11595

132543

10395

041

Hyperin

119910=

27773119909minus87941

09999

020ndash321

0051

016

078

062

9203plusmn

080

087

083

1841

1824

3707

10229

182

Rutin

119910=

30768119909minus37837

09993

053ndash850

0072

021

041

224

18415plusmn

306

166

157

3683

3681

7250

9690

234

Forsytho

sideA

119910=

85466119909minus60245

09999

421ndash6

734

030

105

020

292248499plusmn

1843

074

195

4970

049595

99733

10089

149

Phillyrin

119910=

30390119909+52828

09999

286ndash4

571

071

236

079

163157780plusmn

1011

064

276

31556

31672

62399

10025

160

Rhein

119910=

74736119909minus51727

09996

347ndash5549

087

288

040

028

68192plusmn

1632

239

097

13638

13627

27348

10061

161

Glycyrrhizica

cid

119910=

10296119909minus65313

09999

527ndash8

435

0092

033

034

209162275plusmn

1759

108

215

32455

323939

65216

1013

1327

a 119910isthep

eakarea119909

isthec

oncentratio

nof

stand

ardsolutio

ns

b LODrefersto

thelim

itsof

detection119878119873=3

c LOQrefersto

thelim

itsof

quantity119878119873=10


Table4Con

tentso

fthe

12compo

unds

in10

batches

Sample

Com

poun

d(m

eanplusmnSD

)(120583gg)

Total

RSD(

)Salid

rosid

eCh

lorogenic

acid

Forsytho

sideE

Cryptochlorogenic

acid

Amygdalin

Sweroside

Hyperin

Rutin

Forsytho

sideA

Phillyrin

Rhein

Glycyrrhizic

acid


1003













4 Conclusion






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

4818804

89540

82(28)

7193

849[M

ndashHndashG

lcA]minus

3510

630[2GlcAndash

H]minus

8974

107

(12)

9193

925

22120573-Acetoxy

licorices

apon

inB2

uralsa

poninF

[43]

491919

4271421

C 22H22O10

445116

8(minus56)

2830632

[MndashH

ndashGlc]minus

4691

128

2850775

[M+HndashG

lc]+

Physcion

-8-O

-120573-D

-glucop

yranoside

[41]

5019603

248

C 42H

60O

168193

843(06)

3510

699[2GlcAndash

H]minus

8213

994

(minus01)

8433996

6453612

[M+

HndashG

lcA]+

4693

302[M

+Hndash2GlcA]+

4513

211[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inE2

[35]

5119704

C 16H

24O

73272

180(28)

1649664

[MndashH

ndashGlc]minus

3512

133

Rhod

odendrol-41015840-

O-120573-D

-glucop

yranoside

[44]

5220000

254

C 44H

64O

188794

062(13)

3510

806[M

ndashHndash22A

G]minus

8814

170

(minus01)

7053897

[M+

HndashG

lcA]+

5293

588[M

+Hndash2GlcA]+

5113

395[M

+Hndash2GlcA

ndashH2O

]+

22-

Acetoxyglycyrrhizin

[42]

5320573

352

C 17H

14O

73292

341(39)

3532280

301144

3[M

+HndashC

H2O

]+

2872

002[M

+HndashC

O2]

+ 2591

248[M

+HndashC

O2ndashCO

]+

Tricin

[45]

54a

2119

9260

C 15H

8O6

2830262

(67)

2390

359[M

ndashHndashC

O2]minus

2850515

(minus130)

Rhein

[46]

5521540

253

8373977(12)

8194

404[M

ndashHndashH

2O]minus

6614

100[M

ndashHndashG

lcA]minus

3510

815[2GlcAndash

H]minus

2890

840

[2GlcAndash

HndashH

2OndashC

O2]minus

8394

061

(minus05)

8613

890

6633868

[M+

HndashG

lcA]+

4873395[M

+Hndash2GlcA]+

4693

286[M

+Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inG2

[42]

5621626

236

327370

384

C 21H

20O

63671208(71)

3091

566[M

ndashHndashC

OndashC

H2O

]minus

2650635

[MndashH

ndashCOndashC

H2O

ndashCO

2]minus

2210

221

[MndashH

ndashCOndashC

H2O

ndash2CO

2]minus

3691

369

(minus76

)3911176

Glycycoum

arin

[47]


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

5722087

249

C 42H

62O

168213

977(17)

8034501

[MndashH

ndashH2O

]minus

7594

542[M

ndashHndashH

2OndashC

O2]minus

6454102

[MndashH

ndashGlcA]minus

6274

000[M

ndashHndashG

lcAndash

H2O

]minus

4693

705[M


3510

809[2GlcAndash

H]minus

2890

758[2GlcAndash

HndashH

2OndashC

O2]minus

8234128

(15)

8454557

6473797[M

+HndashG

lcA]+

4713

480[M

+Hndash2GlcA]+

4533

365[M

+Hndash2GlcA

ndashH2O

]+

Glycyrrhizica

cid

[48]

582218

8252

C 42H

62O

168213

986(minus11)

3510

768[M

ndashHndashG

A]minus

8234134

(minus21)

8454127

6473

823[M

+HndashG

lcA]+

4713

365[M

+Hndash2GlcA]+

4533324

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inH2

[26]

5922389

248

C 42H

64O

158074

197(minus06)

74546

01[M

ndashHndashG

lc]minus

6314

210[M

ndashHndashG

lcA]minus

3510

699[M

ndashHndashG

A]minus

8094

410

(minus09)

8314

138

Licoric

esapon

inB2

[49]

6022623

252

C 42H

62O

168213

997(02)

3510

837[M

ndashHndashG

A]minus

8234105

(minus13

)8453900

6473

838[M

+HndashG

lcA]+

4713

288[M

+Hndash2GlcA]+

4533279

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inK2

[50]

61a

23230

288439

C 15H

10O

52690

462(45)

2410

669[M

ndashHndashC

O]minus

2250723

[MndashH

ndashCO

2]minus

21004

27[M

ndashHndashC

O2ndashCH

3]minus

1970

695[M

ndashHndashC

OndashC

O2]minus

1820477

[MndashH

ndashCO

2ndashCH

3ndashCO

]minus

1540552

[MndashH

ndashCO

2ndashCH

3ndash2C

O]minus

Emod

in[40]

a Com

paredwith

referencec

ompo

unds

b 22A

G2


ApiapioseC

acaffeoylGAg

lycyrrhetin

icacidG

lcg

lucoseG

lcAg

lucuronicacidH

CT4

-(hydroxym

ethyl)c

yclobu

tane-123-tr

iolHEP


enolR

ha

rham

noseR

LresorcinolR

utrutinoseVP

4-vinylpheno

l


Table3Linear

regressio

nLO

Dsa

ndLO

Qsintraday

andinterday

precision


for12compo

unds

Com

poun

dRe

gressio

nequatio

na(119899=3)

1198772

Linear

range

(120583gmL)

LOD

b

(120583gmL)

LOQ

c

(120583gmL)

Intraday

(RSD

)

(119899=6)

Interday

(RSD

)

(119899=3)


(RSD

)

Recovery

(119899=6)

Mean

(120583gg)

RSD

()

Orig

inal

(120583g)

Spiked

(120583g)

Detected

(120583g)

Recovery

()

RSD

()

Salid

rosid

e119910=

13980119909minus11265

09999

527ndash8

435

106

350

012

026177955plusmn

1092

061

138

35591

35420

7075

09928

124

Chlorogenica

cid

119910=

26510119909+36733

09998

685ndash10956

171

569

077

212247371plusmn

1274

051

254

49474

49385

9599

09419

242

Forsytho

sideE

119910=

11793119909+50168

09995

485ndash776

412

1404

067

225175403plusmn

1872

107

267

3518

13510

56772

69299

354

Cryptochlorogenic

acid

119910=

21498119909minus50189

09997

665ndash10647

166

553

110

163202949plusmn

2065

102

246

40590

40660

78400

9310

143

Amygdalin

119910=

10530119909minus34647

09998

391ndash6

257

098

326

079

093148538plusmn

2585

174

248

2970

829862

57639

9358

332

Sweroside

119910=

20593119909minus60034

09999

200ndash319

6025

080

011

033

79806plusmn

293

037

048

1596

11595

132543

10395

041

Hyperin

119910=

27773119909minus87941

09999

020ndash321

0051

016

078

062

9203plusmn

080

087

083

1841

1824

3707

10229

182

Rutin

119910=

30768119909minus37837

09993

053ndash850

0072

021

041

224

18415plusmn

306

166

157

3683

3681

7250

9690

234

Forsytho

sideA

119910=

85466119909minus60245

09999

421ndash6

734

030

105

020

292248499plusmn

1843

074

195

4970

049595

99733

10089

149

Phillyrin

119910=

30390119909+52828

09999

286ndash4

571

071

236

079

163157780plusmn

1011

064

276

31556

31672

62399

10025

160

Rhein

119910=

74736119909minus51727

09996

347ndash5549

087

288

040

028

68192plusmn

1632

239

097

13638

13627

27348

10061

161

Glycyrrhizica

cid

119910=

10296119909minus65313

09999

527ndash8

435

0092

033

034

209162275plusmn

1759

108

215

32455

323939

65216

1013

1327

a 119910isthep

eakarea119909

isthec

oncentratio

nof

stand

ardsolutio

ns

b LODrefersto

thelim

itsof

detection119878119873=3

c LOQrefersto

thelim

itsof

quantity119878119873=10


Table4Con

tentso

fthe

12compo

unds

in10

batches

Sample

Com

poun

d(m

eanplusmnSD

)(120583gg)

Total

RSD(

)Salid

rosid

eCh

lorogenic

acid

Forsytho

sideE

Cryptochlorogenic

acid

Amygdalin

Sweroside

Hyperin

Rutin

Forsytho

sideA

Phillyrin

Rhein

Glycyrrhizic

acid


1003













4 Conclusion






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Table2Con

tinued

Peak

number119879119877 (min)120582max

(nm)

Form

ula

ESminus(119898119911)

ES+(119898119911)

Identifi

catio

nRe

ference

[MndashH

]minus(ppm

)MS2

b[M

+H]+

(ppm

)[M

+Na]

+MS2

b

5722087

249

C 42H

62O

168213

977(17)

8034501

[MndashH

ndashH2O

]minus

7594

542[M

ndashHndashH

2OndashC

O2]minus

6454102

[MndashH

ndashGlcA]minus

6274

000[M

ndashHndashG

lcAndash

H2O

]minus

4693

705[M


3510

809[2GlcAndash

H]minus

2890

758[2GlcAndash

HndashH

2OndashC

O2]minus

8234128

(15)

8454557

6473797[M

+HndashG

lcA]+

4713

480[M

+Hndash2GlcA]+

4533

365[M

+Hndash2GlcA

ndashH2O

]+

Glycyrrhizica

cid

[48]

582218

8252

C 42H

62O

168213

986(minus11)

3510

768[M

ndashHndashG

A]minus

8234134

(minus21)

8454127

6473

823[M

+HndashG

lcA]+

4713

365[M

+Hndash2GlcA]+

4533324

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inH2

[26]

5922389

248

C 42H

64O

158074

197(minus06)

74546

01[M

ndashHndashG

lc]minus

6314

210[M

ndashHndashG

lcA]minus

3510

699[M

ndashHndashG

A]minus

8094

410

(minus09)

8314

138

Licoric

esapon

inB2

[49]

6022623

252

C 42H

62O

168213

997(02)

3510

837[M

ndashHndashG

A]minus

8234105

(minus13

)8453900

6473

838[M

+HndashG

lcA]+

4713

288[M

+Hndash2GlcA]+

4533279

[M+

Hndash2GlcA

ndashH2O

]+

Licoric

esapon

inK2

[50]

61a

23230

288439

C 15H

10O

52690

462(45)

2410

669[M

ndashHndashC

O]minus

2250723

[MndashH

ndashCO

2]minus

21004

27[M

ndashHndashC

O2ndashCH

3]minus

1970

695[M

ndashHndashC

OndashC

O2]minus

1820477

[MndashH

ndashCO

2ndashCH

3ndashCO

]minus

1540552

[MndashH

ndashCO

2ndashCH

3ndash2C

O]minus

Emod

in[40]

a Com

paredwith

referencec

ompo

unds

b 22A

G2


ApiapioseC

acaffeoylGAg

lycyrrhetin

icacidG

lcg

lucoseG

lcAg

lucuronicacidH

CT4

-(hydroxym

ethyl)c

yclobu

tane-123-tr

iolHEP


enolR

ha

rham

noseR

LresorcinolR

utrutinoseVP

4-vinylpheno

l


Table3Linear

regressio

nLO

Dsa

ndLO

Qsintraday

andinterday

precision


for12compo

unds

Com

poun

dRe

gressio

nequatio

na(119899=3)

1198772

Linear

range

(120583gmL)

LOD

b

(120583gmL)

LOQ

c

(120583gmL)

Intraday

(RSD

)

(119899=6)

Interday

(RSD

)

(119899=3)


(RSD

)

Recovery

(119899=6)

Mean

(120583gg)

RSD

()

Orig

inal

(120583g)

Spiked

(120583g)

Detected

(120583g)

Recovery

()

RSD

()

Salid

rosid

e119910=

13980119909minus11265

09999

527ndash8

435

106

350

012

026177955plusmn

1092

061

138

35591

35420

7075

09928

124

Chlorogenica

cid

119910=

26510119909+36733

09998

685ndash10956

171

569

077

212247371plusmn

1274

051

254

49474

49385

9599

09419

242

Forsytho

sideE

119910=

11793119909+50168

09995

485ndash776

412

1404

067

225175403plusmn

1872

107

267

3518

13510

56772

69299

354

Cryptochlorogenic

acid

119910=

21498119909minus50189

09997

665ndash10647

166

553

110

163202949plusmn

2065

102

246

40590

40660

78400

9310

143

Amygdalin

119910=

10530119909minus34647

09998

391ndash6

257

098

326

079

093148538plusmn

2585

174

248

2970

829862

57639

9358

332

Sweroside

119910=

20593119909minus60034

09999

200ndash319

6025

080

011

033

79806plusmn

293

037

048

1596

11595

132543

10395

041

Hyperin

119910=

27773119909minus87941

09999

020ndash321

0051

016

078

062

9203plusmn

080

087

083

1841

1824

3707

10229

182

Rutin

119910=

30768119909minus37837

09993

053ndash850

0072

021

041

224

18415plusmn

306

166

157

3683

3681

7250

9690

234

Forsytho

sideA

119910=

85466119909minus60245

09999

421ndash6

734

030

105

020

292248499plusmn

1843

074

195

4970

049595

99733

10089

149

Phillyrin

119910=

30390119909+52828

09999

286ndash4

571

071

236

079

163157780plusmn

1011

064

276

31556

31672

62399

10025

160

Rhein

119910=

74736119909minus51727

09996

347ndash5549

087

288

040

028

68192plusmn

1632

239

097

13638

13627

27348

10061

161

Glycyrrhizica

cid

119910=

10296119909minus65313

09999

527ndash8

435

0092

033

034

209162275plusmn

1759

108

215

32455

323939

65216

1013

1327

a 119910isthep

eakarea119909

isthec

oncentratio

nof

stand

ardsolutio

ns

b LODrefersto

thelim

itsof

detection119878119873=3

c LOQrefersto

thelim

itsof

quantity119878119873=10


Table4Con

tentso

fthe

12compo

unds

in10

batches

Sample

Com

poun

d(m

eanplusmnSD

)(120583gg)

Total

RSD(

)Salid

rosid

eCh

lorogenic

acid

Forsytho

sideE

Cryptochlorogenic

acid

Amygdalin

Sweroside

Hyperin

Rutin

Forsytho

sideA

Phillyrin

Rhein

Glycyrrhizic

acid


1003













4 Conclusion






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Table3Linear

regressio

nLO

Dsa

ndLO

Qsintraday

andinterday

precision


for12compo

unds

Com

poun

dRe

gressio

nequatio

na(119899=3)

1198772

Linear

range

(120583gmL)

LOD

b

(120583gmL)

LOQ

c

(120583gmL)

Intraday

(RSD

)

(119899=6)

Interday

(RSD

)

(119899=3)


(RSD

)

Recovery

(119899=6)

Mean

(120583gg)

RSD

()

Orig

inal

(120583g)

Spiked

(120583g)

Detected

(120583g)

Recovery

()

RSD

()

Salid

rosid

e119910=

13980119909minus11265

09999

527ndash8

435

106

350

012

026177955plusmn

1092

061

138

35591

35420

7075

09928

124

Chlorogenica

cid

119910=

26510119909+36733

09998

685ndash10956

171

569

077

212247371plusmn

1274

051

254

49474

49385

9599

09419

242

Forsytho

sideE

119910=

11793119909+50168

09995

485ndash776

412

1404

067

225175403plusmn

1872

107

267

3518

13510

56772

69299

354

Cryptochlorogenic

acid

119910=

21498119909minus50189

09997

665ndash10647

166

553

110

163202949plusmn

2065

102

246

40590

40660

78400

9310

143

Amygdalin

119910=

10530119909minus34647

09998

391ndash6

257

098

326

079

093148538plusmn

2585

174

248

2970

829862

57639

9358

332

Sweroside

119910=

20593119909minus60034

09999

200ndash319

6025

080

011

033

79806plusmn

293

037

048

1596

11595

132543

10395

041

Hyperin

119910=

27773119909minus87941

09999

020ndash321

0051

016

078

062

9203plusmn

080

087

083

1841

1824

3707

10229

182

Rutin

119910=

30768119909minus37837

09993

053ndash850

0072

021

041

224

18415plusmn

306

166

157

3683

3681

7250

9690

234

Forsytho

sideA

119910=

85466119909minus60245

09999

421ndash6

734

030

105

020

292248499plusmn

1843

074

195

4970

049595

99733

10089

149

Phillyrin

119910=

30390119909+52828

09999

286ndash4

571

071

236

079

163157780plusmn

1011

064

276

31556

31672

62399

10025

160

Rhein

119910=

74736119909minus51727

09996

347ndash5549

087

288

040

028

68192plusmn

1632

239

097

13638

13627

27348

10061

161

Glycyrrhizica

cid

119910=

10296119909minus65313

09999

527ndash8

435

0092

033

034

209162275plusmn

1759

108

215

32455

323939

65216

1013

1327

a 119910isthep

eakarea119909

isthec

oncentratio

nof

stand

ardsolutio

ns

b LODrefersto

thelim

itsof

detection119878119873=3

c LOQrefersto

thelim

itsof

quantity119878119873=10


Table4Con

tentso

fthe

12compo

unds

in10

batches

Sample

Com

poun

d(m

eanplusmnSD

)(120583gg)

Total

RSD(

)Salid

rosid

eCh

lorogenic

acid

Forsytho

sideE

Cryptochlorogenic

acid

Amygdalin

Sweroside

Hyperin

Rutin

Forsytho

sideA

Phillyrin

Rhein

Glycyrrhizic

acid


1003













4 Conclusion






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Table4Con

tentso

fthe

12compo

unds

in10

batches

Sample

Com

poun

d(m

eanplusmnSD

)(120583gg)

Total

RSD(

)Salid

rosid

eCh

lorogenic

acid

Forsytho

sideE

Cryptochlorogenic

acid

Amygdalin

Sweroside

Hyperin

Rutin

Forsytho

sideA

Phillyrin

Rhein

Glycyrrhizic

acid


1003













4 Conclusion






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




4 Conclusion






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

Documents

Research Article Qualitative and Quantitative Analysis of