Analysis of Volatile Omponents In Rhizome Zingibers ... · researches have showed that volatile components are their main medicinal elements which contains Zingiberene, Gingerol and

Article ID: WMC00662 2046-1690

Analysis of Volatile Omponents In RhizomeZingibers, Zingiber Officinale Roscoe And GingerPeel By Gas Chromatography-Mass SpectrometryAnd Chemometric ResolutionCorresponding Author:Mr. Xiao-Ru Li,Professor, College of Chemistry and Chemical Engineering, Central South University, Changsha - China

Submitting Author:Mr. Yu He,Professor' Assistant, College of Chemistry and Chemical Engineering, Central South University, Changsha -China

Article ID: WMC00662

Article Type: Research articles

Submitted on:20-Sep-2010, 08:21:11 AM GMT Published on: 20-Sep-2010, 04:38:09 PM GMT

Article URL: http://www.webmedcentral.com/article_view/662

Subject Categories:CHINESE MEDICINE

Keywords:Heuristic Evolving Latent Projections (HELP), Volatile Constituents, GC-MS,Temperature-Programmed Retention Indices (PTRIs)

How to cite the article:He Y , Li X . Analysis of Volatile Omponents In Rhizome Zingibers, Zingiber OfficinaleRoscoe And Ginger Peel By Gas Chromatography-Mass Spectrometry And Chemometric Resolution .WebmedCentral CHINESE MEDICINE 2010;1(9):WMC00662

Source(s) of Funding:

This work is financially supported by the National Nature Foundation Committee of PR China (Grant Nos.20235020 and 20475066) and the Cultivation Fund of Key Scientific and Technical Innovation Project, Ministry ofEducation of China (No. 704036).

Competing Interests:

None

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Analysis of Volatile Omponents In RhizomeZingibers, Zingiber Officinale Roscoe And GingerPeel By Gas Chromatography-Mass SpectrometryAnd Chemometric ResolutionAuthor(s): He Y , Li X

Abstract

The similarities and differences of essential oilcomponents in rhizome zingibers(RZ)?zingiberofficinale roscoe(ZOR) and ginger pee(GP) wereinvestigated by GC-MS combined with a chemometricmethod named heur is t ic evo lv ing la tentprojections(HELP).And temperature-programmedretention indices(PTRIs) was used together with massspectra for identification of the essential oilcomponents. For essential oils of RZ, ZOR and GP, 85,81 and 80 volatile components were determinedrepresenting 81.43%, 86.38% and 84.79% of the totalrelative content, respectively. Also, the essential oilssignificantly differed both qualitatively andquantitatively. There were total 58 commoncompounds existing in RZ and ZOR, 63 commoncomponents between RZ and GP, 60 commoncomponents between ZOR and GP, and 52 commoncomponents existing among each of the three systems.The results obtained may be helpful to the furtherstudy of pharmacological activity for their potentialutilization as therapeutical agents.

Introduction

1. IntroductionTradition Chinese medicines have gained more andmore popularity in our modern society because of theirpharmacological activity and low toxicity, which makesthem widely used in food and medicine regions. Lowtoxicity, rare complications and nature are theiradvantages. Only after further research can we utilizefull of their values, then the development ofhyphenated chromatographic device combined withChemometric methods give us the opportunity toacknowledge their essential components and exactlyqualify and quantify our targets.The herbal materials rhizome zingibers(RZ) zingiberofficinale roscoe(ZOR) and ginger peel(GP) are widelyused in the region of food industry, which couldimprove appetite and aid digestion combined with the

funct ions of Refreshing and Antibacter ialanti-inflammatory. In traditional Chinese medicineresearch, they also play an important role, with thepharmacological activities of relieving rheumatism andcold, keeping warm and antiemetic. The RZ, ZOR andGP are contained in the medicine against Cold,Stomach pain and Diarrhea etc.The RZ comes from the dry rhizome of ginger, ZOR isthe fresh rhizome, and GP is the scarfskin of freshrhizome of ginger. Previous investigations andresearches have showed that volatile components aretheir main medicinal elements which containsZingiberene, Gingerol and Citral and so on.In this paper, the volatile components extracted weredetected with gas chromatography-mass spectrometry(GC-MS). However, the GC-MS data from volatile oilinvolves a great number of overlapped and evenembedded peaks. These overlapped and embeddedpeaks may bring about many difficulties when carryingout quantitative and qualitative analysis correctly. Inorder to resolve the problems, chemometric methodsas a very useful assistant tool, use comprehensivechromatographic and spectral information to make itpossible to resolve one complex system clearly andaccurately. The resolution of the two-dimensional databy chemometric method heuristic evolving latentprojections (HELP) is applied in this study. Then,qualitative identification of these constituents wasperformed using temperature-programmed retentionindices (PTRIs) and mass spectra. Finally, everycomponent was quantized with the total volumeintegral method. Through the procedures above, wecould compare the same and distinction of volatilecomponents in RZ, ZOR and GP and supplyfoundation for their further application in regions offood and medicine.

Methods

2. TheoryA two-dimensional data Am×n produced by GC–MScan be represented as follows:



Am×n= CSt+E

=∑CiSit+E (i=1, 2… N)

Where Am×n denotes an absorbance matrixexpressing N components of m chromatographic scanpoints at n atom mass units or wavelength points. C isthe pure chromatographic matrix and S is the puremass spectral matrix. E represents the noise. t is thetransform of matrix S. The unique resolution of atwo-dimensional data into chromatograms and spectraof the pure chemical constituents is carried out withlocal full rank analysis in the HELP method. Onlyconcise theoretical explanation is showed here for thesake of brevity, while detail description could be foundin Refs. [1–3].1. Confirm the background and correct a drifting baseline.2. Determine the number of components, the selectiveregion and zero-component region of each componentby the use of the evolving latent projective graph andrankmap on the basis of the eigenstructure trackinganalysis.3. With the help of the selective information andzero-component region, conduct a unique resolution oftwo-dimensional data into pure chromatographicprofiles and mass spectra by means of local full rankanalysis.4. Verify the reliability of the resolved result.After the pure chromatogram and spectrum of the ithcomponent have been resolved, this component canbe determined qualitatively by comprehensive use ofthe chromatographic retention time and massspectrum. Next, the term in Eq. (1) is taken as theoverall volume integration value. Similar to the generalchromatographic quantitative method with peak area,is directly proportional to the mass of the ithcomponent and so it is quantified.3. Experimental3.1 MaterialsAll single herbals were purchased from the market andidentified by Institute of Materia Medica, HunanAcademy of Traditional Chinese Medicine and MateriaMedica (Changsha, Hunan, China). n-Alkane standardsolutions of C8–C20 (mixture no. 04070) andC21–C40 (mixture no. 04071) were purchased fromFluka Chemika (Buchs,Switzerland).3.2 Extraction of volatile oilExtraction of volatile oil of the herbal: 50g of eachdried single herbal, RZ, ZOR and GP, were weightedexactly and mixed with 350ml distilled water and thenprocessed according to the standard extractingmethod for the volatile oil described in ChinesePharmacopoeia (2005 version).3.3 Instruments

The GC-MS instrument was QP2010 with a QP-5000mass spectrometer (both from Shimadzu) employed inthis study.3.4 Detection of volatile oilIn the gas chromatographic system, a DB-1 capillarycolumn (30m×0.25mm I.D.) was applied. The originalcolumn temperature was maintained at 50 degrees for3min, then programmed from 50 degrees to 150degrees at the rate 5 degrees/min, and from 150degrees to 190 degrees at the rate 2 degrees/min, andfrom 190 degrees to 250 degrees at the rate 10degrees/min, finally maintained for 3min. The inlettemperature was kept at 270 degrees and interfacetemperature at 250 degrees. The carrier gas wasHelium with a constant flow-rate of 1.0ml/min. To theexperimental conditions of the mass spectrometer, theelectron impact (EI+) mass spectra was recorded at70 eV. Splitting ratio was 10:1. Scan at 5scan/s fromm/z 35 to 500 amu. The ionization source temperaturewas set at 200 degrees.3.5 Retention indicesVan den Dool and Kratz[19] proposed a quasi-linearequation for temperature- programmed retentionindices as follows:ITX = 100n+ 100 [ ( tRx - tRn ) / ( tR ( n + 1) -tRn ) ]Where ITX is the temperature-programmed retentionindex of the interest, tRn, tR (n + 1), tRx are theretention time in minute of the two standard n-alkanescontaining n and n+1 carbons and the interest,respectively. This equation was used to calculateretention indices in the research work. It could improvedistinguishing components, especially those verysimilar.3.6 Data analysisA l l d a t a a n a l y s i s w a s p e r f o r m e d o nCeleron®2.66GHz(Intel) personal computer, and allprograms of chemometric resolution methods werecoded in MATLAB 6.5 for windows. The librarysearches and spectral matching of the resolved purecomponents were conducted on the National Instituteof Standard and Technology (NIST) 107 MS databasecontaining 107886 compounds. The exactly qualitativeresults were obtained with the help of PTRIs.

Results

4.Results and discussion4.1 Resolution of overlapped peaks by HELPThe Fig.1 shows the real total ionic chromatogram(TIC) of the volatile oil of RZ (a) ZOR (b) and GP (c).We can see each of the TICs is a very complexanalytical system. Although many chromatographic



peaks are separated, here still exist some overlappedpeaks. Due to these, if you directly search with the MSdatabase, definitely fail you will get, because the massspectrum of mixtures measured can never get goodmatching index with that of a pure component in theNIST MS database. Furthermore, for the componentwith low content, it is also very difficult to be identifiedcorrectly with the NIST MS database, since atwo-dimensional data obtained by mass spectralmeasurement unavoidably contains peaks associatedwith column background and residual gases. Withoutbackground correction, both the resolution of theoverlapped peaks and the identification of thecomponents with low content are impossible. Forcommercial GC–MS systems, background subtractionis usually performed as follows. First, a scan point,which only contains the background mass spectrum, issubjectively found. Next, the intensities of the sameinter mass numbers appearing in the target andbackground spectra are subtracted, and so thepractical target mass spectrum is obtained. Obviously,the practical target mass spectrum strongly dependson the selection of the background point. If thisselection is wrong, different target mass spectra maybe obtained. The genuine mass spectrum to besearched is surely confused with the subtractedspectrum. As for the HELP method, the local rankanalysis of the zero-component regions, which containno components eluting, before elution of the firstchemical component starts and after the last chemicalconstituent has eluted, can together provide sufficientinformation for accurately correcting a drifting baseline[1–3]. Hence, a much better background subtractioncould be obtained. After background subtraction, theresolution of the overlapping peaks becomes possible.To illustrate how to extract the pure mass spectraefficiently by HELP resolution, the peak clustersmarked A,B and C are chosen as examples and thenprocessed by HELP.Fig.2 shows the TIC curve of the peak cluster A whichlooks like a pure peak only containing one constituent.L i k e w i s e , o n l y o n e c o m p o u n d n a m e dbeta.-Phellandrene (C10H16) can be searched in theNIST MS library. Therefore, peak cluster A is generallyregarded as a one-compound system in a classicanalytical way. However, if HELP resolution method isapplied to the two-dimensional data matrix of peakcluster A, three distinct components named Eucalyptol(C10H18O), beta.-Phellandrene (C10H16) andD-Limonene(C10H16)can be resolved even they havequite similar mass spectra. Detail procedures would beintroduced in the following part.Peak purity can be identified through a fixed sizemoving window evolving factor analysis (FSWMEFA)

[7] or so-called eigenstructure tracking analysis [3]. Inthe fixed size window method (FSWM) plot, the noiselevel is characterized by eigenvalue curves whichhave similar numerical values and appears together atthe bottom. Eigenalue curves higher than the noiselevel represent the appearance of new components. Ifa studied system contains only one species, there isonly one eigenalue curve higher than the noise level inits FSWM plot. From the FSWM plot of peak cluster Ashown in Fig. 3, there are four eigenvalue curveshigher than the noise level within the peak region. Wecan conclude that the peak A may not be a pure one.Furthermore, after a special pretreatment described inRef. [8] is conducted, the new result are shown inFig.4 from which one could conclude that the region ofi is the pure area of the first component, the region of iiis the overlapping region of the first and secondcomponents, the same to the region iii overlapped bythe second and third components, lastly the region ofIV is the pure region of the third component.The stepwise eluting information of chemicalcomponents in peak cluster A can be further confirmedby evolving latent projection graph (ELPG) [1–3]. Thistechnique is based on the use of ordered nature ofhyphenated data and that the selective regions appearas straight-line segments in bivariate score plots ofprincipal component analysis. Thus, the ELPG isessentially a principal component projective curvefrom chromatographic or spectral spaces. There are afew advantages to use the ELPG: (i) In a bivariatescore plot a straight line segment pointing to the originsuggests selective information in the retention timedirection, while in a bivariate loadings plot a straightline segment pointing to the origin suggests selectiveinformation in the spectral direction. The concept of"straight line" here is, of course, under sense of leastsquares; (ii) The evolving information of theappearance and disappearance of the chemicalcomponents in retention time direction can be alsoprovided in ELPG. In the ELPG from thechromatographic space, the straight line sectionrepresents the pure selective region of one componentwhile the curving section denotes the overlappingregion of at least two constituents; (iii) Informationenabling the detection of shifts of the chromatographicbase line and instrumental background is alsoprovided in ELPG. I f there is an offset inchromatography the points cannot concentrate on theorigin in the plot even i f one includes thezero-component regions in data; (iv) ELPG is also avery good diagnostic tool to identifying the embeddedpeaks in chromatogram. This information is veryimportant for resolution of concentration profiles ofembedded peaks. The ELPG likes a data scope to see



the insight of data structure of the two-way data. Fig. 5shows the ELPG of peak cluster A. From this plot, onecan see that this peak cluster is a three-componentsystem. The marks, say 1, 1+2, 2+3 and 3 in the plot,indicate respectively the pure region of the firstcomponent, the overlapping region of the first andsecond components and the overlapping region of thesecond and third components and the pure region ofthe third component in the chromatographic direction.This is consistent with the results obtained from theFSWM plot after subtracting the heteroscedastic noise.From the discussion above, the chromatographiceluting order can be determined and so the number ofcomponents in the system, the selective regions andzero-concentration regions of all the constituents.Because of all the acknowledged information, thetwo-dimensional data matrix can be uniquely resolvedinto pure chromatographic profiles and mass spectraof all components.The qualitative of the chemical composition of thesample determination can be directly performed bymeans of similarity searches in the NIST mass librarynow, as the pure chromatographic curve and massspectrum of each component have been resolved. Theresult shows that these three components in peakc l u s t e r A a r e E u c a l y p t o l ( C 1 0 H 1 8 O ) ,b e t a . - P h e l l a n d r e n e ( C 1 0 H 1 6 ) a n dD-Limonene(C10H16). Their correspondingchromatographic curves are shown in Fig. 6, and theresolved mass spectra together with the standardspectrum of each component from the NIST MS libraryare also given in Figs. 7, 8 and 9.From the resolved pure chromatographic peaks, it isobvious that the first and the third component bothhave a relatively small quantity in the whole system,and the three peaks overlap seriously, additionally themass spectrums of the second and the thirdcomponent is a little similar. Because of these, if yousearch directly in the mass-library, only the componentcontaining more would be found out, or a wrong resultappear. With the help of chemometric resolutionmethod called heuristic evolving latent projections(HELP), the reliable and accurate results could beobtained.Likewise, Fig.10 shows the TIC curve of peak clusterB, appears to be a mixed system of only twoconstituents. Only two components namedBicyclo[2.2.1]heptane-2,5-diol,1,7,7-trimethyl-,(2-endo,5-exo)-(C10H18O2) and 2-Cyclohexen-1-ol,1-methyl-4-(1-methylethyl)-, trans-(C10H18O)can bedirectly matched in the NIST MS database. However,f o u r i s o m e r i c c o m p o n e n t s w h i c h a r e1 - M e t h y l - 3 - ( 1 - m e t h y c y c l o p r o p y l ) c yclopentene(C10H16), Bicyclo[2.2.1]heptan-2-ol,

1,7,7-trimethyl-,exo-(C10H18O), 2-Cyclohexen-1-ol,1-methyl-4-(1-methylethyl)-, trans-(C10H18O),6-Octen-1-ol, 7-methyl-3-methylene-(C10H18O)can beresolved by means of the HELP resolution methodwith the procedure described above.After the background is removed, the ELPG is plottedin Fig.11, which suggests that the peak cluster B ismuch complex than the peak cluster A. The marks,say 1, 2, 4 in the plot, indicate respectively the pureregion of the first, the second and the third component,and the marks 2+3,3+4 in the plot, indicate theoverlapping region of component 2 and 3 and theoverlapping region of component 3 and 4, respectively.The FSWM plo ts a f ter cor rec t ion o f theheteroscedastic noises for peak cluster B are shown inFigs. 12. The regions marks by i,ii,iii,IV,V and VI,indicate the region of the pure component 1, theoverlapping region of components 1 and 2, the regionof the pure component 2, the overlapping region ofcomponents 2 and 3, the overlapping region ofcomponents 3 and 4 and the region of the purecomponent 4, respectively.The FSWM plot obtained after correcting theheteroscedastic noise clearly shows that there are fourcomponents in peak cluster B. After the eluting regionsof all components are determined the uniqueresolution into chromatograms and mass spectra canbe then conducted on the two-dimensional data.Figs.13—17 show the resolved results. These figuresdefinitely support the presence of four isomericcomponents in peak cluster B.And the TIC curve of peak cluster C is show in Fig.18,relatively more complex systems containing 4constituents named Bicyclo[2.2.1]heptan-2-ol,1,3,3-trimethyl-(C10H18O), cis-2-Pinanol(C10H18O),Bicyclo[2.2.1]heptane,2-methoxy-1,7,7-trimethyl-(C11H 2 0 O ) a n d 6 - O c t e n - 1 - o l ,7-methyl-3-methylene-(C10H18O) could obtained ifyou search in the NIST database directly. However,s i x i s o m e r i c c o m p o n e n t s w h i c h a r eBicyclo[2.2.1]heptan-2-ol, 1,3,3-trimethyl-(C10H18O),Isopulegol(C10H18O), cis-2-Pinanol(C10H18O),Bicyclo[2.2.1]heptan-2-ol, 1,7,7-trimethyl-,e x o - ( C 1 0 H 1 8 O ) ,2-Cyclohexen-1-ol,1-methyl-4-(1-methylethyl)-trans-(C1 0 H 1 8 O ) a n d 6 - O c t e n - 1 - o l ,7-methyl-3-methylene-(C10H18O)can be resolved bymeans of the HELP resolution method with theprocedure described before.Just like the sample shown above, the FSWM plotsafter correction of the heteroscedastic noises for peakcluster C are shown in Figs. 19. The regions marks byi, ii, iii, IV, V, VI, ? and indicate the region of the purecomponent 1, the overlapping region of components 1



and 2, the region of the pure component 2, theoverlapping region of components 2 and 3, theoverlapping region of components 3 and 4, theoverlapping region of components 4 and 5, theoverlapping region of components 5 and 6 and theregion of the pure component 6, respectively.After the background is removed, the ELPG is plottedin Fig.20, which suggests that the peak cluster C ismuch complex than the formers. The marks, say 1, 2,3, 6 in the plot, indicate respectively the pure region ofthe first, the second, the third and the sixth component,and the marks 3+4, 4+5, 5+6 in the plot, indicate theoverlapping region of component 3 and 4, theoverlapping region of component 4 and 5 and theoverlapping region of component 5 and 6, respectively.Figs.21—27 show the resolved results about theunique resolution into chromatograms and massspectra.4.2 Qualitative analysisOther peaks in the sample at other chromatographicscan point were also qualified in the same way asdescribed above. The tentatively qualitative results ofconstituents from RZ, ZOR and GP are displayed inTable 1.4.3 Quantitative analysisUsing the total volume integral method, thequantitative results were calculated and also shown inTable 1. In total, 85, 81 and 80 volatile components involatile oil of RZ, ZOR and GP were respectivelydetermined qualitatively and quantitatively, accountingfor 81.43%, 86.38% and 84.79% total contents ofvolatile oil of RZ, ZOR and GP respectively.4.4 Comparison of volatile components among RZ,ZOR and GPFrom the Table 1, there are total 58 commoncompounds existing in RZ and ZOR, 63 commoncomponents between RZ and GP, 60 commoncomponents between ZOR and GP, and 52 commoncomponents existing among each of the three systems.It is obvious that the volatile oils in RZ, ZOR and GPare nearly the same, only a little different. Becausethey come from a same herb, chemical properties andactive effects are very similar. However, the quantitiesof common volatile oils in different systems aredifferent, it is useful to accurately qualify and quantifythem in food or medicine industries. Just like thispaper did.

Conclusion(s)

With the use of HELP resolution method upontwo-dimensional data combined with the abundant

mass spectral database, one can exactly analyze suchcomplex systems, like the traditional Chinese medicineand natural herbs, further the accurate and reasonableresults could be obtained, and more constituents in aspecial system can be qualified and quantified better.This demonstrated that the combination of hyphenatedinstruments and relevant chemometric methods opensa new way for quick and accurate analysis of realunknown complex samples. The method developed inthis paper can improve controlling quality of thematerials and help examining the value of products infood industries and other regions.

Acknowledgement(s)

This work is financially supported by the NationalNature Foundation Committee of PR China (Grant Nos.20235020 and 20475066) and the Cultivation Fund ofKey Scientific and Technical Innovation Project,Ministry of Education of China (No. 704036).

Authors Contribution(s)

Yu He, Xiao-Ru Li*, Shao-Yin Liu, Shi-Rong Wang,Bing-Xin Li, Yi-Zeng Liang(Research Center of Modernization of Chinese HerbalMedicine, College of Chemistryand Chemical Engineering, Central South University,Changsha 410083, P. R. China)*Corresponding Author:Dr. Xiao-Ru Li, Professor, College of Chemistry andChemical Engineering,Central South University, Changsha 410083, P. R.ChinaE-mail: [email protected] Author:Yu He, graduate student, College of Chemistry andChemical Engineering, Central SouthUniversity, Changsha 410083, P. R. China.

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Illustrations

Illustration 1

Fig.1 TICs of volatile oils from RZ (a) ZOR (b) and GP (c)







Illustration 2

Fig.2 TIC curve for A peak cluster within 10.638-11.02min



Illustration 3

Fig.3 FSWM plot for A peak cluster



Illustration 4

Fig. 4 FSWM plot for A peak cluster after correcting heteroscedastic noise



Illustration 5

Fig.5 ELPG plots for A peak cluster.



Illustration 6

Fig.6 Resolved chromatograms for A peak cluster containing component 1, 2 and 3



Illustration 7

Fig.7 Standard mass spectrum (A) of Eucalyptol and resolved mass spectrum (B) of component1 by HELP



Illustration 8

Fig.8 Standard mass spectrum (A) of beta-Phellandrene and resolved mass spectrum (B) of component2



Illustration 9

Fig.9 Standard mass spectrum(A) of D-Limonene and resolved mass spectrum(B) of component 3 by HELP



Illustration 10

Fig.10 TIC curve for B peak cluster within 13.279-13.513min



Illustration 11

Fig.11 ELPG plot for B peak cluster



Illustration 12

Fig.12 FSWM plot for B peak cluster after correcting heteroscedastic noise



Illustration 13

Fig.13 Resolved chromatograms for B peak cluster containing component 1-4



Fig.14 Standard mass spectrum (A) of 1-Methyl-3-(1-methycyclopropyl)cyclopentene（C10H16）and resolved mass spectrum (B)of component 1 by HELP

Illustration 14

Fig.14 Standard mass spectrum (A) and resolved mass spectrum (B)of component 1 by HELP



Fig.15 Standard mass spectrum(A) of Bicyclo[2.2.1]heptan-2-ol,1,7,7-trimethyl-,exo-（C10H18O）and resolved mass spectrum(B) of component 2 by HELP

Illustration 15

Fig.15 Standard mass spectrum(A) and resolved mass spectrum(B) of component 2 by HELP



Fig.16 Standard mass spectrum(A) of 2-Cyclohexen-1-ol, 1-methyl-4-(1-methylethyl)-,trans-（C10H18O） and resolved mass spectrum (B)of component 3 by HELP

Illustration 16

Fig.16 Standard mass spectrum(A) and resolved mass spectrum (B)of component 3 by HELP



Fig.17 Standard mass spectrum(A) of 6-Octen-1-ol, 7-methyl-3-methylene-（C10H18O） andresolved mass spectrum(B) of component 4 by HELP

Illustration 17




Illustration 18

Fig.18 TIC curve for C peak cluster within13.087-13.526 min



Illustration 19

Fig.19 EFA plot for C peak cluster after correcting heteroscedastic noise



Illustration 20

Fig.20 ELPG plot for C peak cluster and ELPG plot



Illustration 21

Fig.21 Resolved chromatograms for C peak cluster containing component 1-6



Fig.22 Standard mass spectrum(A) of Bicyclo[2.2.1]heptan-2-ol, 1,3,3-trimethyl-（C10H18O）and resolved mass spectrum(B) of component 1 by HELP

Illustration 22




Fig.23 Standard mass spectrum(A) of Isopulegol（C10H18O） and resolved mass spectrum(B) ofcomponent 2 by HELP

Illustration 23

Fig.23 Standard mass spectrum(A) of Isopulegol and resolved mass spectrum(B) of component 2 hy HELP



Fig.24 Standard mass spectrum（A） of cis-2-Pinanol（C10H18O）and resolved massspectrum(B) of component 3 by HELP

Illustration 24

Fig.24 Standard mass spectrum?A?and resolved mass spectrum(B) of component 3 by HELP



Fig.25 Standard mass spectrum (A)of Bicyclo[2.2.1]heptan-2-ol,1,7,7-trimethyl-,exo-（C10H18O） and resolved mass spectrum (B)of component 4 by HELP

Illustration 25

Fig.25 Standard mass spectrum (A) and resolved mass spectrum (B)of component 4 by HELP



Fig.26 Standard mass spectrum (A)of 2-Cyclohexen-1-ol, 1-methyl-4-(1-methylethyl)-,trans-（C10H18O） and resolved mass spectrum(B) of component 5 by HELP

Illustration 26




Fig.27 Standard mass spectrum(A) of 6-Octen-1-ol, 7-methyl-3-methylene-（C10H18O） andresolved mass spectrum(B) of component 6 by HELP

Illustration 27




no Name of components/molecular formula RZ/rc ZOR/rc

GP/rc

Ri

1 2-Heptanone/C7H14O 0.06 0.05 0.04 864.82 Heptanal/C7H14O 0.02 —— 0.01 875.83 2-Heptanol/C7H16O 0.41 0.28 0.16 884.24 Tricyclo[2.2.1.02,6]heptane,

1,7,7-trimethyl-/C10H160.21 0.09 0.07 916.5

5 Bicyclo[3.1.0]hex-2-ene,2-methyl-5-(1-methylethyl)-/C10H16

0.04 0.01 —— 921.7

6 .alpha.-Pinene/C10H16 3.29 1.53 1.12 929.17 Camphene/C10H16 8.65 4.77 3.71 943.38 5-Hepten-2-one, 6-methyl-/C8H14O 0.61 —— 0.42 9639 Bicyclo[3.1.1]heptane,

6,6-dimethyl-2-methylene-, (1S)-/C10H160.41 0.23 0.19 966.9

10 6-Hepten-1-ol, 2-methyl-/C8H16O —— —— 0.14 976.511 Octanal/C8H16O —— —— 0.12 980.112 .beta.-Myrcene/C10H16 1.75 1.36 1 983.513 Bicyclo[3.1.0]hexane,

4-methyl-1-(1-methylethyl)-, didehydroderiv./C10H16

—— 0.54 —— 995.1

14 3-Carene/C10H16 0.08 0.05 0.04 1002.4

15 .alpha.-Phellandrene/C10H16 1.24 —— 0.3 1005.1

16 (+)-4-Carene/C10H16 0.14 —— 0.02 1007.5

17 Benzene,1-methyl-2-(1-methylethyl)-/C10H14

0.04 0.06 —— 1010.2

18 Benzene,1-methyl-4-(1-methylethyl)-/C10H14

0.04 0.14 0.12 1013.1

19 Eucalyptol/C10H18O 5.96 3.67 2.29 1020.5

20 beta.-Phellandrene/C10H16 9.01 6.76 4.45 1024.1

21 D-Limonene/C10H16 4.04 2.33 1.71 1025.5

22 Acetic acid, sec-octyl ester/C10H20O2 —— 0.58 —— 1029.9

23 2-Octenal, (E)-/C8H14O —— 0.11 0.05 1032.1

24 1,3,6-Octatriene, 3,7-dimethyl-, (Z)-/C10H16 0.02 0.02 0.01 1038.6

25 1,4-Cyclohexadiene, 0.17 0.05 0.04 1048

Illustration 28

Table 1 Chemical components of volatile oil from RZ, ZOR and GP



1-methyl-4-(1-methylethyl)-/C10H1626 Bicyclo[3.1.0]hexan-2-ol,

2-methyl-5-(1-methylethyl)-,(1.alpha.,2.beta.,5.alpha.)-/C10H18O

—— 0.04 —— 1051.4

27 .alpha.-Methyl-.alpha.-[4-methyl-3-pentenyl]oriranemethanol/C10H18O2

0.07 —— 0.02 1056.2

28 2-Nonanone/C9H18O 0.84 0.39 0.13 1071.4

29 Cyclohexene, 5-methyl-3-(1-methylethenyl)-,trans-(-)-/C10H16

0.62 0.46 0.46 1077.8

30 1,6-Octadien-3-ol, 3,7-dimethyl-/C10H18O 1.83 2.1 0.95 1086.5

31 2-Decanol/C10H22O 0.61 —— —— 1088.3

32 Fenchol, exo-/C10H18O 0.11 —— 0.05 1096.1

33 Bicyclo[2.2.1]heptan-2-ol,1,3,3-trimethyl-/C10H18O

—— 0.05 0.05 1096.3

34 Isopulegol/C10H18O —— —— 0.01 1098.6

35 1-Methyl-3-(1’-methylcyclopropyl)cyclopentene/C10H16

0.03 —— —— 1101.5

36 cis-2-Pinanol/C10H18O —— 0.09 0.06 1101.8

37 Bicyclo[2.2.1]heptan-2-ol,1,7,7-trimethyl-,exo-/C10H18O

0.08 0.08 0.09 1103.5

38 2-Cyclohexen-1-ol,1-methyl-4-(1-methylethyl)-, trans-/C10H18O

0.35 0.18 0.06 1104.9

39 6-Octen-1-ol,7-methyl-3-methylene-/C10H18O

0.14 0.11 0.08 1106.1

40 Bicyclo[2.2.1]heptan-2-one, 1,7,7-trimethyl-,(1R)-/C10H16O

0.18 0.16 0.19 1115.8

41 2-Cyclohexen-1-ol,1-methyl-4-(1-methylethyl)-, cis-/C10H18O

0.37 0.22 0.11 1121.5

42 6-Octenal, 3,7-dimethyl-, (R)-/C10H18O 0.06 0.31 0.27 1131.2

43 Isoborneol/C10H18O 0.19 3.02 0.1 1141.8

44 Borneol/C10H18O 3.13 0.07 2.69 1145.4

45 2-Cyclohexen-1-one,4-(1-methylethyl)-/C9H14O

0.13 0.34 0.21 1153.2

46 3-Cyclohexen-1-ol,4-methyl-1-(1-methylethyl)-/C10H18O

0.88 —— —— 1160.4

47 Bicyclo[3.1.1]hept-2-ene-2-carboxaldehyde,6,6-dimethyl-/C10H14O

0.15 —— 0.08 1165.8



48 3-Cyclohexene-1-methanol,.alpha.,.alpha.4-trimethyl-/C10H18O

1.52 1.43 1.34 1172.3

49 Dodecanal/C12H24O —— —— 0.13 1184.6

50 Decanal/C10H20O —— 0.06 —— 118551 2-Cyclohexen-1-ol,

3-methyl-6-(1-methylethyl)-, trans-/C10H18O0.21 —— —— 1188.

952 Acetic acid, octyl ester/C10H20O2 —— 0.04 —— 119553 2-Octen-1-ol, 3,7-dimethyl-/C10H20O 2.14 5.34 —— 1216.

654 .alpha.-2,2,6-tetramethyl-Cyclohexanepropan

ol/C13H26O—— —— 3.72 1216.

7

55 2,6-Octadienal, 3,7-dimethyl-, (E)-/C10H18O 1 2.06 2.8 1219.2

56 2-Acetoxytridecane/C15H30O2 0.11 —— —— 1223.3


58 3-Cyclohexen-1-one2-isopropyl-5-methyl-/C10H16O

—— 0.02 0.01 1226.8

59 2,6-Octadien-1-ol, 3,7-dimethyl-,(Z)-/C10H18O

—— 0.42 —— 1238.2

60 2,6-Octadien-1-ol, 3,7-dimethyl-/C10H18O 2.37 —— 3.97 1243.1

61 2,6-Octadienal, 3,7-dimethyl-/C10H16O 2.39 4.55 7.08 1251.1

62 1,6-Octadien-3-ol, 3,7-dimethyl-,(.+/-.)-/C10H18O

—— 8.8 —— 1251.3

63 1,5-Cyclohexadiene-1-methanol,4-(1-methylethyl)-/C10H16O

0.05 0.03 —— 1253.3

64 4,8-Dimethyl-nona-3,8-dien-2-one/C11H18O —— 0.01 —— 1258.5

65 Benzenemethanol,4-(1-methylethyl)-/C10H14O

—— 0.01 —— 1266.6

66 Bornyl acetate/C12H20O2 0.44 0.92 0.59 1269.8

67 2-Undecanone/C11H22O 1.61 0.84 0.44 1276.2

68 2-Pentadecanol/C15H32O 0.21 0.09 0.07 1288.2

69 Ethanone,1-[3-methyl-3-(4-methyl-3-pentenyl)oxiranyl]-/C11H18O2

—— 0.01 1292.9

70 (-)-Myrtenyl acetate/C12H18O2 —— 0.1 0.04 1304.4

71 Phenol,2-methoxy-3-(2-propenyl)-/C10H20O2

0.01 —— —— 1326.3



72 6-Octen-1-ol, 3,7-dimethyl-,acetate/C12H22O2

0.39 1.03 0.6 1336

73 Copaene/C15H24 0.02 0.21 0.02 1355.1

74 2,6-Octadien-1-ol, 3,7-dimethyl-, acetate,(Z)-/C12H20O2

1.44 0.09 2.53 1356.6

75 2,6-Octadien-1-ol, 3,7-dimethyl-, acetate,(E)-/C12H22O2

—— 6.2 —— 1368

76 n-Decanoic acid/C10H20O2 0.23 —— —— 1369.6

77 alpha.-Cubebene/C15H24 0.13 0.27 1372.3

78 Cyclobuta[1,2:3,4]dicyclopentene,decahydro-3a-methyl-6-methylene-1-(1-methylethyl)-,[1S-(1.alpha.,3a.alpha.,3b.beta.,6a.beta.)]-/C15H24

0.02 —— —— 1379.1

79 Cyclohexane,1-ethenyl-1-methyl-2,4-bis(1-methylethenyl)-,[1S-(1.alpha.,2.beta.,4.beta.)]-/C15H24

0.22 0.59 0.05 1383.2

80 Cyclohexane,1-ethenyl-1-methyl-2,4-bis(1-methylethenyl)-/C15H24

—— —— 0.89 1386.1

81 1,3-Cyclohexadiene,5-(1,5-dimethyl-4-hexenyl)-2-methyl-,[s-(R@,S@)]-/C15H24

0.07 0.14 0.16 1400.1

82 1H-3a,7-Methanoazulene,2,3,4,7,8,8a-hexahydro-3,6,8,8-tetramethyl-,[3R-(3.alpha.,3a.beta.,7.beta.,8a.alpha.)]-/C15H24

0.03 —— —— 1406.2

83 Bicyclo[7.2.0]undec-4-ene,4,11,11-trimethyl-8-methylene-/C15H24

0.03 —— —— 1411.7

84 Phenol,2-methoxy-4-(1-propenyl)-/C10H12O2

0.14 0.02 —— 1419.2

85 1H-Cyclopenta[1,3]cyclopropa[1,2]benzene,octahydro-7-methyl-3-methylene-4-(1-methylethyl)-,[3aS-(3a.alpha.,3b.beta.,4.beta.,7.alpha.,7aS@)]- /C15H24

0.01 0.25 0.05 1422.8

86 .gamma.-Elemene/C15H24 0.14 —— 0.41 1424.7

87 5,9-Undecadien-2-one,6,10-dimethyl-/C13H22O

0.02 —— —— 1427.5

88 Bicyclo[3.1.1]hept-2-ene,2,6-dimethyl-6-(4-methyl-3-pentenyl)-/C15H24

—— 0.06 0.08 1429.7



89 .beta.-Sesquiphellandrene/C15H24 —— —— 0.02 1433.1

90 Humulen-(v1)/C15H24 0.22 0.06 0.1 1433.7

91 1H-Cycloprop[e]azulene,1a,2,3,4,4a,5,6,7b-octahydro-1,1,4,7-tetramethyl-,[1aR-(1a.alpha.,4.alpha.,4a.beta.,7b.alpha.)]-/C15H24

0.11 0.08 0.09 1441.5

92 1,6,10-Dodecatriene,7,11-dimethyl-3-methylene-, (Z)-/C15H24

0.1 —— 0.44 1446

93 Cyclohexene,3-(1,5-dimethyl-4-hexenyl)-6-methylene-,[s-(R@,s@)]-/C15H24

—— 0.29 —— 1446.4

94 1H-Cycloprop[e]azulene,decahydro-1,1,7-trimethyl-4-methylene-,[1aR-(1a.alpha.,4a.beta.,7.alpha.,7a.beta.,7b.alpha.)]-/C15H24

0.18 0.13 0.16 1451.4

95 Benzene,1-(1,5-dimethyl-4-hexenyl)-4-methyl-/C15H22

4.36 4.63 7.73 1472.5

96 Spiro[5.5]undec-2-ene,3,7,7-trimethyl-11-methylene-, (-)-/C15H22

—— 0.17 1477.5

97 Naphthalene,1,2,3,4,4a,5,6,8a-octahydro-7-methyl-4-methylene-1-(1-methylethyl)-,(1.alpha.,4a.alpha.,8a.alpha.)-/C15H24

0.75 —— —— 1490.4


4.79 6.86 13 1491.1

99 .alpha.-Farnesene/C15H24 1.18 2.53 3.72 1501.1

100 Cyclohexene,1-methyl-4-(5-methyl-1-methylene-4-hexenyl)-, (S)-/C15H24

1.69 1.79 2.92 1503.9

101 Cyclohexene,3-(1,5-dimethyl-4-hexenyl)-6-methylene-,[s-(R@,s@)]-/C15H24

3.15 3.61 6.22 1517.3

102 Cyclohexanemethanol,4-ethenyl-.alpha.,.alpha.,4-trimethyl-3-(1-methylethenyl)-,[1R-(1.alpha.,3.alpha.,4.beta.)]-/C15H26O

0.6 1.13 1.31 1531.7

103 1,6,10-Dodecatrien-3-ol, 3,7,11-trimethyl-,(E)-/C15H26O

1.02 0.65 0.94 1545.8

104 1-Hydroxy-1,7-dimethyl-4-isopropyl-2,7-cyclodecadiene/C15H26O

—— —— 0.08 1558.7



105 Dodecanoic acid/C12H24O2 0.56 —— —— 1559.2

106 2-Naphthalenemethanol,2,3,4,4a,5,6,7,8-octahydro-.alpha.,.alpha.,4a,8-tetramethyl-,[2R-(2.alpha.,4a.beta.,8.beta.)]-/C15H26O

—— —— 0.81 1626.9

107 Farnesol isomer a/C15H26O 0.1 —— —— 1698.2

108 2,6,10-Dodecatrienal,3,7,11-trimethyl-/C15H24O

—— 0.13 0.17 1710.9

109 Tetradecanoic acid/C14H28O 0.17 —— —— 1746110 2,6,10-Dodecatrien-1-ol, 3,7,11-trimethyl-,

acetate, (E,E)-/C17H28O2—— 0.03 —— 1813.

7111 9-Hexadecenoic acid/C16H30O2 0.07 0.01 —— 1919112 Eicosanoic acid/C20H40O2 1.09 0.33 0.19 1948.

4113 Phytol/C20H40O 0.03 0.02 0.01 2096.

3114 9,12-Octadecadienoic acid (Z,Z)-/C18H32O2 0.22 0.11 0.02 2107115 9-Octadecenoic acid, (E)-/C18H34O2 0.12 0.05 0.02 2116.

9116 Octadecanoic acid/C18H36O2 0.01 —— —— 2146.

5117 Heneicosane/C21H44 —— 0.01 0.01 2450.

7total 81.43 86.38 84.79



Table 1 Chemical components of volatile oil from RZ, ZOR and GPNo. Name of components/molecular formula RZ/rc ZOR/r

cGP/r

cRi

1 2-Heptanone/C7H14O 0.06 0.05 0.04 864.82 Heptanal/C7H14O 0.02 —— 0.01 875.83 2-Heptanol/C7H16O 0.41 0.28 0.16 884.24 Tricyclo[2.2.1.02,6]heptane, 1,7,7-trimethyl-/C10H16 0.21 0.09 0.07 916.55 Bicyclo[3.1.0]hex-2-ene,

2-methyl-5-(1-methylethyl)-/C10H160.04 0.01 —— 921.7

6 .alpha.-Pinene/C10H16 3.29 1.53 1.12 929.17 Camphene/C10H16 8.65 4.77 3.71 943.38 5-Hepten-2-one, 6-methyl-/C8H14O 0.61 —— 0.42 9639 Bicyclo[3.1.1]heptane, 6,6-dimethyl-2-methylene-,

(1S)-/C10H160.41 0.23 0.19 966.9

10 6-Hepten-1-ol, 2-methyl-/C8H16O —— —— 0.14 976.511 Octanal/C8H16O —— —— 0.12 980.112 .beta.-Myrcene/C10H16 1.75 1.36 1 983.513 Bicyclo[3.1.0]hexane, 4-methyl-1-(1-methylethyl)-,

didehydro deriv./C10H16—— 0.54 —— 995.1

14 3-Carene/C10H16 0.08 0.05 0.04 1002.4

15 .alpha.-Phellandrene/C10H16 1.24 —— 0.3 1005.1

16 (+)-4-Carene/C10H16 0.14 —— 0.02 1007.5

17 Benzene, 1-methyl-2-(1-methylethyl)-/C10H14 0.04 0.06 —— 1010.2

18 Benzene, 1-methyl-4-(1-methylethyl)-/C10H14 0.04 0.14 0.12 1013.1

19 Eucalyptol/C10H18O 5.96 3.67 2.29 1020.5

20 beta.-Phellandrene/C10H16 9.01 6.76 4.45 1024.1

Illustration 29

Table 1 Chemical components of volatile oil from RZ, ZOR and GP



21 D-Limonene/C10H16 4.04 2.33 1.71 1025.5


23 2-Octenal, (E)-/C8H14O —— 0.11 0.05 1032.1

24 1,3,6-Octatriene, 3,7-dimethyl-, (Z)-/C10H16 0.02 0.02 0.01 1038.6

25 1,4-Cyclohexadiene,1-methyl-4-(1-methylethyl)-/C10H16

0.17 0.05 0.04 1048

26 Bicyclo[3.1.0]hexan-2-ol, 2-methyl-5-(1-methylethyl)-,(1.alpha.,2.beta.,5.alpha.)-/C10H18O

—— 0.04 —— 1051.4

27 .alpha.-Methyl-.alpha.-[4-methyl-3-pentenyl]oriranemethanol/C10H18O2

0.07 —— 0.02 1056.2

28 2-Nonanone/C9H18O 0.84 0.39 0.13 1071.4

29 Cyclohexene, 5-methyl-3-(1-methylethenyl)-,trans-(-)-/C10H16

0.62 0.46 0.46 1077.8

30 1,6-Octadien-3-ol, 3,7-dimethyl-/C10H18O 1.83 2.1 0.95 1086.5

31 2-Decanol/C10H22O 0.61 —— —— 1088.3

32 Fenchol, exo-/C10H18O 0.11 —— 0.05 1096.1

33 Bicyclo[2.2.1]heptan-2-ol, 1,3,3-trimethyl-/C10H18O —— 0.05 0.05 1096.3

34 Isopulegol/C10H18O —— —— 0.01 1098.6WebmedCentral > Research articles Page 45 of 53


35 1-Methyl-3-(1’-methylcyclopropyl)cyclopentene/C10H16

0.03 —— —— 1101.5

36 cis-2-Pinanol/C10H18O —— 0.09 0.06 1101.8

37 Bicyclo[2.2.1]heptan-2-ol,1,7,7-trimethyl-,exo-/C10H18O

0.08 0.08 0.09 1103.5

38 2-Cyclohexen-1-ol, 1-methyl-4-(1-methylethyl)-,trans-/C10H18O

0.35 0.18 0.06 1104.9

39 6-Octen-1-ol, 7-methyl-3-methylene-/C10H18O 0.14 0.11 0.08 1106.1

40 Bicyclo[2.2.1]heptan-2-one, 1,7,7-trimethyl-,(1R)-/C10H16O

0.18 0.16 0.19 1115.8

41 2-Cyclohexen-1-ol, 1-methyl-4-(1-methylethyl)-,cis-/C10H18O

0.37 0.22 0.11 1121.5

42 6-Octenal, 3,7-dimethyl-, (R)-/C10H18O 0.06 0.31 0.27 1131.2

43 Isoborneol/C10H18O 0.19 3.02 0.1 1141.8

44 Borneol/C10H18O 3.13 0.07 2.69 1145.4

45 2-Cyclohexen-1-one, 4-(1-methylethyl)-/C9H14O 0.13 0.34 0.21 1153.2

46 3-Cyclohexen-1-ol,4-methyl-1-(1-methylethyl)-/C10H18O

0.88 —— —— 1160.4

47 Bicyclo[3.1.1]hept-2-ene-2-carboxaldehyde,6,6-dimethyl-/C10H14O

0.15 —— 0.08 1165.8

48 3-Cyclohexene-1-methanol,.alpha.,.alpha.4-trimethyl-/C10H18O

1.52 1.43 1.34 1172.3



49 Dodecanal/C12H24O —— —— 0.13 1184.6

50 Decanal/C10H20O —— 0.06 —— 118551 2-Cyclohexen-1-ol, 3-methyl-6-(1-methylethyl)-,

trans-/C10H18O0.21 —— —— 1188.

952 Acetic acid, octyl ester/C10H20O2 —— 0.04 —— 119553 2-Octen-1-ol, 3,7-dimethyl-/C10H20O 2.14 5.34 —— 1216.

654 .alpha.-2,2,6-tetramethyl-Cyclohexanepropanol/C13H2

6O—— —— 3.72 1216.

7

55 2,6-Octadienal, 3,7-dimethyl-, (E)-/C10H18O 1 2.06 2.8 1219.2

56 2-Acetoxytridecane/C15H30O2 0.11 —— —— 1223.3


58 3-Cyclohexen-1-one 2-isopropyl-5-methyl-/C10H16O —— 0.02 0.01 1226.8

59 2,6-Octadien-1-ol, 3,7-dimethyl-, (Z)-/C10H18O —— 0.42 —— 1238.2

60 2,6-Octadien-1-ol, 3,7-dimethyl-/C10H18O 2.37 —— 3.97 1243.1

61 2,6-Octadienal, 3,7-dimethyl-/C10H16O 2.39 4.55 7.08 1251.1

62 1,6-Octadien-3-ol, 3,7-dimethyl-, (.+/-.)-/C10H18O —— 8.8 —— 1251.3

63 1,5-Cyclohexadiene-1-methanol,4-(1-methylethyl)-/C10H16O

0.05 0.03 —— 1253.3

64 4,8-Dimethyl-nona-3,8-dien-2-one/C11H18O —— 0.01 —— 1258.5



65 Benzenemethanol, 4-(1-methylethyl)-/C10H14O —— 0.01 —— 1266.6

66 Bornyl acetate/C12H20O2 0.44 0.92 0.59 1269.8

67 2-Undecanone/C11H22O 1.61 0.84 0.44 1276.2

68 2-Pentadecanol/C15H32O 0.21 0.09 0.07 1288.2

69 Ethanone,1-[3-methyl-3-(4-methyl-3-pentenyl)oxiranyl]-/C11H18O2

—— 0.01 1292.9

70 (-)-Myrtenyl acetate/C12H18O2 —— 0.1 0.04 1304.4

71 Phenol, 2-methoxy-3-(2-propenyl)-/C10H20O2 0.01 —— —— 1326.3

72 6-Octen-1-ol, 3,7-dimethyl-, acetate/C12H22O2 0.39 1.03 0.6 133673 Copaene/C15H24 0.02 0.21 0.02 1355.

174 2,6-Octadien-1-ol, 3,7-dimethyl-, acetate,

(Z)-/C12H20O21.44 0.09 2.53 1356.

675 2,6-Octadien-1-ol, 3,7-dimethyl-, acetate,

(E)-/C12H22O2—— 6.2 —— 1368

76 n-Decanoic acid/C10H20O2 0.23 —— —— 1369.6

77 alpha.-Cubebene/C15H24 0.13 0.27 1372.3

78 Cyclobuta[1,2:3,4]dicyclopentene,decahydro-3a-methyl-6-methylene-1-(1-methylethyl)-,[1S-(1.alpha.,3a.alpha.,3b.beta.,6a.beta.)]-/C15H24

0.02 —— —— 1379.1

79 Cyclohexane,1-ethenyl-1-methyl-2,4-bis(1-methylethenyl)-,[1S-(1.alpha.,2.beta.,4.beta.)]-/C15H24

0.22 0.59 0.05 1383.2



80 Cyclohexane,1-ethenyl-1-methyl-2,4-bis(1-methylethenyl)-/C15H24

—— —— 0.89 1386.1


0.07 0.14 0.16 1400.1

82 1H-3a,7-Methanoazulene,2,3,4,7,8,8a-hexahydro-3,6,8,8-tetramethyl-,[3R-(3.alpha.,3a.beta.,7.beta.,8a.alpha.)]-/C15H24

0.03 —— —— 1406.2

83 Bicyclo[7.2.0]undec-4-ene,4,11,11-trimethyl-8-methylene-/C15H24

0.03 —— —— 1411.7

84 Phenol, 2-methoxy-4-(1-propenyl)-/C10H12O2 0.14 0.02 —— 1419.2

85 1H-Cyclopenta[1,3]cyclopropa[1,2]benzene,octahydro-7-methyl-3-methylene-4-(1-methylethyl)-,[3aS-(3a.alpha.,3b.beta.,4.beta.,7.alpha.,7aS@)]-/C15H24

0.01 0.25 0.05 1422.8

86 .gamma.-Elemene/C15H24 0.14 —— 0.41 1424.7

87 5,9-Undecadien-2-one, 6,10-dimethyl-/C13H22O 0.02 —— —— 1427.5

88 Bicyclo[3.1.1]hept-2-ene,2,6-dimethyl-6-(4-methyl-3-pentenyl)-/C15H24

—— 0.06 0.08 1429.7

89 .beta.-Sesquiphellandrene/C15H24 —— —— 0.02 1433.1

90 Humulen-(v1)/C15H24 0.22 0.06 0.1 1433.7

91 1H-Cycloprop[e]azulene,1a,2,3,4,4a,5,6,7b-octahydro-1,1,4,7-tetramethyl-,

0.11 0.08 0.09 1441.5



[1aR-(1a.alpha.,4.alpha.,4a.beta.,7b.alpha.)]-/C15H24

92 1,6,10-Dodecatriene, 7,11-dimethyl-3-methylene-,(Z)-/C15H24

0.1 —— 0.44 1446

93 Cyclohexene, 3-(1,5-dimethyl-4-hexenyl)-6-methylene-,[s-(R@,s@)]-/C15H24

—— 0.29 —— 1446.4

94 1H-Cycloprop[e]azulene,decahydro-1,1,7-trimethyl-4-methylene-,[1aR-(1a.alpha.,4a.beta.,7.alpha.,7a.beta.,7b.alpha.)]-/C

15H24

0.18 0.13 0.16 1451.4

95 Benzene,1-(1,5-dimethyl-4-hexenyl)-4-methyl-/C15H22

4.36 4.63 7.73 1472.5

96 Spiro[5.5]undec-2-ene, 3,7,7-trimethyl-11-methylene-,(-)-/C15H22

—— 0.17 1477.5

97 Naphthalene,1,2,3,4,4a,5,6,8a-octahydro-7-methyl-4-methylene-1-(1-methylethyl)-, (1.alpha.,4a.alpha.,8a.alpha.)-/C15H24

0.75 —— —— 1490.4


4.79 6.86 13 1491.1

99 .alpha.-Farnesene/C15H24 1.18 2.53 3.72 1501.1

100 Cyclohexene,1-methyl-4-(5-methyl-1-methylene-4-hexenyl)-,(S)-/C15H24

1.69 1.79 2.92 1503.9



101 Cyclohexene, 3-(1,5-dimethyl-4-hexenyl)-6-methylene-,[s-(R@,s@)]-/C15H24

3.15 3.61 6.22 1517.3

102 Cyclohexanemethanol,4-ethenyl-.alpha.,.alpha.,4-trimethyl-3-(1-methylethenyl)-,[1R-(1.alpha.,3.alpha.,4.beta.)]-/C15H26O

0.6 1.13 1.31 1531.7

103 1,6,10-Dodecatrien-3-ol, 3,7,11-trimethyl-,(E)-/C15H26O

1.02 0.65 0.94 1545.8

104 1-Hydroxy-1,7-dimethyl-4-isopropyl-2,7-cyclodecadiene/C15H26O

—— —— 0.08 1558.7

105 Dodecanoic acid/C12H24O2 0.56 —— —— 1559.2

106 2-Naphthalenemethanol,2,3,4,4a,5,6,7,8-octahydro-.alpha.,.alpha.,4a,8-tetramethyl-, [2R-(2.alpha.,4a.beta.,8.beta.)]-/C15H26O

—— —— 0.81 1626.9

107 Farnesol isomer a/C15H26O 0.1 —— —— 1698.2

108 2,6,10-Dodecatrienal, 3,7,11-trimethyl-/C15H24O —— 0.13 0.17 1710.9

109 Tetradecanoic acid/C14H28O 0.17 —— —— 1746110 2,6,10-Dodecatrien-1-ol, 3,7,11-trimethyl-, acetate,

(E,E)-/C17H28O2—— 0.03 —— 1813.

7111 9-Hexadecenoic acid/C16H30O2 0.07 0.01 —— 1919112 Eicosanoic acid/C20H40O2 1.09 0.33 0.19 1948.

4113 Phytol/C20H40O 0.03 0.02 0.01 2096.

3114 9,12-Octadecadienoic acid (Z,Z)-/C18H32O2 0.22 0.11 0.02 2107



115 9-Octadecenoic acid, (E)-/C18H34O2 0.12 0.05 0.02 2116.9

116 Octadecanoic acid/C18H36O2 0.01 —— —— 2146.5

117 Heneicosane/C21H44 —— 0.01 0.01 2450.7

total 81.43 86.38 84.79Note: rc--relative content�%��Ri-- Retention index�——�Fail to qualify



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