1

rev

SUPPLEMENTARY DATA

Title: Dispersive and FT-Raman Spectroscopic Methods in Food Analysis

Authors

Ismail Hakki Boyaci1,2*, Havva Tümay Temiz1, Hüseyin Efe Geniş1, Esra Acar Soykut2, Nazife Nur Yazgan1, Burcu Güven1, Reyhan Selin Uysal1, Akif

Göktuğ Bozkurt1, Kerem İlaslan1, Ozlem Torun1, Fahriye Ceyda Dudak Şeker1

Affiliation of the authors:1 Department of Food Engineering, Faculty of Engineering, Hacettepe University, Beytepe 06800 Ankara, Turkey

2 Food Research Center, Hacettepe University, Beytepe 06800 Ankara, Turkey

*Corresponding author:Prof. Dr. İsmail Hakkı Boyacı

Hacettepe UniversityDepartment of Food Engineering

Beytepe, 06800 Ankara, TURKEYPhone: +90 312 297 61 46Fax: +90 312 299 21 23

e-mail: ihb@hacettepe.edu.tr

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2015

2

Table 1S. Raman spectra of some proteins

Band position cm-1

Assignment of Bonds(Molecule/Group)

Mode of Vibration Strengthof bonds

Sample / Food Matrix Wavenumberof laser source (nm)

Type of Raman

References

1665

1610

1555

C=OC-NN-HAmino acid ringAmide (II)C-NN-HC-C

StretchingStretchingBendingBreathing

StretchingBendingStretching

--------

Jack bean concanavalinA (Con A), bovine pancreas trypsin (trypsin), bovineserum albumin (BSA), bovine pancreas ribonuclease A(RNase A), horse heart cytochrome c (cyt c), humanhemoglobin (Hb), horse skeletal muscle myoglobin (Mb), bovine pancreas R-chymomyosin (Chy), porcine pancreas elastase (Elas), chicken egg white lysozyme (Lyso), human erythrocyte carbonic anhydrase (Carb), porcine muscle triosephosphate isomerase (Trio), bovine pancreas insulin(Ins), tyrosine (Tyr), phenylalanine (Phe), tryptophan (Trp), histidine (His), arginine (Arg), cysteine (Cys), proline (Pro), methionine (Met), cystine / -

206.5 UV-Raman 1

3

800-9001000-1100130214431660175027302850,28703010

C-CC-CCH2CH2C=CC=OCH2 or CH3CH2,CH3=CHR or =CH2

StretchingStretchingPhase twistScissoringStretch (cis)Ester stretchDeformationSymmetric stretch=CH stretch

---------

Mineral oil and corn oil / Protein and oil interface

782 Raman microspectros

copy2

503

750830,850

936-946965-970

980-990

10031338

14481654

S-S

TryptophanTyrosine doublet

Amide III helixAmide III random

amide III antiparallel β-sheet

PhenylalanineC-H TryptophanC-HAmide I band

Stretching vibrations (gauche-gauche-gauche)

-

--

-

---Bending-Bending

-

--

--

-

--

--

Bovine Serum Albumin / Protein and oil interface 782

Raman microspectros

copy2

4

2930

3076

3200

C-H

=C-H

O-H

Stretching

Stretching

Stretching

-

-

-

Various amino acids / BSA and oil interfaceAromatic amino acids / BSA and oil interfaceWater molecules / BSA and oil interface

782Raman

microspectroscopy

2

497,524761831,852

1337

14541060933, 947, 960991

1317

Cysteine S-S TryptophanTyrosine doublet

C-H / Tryptophan

CH2C-N / C-CAmide III’Β-sheet structure

Α- helix structure

---

Bending

BendingStretching

--

-

---

-

----

-

Egg albumen(unheated) / - FT-Raman 3

500, 511758831,851

1350

141814501051938, 951986

12391321

Cysteine S-STryptophanTyrosine doublet

CHTryptophanCOO-CH2C-N / C-CAmide III’Β-sheet structure

Amide IIIα- helix structure

----

Bending--

BendingStretching

--

--

---

-

-----

--

Whey proteins (unheated) / - FT-Raman 3

5

1650-16601260-1300850, 830

2935 (2939-2950)500-550

(534)

(503)

(533)

(514,497)

1361

(880,760)

Amide IAmide IIITyrosine doublet

Native gluten

S-S vibrational bands(trans-gauche-trans)rotamer(gauche-gauche-gauche) form

(trans-gauche-trans)

(gauche-gauche-gauche)

Indicator of buried tryptophan residues

Strength of H bonding and the hydrophobicity of the enviroment

-Weak

-

-

-

-

-

-

-

-

-

-Weak

-

-

-

-

-

-

-

-

-

Gluten and chemically modified gluten / wheat

flour or mix composed by flour and emilsifier (SSL)

1064 FT-Raman 4

508540541-576759

S-STryptophanTryptophanTryptophan

Stretching---

----

6

761831,856832,858883886941

947

960984

1005100710141033,10341072,1130, 11621084,1130,1161(1180) 1183(1207) 1211

1336, 1385(1453) 14551556(1658) 1651

TryptophanTyrosine TyrosineTryptophanTryptophanAmide III’ (α-helix) Amide III’ (α-helix)Amide III’Amide III’ (β-sheet)Phenylalanine PhenylalanineTryptophanPhenylalanineC-N

C-N

TyrosineTyrosine, phenylalanineTryptophanCH2TryptophanAmide I’

-----------

-Shoulder

-Stretching

-Stretching

-----

Deformation---

-----------

---------------

α-lactalbumin, β-lactoglobulin / -

488 Raman spectroscopy

5

1003

1780

1900-1550

Phenylalanine (internal standard)C=O (glutamate or aspartate*)C=O (Carbonyl groups)

-

Stretching

Stretching

-

Strong

7

1800-1740

1732

1667-1673

1230-1240

1650-1660

1260-1300

1665

1245

2800-3000

Near 1450

I850/I830

757

C=O (carboxylic acid monomers)C=O (α-carboxyl groups)Amide I band (predominantly β-sheet)

Amide III band (predominantly β-sheet)Amide I band (high propotion of α-helix) Amide III band (high propotion of α-helix) Amide I (high proportion of undefined or random coil)Amide III (high proportion of undefined or random coil)Amino acid functional groupsAmino acid functional groupsParticipation of tyrosine phenolic groupsTryptophan

Stretching

-

-

-

-

-

Stretching

Bending

-

-

-

-

More intense

-

-Weak

-

-

-

-

-

-

Soy protein isolate, whey protein isolate, egg White /

-

514Raman

microspectroscopy

6

8

10038537571254, 1299,13401393

1525, 1552

1649, 16851241, 1300,13631399

1537, 1562

1630, 1670

1244, 1297,133213741542

16521253, 1279,1332

1386

1552

1664

PhenylalanineTyrosineTryptophanAmide III (α-helix)Amide S (CαH) (α-helix)Amide II(α-helix)

Amide I (α-helix)Amide III (β-sheet)Amide S (β-sheet)

Amide II (β-sheet)

Amide I (β-sheet)

Amide III (β-turn)Amide S (β-turn)Amide II (β-turn)

Amide I (β-turn)Amide III (unordered)Amide S (unordered)Amide II (unordered)Amide I (unordered)

-----

-

(Amide I bands, mainly C=O stretching and particularly sensitive to H-bond donation to the C-O groups)

-

-(Amide II and III bands, in and out of phase combinations of C-N stretching and N-H in plane bending)

-

-

-

Myoglobin, Lysozyme, Cytochrome c, Concanavlin

A, Concanavalin A, Ribonuclease A , Trypsin , α- Chymotrypsin, Carbonic

anhydrase, Alcohol dehydrogenase , α-

Lactalbumin, Conalbumin / -

- / (Hemoglobin) Human blood

197, 206.5 UVRR-spectroscopy 7

1658-16501680-16651665-16601309, 1273

2938

α-helicesβ-sheetsRandom coilCα-C, C=O

CH2 asymmetric,

---

Stretching, plane bendingStretching

9

850, 830(I850/I830)322034002500

CH3 symmetric (aliphatic residues)

Tyrosine doublet

O-H symmetricO-H asymmetricO-D

--

StretchingStretchingStretching

Fish Surimi & gels 1064 FT-Raman Spectroscopy

8

937879856829

480

v(C-CN)v(C-CN)v(C-CN)γ(COO)

-

StretchingStretchingStretchingOut of plane bendingOut of plane bending

------

Meat 1064 FT-Raman 9

1265815,1032

974

1213

γ(C-H),R-HC=CH-R

C-C

=C-H

-

-Skeletal VibrationOut of plane deformationAnti-symmetric stretching

----

-

Meat 785 Raman 10

16541517

115396514502930293532203400

C=ON-H, C-N

C-N-

CH2,CH3,CHCH2,CH3,CHC-HO-HO-H

Amide IIn plane bending, StretchingStretchingAmide IIIBendingBending

-StretchingStretching

----------

Meat 514.5 Raman 11

1060-10801250-12701390-1440

CCC=C-HCH2

StretchingSymmetric RockScissoring

---

Fish 785 Raman 12

10

1600-16601700-1750

C=CC=O

StretchingStretching

--

8701122930

C-NC-CC-C

StretchingStretchingStretching

---

Ovine 671 Raman 13

1655-16501340940-9341668-16631243-1237

-C-HC-C

--

Amide IBendingStretchingAmide IAmide III

-----

Meat 785 Raman 14

16581262144710031043

941-944

848-868

1331-13391455-15991500-1200

1350

146014551263-1255

Amide IAmide IIC-HC-OHC-C-1-H

O-C-1-H

O-C-1-H

C-HCH2CH2-C-6-O-H, C-

5-C-6-H,C-O-H, C-C-HCOCOHCH2

-C-1-O-H, C-6-O-H

--

Bending-

Stretching, bendingStretching, bendingStretching, bending

-----

StretchingBendingBendingAmide I

-

--------------------

Bread 785 Raman 15

933450-5502800-31002934-2945

C-CS-SCHOH

-StretchingStretching

-

Gluten 1064 FT-Raman 16

11

15821360101487775712681207

852

850/830827

16051002622

IndoleIndoleIndoleCH2IndoleTyrosineTyrosine or PhenylalanineCCH

TyrosineCCH

PhenylalaninePhenylalanineC-S

RingRingRingRock/indole ringRing

---

Aromatic DeformationRingAliphatic deformation

-Ring BreatheStretching

Protein, Salt and Water 632.8 Raman 17

53062082010051600450930118012001580128015501600760,1005,135029301600

S-SPhePhePhe

-C-CC-CPhePheTrp

-Trp

-Trp, PheC-H

-

----

Amide IStretchingStretching

---

Amide III-

Amide I-

StretchingAmide I

Protein Extract and Winter Rye 785 Raman 18

3080-3200460-5101645-1690

OH-

Amide I

StretchingStretching

-

12

740-766

3300-34201580-16402800-3050

Tryptophan

OHOHCH

Ring Breathing VibrationStretchingBendingStretching

Bread 532 Raman 19

Table 2S. Raman spectra of some carbohydrates

Band position cm-1

Assignment of Bonds(Molecule/Group)

Mode of Vibration Strengthof bonds

Sample / Food Matrix Wavenumberof laser source (nm)

Type of Raman

References

272517431338866480

C-HC=OCH2OHCOC

-

Stretching vibrationStretching vibrationDeformation vibrationSymmetric stretchingSkeletal mode

----

Methyl group of acetylsubstituent/Starchacetate- / Starchacetate- / Starchacetate- / Starchacetate

1064 FT-Raman 20

29101460

14031381

1341

13051264

120511551127

C-HCH2C-HC-HC-OHCHCH2CH2C-OHC-HCH2C-OHCH2OHC-HC1–O–C4C-OH

Stretching vibrationTwisting deformationBendingDeformation bendingDeformationDeformation bendingScissor deformationTwisting deformationDeformation bendingDeformationDeformation

-(sidechain) relatedmodeDeformationAsymmetric

---

Shoulder-

-

--

-Shoulder

-

- / Starch- 1064 FT-Raman 21

13

1110

10841053

1003943910

865

770721411, 443, 480, 530, 576, 618

C-OHC-OC-CC-OC-HC-OHC-OHC-OHC-CCH2C1–O–C4C-OHCH2C1-HC1–O–C5CH2C-HC-CC-CC-C-O

stretchingStretching vibrationDeformationStretching vibrationRelated modeRelated modeRelated modeDeformation bendingStretching vibrationDeformationStretching vibrationRelated modeStretching vibrationDeformationDeformationDeformationStretching vibrationDeformationDeformationRing modeRing modeStretching vibration, pyranose ring skeletalmodes (deformation)

--

ShoulderShoulderShoulder

------

ShoulderShoulderShoulder

--------

30462800-3000165716571641810-975

O-HC-H

-C=CC=OC-C

Stretching,vibrationStretches

-StretchingvibrationStretchingvibrationstretches

------

Maleinated starchStarchAmyloseMaleinated starchMaleinated starchStarch

1064 FT-Raman 22

1456

13751332

-

--

-

--

-

--

glucose, fructose/ sport drinkα-anomer of glucoseα-anomer of glucose

633 Micro-Raman 23

14

126411281065918867836789742710634

----------

---------

-

----------

fructoseβ-anomer of glucoseβ-anomer of glucoseα-anomer of glucosefructoseα-anomer of glucoseα-anomer of glucoseothersucrosefructose

975 C-O-P Asymmetric stretching

strong Starch phosphate 1024 FT-Raman 24

3030970761

CH3(CH3)3N+

(CH3)3N+

Asymmetric stretchingAsymmetric stretchingSymmetric stretching

---

Cationicstarch / CationicQuaternary Ammonium Starch 785 Dispersive

Raman25

1459

1127

1127

856

480

CH2

C-O

C-O-H

C-C

Glucose

Deformation

Stretching

Deformation

Skeletal modes of α–glucoseVibration

decreasing in intensitydecreasing in intensitydecreasing in intensitydecreasing in intensitydisappearing of the band

Retrogradatedstarch

- FT-IR Raman 26

1607 C=O Stretching vibration - Carboxymethylatednon-starchpolysaccharides -

514 Laser 27

415

437

δ(C2-C1-O1), α-glucoseδ(C2-C1-O1) β-

glucose

Bending

Bending

---- Glucose

15

523838856820-950

1106

-ν(C-C)δ (C1-H1)ν(C-O)ν(C-C)δ (C-C-H)δ(C-C-O)δ(C-O-C)

Skeletal Vibration------

Angle Bending

--------

785 Dispersive Raman

28

314353631709800870102810541074

δ(C-C-C)δ(C-C-C)

-Fructoseν(C-C)C-O-Cν(C-O)ν(C-O)C-O-C

Ring VibrationRing VibrationRing DeformationSkeletal Vibration

-----

---------

Fructose 785 Dispersive Raman

28

4195447448001127

δ(C-C-O)α-glycosidic bondν(C-C)ν(C-C)C-OH

Ring Vibration---

Deformation

-----

Sucrose 785 Dispersive Raman

28

32001640287829292972145410961054883146211301050-1080

O-H,WaterO-H,WaterCH2-CH3,EthanolCH2-CH3,EthanolCH2-CH3,EthanolCH2-CH3,EthanolCH3,EthanolC-O,EthanolC-C,EthanolCH2 SugarC-C,C-O, SugarC-C,C-O, Sugar

StretchingStretchingStretchingStretchingStretchingStretchingRocking VibrationStretchingStretchingBendingBendingBending

------------

Wine 1064 FT-Raman 28

16

144916591004161010951120480901160416313420858894

CH2C=O

--

COCCOC

---

C=COHP-OHP-OH

BendingStretchingBreathingStretchingStretchingStretchingSkeletal VibrationSkeletal VibrationAromatic RingStrechingStretchingStretchingStretching

--------

Barley and Wheat

532 Raman 29

13581453

C-HC-H

--

--

Hydroxypropyl methylcellulose - Raman 30

47811509441130

C-O-C, δ(C-C-O)va(C-O-C)vs(C-O-C)v(C-OH)v(C-O)δ(C-OH)

Skeletal ModeStretchingStretchingStretching and In plane bending

----

Cereal Starch 785 Raman 31

15025010301130

----

----

----

Mannitol 785 Raman 32

17

Table 3S. Raman spectra of some lipids

Band position cm-1

Assignment of Bonds(Molecule/Group)

Mode of Vibration Strengthof bonds

Sample / Food Matrix Wavenumberof laser source (nm)

Type of Raman

References

3020

3007

2943

2870-2840

1665-16301480-144012961269

=C-H

=C-H

-CH2

-CH2

C=CCH2=CH2=C-H

Asymmetric stretching vibrationSymmetric stretching vibrationAsymmetric stretching vibrationSymmetric stretching vibrationStretching vibrationScissoring vibrationDeformation in planeSymmetric rocking

Medium-Strong

Medium

Medium

Strong –very strongMedium -strongVery weakShoulderShoulder

- / Animal fat 1064 FT-Raman 33

1670

16581266

C=C

C=CCH=CH

Stretching vibration

Stretching vibrationSymmetric rock

-

--

trans-olefin / soybean oilcis-olefincis-olefin

1064 FT-Raman 34

3015

2931

2898

2852

=C-H

CH2

CH3

CH2

Stretching vibration

Asymmetric stretching

Symmetric stretching

Symmetric stretching

-

-

-

-

cis-olefinic group / Hake Lipidmethyl and methylene groups in aliphatic moleculesmethyl and methylene groupsin aliphatic moleculesmethyl and methylene groups in aliphatic molecules

1064 FT-Raman 35

18

174616581440130112661079970928868

C=OC=CCH2CH2=CHCCCCCCCCCCCC

Stretching vibrationStretching vibrationScissoring vibrationtwisting motionsymmetric rock (cis)Asymmetric stretchingSymmetric stretchingSymmetric stretchingSymmetric stretching

StrongStrong

-------

esters---------

3015

2970

2940

290028601750167016601445131012751100-1000900-800

=C-H

C-H

C-H

C-HC-HC=OC=CC=CC-HC-H=C-HC-CC-C

Asymmetric stretchingAsymmetric stretchingAsymmetric stretchingSymmetric stretchingSymmetric stretchingStretching vibrationStretching vibrationStretching vibrationDeformationDeformationDeformationStretching vibrationStretching vibration

-

-

-

----------

Edible oil 1064 FT-Raman 36

1657144013011267

1076

1064

C=CCH2CH2=C-H

CCC

CCC

Stretching vibrationScissoring vibrationPhase twistSymmetric rock (cis)

Stretching vibration

Stretching vibration

StrongStrongStrongStrong

Strong

Strong

Lipid / Fish SalmonCarotenoidsCarotenoids Collagen (phenylalanine)Collagen (peptide backbone)Collagen (proline)

785 Raman 37

19

115915181004940857

---

C-C-

---

Stretching vibration-

StrongStrongWeakWeakWeak

30602927290028531745166516541455130312621121108210651005860-920

445355

N-HC-HC-HC-HC=OAmide IC=CCH2CH2Amide IIIC-CC-CC-CPhenylalanineC-CC-OCH3Phenylalanine

vibrationvibrationvibrationvibrationvibration

-VibrationScissor deformationTwisting deformation

-VibrationVibrationVibrationRing breathingVibrationVibrationRockingRing breathing

--

--------------------

Protein / Milk Powder---

FatProtein

---

Protein---

Protein----

Lactose

1024 FT-Raman 38

20

161814571379133964714601380126110658757401701

1428

75616111209804146012611065870760

ν (C=C)---

δ (ring)-----

δ (ring)ν(nonconjugated C=C)Methyl and isopropyl C-H bending appears as a double broad bandδ (ring)ν (ring)δ (ring)δ (ring)

----

δ (ring)

---------------------------

---------------------------

PulegonePulegonePulegonePulegonePulegoneThymolThymolThymolThymolThymolThymolγ-Terpinene

γ-Terpinene

γ-Terpinenep-Cymenep-Cymenep-CymeneCarvacrolCarvacrolCarvacrolCarvacrolCarvacrol

785 Dispersive Raman

39

718724840908

C=C-H out of planeνs(C-C)ν(C-C)

----

----

linoleic acidlinoleic acidlinoleic acidlinoleic acid

21

94998010641078144028853011

ν(C-C), Cα-atom--

νas(C-C)transν(C-C) CH2 scissoringνs(CH2)ν(=C-H)

-------

-----

strong-

linoleic acidlinoleic acidlinoleic acidlinoleic acidlinoleic acidlinoleic acid

514.5 Raman 40

1265130014401650174710081150152528502950

3015

δ(C-H)C-Hδ(C-H)v(C=C)v(C=O)C-CH3C-CC=Cv(C-H)v(C-H)

=C-H

-BendingScissoring

---

StretchingStretchingSymmetric StretchingAsymmetric StretchingSymmetric Scissoring

Carotenoid in olive oil 514.5 Raman 41

Table 4S. Raman spectra of some vitamins

Band position cm-1

Assignment of Bonds(Molecule/Group)

Mode of Vibration Strengthof bonds

Sample / Food Matrix Wavenumberof laser source (nm)

Type of Raman

References

811811104430872932

C-H bendC=C-C bendC-C-C bendC-H stretchC-Hstretch

Ring breathingRing-related vibrationTrigonal

--

-----

Vitamin B3/-Vitamin B3/-Nicotinic acid/-VitaminB3/-VitaminB6/-

1064 FT-Raman 42

22

1507 Cyanocobalamin bands

Ring vibration strong VitaminB12/-360 Resonance

raman 43

1582/15932845/2865

1635/1655

Aromatic partCHstretch,(CH, polymethylene chain)C=C,C=O bend

chromanol ring-

Vibrational mode of quinone group

--

strong

alfa-tocopherol/-Vitamin E/-

Vitamin E/- 633 Raman 44

30001580/1590

C-H stretchTerminal group

--

--

Vitamin A/-retinol,retinal,retinoic acid/- -

Laser-excited raman spectra

45

111317581193166113231258

1484984

C-O-C stretchingC=O stretchC-C(=O)-O stretchingC=C stretchCH bending (wagging)C-O-H bending (twisting)CH bendingC-H,O-H bending

-Lactone ring

----

--

strongweakweakstrongstrongstrong

mediumstrong

Vitamin C/- - FT-Raman 46

338029161751165914571257

1126

O-H stretchingC-H stretchingC=O stretchingC=CC-H bendingC-H bending(wisting)C-O-C stretching

---

Ring stretching--

-

weakstrongweakweakmediummedium

medium

Vitamin C/- 1064 FT-Raman 47

23

1034934/871/825710/633

C-O-HbendingC-CC-C

-Ring stretching Ring stretching

weakmediumMedium

16541259

C4=O uracilC2-N3-C4 stretc+N3-H bend

NH3 bending vibrationalvibrational

-- Riboflavin/- 266

Red-excited raman

spectrum 48

Table 5S. Raman spectra of microorganisms and viruses

Band position,cm-1

Assignment of Bonds(Molecule/Group)

Mode of Vibration

Strengthof bonds

Sample/Food Matrix

Wavenumberof laser source

(nm)

Type of Raman References

~722 CH2 Rocking 746 -~778 Cytosine, urasil ring stretching -850 CC ring breathing

COC 1,4 Glycosidic linkStretching

1001 CC aromatic ring breathing(phenylalanine)

Stretching

1125 COC symmetric glycosidic link(C-N) and (C-C)

Stretching Staphylococcus strains/-

1200-1280 Amide III -~1327 C-H Deformation 1440-1460 CH2 scissoring Deformation 1575 Amide II

Guanine, adenine ring stretching-

1650-1680 Amide I -2935 CH2 assymetric Stretching 3060 CH olefinic Stretching

532 Micro-Raman 49

856 C-C stretching -1088 C-C Stretching1304 C-H stretching bending1458 C-H stretching bending

Bacteria, yeast and mold/- 1064 FT-Raman 50

24

1658 C=C stretching Stretching2931 C-H Stretching3379 O-H Stretching1528 C=C Stretching R. mucilaginosa -

β caroten/-1508 C=C Stretching M. luteus -

sarcinaxantin/-1156 C-C Stretching R. mucilaginosa -

β caroten/-1151 C-C Stretching M. luteus -

sarcinaxantin/-1003 C-C of the

C-CH3 groupStretching R. mucilaginosa-β

caroten/-1001 C-C of the

C-CH3 groupStretching M. luteus-

sarcinaxantin/-1660 Amide I - B. sphaericus/-1445 CH2 scissor mode - B. sphaericus/-1002 Aromatic ring breathing mode - B. sphaericus/-1449 CH2 Deformation B. subtilis/-

633 Confocal Raman

51

3059 C=C–H aromatic Stretching2975 CH3 Stretching2935 C–H Stretching2870–2890 CH2 Stretching1735 >C=O ester Stretching1650–1680 Amide I -1614 Tyrosine -1605–1606 Phenylalanine -1582, 1593 Protein -1575–1578 Guanine, adenine ring stretching E. feacalis/-1440–1460 C–H2 deformation1129 C-C, C-N stretching1102 > PO2ˉ Symetric

stretching1098 CC skeletal, and COC stretching from

glycosidic link

1064 FT-Raman

52

25

1085 C–O stretching1061 C–N and C–C Stretching1004 Phenylalanine -897 COC stretching858 CC str, COC 1,4 glycosidic link -852 Buried tyrosine -829 Exposed tyrosine -785 Cytosine, uracil ring, stretching720 Adenine -665 Guanine -640 Tyrosine (skeletal) -620 Phenylalanine (skeletal) -540 COC glycosidic ring

deformation520–540 S–S stretching1172 Tyrosine -1247 Guanine, adenine, urasil -1324 Guanine, adenine, tyrosine -1359 Thymine, adenine -1475 Guanine, adenine -1524 Cytosine -1567 Guanine, adenine -1607 Tyrosine, tryptophan -1638 Thymine -

Bacillus species/- 244UV-

Resonance Raman

53

1573 C=C, N–H, and C–N str (amide II) N–H deformation C–N streching

1482–1487 Nucleic acids -~1320 Amide III, C–H deformation1220–1290 Amide III random, lipids -1030-1130 Carbohydrates, –C–C– (skeletal),

C–O, def(C–O–H)C–O–H deformation

~1130 =C–C= (unsaturated fatty acids in lipids) -810–820 Nucleic acids (C–O–P–O–C in RNA

backbone)-

550 Range glass background -

Clostridium species/- 633 Confocal

Raman 54, 55

26

481 Skeletal modes of carbohydrates (starch) -407 Skeletal modes of carbohydrates

(glucose)-

757 Tryptophan W18785 Thymine, cytosine Ring stretching853 Tyrosine Ring stretching876 Tryptophan W17, N1H

deformation1010 Tryptophan W16, CC 1178 Tyrosine Y9a1205 Tyrosine Y7a1239 Tryptophan W101243 Thymine C2N3 stretching1307 Adenine C8H deformation1335 Adenine N7C5 stretching,

C8N7 stretching1372 Adenine, Guanine, Thymine C1N9 stretching,

C6N6 stretching1420 Adenine C4C9 stretching,

C8H deformation1483 Adenine C2H deformation,

N9C8 stretching

1507 Adenine N7C8 stretching1530 Cytosine, Guanine N3C4 stretching1560 Tryptophan W3, C2C3

stretching1575 Guanine, Adenine, Tryptophan C5C4, C4N3

stretching, W21616 Tryptophan, Tyrosine W1, Y8a1646 Thymine, Cytosine C4=O, C5=C6

stretching

fd virus/- 257 UVRR 56

1660 Amide I Protein - 1572 Guanin/adenin Ring Stretching

27

1448 CH2 Deformation1240 C-C and C-N

Adenin/Timin

Amide I - Natural Mineral Water Raman 57

1003 - Ring Breathing mode of phenylalanine

780 O-P-O - 720 Adenin -2975

2931

2870-2890

1735 16691614 160515751450

1360 1332131412361208 11751124

1098

1030

CH3 str

CH3 and CH2 str

CH2 str

-C=O str Amide I Tyr, Phe, Phenylalanine (ring str),Guanine, adenine (ring str)CH2 def scissoring

Tryptophan (indole ring str)Cytosine, uracil (ring str)CH2 def Amide III T,C,A,Tyr, PheT, GC-N str, C-C str skeletal trans Conformation>PO-

2 str (sym) CC skeletal and COC str from glycosidic link Phenylalanine, CC skeletal cis conformation

-

-

-

------

-------------

Protein, carbohydrate, lipids, cell wall Protein, carbohydrate, lipids, cell wall Protein, carbohydrate, lipids, cell wallPHB ProteinProtein Protein DNA / RNA Protein, carbohydrate, lipids, cell wall ProteinDNA / RNA ProteinProteinProteinDNA / RNA Protein, carbohydrate, lipids, cell wall Nucleic acids and Cell wall

Protein and Cell wall

532 Raman 58

28

1006950852826778745723695665640620560

540

Phenylalanine, TryptophanPolysaccharide, DNA backbone “buried” tyrosine “exposed” tyrosine Cytosine, uracil (ring stretching) Adenine, thymineAdenineGuanine Thymine, guanineTyrosine (skeletal) Phenylalanine (skeletal) COC glycosidic ring def

S-S str - disulfide conformation

------------

-

ProteinPolysaccharide, DNA Protein Protein DNA / RNA DNA / RNA DNA / RNA DNA / RNA DNA / RNA Protein ProteinProtein, carbohydrate, lipids, cell wall Protein

16561437130012621742

-CH2CH2=CHC=O

StretchingDeformationTorsionDeformationStretching

Oil 532 Micro Raman 59

2900165014201007138514401565153211571005

C-H-

CH2-

C-O-C--

C=CC-CC-CH3

StretchingAmide IDeformationRing BreathingStretchingRingRing

--

Deformation

- -

--------

- Micro Raman 60

2933165915781447

CH2, CH--

C-H

-Amide I

--

----

29

1317,124310941003785

--

PheDNA-RNA

Amide III---

----

532.11

Raman 61

Table 6S. Raman spectra of toxins and chemicals

Band position cm-1

Assignment of Bonds(Molecule/Group)

Mode of Vibration Strengthof bonds

Sample / Food Matrix Wavenumberof laser source (nm)

Type of Raman

References

145012501083, 1105, 1128, 1157510, 525, 540

C-HAmide IIIC-NS-S

Bending--

Streching

Ricin and ricin aggluitinin/ Ricinus communis seeds 488 Raman

Laser 62

993, 1348, 1591624, 1003, 1065786, 1449, 16071393

----

----

ZhibaoboshiChongmanjue

Abameclin PetroleumoilCypermethrin

/pear,grapes, apple, longan, spicy-pear, Chinese

goosebeery, orange, banana etc.

1064 FT-Raman 63

1068

1220.7

B–O

C–O

Symmetric strechingAsymmetric streching T-2 Toxin/- 785 Raman

Microscope 64

934 Cl-O Symmetric streching

Perchlorate /Ground waters 670 Raman

65

30

708665490215819963

NH2H2CC-OC-OCHCH2

TwistingTwistingTorsionTorsionWaggingWagging

WeakWeak

-WeakMediumWeak

Acrylamide/- 514.5-488 Raman laser 66

3066292116991571

2983-3050119496

CHCH3C=OC-C

CH2BrCH2BrCH3

StrechingAsymetric strechStrechingStrechingSkel defStrechingDeformationTorsion Skel def

StrongMediumStrongVery strong

WeakStrongVery strong

6-Methyl-4-bromomethylcoumarin/- 1064 FT-Raman 67

766399, 756, 1407386, 745, 1386582,1393, and 1622

----

----

StrongStrong

Naphthalene/-Anthracene/-

Phenanthrene/-Pyrene/- 1064

UV resonance

Raman 68

1513, 1156, 1008

1406, 1142, 407

3054, 1627, 1594, 592

1401, 394

3055, 1381

1576, 1463, 1020

ν (C C), ν (C–C), (C–CH3)

C C, CH

C C, CCC

CH, C C

C=C ,=C–H

Stretching, Stretching rocking

in-plane vibration, skeletal ring vibrations, bending

in-plane vibration, bending

stretching, in-plane vibrationstretching, in-plane deformation vibration

Strong, strongmedium

StrongMedium

Strong, medium

Strong

medium

Beta-carotene/-

Pyrene/-

Anthracene/-

Napthalene/-

1064 FT-Raman 69

31

6867608289561440146016121760

C-HC-H-ν(C-C)β (C-H)β (C-H)ν(C-C)ν(C=O)

out of plane bendingout of plane bendingring deformation

-ring modering modering modering mode

--------

Aflatoxin in maize 785 Raman 70

3015293828441454121610661036946786712615576

CH3CH3CH3CH3v(PO)2+ CH3CH3CH3v(CO3)+vO3PvSC + NH2vO3+NH2vPS+vNPvCS+vPS

----

Stretching--

StretchingStretchingStretchingStretchingStretching

Metamidophos 633 Raman

71

3261325232653112

2974293928712719318230873019298229722935

N-HN-HN-HvC52-H+vC53-HvC51-HvC51-HvsC-HvsC-HvsCH3vC52(53)-HvC51-HvC52(53)-HvC51-HvC31-H+vC32-

StretchingStretchingStretching

-

-----

StretchingStretchingStretchingStretchingStretching

32

2913

2874276024613100

297629382877274624571610

1599

1550

14481388137813431168112710849931343,1310,1251,1168924648

25316211606

H+vC33-HvC51-H+vC52-H+vC53-HC-HδH-C-CvC31-HvC52-H+vC51-HvcC52(C32)-Hvs(C51(C31)-HC-Hv(C-H)v(C-C)δC3-N3-H

δC5-N5-H

vC5-N6, vC3-N2δCH3 δCH3 δC-C-HvC-ClδC-C-HδC-C-HδN-C-HδC-C-HvC1-C1

vC-ClδN6-C1-N2, δC5-N4-C3C53-H, C52-HδC3-N3-HδC5-N5-

Stretching

StretchingStretchingStretchingStretching

StretchingStretchingStretchingStretchingStretchingDeformation in plane

Deformation in plane

In phase, in plane

In plane bendingIn plane bendingIn plane bendingStretchingIn plane bendingIn plane bendingIn plane bendingIn plane bendingStretching

StretchingIn plane bending

-In plane bendingIn plane bending

Atrazine, Prometryn, Simetryn triazine 1064 Raman 72

33

158115471462135011821133971993

vC5-N6vC3-N2δCH3δC-C-HC-SC-S--

Out of and in phaseOut of and in phaseIn plane bendingIn plane bendingStretchingStretchingRing BreathingRing Breathing

<700

82895610801400-1500

-

-v(C-C)v(C-O)β (C-H)

Skeletal modes of ring structureRing deformation

--

Ring mode

Maize 785 Raman

73

Table 7S. Raman spectra of food additives

Band position cm-1

Assignment of Bonds(Molecule/Group)

Mode of Vibration Strengthof bonds

Sample / Food Matrix Wavenumberof laser source (nm)

Type of Raman

References

- C=C C=C Stretching - Astaxanthin and Cantaxanthin/

Salmon-

Resonance Raman 74

1600

1575

1515

1459

1442

-

-

-

-

-

Naph (1) ring stretchingNaph (2) ring stretchingO12–H19 i. p. bend + Naph (2) ring stretchingNaph (1) ring stretchingC3–O12 stretching +

Naph (2) ring stretchingN11–N28 stretching +

Naph (2) stretchingC2–N11 stretching +

Strong

Very Strong

Very Strong

Strong

Strong

Amaranth/- - FT-Raman 75

34

1365

1300

1240

-

-

-

CH Naph (2) i.p.bending

CH Naph (1) i.p.bending + C29–N28 stretching

Very very StrongStrong

Very Strong1598

150213571129

-

-C–N8=N9–C-

Phenyl ring stretching

Phenyl ring bendingStretchingOut of plane C-H deformation

Very strong

StrongStrongStrong

Tartrazine/- 1064 FT-Raman76

1500-1700 - - Strong Deuterated maltol/- 1064 FT-Raman 77

3100-3350 O-H Stretching Very veak Maltol/- 1064 FT-Raman 77

2943

1407

1341

931

180

-

COO-

-

-

COO-

Symmetrical CH2 stretchingSymmetrical stretchingCH2 deformation

Completely ionized formTwisting

Very strong

Very strong

Strong

Strong

Very very strong

Monosodium glutamate/- 514.5

Raman micro-

spectrometer

78

3063

3054

2955

2948

CH

CH

C6H2, C5H

C6H2

Symmetrical phenyl ringIn plane phenyl ring bendingSymmetrical phenyl ringSymmetrical phenyl

Strong

Strong

Strong

Very strong

Aspartame/-514.5

Raman microspectr

ometer79

35

1005

90

61

57

42

C5C6C13

CH3

-

-

-

ringTorsion

Rocking

Skeletal deformation

Skeletal deformation

C13O19, C13O18, CH3 deformation

Very very strongVery very strongVery very strongVery very strongVery very strong

16531585

14621442140813061258748663632

C=OCOOH

CH2 and CH3CH2 and CH3C-CC-HCOHCH2 COOHCOH

StretchingAsymmetric stretching vibrationDeformationsDeformationsStretchingIn-plane deformationWaggingRockingWaggingDeformatiion bending

StrongWeak

Very strongVery strongVery strongStrongMediumVery strongStrongMedium

HMB/- 514.5 Conventional Raman

80

1584

1463138512451195

971948

913772634

COOH

CH3C-CCOHCCO

C-N+ (CH3)3C-N+ (CH3)3

C-COOHCH2COH

Asymmetrical stretchingDeformationStretchingWaggingOut of plane stretchingStretchingAsymmetrical stretchingStretchingRockingDeformation bending

Strong

Very strongStrongStrongStrong

StrongStrong

StrongVery strongStrong

L-carnitine/- 514.5 Conventional Raman

80

36

5225051610-17001225-1330

S-SS-SAmide IAmide III

----

---- Human Serum Albumin

785

Raman 81

33543292289227361468

14141379

13381292-1267-1241

1153-1119-1095-1056-1036-1026-995-972-911-898

457437-379-352

v(OH)HB v(OH)HBv(CH2)v(CH)δ(CH)+ω(CH2)+ δ(OH)

δ(CH)+ δ(OH)δ(CH2)+δ(CH)+ δ(OH)+v(Φ)δ(CH)δ(OH...O)+v(C-C)+v(C-O)+ δ(CH)+ρ(CH2)v(C-O-C)+v(Φ)+v(C-OH)+v(C-CH2)+ δ(CH)+ρ(CH2)δ(COC)γ(OH)+γ(ϕ)

StretchingStretchingStretchingStretchingIn plane bending+out of plane bending

In-plane bendingIn-plane bending+StretchingIn-plane bendingIn-plane bending+stretching

Stretching+ In-plane bending

In-plane bendingOut of plane bending

--------------------

Cellulose - FT-Raman 82

2963293528802719165616201451

14151377

v(CH3)v(CH3)v(CH2)v(CH)v(CO)AmIδ(NH)δ(CH)+ω(CH2)+ δ(OH)δ(CH3)+ δ(CH)δ(CH2)+

StretchingStretchingStretchingStretchingStretchingIn plane bendingIn plane +out of plane bendingIn plane bendingIn plane

----------

37

1326

1265+1204

1150+1112+1057

1043

954896710

661+647+597

501

451+397+366+325253

δ(CH)+ δ(OH)+v(ϕ)v(CN)+ δ(CH)δ(OH..O)+v(C-C)+v(C-O)+ δ(CH)+ρ(CH2)v(C-O-C)+v(ϕ)+v(C-OH)+v(C-CH2)+ δ(CH)+ρ(CH2)+ρ (CH3)ρ(CH3) +δ(CH)+ δ(OH)v(CN)v(ϕ)+ρ(CH2)ω(NH2)+ δ(ϕ)

γ(OH..O)

δ(CO-NH)+ δ(C-CH3)γ(OH)+γ(ϕ)

δ(C-NH-C)+γ(OH)

bending+StretchingIn plane bending+StretchingIn plane bending+Stretching

In plane bending+Stretching

In plane bending

StretchingStretchingIn and out of plane bendingOut of plane bending

In plane bending

Out of plane bending

In and out of plane bending

-----

--

-

-----

-

-

-

Chitin - FT-Raman 82

33622932288528182743165415911458

v(OH)HBv(NH2)v(CH2)v(NH2)v(CH)v(CO)δ(NH2)δ(CH)+ω(CH2)+ δ(CH)+ δ(OH)

StretchingStretchingStretchingStretchingStretchingStretchingIn plane bendingIn and out out plane bending

---------

38

14111377

1325

1263

1146+1114+1093

1044

991

936896703

566

493

479444+424+357

285

δ(CH3)+ δ(CH)δ(CH2)+ δ(CH)+ δ(OH)+v(ϕ)v(CN)+ δ(CH)

δ(OH...O)+v(C-C)+v(C-O)+ δ(CH)+ρ(CH2)v(C-O-C)+v(ϕ)+v(C-OH)+v(C-CH2)+ δ(CH)+ ρ(CH3)+ ρ(CH2)v(ϕ)+ δ(CH)+ δ(OH)v(ϕ)+ δ(CH)

v(CN)v(ϕ)+ρ(CH2)ω(NH2)+δ(ϕ)

γ(NH)+ v(C=O)+ω(CH3)

δ(CO-NH)+ δ(C-CH3)δ(COC)γ(OH)+ γ(ϕ)

δ(C-NH-C)+ γ(OH)

In plane bendingIn plane bending and stretchingIn plane bending and stretchingIn plane bending and stretching

In plane bending and stretching

In plane bending and stretchingIn plane bending and stretchingStretchingStretchingIn and out of plane bendingIn and out of plane bending and stretchingIn plane bending

In plane bendingOut of plane bendingIn and out of plane bending

------------------------------

Chitosan FT-Raman

82

1151

1250

δ(CCH), δ(C-OH)δ(CH) of C=CH,

In plane bending

In plane bending and

-

-

39

1317143016001627

v(CCH)δ(CCH)δ(CCC), δ(CCH), v(C=C)v(C=C), v(C=O)

stretchingIn plane bendingIn plane bendingStretchingStretching

----

Curcumin 785 FT-Raman

83

152811631009958

---C-H

---

Out of plan

----

Carrot Roots 532 Raman84

962

1120

1332

1574

1712

δC-N=N+v(C-N)δH-N-H+v(C=O+v(C-N)δH-N-H+vC-N+δN-C=OvN=NδN-H+vC=OvC=O+vC-N

In plane bending, stretching

-

In plane bending, stretching

-

Stretching

Azodicarbonamide 785 Raman 85

602

984

1092

1242

1602

1676

δN-C=O+δN-C-N+δC-N-NvC-N+δC-N-N

δNH2+vC-N+vC=OvN-NvC-N+vN-N+δN-HvC-N+δN-H+vC=OvC-N+δN-H+vC=O

In plane bending

In plane bending, stretchingIn plane bending, stretchingStretchingIn plane bending, stretchingIn plane bending, stretchingIn plane bending, stretching

Biurea 785 Raman 85

508716936

δN-C=O+δN-HδC-N+δN-HvC-N

In plane bendingIn plane bendingStretching

Semicarbazide hydrochloride 785 Raman 85

40

1098118412241388

15381952

vC-NvC-NvC-NvC-N,δN-C=O,δN-HδN-HvN-H

StretchingStretchingStretchingIn plane bending, stretchingIn plane bendingStretching

172013501200-1415

11161094112333112885291710701014580610823834

C=OHCOCH2,HCC,HCO,COH--C=ON-HC-HC-HO=S=OO=S=OO=S=OO=S=OC-O-SC-O-S

Stretching-

Deformation, StretchingSymmetric StretchingSymmetric StretchingStretching

-StretchingStretching StretchingStretchingDeformationDeformationStretchingStretching

Chitosan 1064 FT Raman 86

41

Table 8S. Raman spectra of raw material

Band position cm-1

Assignment of Bonds(Molecule/Group)

Mode of Vibration

Strengthof bonds

Sample / Food Matrix Wavenumberof laser source (nm)

Type of Raman References

1745

1655

14421265

1301

C=O

cis C=C

CH2 bend=CH

=CH

Stretching vibrationStretching vibrationBending vibrationIn-plane deformation(CH2) wagging, twisting

Weak

Medium

StrongMedium

Medium

- / Marama Bean Oil 1064 FT-Raman 87

10081156126713021442152216551747

HC-CH3-(CH2)n-cis RHC=CHR-CH2-CH2RHC=CHRcis RHC=CHRRC=OOR

CH3 bendingC-C stretching=C-H bendingC-H bendingC-H bendingC=C stretchingC=C stretchingC=O stretching

WeakMediumWeakMediumStrongMediumStrongMedium

- / Oil 532 Confocal Raman 88

353

423

518630704775824866

Unknown carbohydrate and proteinUnknown carbohydrate and proteinUnknown carbohydrateUnknown carbohydrateUnknown carbohydrateUnknown carbohydrateUnknown C(1)H

-

-

-----

Bending

Weak

Strong

StrongStrongWeakWeakWeakWeak

- / Honey 1064 FT-Raman 89

42

9159811072

1126

1267

13741461

29453384

C(1)H and COHUnknownC(1)H and COHC-N (protein or amino acids)Unknown carbohydrateC-N (protein or amino acids)C(6)OH and C(1)OHAmide III (peptide bond)CH and OHCH2COO-CHOH

-Bending

-

-

-Bending

Bending-

StretchingStretchingStretching

WeakWeakMedium

Medium

MediumMedium

MediumStrongStrongMediumWeak

3013

2909

1750166012941447

=C-H

C-H

C=OC=Ccis =C-HC-H

Stretching asymmetryStretching asymmetryStretchingStrechingBendingBending

Medium

Strong

WeakMediumWeakMedium

- / Edible Oils 1064 FT-Raman 90

1605163011201165119312701690290529343010

Phenyl RingC=CCyclohexane CH, COH Phenyl ringPhenyl ring CH, COHPhenyl ringC=OCH2 of lipidsCH2 of lipidsEthylenic group

StretchingStretchingBendingBendingBendingDistortion vibrationStretchingSymmetric VibrationAsymmetric

StrongStrongMediumMediumMediumMediumMediumStrongStrongWeak

- / Coffee 514.5 Micro Raman 91

43

Vibration

3008292328932851175016571440

1302

1266

Ethylenic groupC-H C-H C-H C=OC=CCH3

CH2

CH

StretchingStretching Stretching Stretching StretchingStretchingDeformation vibration Deformation vibration Deformation vibration

MediumStrongStrongStrongMediumWeakMedium

Weak

Weak

- / Coffee 1064 FT-Raman 92

879103010791019921

C-CC-OCH3C-OC-C

StretchingStretchingRockingStretchingSkeletal vibration

StrongMediumWeakMediumWeak

- / Alcoholic beverage 785 Raman 93

317341415-437

776

790976-10281106

C–C–CC–C–O ring modeC2–C1–O1

C-C

C1-H1C-OC-O-C

DeformationDeformationDeformation bending StretchingdeformationStretchingAngel-bending model-deformation

--------

Glucose / Honey 785 Raman 94

44

314-35341974480091193310281054

C-C-C ring vibrationC-C-O Ring vibrationC-CC-CCOHC-OC-OC-O

deformationdeformationstretchingstretchingdeformationstretchingstretchingstretching

--------

Fructose / Honey 785 Raman 94

3414345448428551028

C-C-O Ring modeC2–C1–O1α-glycosidic bondC-CC1-H1C-O

DeformationDeformation

StretchingDeformationStretching vibration of glucose ring

------

Maltose / Honey 785 Raman 94

4515201063

C–C–OC2–C1–O1C–O

DeformationDeformationStretching

--- Glucose / Grape Juices 785 Raman 95

629710821870

CCO exoCCOC-CC-C

DeformationDeformationStretchingStretching

----

Fructose / Grape Juices 785 Raman 95

87910301079

C-CC-OCH3

StretchingStretchingRocking

StrongWeakWeak

Ethanol / Grape Juices 785 Raman 95

891632

C-C Stretching Strong weak

Acetic acid / Grape Juices 785 Raman 95

45

300030923008167615001379,1293, 797

C-H=C-HC-H, C=CC=C-C-H,C-C

StretchingStretchingStretchingStretchingStretching

-

------

- / Oil 785 Raman 96

932974

12661302144216621262

C-C=C-H

=C-HCH2CH2C=C=C-H

StretchingOut of plan deformationSymmetric rockTwistingScissoringStretchingStretching

--------

- / Caviar 785 Raman 97

160416301690

1656

14791567

C=CC=C-

-

--

StretchingStretchingamide I bands of β-sheetamide I bands of - α-helix --

---

-

--

Kahweol / Green Arabica and Robusta Coffee Beans

1064 FT-Raman 98

85310031065115811681267130314391521158716051623

v(C-O-C)v(C-CH3)v(C-C)v(C-C)Ring δ(CH)δ(=C-H)τ(CH2)δ(CH2)v(C=C)Aromatic v(C-C)Aromatic RingC=C

Stretching Stretching Stretching StretchingDeformation DeformationTwistingDeformationStretchingStretching

-Stretching

------------

99

46

163017202727285329042921915

1623

7449159589649851325137115538539589641007106211561167126914411518158516061720231128542906

v(C=C)v(C=O)v(CH)v(CH2)v(CH3)v(CH2)C-C-C

C=C

δ(N-C-C)δ(C-C-C)--δ(CH3)δ(CH)ω(CH2)v(C=C)vas(C-O-C)pip(CH3)(v4)pip(CH3)(v4)v(C-CH3)(v3)v(C-C)v(C-C)(v2)Ring δip(CH)V4 δip(=C-H)δ(CH2)v(C=C)(v1)v(C-C)Ringv(C=O)2v2v(CH2)v(CH3)

StretchingStretchingStretchingStretchingStretchingStretchingBending DeformationStretching

DeformationDeformation

--

DeformationDeformationWagginhStretchingStretching In plane rockingIn plane rockingStretchingStretchingStretchingDeformationDeformationDeformationStretchingStretching

-StretchingStretchingStretchingStretching

------

-

---

--------------------

Organic Compounds / Red and Green Tomato

Organic Compounds / Red and Green Tomato

514

785

Confocal Raman

Confocal Raman

47

1078, 11241657

C-C, C-N, C-OAmide I

--

--

Protein and Oil / Soybean 785 Raman 100

124119973275326133003397-33091132-12071196

N-HO-HN-HN-HN-HO-HAmide IIIC-O, C-O-C, NH2

StretchingStretchingStretchingStretchingStretchingStretchingStretchingStretching

--------

- / Meat 633 Raman 101

220-200107811221155-960922

867

CH2-OHC-OC-OP-OHP-O-C

P-O-C

Torsial VibrationStretchingStretchingStretchingAsymmetric StretchingSymmetric Stretching

--------

- / Yogurt 785 Raman 102

23361557416029251391

--H-HC-HC=O

--

StretchingStretchingStretching

-----

- / Fermentation Gases 488 Raman 103

48

137415851632137013801630

------

Stretching StretchingStretching Stretching Stretching Stretching

------

Nitrosylmyoglobin / Meat 457.9 Resonance Raman 104

12671302

144216551747

cis δ(=CH)-

δ(CH2)v(C=C)v(C=O)

Symmetric rockIn-phase twist methyleneScissoringScissoringStretching

--

---

Oxidation Parameters / Olive oil 785 Raman 105

2126739731009

----

----

----

Adulterants / Dry Milk 785 Raman 106

514

530

547

630–670

825, 852 758, 882 932100310341063112612441304

ν S–S gauche–gauche–gauche conformationν S–S gauche–gauche–trans conformationν S–S trans–gauche–trans conformationν S–S gauche conformation Tyr ν-ring Trp ν-ring νCC α-helix Phe ν-ring Phe ν-ring νCN, νCH νCN Amide III (β-helix) Amide III (α-helix) δCH

-

-

-

-

-----------

-

-

-

-

-----------

Myofibrillar proteins / Pork 514.5 Raman 107

49

1322, 1340 1410 1450

1600–1700 2936

νCOO− Asp, Glu δasCH3, δCH2, and δCH Amide I νCH3, νCH2, and νCH2

-

---

-

---

174916511439

1303

1267

100911501523

υ (C=O) v(C=C)CH2

CH2

δ (=C-H)

C-CH3v(C-C)v(C=C)

StretchingStretchingScissoring DeformationTwisting DeformationScissoring deformationDeformation

--

---

-

-

---

Maturation Stages / Olive Oil 488 Raman 108

13001500-14001200-10503100-28001440164328701060-10901110-11801400-1500113011781653-16722832-28882090-296730001260

CH3CH2C-CC-HCH2C=OC-Hv(C-C)δ(CH3)δ(CH2)C-CC-CC=CCH2CH3=C-H=C-H

TwistingScissoringStretchingStretchingStretching

-StretchingStretchingDeformationDeformationStretchingStretchingStretching StretchingStretching StretchingDeformation

50

16551086106811201655144489891212941433140914263005126528502890300329232858287510641116890284629341729174217461440130412661269106710791114

C=CC-C C-CC-Cn(C=C)n(CH2)CH2CH2 CH2C-HCH2-=C-H=C-Hv(C-H)v(C-H)=C-HCH2CH2CH2C-CC-CCH3C-H in CH2C-H in CH3C=OC=OC=OCH2-=C-H=C-HC-CC-CC-C

StretchingStretchingStretchingStretching

--

RockingRockingTwistingBendingBending

-StretchingStretchingSymmetricAsymmetricStretchingStretchingSymmetricSymmetricStretchingStretchingRockingSymmetricSymmetricStretchingStretchingStretchingScissoringTwistingDeformationDeformationStretchingStretchingStretching

- / Lipids 532, 1064 Raman 109

51

10691082111830011656126712521672301116601062286429301442108711301178800-1000701

4245482846288129372957173916681298285228851741300916701659

C-CC-CC-C=C-HC=CC-H-C=C=C-HC=CC-CCH2CH3CH2C-CC-HC-HC-H-

C-HC-HCH2CH2CH3CH3C=OC=CCH2 CH2CH2C=C=C-Hv(C=C)v(C=C)

StretchingStretchingStretchingStretchingStrechingIn plane bending

-StretchingStretchingStretching StretchingSymmetricSymmetricStretching Stretching Stretching StretchingBackboneIn plane deformationBendingBendingStretching StretchingStretching Stretching StretchingStretchingTwistingStretchingStretchingStretching Stretching

--

52

130614413013166213064317032600-3200284728822959300717371657144213001267

10907198761096723882

CH2CH2=CHC=CCH2C-CC-HC-HCH2CH2CH3=CHC=OC=CCH2CH2=C-H

C-C(CH3)3(CH3)3P-O(CH3)3(CH3)3

StretchingBendingStretchingBackboneTwisting

---

Symmetric-

AsymmetricStretchingStretching StretchingScissoringTwistingIn plane deformationStretchingSymmetricAsymmetricStretchingSymmetricAsymmetric

1655-16501340940-934550-5101668-16631230-1237

Amide ICHC-CS-SAmide IAmide III

-BendingStretchingStretching

--

- / Meat 785 Raman 110

53

Table 9S. Raman spectra of food adulterant

Band position cm-1

Assignment of Bonds(Molecule/Group)

Mode of Vibration

Strengthof bonds

Sample / Food Matrix Wavenumberof laser source (nm)

Type of Raman References

1441 108213021265 16571747

-CH2-(CH2)n- -CH2cis-RHC=CHRcis-RHC=CHRRC=OOR

C-H bend (shear)C-C stretchC-H bend (twist)=C-H stretchC=C stretchC=O stretch

StrongMediumMediumMediumMediumWeak

- / Oil 785 Portable RamTracer 111

10821265130014411742 (1747)1654 (1657)

-(CH2)n-Cis- RHC=CHR-CH2-CH2RC=OORCis- RHC=CHR

C-C stretch=C-H stretch C-H bend (twist) C-H bend (shear)C=O stretch C=C stretch

MediumMediumMediumStrongWeakMedium

- / Oil 785 Portable 112

3005

2924

2897

2850

cis RHC=CHR

–CH2

–CH3

–CH2

C–H symmetric stretchingC–H asymmetric stretchingC–H symmetric stretchingC–H symmetric stretching

Middle

Strong

Strong

StrongCarotenoid / Oil 514.5 VIS Raman

113

1750 1650 1525 1440 1300 1265 1150

RC=OORcis RHC-CHRRHC=CHR–CH2–CH2cis RHC=CHR–(CH2)n –

C-O stretchingC-C stretchingC=C stretchingC–H bending (scissor.)C–H bending (twisting)

WeakMediumStrong

MediumWeakStrong

54

1008968 868

HC–CH3trans RHC-CHR–(CH2)n –

=C–H bending (scissor.) C–C stretchingCH3 bendingC-C bendingC–C stretching

WeakWeakWeak

10751263 12981440

16521741

2851

-(CH2)n-cis-RHC=CHR-CH2-CH2

cis-RHC=CHRRC=OOR

CH2

C-C stretching=C-H bendingBending (twisting)C-H bending (scissor.) C=C stretchingC=O stretchingC-H stretching (sym)

WeakMediumMediumStrong

StrongWeakWeak

- / Olive and Hazelnut Oils 780 Raman 114

673

982

-

-

In-plane deformationTriazine ring breathing

Strong

Weak Melamine / Milk Powder 785 Conventional Raman 115

676

9853126

C-N-C

C-N-CN-H

Bending Stretching (sym)Stretching (sym)Stretching

Strong

MediumWeak

Melamine / Dried Milk 785 Conventional Raman 116

33832924146013721070923842740

O-HC-HCH2CH and OHC(1)H , COHC(1)H , COHC(1)HC-C, CO stretching

StretchingStretchingBendingBendingBendingBendingBendingStretching

StrongStrongStrongStrongMediumWeakMediumWeak

- / Maple syrup 1064 FT-Raman 117

3005 cis RHC=CHR =C–H stretching Medium

55

2924

2897

2850

2723

1747 1651

1439

1300

1265

1076

968

868

–CH2

–CH3

–CH2

–(CH2)n

RC=OORcis RHC=CHR

–CH2

–CH2

cis RHC=CHR

–(CH2)n–

trans RHC=CHR

–(CH2)n–

(sym)C–H stretching (asym)C–H stretching (sym)C–H stretching (sym)– C–H stretching

C=O stretchingC=C stretching

C–H bending (scissoring)C–H bending (twisting)=C–H bending

C–C stretching

C=C bending

C–C stretching

Shoulder

Strong

Strong

Weak

WeakMedium

Strong

Medium

Shoulder

very weak

Weak

Weak

- / Olive oil 1064 FT-Raman 118

879

1085 and1304112512711442

vC1–C2,CH3 rocking, vC–OvC–C aliphatic C–C stretchv C-Cδ=CHδCH2

Stretching

StretchingStretchingStretchingStretchingDeformationDeformation

-

------

- / butter 785 Raman 119

838 C-C Stretching - Hazelnut / Olive and 532 Raman 120

56

950107212641301144316561745

C=CCH3=C-HC-HC-HC=CC=O

BendingBendScissoringScissoringTwistingStretchingStretching

-------

adulterated olive oil

3312-333429452938-2944

2900-29071636-16421458-14611372-13741364-136913491265-12671126-112710771070-1077

1069-1064922-916904821777707-706629-630590-592519-522449-450420-424

O-HC-HCH2

C-HO-HCH2O-H, C-HCH2CH2COH,Amide IIICN,ProteinsC-OCH,COH,CNProteinC-OC-H,COHC-HC-HC-HCO,CCO,OCO--CCO,CCC-CCO,CCC

StretchingStretchingAsymmetric StretchingStretchingBendingBendingBendingBendingWaggingStretchingStretchingStretchingBending

StretchingBendingBendingStretchingBendingStretchingRing BendingSkeletal StretchingBendingSkeletal StretchingBending

--------------------------

- / Honey 532 FT-Raman Micro Raman

121

680 Melamine - - Melamine / Milk - - 122

57

695682

MelamineMelamine

-Ring Breathing Mode II and plane deformation of ring

--

85012539051391134213141452136010321004

AmyloseAmyloseAmylopectinAmylopectinCH2 CH2CH2---

----

TwistingWaggingDeformationVibrationVibrationRing breathing

----------

Paraffin / Rice 514 Raman 123

705108513001440

-Milk powder--

----

----

Calcium / Milk Powder 1064 FT-Raman 124

212673973

1009

DicyandiamideMelamineAmmonium Sulphate

Urea

---

-

---

-

- / Dry milk 785 Raman 125

127016601060-11301209-130516551400-1500

=C-HC=CC-CCH2 -CH2

BendingStretchingStretchingTwistingOlefinic BondScissoring

------

Adipose Tissue / Meat 785 Raman 126

1450166093913101450

CH-C-C-CH

BendingAmide IStretchingAmide IIIBending

-----

58

1650 - Amide I - Meat 671, 783 Raman 127

16509371310165513408999321650

-C-C--C-HC-CC-C-

Amide IStretchingAmide IIIAmide IBendingStretchingStretchingAmide I

--------

800-920

1070-11001295-13051400-1500

v(C1-C2)v(C1-C2)v(C-C)δ(CH2)δ(CH2)

StretchingRockingStretchingTwistingScissor deformation

-----

Meat 785 Raman 128

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