Additional file 7: Metabolite annotations and tandem

Additional file 7: Metabolite annotations and tandem MS fragmentation patterns of compound detected in EBC. EBC was collected from four groups of volunteers: healthy smokers, healthy non-smokers, non-smokers with nasal congestion, and non-smokers with the common cold. Samples were pooled, lyophilized, reconstituted in 20µL of buffer, and analyzed using LCMS based metabolomics. Metabolite peaks were extracted with Mass Hunter Profinder software (Agilent) using exact mass and isotope ratios. Tandem MS was performed, spectra was exported to NIST MS Search v2.2, and matched to the NIST14 Mass Spectral library. Fragments in red indicate EBC sample, fragments in blue indicate NIST standard reference spectra. Compound (R)-4'-Deoxyindenestrol (R)-5-Deoxyindenestrol N-Acetyl-D-fucosamine Heptadecatrienoic acid (+)-Prosopinine 1,3-Dicyclohexylurea 10-Hydroxydecanoic acid 11-Aminoundecanoic acid 1-Hydroxy-2-naphthoic acid 2-(Methylthiomethyl)-3-phenyl2-propenal 2,4-Diamino-6-nitrotoluene 13,14-dihydro Prostaglandin F1a 2-Anthramine 2-Amino-3,7-dideoxy-D-threohept-6-ulosonic acid 2-Carboxy-4-dodecanolide 2-Methylisoborneol 4-Heptadecene 3-Deoxyestrone 4-Vinylcyclohexene 5-Nitro-2-furfuryl methyl ether 9-(Methylthio)nonanenitrile Allotetrahydrodeoxycorticosteron e beta-Santonin Butoctamide hydrogen succinate C14 sphingosine Arachidonoyl-1-thio-Glycerol cis-Hydroxy Perhexiline Citronellyl formate Diethylene glycol Dimethyl suberate Dizocilpine Ethyl 3-(Nbutylacetamido)propionate Ethyl 3,4,5-trimethoxybenzoate Furmecyclox Enhydrin Ganoderic acid Mg Gnididilatin Gomphrenin-I Gossypetin 3,5,8,3',4'pentamethyl ether Heptanal Icosenoic acid Indicumenone 12,14-Pentacosadiynoic acid Isodictamnine N-cis-tetradec-9Z-enoyl-LHomoserine lactone Oxprenolol Pantothenol p-Cymene Pulcherriminic acid Tamarixetin Teniposide Tremetone Ureidoglycine Zeatin 3-Cyano-6-methoxycoumarin

Smkr

Nasal

Cold

Hlthy

RT (mins)

Mass

Formula

Mode

X X X X X X X X X X

X X X X X X X X X X

X X X X X X X X X X

X X X X X X X X X X

6.620 7.839 8.079 8.080 10.422 8.876 7.523 7.418 6.258 6.388

250.1358 250.1358 205.0950 264.2089 313.2609 224.1889 216.1357 229.1680 188.0472 230.0169

C18 H18 O C18 H18 O C8 H15 N O5 C17 H28 O2 C18 H35 N O3 C13 H24 N2 O C10 H20 O3 C11 H23 N O2 C11 H8 O3 C11 H12 O S

+ + + + + + + +

X X X X

X X X X

X X X X

X X X X

7.112 6.814 6.672 6.380

167.0703 358.2736 193.0897 213.0620

C7 H9 N3 O2 C20 H38 O5 C14 H11 N C7 H13 N O5

+ + + +

X X X X X X X X

X X X X X X X X

X X X X X X X X

X X X X X X X X

6.301 10.458 10.081 7.300 7.491 6.855 6.799 6.756

282.1449 185.1778 255.2924 254.1676 233.2141 139.0270 185.1234 351.2768

C13 H22 O4 C11 H20 O C17 H34 C18 H22 O C8 H12 C6 H7 N O4 C10 H19 N S C21 H34 O3

+ + + + + + +

X X X X X X X X X X

X X X X X X X X X X

X X X X X X X X X X

X X X X X X X X X X

7.790 5.933 9.628 6.303 7.714 8.918 1.201 6.940 7.245 6.857

286.1171 375.2285 271.2141 428.3085 331.2304 184.1461 202.0454 202.1207 221.1209 215.1522

C15 H18 O3 C16 H29 N O5 C14 H29 N O2 C23 H38 O3 S C19 H35 N O C11 H20 O2 C4 H10 O3 C10 H18 O4 C16 H15 N C11 H21 N O3

+ + + + -

X X X X X X X

X X X X X X X

X X X X X X X

X X X X X X X

6.664 13.492 7.002 6.451 7.590 11.228 0.979

219.1691 251.1517 464.1678 602.3877 669.3502 646.1258 388.1127

C12 H16 O5 C14 H21 N O3 C23 H28 O10 C35 H54 O8 C37 H48 O10 C24 H26 N2 O13 C20 H20 O8

+ + + +

X X X X X X

X X X X X X

X X X X X X

X X X X X X

6.502 13.666 12.421 6.122 6.491 10.715

210.0870 327.3138 234.1620 374.3185 199.0637 309.2301

C7 H14 O C20 H38 O2 C15 H24 O3 C25 H42 O2 C12 H9 N O2 C18 H31 N O3

+ + +

X X X X X X X X X X

X X X X X X X X X

X X X X X X X X X

X X X X X X X X X

8.085 6.088 9.382 6.774 6.420 11.221 1.200 0.980 7.333 5.936

265.1652 187.1208 152.1205 238.1332 298.0486 656.1547 264.0154 380.0903 219.1122 201.0426

C15 H23 N O3 C9 H19 N O4 C10 H14 C12 H20 N2 O4 C16 H12 O7 C32 H32 O13 S C13 H14 O2 C3 H7 N3 O3 C10 H13 N5 O C11 H7 N O3

+ + +

NIST MF

NIST RMF

713

880

KEGG C14541 C14543 C15480 C16344 C10167

C03203

PubChem 11954028 11954030 11954186 16061034 442654 4277 74300 17083 6844

C16396

6435634 96177

C14417

11937

C16850

25137912

C02774

16913 C14972 C14293

C13713 C09545 C12946

101771 237619 2486

C12295 C14689 C17803 C13737

7778 8117 15611 1207

C09405

231162 43359 325606

C09101 C08544

442032 4480887

C14390 C16526 C17612

8130 5282768

C10697

C05944 C06575 C10188 C11153 C08992 C02091 C00371 508

5882 7499 11469 93987

9543642 442913

4631 4678 7463 3083664 482576 5396 78673 503 15419

970

1

1,2-Dimethylimidazole 1-Hexadecylamine 2,6-Di-tert-butyl-4hydroxymethylphenol 2-Aminobenzamide 2-Amino-m-cresol 3-Methylhistidine Arginine Carnosine p,p’-Ditolylamine Tryptophan 4-Hydroxy-3-methoxyphenethyl alcohol 4-Imidazoleacrylic acid 5-Aminosalicylic acid D-erythro-Sphinganine Triethyl citrate Acetylarginine 5-Methoxytryptophan 1,2-Benzenecarboxylic acid 2-Butyl-4-propylthiazole 3-Hydroxymorphinan Gabaculine Thyrotropin releasing hormone 12-Nitrolinoleic acid 12-O-Palmitoyl-16hydroxyphorbol 13-acetate 15(S)-HPETE 2-chloro-2-iodoacetamide 2-Oxo-4-hydroxy-5aminovalerate 2-Oxo-6-methylthiohexanoic acid 2S-Amino-tridecanoic acid 3,4-Dihydrocadalene 3-Hydroxy-2-(4morpholinylmethyl)estra1,3,5(10)-trien-17-one 6-hydroxy caproic acid 6-Hydroxy-3,7-dimethyloctanoate Bisdiphosphoinositol tetrakisphosphate Carteolol Chalcogran Cybutryne Deaminohydroxyblasticidin S Homoserine Dodecanedioic acid Eleganin Ethirimol gamma-Chaconine Hallactone B Hydnocarpic acid Levan Lys Lys Gly Met Trp Glu Meteloidine N-Acetylleucine N-Methylpelletierine PA(22:2/0:0) Pachymic acid Paromamine PI(12:0/12:0) Tetrahydrodipicolinate Threonine 1,8-Diazacyclotetradecane-2,9dione 13,14-dihydroxy-docosanoic acid (R,S)Tetrahydrobenzylisoquinoline 2-Methylpropanal oxime 3-Hydroxy-4-methoxybenzyl alcohol 3-Oxosteroid

X X X

1.538 9.087 6.806

96.0687 241.277 236.1776

C5 H8 N2 C16 H35 N C15 H24 O2

+ + +

520 398 823

987 858 922

X X X X X X X X

1.58 0.811 0.809 0.81 0.809 6.038 4.079 5.255

136.0637 123.0684 169.0851 174.1117 226.1066 197.1204 204.0899 166.063

C7 H8 N2 O C7 H9 N O C7 H11 N3 O2 C6 H14 N4 O2 C9 H14 N4 O3 C14 H15 N C11 H12 N2 O2 C9 H12 O3

+ + + + + + + +

425 560 383 610 262 597 679 560

977 999 860 908 841 933 926 999

X X X X X X X X X X X X X

138.0429 153.0426 301.2981 276.1209 216.1222 234.1004 148.016 205.0902 243.1623 121.0524 362.1702 325.2245 756.4039

C6 H6 N2 O2 C7 H7 N O3 C18 H39 N O2 C12 H20 O7 C8 H16 N4 O3 C12 H14 N2 O3 C8 H4 O3 C10 H17 N S C16 H21 N O C7 H9 N O2 C16 H22 N6 O4 C18 H31 N O4 C38 H60 O9

+ + + + + + + + + + -

557 553 51 360 404 532 679

998 997 299 945 910 993 946

535

989

X X

5.023 1.612 5.186 7.519 4.91 6.124 12.835 7.548 5.004 6.387 9.248 6.303 5.803

X X X

X X X

X

10.185 8.499 1.604

264.2089 278.9149 129.0426

C20 H32 O4 C2 H3Cl I N O C5 H9 N O4

+ -

X X X X

X X X X

X X

8.085 8.835 10.501 5.178

193.0780 257.1986 200.1563 431.1463

C7 H12 O3 S C13 H27 N O2 C15 H20 C23 H31 N O3

+ + + -

X X X

X X X

X

6.131 8.518 0.771

174.0890 188.1410 705.8145

C6 H12 O3 C10 H20 O3 C6 H20 O24 P8

-

X X X X X X X X X X X X X X X X X X X X X X X

X X X X X X X X X X X X X X X X X X X X X X X X

X

X X X X X

6.385 6.409 2.275 5.769 6.707 8.186 7.474 6.063 6.247 9.784 9.749 1.016 5.934 10.589 5.385 5.710 6.429 6.118 5.487 5.176 5.703 7.780 8.939 6.118

274.1687 156.1151 281.1293 483.2076 215.0406 230.1517 434.1566 532.2984 601.3965 468.1098 252.2089 504.1672 377.2258 492.1678 315.1683 173.1055 201.1364 490.3105 642.3713 369.1758 698.3983 153.0427 233.0513 498.3410

C16 H24 N2 O3 C9 H16 O2 C11 H19 N5 S C17 H25 N7 O6 C4 H9 N O3 C12 H22 O4 C22 H26 O9 C11 H19 N3 O C33 H53 N O6 C20 H24 O9 S C16 H28 O2 C18 H32 O16 C14 H29 N5 O4 C21 H28 N4 O6 S C13 H21 N O4 C8 H15 N O3 C9 H17 N O C25 H47 O7 P C33 H52 O5 C12 H25 N3 O7 C33 H63 O13 P C7 H9 N O4 C4 H9 N O3 C12 H22 N2 O2

+ -

X X

X X

X

10.059 7.463

394.3109 223.1366

C22 H44 O4 C16 H17 N

+ +

X X

X

X X

6.879 5.078

87.0683 154.063

C4 H9 N O C8 H10 O3

+ +

X

X

X

8.419

291.2562

C19 H30 O

+

X X X X X

X X X X

X

X

X X

X X X X X X X X X

X X

15617 8926

C01152 C02385 C00386

6929 6942 3014138 64969 232 9369 69293

16928 1178 4075 91486 6506 119802 181977

C12110 C03958

3445 4968

C09153 C05966

124127 1440

C05941 C17216 C13795

440852 44237195 656741

C14926

235463 14490

C18067

C06874 C08471 C03860 C02678 C09401

C09105 C16795 C06215

C10861

25245165 2583 441558 91590 629 779 12736 5281440 32152 160496 442036 110680 440946

C06184

443006 1995 86786

C17044 C01743

316448 439560 5460758 205

479

C04277

16 102450

C05201 C03219

98468 5324281

C01876

78089 439594

804

2

4-Dodecylphenol 5-(1-oxopropan-2-yl)isolongifol5-ene 6-(2-Chloroallylthio)purine Aniracetam Benzylamine 1α,24,25,28-tetrahydroxyvitamin D2 MG(18:1) Miotine O-decanoyl-R-carnitine Palmitoylglycine PC(18:1/22:6) PG(18:4/20:4) Purine S-(4,5-Dihydro-2-methyl-3furanyl) ethanethioate Tris(2-butoxyethyl)phosphate 3-Acetyl-8-methoxycoumarin 1-(2-Pyrimidyl)piperazine 1-Butylimidazole 2-Hydroxy-6’methoxyacetophenone 4-(4-Aminophenoxy)aniline 6-Hydroxymelatonin Atractyloside C Benzofuran α-Lipoic acid Ephedrine Hexaethylene glycol Arogenate Tetradecyamine

X X

X X

X X

X X X X

X X

X

X X X X X X X X

X X X

X

X X X

X X

X X X

X

X

X X

X X

X X

11.465 11.149

279.2561 260.2132

C18 H30 O C18 H28 O

+ +

C14245

66030

7.239 8.231 8.278 6.213

247.9896 201.0790 107.0735 460.3189

C8 H7 Cl N4 S C12 H13 N O3 C7 H9 N C28 H44 O5

+ + -

C15397 C13355 C15562

3247797 2196 7504

8.908 6.023 6.305 9.931 6.813 12.183 8.811 5.915

373.3185 222.1369 361.2453 335.2469 831.5785 790.4734 120.0436 186.0353

C21 H40 O4 C12 H18 N2 O2 C17 H33 N O4 C18 H35 N O3 C48 H82 N O8 P C44 H71 O10 P C5 H4 N4 C7 H10 O2 S

+ + + + + + -

C11763

46092

12.185 5.846 5.37 4.977 10.183

398.2433 218.0579 164.1062 124.1 166.063

C18 H39 O7 P C12 H10 O4 C8 H12 N4 C7 H12 N2 C9 H10 O3

5.892 1.184 13.415 7.921 5.666 31.317 5.443 6.828 7.876

200.095 248.1161 442.2598 118.0419 206.0435 165.1154 282.1679 227.0775 213.2456

C12 H12 N2 O C13 H16 N2 O3 C21 H36 O7 C8 H6 O C8 H14 O2 S2 C10 H15 N O C12 H26 O7 C10 H13 N O5 C14 H31 N

539

983

151008

791

993

C15587

1044

+ + + + +

829 661 559 449 153

922 881 998 852 601

C14446

5463955 6540

+ + + + + + +

454 422

893 890

476 560 765

775 999 949

522

957

88747 61347 69709

X X X X X X X

X X X X

X

C05643

1864

C14512 C00725 C01575

9223 864 5032 17472 193887

EBC from healthy non-smokers 232.1804

100 50

189.1388

0 130.0654 50 100

158.0604

175.0632

190.0868

232.0975

70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 Cpd 3: 1.184: (M+H)+: +ESI Product Ion (rt: 0.058, 0.121, Head0.593, to Tail 0.639 MF=422 ... min,RMF=890 8 scans) Frag=390.0V [email protected] 6-Hydroxymelatonin (232.1813[z=1] -> **) EBC_Healthy_AutoMSMS_SB 244.1801

100 50

201.1362

0 50 100

201.1280

244.1704

200 205 210 215 220 225 230 235 240 245 Cpd 17: 5.004: (M+H)+: +ESI Product Ion (rt: 4.792, 4.862 Headmin, to Tail 1 scans) MF=535 Frag=380.0V [email protected] (244.1813[z=1] 3-Hydroxymorphinan -> **) EBC_Healthy_AutoMSMS_SB-AQ_Pos.d

3

137.1074

100 50

94.0653

0 94.04

122.03

50 100

137.06

60 70 80 90 100 110 120 130 140 150 Cpd 21: 5.072: (M+H)+: +ESI Product Ion (rt: 4.929,Head 5.058tomin, Tail2 MF=413 scans) Frag=380.0V RMF=928 [email protected] (137.1081[z=1] 3-Hydroxy-4-methoxybenzyl -> **) EBC_Healthy_AutoMSMS_SB-AQ_Pos alcohol 165.1381

100 50

122.0933

0 122.0713

50 100

165.1135

70 80 90 100 110 120 130 140 150 160 170 180 Cpd 71: 5.370: (M+H)+: +ESI Product Ion (rt: 5.390 min) Head Frag=390.0V to Tail MF=559 [email protected] RMF=998 (165.1385[z=1] -> **) EBC_Healthy_AutoMSMS_SB-AQ_Pos.d 1-(2-Pyrimidyl)piperazine 184.1122

100 50 129.0702

156.0788

0 156.0809 50 100

184.0763

110 120 130 140 150 160 170 180 190 200 Cpd 125: 5.892: (M+H)+: +ESI Product Ion (rt: 5.906,Head 5.942 to min, Tail 2 scans) MF=454 Frag=380.0V RMF=893 [email protected] (184.1126[z=1] 4-(4-Aminophenoxy)aniline -> **) EBC_Healthy_AutoMSMS_SB-AQ_Pos.d 100

135.0898

151.1228

50 0 50

135.0331

100

151.0517

50 60 70 80 90 100 110 120 130 140 150 160 Cpd 2: 5.182: +ESI Product Ion (rt: 5.138 min) Frag=380.0V Head to [email protected] Tail MF=527 (151.1226[z=1] RMF=993 -> **) EBC_Healthy_AutoMSMS_SB-AQ_Pos.d 2-Aminobenzenecarbohydroxamic acid 225.1968

100.1111

100 50 0 61.0390

83.0847

143.1169

50 100.1113 100

225.1947

50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 Cpd 362: 8.876: (M+H)+: +ESI Product Ion (rt: 8.889, Head 8.933 to min, Tail 2 scans) MF=473 Frag=390.0V RMF=789 [email protected] (225.1960[z=1] 1,3-Dicyclohexylurea -> **) EBC_Healthy_AutoMSMS_SB-AQ_Pos.d

4

100

61.0387 55.0520

50 0 143.1169 50 100

83.0847 55.0536

50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 Cpd 362: 8.876: (M+H)+: +ESI Product Ion (rt: 8.891, Head 8.936 to min, Tail 1 scans) MF=395 Frag=360.0V RMF=873 [email protected] (225.1960[z=1] 1,3-Dicyclohexylurea -> **) EBC_Healthy_AutoMSMS_SB-AQ_Pos.d 95.0487

100

149.0597 167.0698

121.0268

50 0

121.06

50

149.06

100

167.07

40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 Cpd 493: 10.183: (M+?): +ESI Product Ion (rt: 10.161,Head 10.199 tomin, Tail2MF=153 scans) Frag=390.0V RMF=601 [email protected] (167.0707 2'-Hydroxy-6'-methoxyacetophenone -> **) EBC_Healthy_AutoMSMS_SB-AQ_Pos.d 199.0728

100 50

57.0685 83.0843

399.2491

299.1595

0 50

57.0693

101.0954

143.0095

399.2484 299.1600

100

199.0719

60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 Cpd 579: 12.185: (M+H)+: +ESI Product Ion (rt: 12.163, Head 12.202 to Tail min,MF=519 2 scans)RMF=805 Frag=390.0V [email protected] (399.2507[z=1] Tris(2-butoxyethyl) -> **) EBC_Healthy_AutoMSMS_SB-AQ_Pos phosphate 100

57.0685

50

124.9985

0 50 100

98.9835 57.0693

60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 Cpd 579: 12.185: (M+H)+: +ESI Product Ion (rt: 12.163, Head 12.202 to Tail min,MF=537 2 scans)RMF=811 Frag=380.0V [email protected] (399.2507[z=1] Tris(2-butoxyethyl) -> **) EBC_Healthy_AutoMSMS_SB-AQ_Pos phosphate

149.0226

100 50

121.0278

0 50

121.028

100

149.023

100 105 110 115 120 125 130 135 140 145 150 155 160 Cpd 614: 12.826: (M+?): +ESI Product Ion (rt: 12.789, Head 12.850 to Tail min,MF=523 2 scans)RMF=973 Frag=390.0V [email protected] (149.0234 1,2-Benzenedicarboxylic -> **) EBC_Healthy_AutoMSMS_SB-AQ_Pos.d acid

EBC from non-smokers with the common cold 5

125.1064

100 50

107.0582

84.0800

69.0572

0 50

69.0445

100

125.1073

50 60 70 80 90 100 110 120 130 140 Cpd 14: 4.977: (M+H)+: +ESI Product Ion (rt: 4.877, 4.949 Headmin, to Tail 2 scans) MF=449 Frag=380.0V [email protected] (125.1071[z=1]1-Butylimidazole -> **) EBC_Sick_Cold_or_Flu_AutoMSMS_SB-AQ 100

89.0596 133.0854

283.1930

50 0 177.1121

283.1751

50 133.0859 100

89.0595

80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 Cpd 58: 5.443: (M+H)+: +ESI Product Ion (rt: 5.421, 5.451 Headmin, to Tail 1 scans) MF=765 Frag=390.0V [email protected] (283.1758[z=1] Hexaethylene -> **) EBC_Sick_Cold_or_Flu_AutoMSMS_SB-AQ glycol 189.1365

161.1052

100 50 0

171.03

50 100

161.04

189.04

145 150 155 160 165 170 175 180 185 190 195 200 Cpd 94: 5.666: (M+H)+: +ESI Product Ion (rt: 5.014, 5.516 Headmin, to Tail 2 scans) MF=476 Frag=390.0V [email protected] (189.1389[z=1]DL-α-Lipoic -> **) EBC_Sick_Cold_or_Flu_AutoMSMS_SB-AQ acid 201.1398

100 50

145.0890

186.1122

0 145.0648 50 100

173.0597

186.0311

201.0546

90 100 110 120 130 140 150 160 170 180 190 200 210 Cpd 126: 5.846: (M+?): +ESI Product Ion (rt: 5.889, 5.950 Headmin, to Tail 2 scans) MF=661 Frag=380.0V [email protected] (201.1387 3-Acetyl-8-methoxycoumarin -> **) EBC_Sick_Cold_or_Flu_AutoMSMS_SB-AQ_Pos 214.2512

100 71.0862 50 0

214.2470 50 100

60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 Cpd 504: 7.876: (M+H)+: +ESI Product Ion (rt: 7.884, Head 7.910 to min, Tail 1 scans) MF=522 Frag=390.0V RMF=957 [email protected] (214.2532[z=1] Tetradecylamine -> **) EBC_Sick_Cold_or_Flu_AutoMSMS_SB-A

6

100

57.0711

214.2517

50 0 214.2470 50 100

57.0701

50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 Cpd 504: 7.876: (M+H)+: +ESI Product Ion (rt: 7.885, Head 7.911 to min, Tail 2 scans) MF=255 Frag=380.0V RMF=870 [email protected] (214.2532[z=1] Tetradecylamine -> **) EBC_Sick_Cold_or_Flu_AutoMSMS_SB-A 225.1972

100 50 100.1107 0 100.1113

50 100

225.1947

50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 Cpd 639: 8.906: (M+NH4)+: +ESI Product Ion (rt: 8.884, Head 8.914 to Tail min,MF=368 2 scans)RMF=937 Frag=390.0V [email protected] (225.1965[z=1] 1,3-Dicyclohexylurea -> **) EBC_Sick_Cold_or_Flu_AutoMSMS_SB 83.0849

100 50

61.0398

143.1157

183.1141

0 100.1113 50 100

55.0536

143.1169

83.0847

61.0390

50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 Cpd 639: 8.906: (M+NH4)+: +ESI Product Ion (rt: 8.885, Head 8.915 to Tail min,MF=376 1 scans)RMF=848 Frag=380.0V [email protected] (225.1965[z=1] 1,3-Dicyclohexylurea -> **) EBC_Sick_Cold_or_Flu_AutoMSMS_SB 299.1647

100 50

199.0759 57.0704 83.0846

0 50 100

57.0693

101.0954

143.0095

399.2484 299.1600 199.0719

60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 Cpd 905: 12.190: (M+H)+: +ESI Product Ion (rt: 12.198 Head min)toFrag=390.0V Tail [email protected] RMF=841(399.2512[z=1] -> **) Tris(2-butoxyethyl) EBC_Sick_Cold_or_Flu_AutoMSMS_SB-AQ_Pos.d phosphate

149.0232

100 50 121.0269

133.0123

0 50 100

121.028 149.023

100 105 110 115 120 125 130 135 140 145 150 155 160 Cpd 928: 12.873: (M+?): +ESI Product Ion (rt: 12.835, Head 12.888 to Tail min,MF=438 2 scans)RMF=908 Frag=390.0V [email protected] (149.0237 1,2-Benzenedicarboxylic -> **) EBC_Sick_Cold_or_Flu_AutoMSMS_SB-A acid

7

148.1109

100 50

133.0911

0 132.08 133.09

50 100

148.11

124 126 128 130 132 134 136 138 140 142 144 146 148 150 152 154 156 158 160 Cpd 1047: 31.317: (M+H)+: +ESI Product Ion (rt: 31.211, Head 31.304 to Tail min, MF=560 2 scans) RMF=999 Frag=390.0V [email protected] (148.1124[z=1] Ephedrine -> **) EBC_Sick_Cold_or_Flu_AutoMSMS_S

EBC from non-smokers with nasal congestion 100

137.1064

122.0815

107.0610

118.9227 50 0 107.1 50 100

122.0

137.0

100 105 110 115 120 125 130 135 140 145 150 Cpd 33: 5.078: (M+H)+: +ESI Product Ion (rt: 5.014 min) Head Frag=380.0V to Tail MF=479 [email protected] RMF=804 (137.1083[z=1] -> **) 3-Hydroxy-4-methoxybenzyl EBC_Nasal_Decongestion_AutoMSMS_SB-AQ_Pos.d alcohol 65.0376

100

91.0532

50 0 63.0229

91.0540

50 100

65.0383

50 55 60 65 70 75 80 85 90 95 100 Cpd 779: 8.278: (M+Na)+: +ESI Product Ion (rt: 7.424,Head 7.516, to8.406, Tail MF=539 8.439 ... RMF=983 min, 3 scans) Frag=380.0V [email protected] (91.0537[z=1] -> **) EBC_Nasal_Decongestion_A 67.0300

100

94.0400

121.0501

50 0 52.02 50 67.03 100

94.04

121.05

40 50 60 70 80 90 100 110 120 130 Cpd 848: 8.811: (M+H)+: +ESI Product Ion (rt: 8.558 min) HeadFrag=380.0V to Tail MF=791 [email protected] RMF=993 (121.0509[z=1] -> **) EBC_Nasal_Decongestion_AutoMSMS_SB-AQ_Pos.d Purine

8

100 50

55.0545 225.1984

61.0409

83.0867

0 83.0847 50 100

61.0390 55.0536

50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 Cpd 869: 8.909: (M+H)+: +ESI Product Ion (rt: 8.892, Head 8.919 to min, Tail 2 scans) MF=713 Frag=390.0V RMF=880 [email protected] (225.1971[z=1] 1,3-Dicyclohexylurea -> **) EBC_Nasal_Decongestion_AutoMSMS_SB 100 50

143.1160 61.0393 55.0536

225.1966

83.0883

0 50 100

55.0536

225.1947 83.0847

61.0390

143.1169

100.1113

50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 Cpd 869: 8.909: (M+H)+: +ESI Product Ion (rt: 8.894, Head 8.920 to min, Tail 2 scans) MF=418 Frag=380.0V RMF=714 [email protected] (225.1971[z=1] 1,3-Dicyclohexylurea -> **) EBC_Nasal_Decongestion_AutoMSMS_SB 299.1648

100

399.2515 50

124.9991

199.0737

0 57.0696

101.0954

50

199.0719

399.2485

100

299.1601

60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 Cpd 1192: 12.198: (M+H)+: +ESI Product Ion (rt: 12.188, Head 12.223 to Tail min, MF=829 2 scans) RMF=922 Frag=390.0V [email protected] (399.2507[z=1] Tris(2-butoxyethyl) -> **)phosphate EBC_Nasal_Decongestion_AutoMSM 421.2322

100 50 321.1435 0 146.9809 321.1418

50 100

421.2301

140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 310 320 330 340 350 360 370 380 390 400 410 420 430 Cpd 1192: 12.198: (M+Na)+: +ESI Product Ion (rt: 12.190, Head12.225 to Tailmin, MF=432 2 scans) RMF=984 Frag=390.0V [email protected](2-butoxyethyl) (421.2328[z=1] -> **) phosphate EBC_Nasal_Decongestion_AutoMSM

EBC from healthy non-smokers 110.0697

100

156.0765

50 0 95.06

122.07

50 100

156.07

110.07

80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 Cpd 5: 0.809: (M+?): +ESI Product Ion (rt: 0.829 min)Head Frag=380.0V to Tail MF=262 [email protected] RMF=841 (227.1147 -> **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d L-Carnosine

9

109.0738

100

170.0937

50 0 83.06 126.10

50

170.09

109.07

100

96.07

50 60 70 80 90 100 110 120 130 140 150 160 170 180 Cpd 8: 0.809: (M+H)+: +ESI Product Ion (rt: 0.817 min) Head Frag=390.0V to Tail MF=383 [email protected] RMF=860 (170.0933[z=1] -> **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d L-Histidine, 3-methyl100 70.0653

50

116.0715

0 130.0975

175.1188

116.0706

50 100

70.0648

60 70 80 90 100 110 120 130 140 150 160 170 180 Cpd 13: 0.810: (M+H)+: +ESI Product Ion (rt: 0.819, 0.851 Headmin, to Tail 2 scans) MF=610 Frag=390.0V [email protected] (175.1196[z=1] ->L-Arginine **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d 70.0652

100 50

130.1004

0 116.07

50 60.05 100

130.09

175.12

70.06

60 70 80 90 100 110 120 130 140 150 160 170 180 190 Cpd 13: 0.810: (M+H)+: +ESI Product Ion (rt: 0.819, 0.852 Headmin, to Tail 2 scans) MF=605 Frag=380.0V [email protected] (175.1196[z=1] -> DL-Arginine **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d 124.0860

100 50

109.0654

0 124.075 106.064

50 100

90 95 100 105 110 115 120 125 130 Cpd 14: 0.811: (M+?): +ESI Product Ion (rt: 0.823, 0.858 Head min, to1Tail scans) MF=560 Frag=390.0V RMF=999 [email protected] (124.0872 -> **) 2-Amino-m-cresol EBC_Smoker_AutoMSMS_SB-AQ_Pos.d 70.0656

100 50 0 43.055

59.991

50 100

70.065

40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 Cpd 21: 1.002: (M+H)+: +ESI Product Ion (rt: 1.011, 1.096 Headmin, to Tail 1 scans) MF=321 Frag=360.0V [email protected] (192.1597[z=1]L-Thiocitrulline -> **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d

10

102.0905

100 50

84.0806

0 46.03

56.05

84.05

50 74.02

100

102.06

40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 Cpd 26: 1.364: (M+H)+: +ESI Product Ion (rt: 1.330, 1.387 Headmin, to Tail 2 scans) MF=544 Frag=390.0V [email protected] (102.0918[z=1] L-α-Amino-γ-butyrolactone -> **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d 100

56.0505

97.0770

50 0 50 100

97.0759 56.0496

50 55 60 65 70 75 80 85 90 95 100 105 110 Cpd 32: 1.538: (M+NH4)+: +ESI Product Ion (rt: 1.326, Head 1.384 tomin, Tail 2MF=520 scans) Frag=380.0V RMF=987 [email protected] (97.0760[z=1] 1,2-Dimethylimidazole -> **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d 92.0576

100

120.0509

50 0 64.9 50 100

92.0

120.0

30 40 50 60 70 80 90 100 110 120 130 140 150 Cpd 35: 1.580: (2M+H)+: +ESI Product Ion (rt: 1.587 min) HeadFrag=390.0V to Tail MF=425 [email protected] RMF=977 (137.1069[z=1] -> **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d 2-Aminobenzamide 136.1110

100 108.0775

50 0 50

108.0443

100

136.0393

80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 Cpd 41: 1.612: (M+NH4)+: +ESI Product Ion (rt: 1.631Head min)to Frag=390.0V Tail MF=553 [email protected] RMF=997 (136.0751[z=1] -> **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d 5-Aminosalicylic acid 146.0611

100 50

118.0646

0 170.0600 50 100

188.0706

118.0651 146.0600

110 120 130 140 150 160 170 180 190 200 Cpd 52: 4.079: (M+Na)+: +ESI Product Ion (rt: 4.007,Head 4.090 to min, Tail 2 scans) MF=336 Frag=390.0V RMF=842 [email protected] (188.0712[z=1]L-Tryptophan -> **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d

11

118.0654

100 50

91.0526

143.0705

91.0540

143.0729

0 50 100

118.0650

50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 Cpd 52: 4.079: (M+Na)+: +ESI Product Ion (rt: 4.008,Head 4.091 to min, Tail 2 scans) MF=506 Frag=380.0V RMF=831 [email protected] (188.0712[z=1]L-Tryptophan -> **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d 100

115.0549

91.0544

50 0 50 100

91.0540 115.0542

90 100 110 120 130 140 150 160 170 180 190 Cpd 52: 4.079: (M+Na)+: +ESI Product Ion (rt: 4.009,Head 4.091 to min, Tail 2 scans) MF=679 Frag=360.0V RMF=926 [email protected] (188.0712[z=1]L-Tryptophan -> **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d 217.1069

100 50 175.0873 0 175.12

200.10

50 100

217.13

165 170 175 180 185 190 195 200 205 210 215 220 225 230 Cpd 12: 4.910: (M+?): +ESI Product Ion (rt: 4.854, 4.924 Head min, to2Tail scans) MF=404 Frag=390.0V RMF=910 [email protected] (217.1051 -> N-α-Acetyl-L-arginine **) EBC_Healthy_AutoMSMS_SB-AQ_Pos.d 139.1240

100 120.9525

50 0 50

121.03

100

139.05

100 105 110 115 120 125 130 135 140 145 150 Cpd 68: 5.023: (M+NH4)+: +ESI Product Ion (rt: 5.060, Head 5.092 tomin, Tail 2MF=557 scans) Frag=390.0V RMF=998 [email protected] (139.1229[z=1] 4-Imidazoleacrylic -> **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d acid 244.1795

76 147.0539

201.1386

38 0 157.0652 38 76

199.1124

244.1704

150 160 170 180 190 200 210 220 230 240 250 Cpd 84: 5.154: (M+2H)+2: +ESI Product Ion (rt: 4.923Head min) to Frag=390.0V Tail MF=402 [email protected] RMF=779 (244.1832[z=2] -> **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d 3-Hydroxymorphinan

12

100 50

58.0646

67.0544

81.0699

0 57.07

67.05

50 100

79.05

69.07

81.07

60.05

56 58 60 62 64 66 68 70 72 74 76 78 80 82 Cpd 88: 5.186: (M+H)+: +ESI Product Ion (rt: 5.153 min) Head Frag=360.0V to Tail MF=51 [email protected] RMF=299 (302.1964[z=1] -> **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d D-erythro-Sphinganine 151.1235

100 50

136.0994

0 136.050 50

151.074

119.047

100 100 105 110 115 120 125 130 135 140 145 150 155 160 Cpd 110: 5.255: (M+H)+: +ESI Product Ion (rt: 5.115,Head 5.166 to min, Tail 2 scans) MF=560 Frag=390.0V RMF=999 [email protected] (151.1231[z=1] 4-Hydroxy-3-methoxyphenethyl -> **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d alcohol 100

202.1245 174.0923

50 0 187.0265 50

174.0551

100

202.0501

165 170 175 180 185 190 195 200 205 210 Cpd 289: 5.936: (M+H)+: +ESI Product Ion (rt: 5.950 min) HeadFrag=380.0V to Tail MF=508 [email protected] RMF=970 (202.1228[z=1] -> **)3-Cyano-6-methoxycoumarin EBC_Smoker_AutoMSMS_SB-AQ_Pos.d 198.1280

100 50

182.0917

0 50

183.1048 198.1284

100

174 176 178 180 182 184 186 188 190 192 194 196 198 200 Cpd 333: 6.038: (M+H)+: +ESI Product Ion (rt: 5.958,Head 5.986 to min, Tail 2 scans) MF=597 Frag=380.0V RMF=933 [email protected] (198.1279[z=1] p,p'-Ditolylamine -> **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d 218.0995

100 50

200.1480

0 200.0709 50

218.0815

100 180 185 190 195 200 205 210 215 220 225 230 Cpd 366: 6.124: (M+H)+: +ESI Product Ion (rt: 6.111,Head 6.184 to min, Tail 2 scans) MF=532 Frag=390.0V RMF=993 [email protected] (218.0985[z=1] 5-Methoxytryptophan -> **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d

13

203.1431

100

219.1744

50 79.0545 91.0538 105.0706

0

121.1006

147.1176 161.1323 175.1496 188.1205

105.0698 119.0855 133.1012

161.1325

50

219.1744

100

203.1431

50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 Cpd 535: 6.806: (M+H)+: +ESI Product Ion (rt: 6.803 min) HeadFrag=380.0V to Tail MF=823 [email protected] RMF=922 (219.1744[z=1] -> 2,6-Di-tert-butyl-4-hydroxymethylphenol **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d 91.0549

100 50

77.0375

55.0540

105.0694

145.1014 119.0842 158.0725

0 50

65.0384

115.0542 128.0621 105.0698

79.0540

100

145.1011

91.0540

50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 Cpd 535: 6.806: (M+H)+: +ESI Product Ion (rt: 6.803 min) HeadFrag=360.0V to Tail MF=683 [email protected] RMF=817 (219.1744[z=1] -> 2,6-Di-tert-butyl-4-hydroxymethylphenol **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d 91.0545

100 50

105.0697 55.0549

79.0535 69.0701

145.1007

119.0855 131.0845

155.0851

0 50

173.0948 173.0961

55.0540 67.0540

145.1012

119.0855

79.0540 105.0698

100

91.0541

50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 Cpd 328: 6.838: (M+H)+: +ESI Product Ion (rt: 6.832, Head 6.870 to min, Tail 2 scans) MF=686 Frag=360.0V RMF=828 [email protected] (219.1743[z=1] 2,6-Di-tert-butyl-4-hydroxymethylphenol -> **) EBC_Sick_Cold_or_Flu_AutoMSMS_SB-A 219.1747

100

203.1436

50

133.1016

147.1160 161.1324

105.0697 119.0855 133.1012

161.1324

119.0863

91.0550

0

187.1125

50

203.1430

100

219.1743

60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 Cpd 496: 6.845: (M+H)+: +ESI Product Ion (rt: 6.827 min) HeadFrag=380.0V to Tail MF=822 [email protected] RMF=920 (219.1749[z=1] -> 2,6-Di-tert-butyl-4-hydroxymethylphenol **) EBC_Nasal_Decongestion_AutoMSMS_SB-AQ_Pos.d 91.0547

100

105.0705

67.0536 79.0550 50

55.0537

117.0706

145.1024

161.1314

0 50 100

173.0961

55.0540 67.0540

119.0855

79.0540

145.1012

105.0698 91.0541

50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 Cpd 496: 6.845: (M+H)+: +ESI Product Ion (rt: 6.828 min) HeadFrag=360.0V to Tail MF=721 [email protected] RMF=859 (219.1749[z=1] -> 2,6-Di-tert-butyl-4-hydroxymethylphenol **) EBC_Nasal_Decongestion_AutoMSMS_SB-AQ_Pos.d

14

299.1105

100 50

211.0586

0 211.0577

271.0787

50 100

299.1099

60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 310 Cpd 679: 7.519: (M+Na)+: +ESI Product Ion (rt: 7.506,Head 7.541tomin, Tail2MF=360 scans) Frag=390.0V RMF=945 [email protected] (299.1103[z=1] Triethyl -> **)citrate EBC_Smoker_AutoMSMS_SB-AQ_Pos.d 225.1946

100 50

100.1131

0 100.1113

50 100

225.1947

50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 Cpd 878: 8.873: (M+H)+: +ESI Product Ion (rt: 8.871, Head 8.908 to min, Tail 2 scans) MF=550 Frag=390.0V RMF=987 [email protected] (225.1963[z=1] 1,3-Dicyclohexylurea -> **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d 100

83.0852

55.0528

100.1114

225.1972

50 0 50

61.0390

83.0847

100

143.1169 100.1113

225.1947

50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 Cpd 878: 8.873: (M+H)+: +ESI Product Ion (rt: 8.872, Head 8.909 to min, Tail 1 scans) MF=524 Frag=380.0V RMF=793 [email protected] (225.1963[z=1] 1,3-Dicyclohexylurea -> **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d 100

242.2833 57.0684

50 0 85.1012

50 100

71.0855 57.0701

242.2849

50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 Cpd 903: 9.087: (M+H)+: +ESI Product Ion (rt: 9.071, Head 9.133 to min, Tail 1 scans) MF=398 Frag=380.0V RMF=858 [email protected] (242.2832[z=1] 1-Hexadecylamine -> **) EBC_Smoker_AutoMSMS_SB-AQ_Pos.d 149.0237

100 93.0331 50

121.0295

0 65.039 50 100

93.033

121.028 149.023

60 70 80 90 100 110 120 130 140 150 160 Cpd 1150: 12.835: (M+H)+: +ESI Product Ion (rt: 12.775, Head 12.846 to Tail min, MF=679 2 scans) RMF=946 Frag=390.0V [email protected] (149.0232[z=1] 1,2-Benzenedicarboxylic -> **) EBC_Smoker_AutoMSMS_SB-AQ_Po acid

15

65.0385

100 50

93.0336

0 39.024

93.033

50 100

121.028

65.039

30 40 50 60 70 80 90 100 110 120 130 140 150 160 Cpd 1150: 12.835: (M+H)+: +ESI Product Ion (rt: 12.777, Head 12.847 to Tail min, MF=492 2 scans) RMF=941 Frag=380.0V [email protected] (149.0232[z=1] 1,2-Benzenedicarboxylic -> **) EBC_Smoker_AutoMSMS_SB-AQ_Po acid

16