Supporting Information

Fig. S1. The sum of peak area obtained by LC-MS using different extraction methods and solvents

Fig. S2. Total ion chromatogram (TIC) of a QC sample, (a), acquired by GC-MS, (b), acquired by LC-MS in positive ionization mode

1

Fig. S3. PCA scores plot of QC and real samples of the three types of teas obtained from GC-MS (R2 = 0.84).

Fig. S4. PCA scores plot of QC and real samples of the three types of teas obtained from LC-MS (R2 = 0.75).

2

Fig. S5. Box plots of relative intensities of 24 key compounds discovered in the three types of tea. Each horizontal line across two types of tea represents a significant

3

difference (p<0.05) among them.

4

Table S1. List of the identified compounds by using GC-MSCompound Tr/s aI bI Similarity Reverse 　Ethylene glycol 381.2 983 989 921 9211,2-Propanediol 402.4 998 1005 948 948 aPyruvic acid 477.4 1049 1049 864 864 aPhenol 478.8 1050 1055 898 898Lactic acid 491.2 1059 1066 931 931 aHexanoic acid 512.2 1073 1073 899 899 aGlycolic acid 516.2 1076 1080 934 934 aValine 1 533.6 1088 1083 927 927 aAlanine 552.6 1101 1093 943 943 aHydroxylamine 563.4 1108 1111 909 909Oxalic acid 600.8 1135 1131 954 9543-Hydroxypropanoic acid 613.4 1144 1144 953 953Phenylmethyl alcohol 624.0 1152 1156 929 940Leucine 1 629.8 1156 1155 933 933 a2-Hydroxybutyric acid 634.4 1159 1157 802 802 a2-Aminobutyric acid 649.4 1170 1177 932 932 aProline 1 655.0 1174 1178 938 938 aIsoleucine 1 658.0 1176 1178 959 959 aMalonic acid 696.0 1203 1205 951 951 aValine 2* 707.6 1212 1221 922 951 aPhenylethyl alcohol 723.0 1224 1223 881 903Urea 757.2 1250 1249 898 903 aSerine 1 764.2 1255 1252 914 914 aEthanolamine 772.6 1262 1265 928 928 aPipecolic acid 776.4 1264 1267 955 988Leucine 2* 781.8 1268 1275 829 829 aPhosphoric acid 784.6 1271 1280 901 901 aGlycerol 785.2 1271 1283 818 820 aIsoleucine 2* 808.6 1289 1300 914 914 aThreonine 1 810.8 1290 1299 810 810 aProline 2* 812.6 1292 1302 851 895 aNicotinic acid 813.0 1292 1299 876 935Phenylacetic acid 817.2 1295 1302 946 946Glycine 823.4 1300 1310 906 921 aSuccinic acid 839.2 1313 1318 947 947 a2-Methyl succinic acid 852.8 1324 1328 892 892Glyceric acid 856.0 1327 1335 890 890 aUracil 864.6 1333 1340 872 886 aFumaric acid 885.2 1350 1348 947 947 aHomoserine 892.4 1356 1350 898 898 aSerine 2* 893.0 1357 1368 903 965 a

5

Threonine 2* 923.0 1381 1367 838 838 aHydroquinone 943.0 1397 1408 877 887 aGlutaric acid 951.0 1404 1412 862 876 aAspartic acid 1 971.6 1422 1412 936 936 abeta-Alanine 972.8 1423 1434 902 919 aMalic acid 1045.0 1486 1483 945 945 aThreitol 1063.6 1502 1507 915 926 aSalicyclic acid 1065.4 1504 1508 892 892Aspartic acid 2* 1079.8 1517 1521 957 957 aTheanine 1082.6 1519 1524 950 950 a4-Aminobutyric acid 1088.6 1525 1542 829 915 aGlutamic acid 1 1095.6 1531 1518 871 903 aPyrogallol 1096.8 1532 1537 820 820Threonic acid 1102.2 1537 1523 898 903 aPhenylalanine 1110.4 1545 1554 836 881 aCinnamic acid 1114.2 1548 1543 846 906 a2-Isopropylmalic acid 1135.4 1568 1562 829 853Asparagine 1167.4 1597 1589 888 888 aGlutamic acid 2* 1187.6 1616 1629 816 835 aArabinonic acid-1,4-lactone 1201.8 1630 1647 819 8311,3,5-Benzenetriol 1212.0 1640 1647 893 897Xylose 1220.4 1648 1646 879 879 aArabinose 1227.4 1655 1654 912 912 aRibose 1242.8 1670 1668 806 825 aXylitol 1261.2 1688 1682 887 887 aArabinitol 1284.4 1711 1710 861 861 aRibitol 1289.0 1715 1727 892 900 aPutrescine 1301.6 1728 1719 875 935 atrans-Aconitic acid 1319.8 1747 1745 846 884 aGlycerol 1-phosphate 1330.4 1758 1744 805 805 ao-Phosphocolamine 1349.2 1777 1768 822 841Shikimic acid 1377.6 1806 1794 898 898 aCitric acid 1384.2 1814 1815 928 934 aProtocatechuic acid 1385.2 1815 1828 826 874 aQuinic acid 1420.8 1853 1849 852 855 aFructose 1 1430.0 1863 1859 895 895 aCaffeine 1430.8 1863 1848 855 937Fructose 2* 1438.8 1872 1868 901 932 aMannose 1442.6 1876 1885 828 936 aGalactose 1446.4 1880 1882 850 899 aTyrosine 1449.4 1883 1901 849 849 aGlucose 1 1452.8 1887 1882 905 905 aGlucose 2* 1469.6 1905 1900 947 947 aMannitol 1480.8 1918 1925 911 911 a

6

p-Coumaric acid 1498.4 1938 1943 879 879 aGallic acid 1510.8 1952 1962 806 824 aGluconic acid 1555.4 2002 1991 875 875 aMucic acid 1580.6 2032 2014 828 828 an-Hexadecanoic acid 1591.2 2045 2054 899 901Inositol 1621.4 2081 2083 908 908 aPhytol 1695.4 2171 2179 824 874Linoleic acid 1726.4 2210 2208 886 901 aLinolenic acid 1731.2 2216 2218 839 867 aStearic acid 1752.6 2244 2243 875 877 aGlucose-6-phosphate 1804.2 2312 2320 822 841 aSucrose 2033.0 2631 2627 818 818 aLactose 2062.2 2674 2675 848 848 aMaltose 2094.8 2721 2723 801 801 aGalactinol 2264.4 2966 2959 916 916 a

aI, The retention index was calculated in this experiment.bI, The retention index was reported in Wiley library.*, These compounds have two peaks in gas chromatography for the derivatization.a, These compounds were confirmed by the standards.

7

Table S2. List of the identified compounds by using LC-MS

Compound Tr/min m/zESI

modeDetected

m/zMass

accuracy/ppmMS/MS Fragment Metlin ID 　

Choline 1.02 104.1070 M+H 104.1078 7.7 60.0809, 58.0651 56 bPhosphocholine 1.04 184.0733 M+H 184.0722 -6.0 124.9919, 86.091, 98.9784, 60.0776 3318 b

Glycerophosphocholine 1.05 258.1101 M+H 258.1116 5.8 104.1059, 124.9984, 86.0959, 184.07114, 60.0796

370 a,b

Glutamic acid 1.06 148.0604 M+H 148.0616 8.1 84.0326, 56.0415 19 a,bProline 1.07 116.0706 M+H 116.0699 -6.0 70.0606 29 a,bValine 1.09 118.0863 M+H 118.0854 -7.6 72.0782, 55.0547 35 a,bBetaine 1.09 118.0863 M+H 118.0854 -7.6 58.0623, 59.0704 287 a,bTheanine 1.2 175.1076 M+H 175.1085 5.1 84.0454, 158.0808 44433 a,bLeucine 1.45 132.1019 M+H 132.1008 -8.3 86.0965, 69.0707 23 a,b

Tyrosine 1.47 182.0812 M+H 182.0803 -4.9 95.0463, 136.0708, 123.04, 119.0451, 91.0511, 123.04

34 a,b

Adenine 1.49 136.0618 M+H 136.0631 9.6 119.0313, 94.0505, 109.0508 85 a,bNiacinamide 1.6 123.0553 M+H 123.0543 -8.1 80.0451, 78.0296, 53.0359 1497 bGuanine 1.79 152.0567 M+H 152.0563 -2.6 134.9958, 110.0074 315 bPhenylalanine 1.79 166.0863 M+H 166.0865 1.2 120.0498, 103.0278, 93.0462 28 a,bAdenosine 1.9 268.1043 M+H 268.1045 0.7 136.0738, 182.9767, 154.9758, 108.9675 86 a,bPipecolic acid 2.06 130.0863 M+H 130.0859 -3.1 84.0817, 67.0547, 56.0501 58337 a,bNipecotic acid 2.06 130.0863 M+H 130.0859 -3.1 112.0763, 84.0436, 56.0504 44223 a,bTheogallin 2.47 345.0816 M+H 345.0782 -9.9 153.0178 68616Tryptophan 2.58 205.0974 M+H 205.0963 -5.4 146.05, 118.0567, 132.0716, 188.0591 33 a,bGallocatechin 3.48 307.0812 M+H 307.0808 -1.3 139.0355, 163.0350, 195.0572 47219 a

8

5-Caffeoylquinic acid 4.34 355.1024 M+H 355.1032 2.3 163.0392, 145.0291 95165 a5'-Deoxy-5'-(methylthio)adenosine 5.28 298.0968 M+H 298.0962 -2.0 136.0564, 61.0077 3425 bEpigallocatechin 5.32 307.0812 M+H 307.0831 6.2 139.0387, 163.0382 44010 aTheobromine 5.38 181.0720 M+H 181.0705 -8.3 138.0651, 110.0703 1456Catechin 5.95 291.0863 M+H 291.0857 -2.1 139.0384, 207.0638, 123.0437, 165.0532 3419 a,b3-p-Coumaroylquinic acid 5.98 339.1074 M+H 339.1091 5.0 147.0437, 119.0500 864213-Caffeoylquinic acid 6.54 355.1024 M+H 355.1011 -3.7 163.0392, 145.0290 3498 a,bTheophylline 6.69 181.0720 M+H 181.0714 -3.3 124.0501, 96.0554 1458 a,b4-Caffeoylquinic acid 6.87 355.1024 M+H 355.1007 -4.8 163.0392, 145.0292 3498 aEpicatechin 7.2 291.0863 M+H 291.0891 9.6 139.0376, 123.0430, 161.0579, 207.0621 3420 a,b2-Benzofurancarboxaldehyde 7.88 147.0441 M+H 147.0438 -2.0 119.0363, 91.0446, 65.0325 89059Caffeine 8.1 195.0877 M+H 195.0894 8.7 138.0623, 110.0597, 83.0522, 69.0382 1455 bEpigallocatechin gallate 8.34 459.0922 M+H 459.0955 7.2 139.0415, 153.0204, 151.0414 3550 a,bGallocatechin gallate 9.08 459.0922 M+H 459.0912 -2.2 139.0445, 151.0448, 153.0241 47336 a

Luteolin-8-C-glucoside 9.25 449.1078 M+H 449.1092 3.1 299.0431, 329.0523, 353.0518, 413.0701, 431.0792

48901 a

Myricetin 3-O-rutinoside 9.3 627.1556 M+H 627.1547 -1.4 481.1386, 319.0708 50838Catechin-4a-epicatechin 3-O-gallate 9.4 731.1607 M+H 731.1656 6.7 409.0836, 289.0646, 123.0413 92754Myricetin 3-O-galactoside 9.45 481.0977 M+H 481.1013 7.5 319.0536 50828Myricetin 3-O-glucoside 9.5 481.0977 M+H 481.0970 -1.5 319.049 50836Quercetin 3-O-galactosylrutinosid 9.67 773.2135 M+H 773.2125 -1.3 465.0791, 303.0311, 611.1250 c

Luteolin-6-C-glucoside 9.75 449.1078 M+H 449.1064 -3.1 299.0620, 329.0732, 353.0735, 395.0846, 431.1071

48900 a

Apigenin-6-C-glucosyl-8-C-pentoside 9.87 565.1552 M+H 565.1534 -3.2 427.0962, 511.1164, 379.0750 86134Quercetin 3-O-glucosylrutinoside 9.98 773.2135 M+H 773.2109 -3.4 465.0736, 303.0305, 611.1234 50523

9

Epicatechin gallate 10.08 443.0976 M+H 443.0996 4.5 123.0425, 139.0368, 153.0158, 165.0615 43599 a,b

Epigallocatechin 3-O-(3-O-methylgallate)

10.14 473.1078 M+H 473.1103 5.3 139.0360, 167.0312, 151.0359, 289.0657 47337

Apigenin-6,8-C-diglucoside 10.18 595.1657 M+H 595.1696 6.6 283.0699, 313.0804, 337.0808, 415.1281, 433.1281, 475.1409

48649

Myricetin 3-O-rhamnoside 10.26 465.1028 M+H 465.1047 4.1 319.0527 50852 a,bQuercetin 3-O-rutinoside 10.41 611.1607 M+H 611.1640 5.4 303.0594, 465.0655 50514 aKaempferol 3-O-galactosylrutinosid 10.45 757.2186 M+H 757.2244 7.7 287.0411, 449.0882, 595.1417

Apigenin-8-C-glycoside 10.6 433.1129 M+H 433.1160 7.2 283.0775, 313.0908, 337.0908, 397.1178, 415.1307

45737 b

Quercetin 3-O-galactoside 10.6 465.1028 M+H 465.1058 6.5 303.0598 87190 aCatechin gallate 10.7 443.0976 M+H 443.0994 4.1 123.0438, 139.0386, 153.0173, 165.0547 47307 a,bEpicatechin-4a-epicatechin 3,3'-digallate 10.71 883.1716 M+H 883.1687 -3.3 563.1292, 409.0974, 271.0646, 153.0197 95677Quercetin 3-O-glucoside 10.75 465.1028 M+H 465.1004 -5.2 303.0607 64941 a,b

Isovitexin 10.86 433.1129 M+H 433.1143 3.2 283.0493, 313.0588, 337.0576, 379.0663, 415.0855

48769 a

Kaempferol 3-O-glucosylrutinoside 10.92 757.2186 M+H 757.2160 -3.4 287.0419, 449.0879, 595.1496 93416Kaempferol 3-O-rhamnosylrutinoside 11.33 741.2237 M+H 741.2195 -5.7 287.0436, 449.0947, 595.1456 50091Kaempferol-3-O-rutinoside 11.45 595.1657 M+H 595.1695 6.4 287.0622, 449.1232 50150 aKaempferol 3-O-galactoside 11.48 449.1078 M+H 449.1110 7.1 287.0705 64225

Kaempferol 3-O-glucoside 11.82 449.1078 M+H 449.1102 5.3 287.060950141 / 45733

a,b

Quercetin 3-O-rhamnoside 11.86 449.1078 M+H 449.1064 -3.1 303.0300 43747 aEpicatechin 3-O-(3-O-methylgallate) 11.88 457.1129 M+H 457.1097 -7.0 123.0495, 139.0451, 167.0471, 151.0455 47309Myricetin 12.09 319.0448 M+H 319.0443 -1.6 153.0181, 273.0391, 165.0185 3448 a,b

10

Kaempferol 3-O-rhamnoside 12.41 433.1129 M+H 433.1125 -0.9 287.0508 50258Theaflavin 14.12 565.1341 M+H 565.1374 5.8 139.0406, 259.0627, 427.1044, 529.1139 44483 b

Quercetin 14.14 303.0499 M+H 303.0492 -2.3 229.0505, 153.0191, 165.0189 409 a,b

Theaflavin 3-gallate 14.6 717.1450 M+H 717.1431 -2.6 139.0423, 277.0765, 409.1004, 529.1268, 579.1238

58315 a

Theaflavin 3'-gallate 14.92 717.1450 M+H 717.1434 -2.2 139.0423 277.0795, 333.0707, 409.1034, 579.1310

43596 a

Theaflavin 3,3'-digallate 15.04 869.1560 M+H 869.1538 -2.5 139.0366, 277.0651, 333.0531, 391.0736, 561.0915, 731.1084

43979 a,b

Apigenin 15.75 271.0601 M+H 271.0617 5.9 153.0139 3393 bKaempferol 16.13 287.0550 M+H 287.0531 -6.6 165.0195, 153.0201 3410 a,bLysoPE(18:2) 18.65 478.2928 M+H 478.2899 -6.1 337.2998, 62.0645, 306.3054 62292MG(18:3) 18.8 353.2686 M+H 353.2701 4.2 261.2426 95.0928 81.0759 135.1275 62351LysoPC(18:3) 18.85 518.3241 M+H 518.3206 -6.8 184.0456, 104.0902, 500.2392 61698LysoPC(18:2) 19.13 520.3395 M+H 520.3399 0.8 184.0793, 104.1099, 502.3488 61696LysoPC(16:0) 19.33 496.3398 M+H 496.3417 3.8 184.0890, 104.1155 61692LysoPC(18:1) 19.56 522.3554 M+H 522.3555 0.2 184.0871, 104.1141 61695

gamma-Linolenic acid 19.84 279.2319 M+H 279.2314 -1.8 67.0580, 81.0745, 95.0915, 109.1069, 243.2037

386 a,b

DG(16:0/18:4) 20.08 589.4818 M+H 589.4806 -2.0 313.2623, 333.2300, 259.1573 58869Palmitic amide 20.18 256.2635 M+H 256.2621 -5.5 88.072, 57.0681, 102.0864 62905 a,bLysoPC(18:0) 20.23 524.3711 M+H 524.3740 5.5 184.0611, 104.1000, 506.3215 61694

Oleamide 20.29 282.2791 M+H 282.2777 -5.0 69.0571, 83.0922, 57.0387, 97.1068, 135.1268, 247.2639, 163.1546

4115 a,b

PG(18:3/18:0) 20.29 773.5327 M+H 773.5266 -7.9 755.6093, 611.5211, 184.0897, 335.2883, 79141

11

259.224

DG(18:4/18:3) 20.3 611.4670 M+H 611.4657 -2.1 335.2810, 333.2693, 593.4746, 259.2121, 149.1360

58860

DG(16:0/18:3) 20.62 591.4983 M+H 591.4963 -3.4 335.2570, 313.2676 261.2228 58853DG(18:3/18:3) 20.82 613.4827 M+H 613.4793 -5.5 335.2843, 595.5200 58830PE(18:3/16:0) 20.94 714.5068 M+H 714.5100 4.5 573.5212 317.2654 77459DG(18:2/18:3) 20.95 615.4983 M+H 615.4956 -4.4 335.2819, 337.2980, 261.2429 58858

Docosenamide 21 338.3417 M+H 338.3414 -0.9 321.2556, 303.2490, 83.0712, 69.0582, 57.0608, 97.0835

64926 a,b

DG(18:1/18:3) 21.08 617.5142 M+H 617.5172 4.9 339.2844, 335.2551, 261.2155 58857DG(18:0/18:3) 21.28 619.5289 M+H 619.5270 -3.1 335.2412, 341.2937, 261.2140 58855Digallocatechin-catechin 9.57 899.1665 M+H 899.1664 -0.1 579.1259, 425.0965, 287.0596, 153.0195 　 c

a, These compounds were confirmed by standards.b, These compounds were confirmed through the fragment ions from the Metlin database.c, These compounds were confirmed by literature. (Y. Zhao, P. Chen, L. Lin, J. Harnly, L.L. Yu, Z. Li, Food Chem., 126 (2011) 1269-1277.)

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Table S3. List of tea samples purchased from different production sitesGreen

tea

Brands Production sites Oolong

tea

Brands Production sites Black

tea

Brands Production sites

1 High-grade green tea Fujian, China 1 Tieguanyin tea Fujian, China 1 Organic black tea Fujian, China

2 Organic green tea Fujian, China 2 Tieguanyin tea Fujian, China 2 High-grade black tea Fujian, China

3 Green tea Fujian, China 3 Tieguanyin tea Fujian, China 3 Lapsang sauchong tea Fujian, China

4 Biluochun tea Jiangsu, China 4 Tieguanyin tea Fujian, China 4 Lapsang sauchong tea Fujian, China

5 Longjing tea Zhejiang, China 5 Tieguanyin tea Fujian, China 5 Darjeeling tea India

6 Cha-zhuangyuan green

tea

Sichuan, China 6 Tieguanyin tea Fujian, China 6 Ceylon tea Sri Lanca

7 Wuniuzao tea Zhejiang, China 7 Tieguanyin tea Fujian, China 7 Ahmad English

breakfast tea

Sri Lanca

8 Qixianyinya tea Jiangsu, China 8 High mountain

tieguanyin tea

Taiwan, China 8 Ahmad English No.1

tea

Sri Lanca

9 Duyun Maojian tea Guizhou, China 9 A-li mountain tea Taiwan , China 9 Lipton yellow label tea Anhui, China

10 Huangshan Maofeng

tea

Anhui, China 10 Huangjingui tea Fujian , China

11 Fangshan Ziwu tea Jiangsu, China 11 Benshan tea Fujian, China

12 Lipton green tea Anhui, China 12 Maoxie tea Fujian, China

13

Table S4. Results list of the eight compounds used for linear calibration in GC-MS analysis.

Compound Tr/s aILinear

range/(μg/mL)LOD/(ng/mL)

Correlation coefficient

Pyruvic acid 477 1049 1-500 13 0.993Lactic acid 491 1058 1-50 3 0.999

Serine* 764/893 1255 1-500 24 0.998Malic acid 1045 1485 1-300 4 0.990

Aspartic acid* 971/1080 1421 5-500 50 0.994Fructose* 1430/1438 1862/1871 1-100 4 0.993Glucose* 1452/1469 1886/1905 1-100 4 0.994

Gallic acid 1510 1951 1-100 6 0.995* These compounds had two peaks in gas chromatography, the sum of the two peak areas were used here.

Table S5. Results list of the ten compounds used for linear calibration in LC-MS analysis.

Compound Tr/min m/z Linear rage/(ng/mL) LOD/(ng/mL)Correlatio

n coefficient

Theanine 1.20 175.1016 4-40000 0.05 0.998Adenosine 1.90 268.1043 0.8-8000 0.05 0.999Tryptophan 2.58 205.0974 4-40000 0.2 0.999

Chlorogenic acid 6.54 355.1024 4-40000 0.4 0.999Gallocatechin gallate 9.08 459.0922 4-40000 0.2 0.994

Rutin 10.41 611.1607 4-8000 0.2 0.999Quercitrin 11.86 449.1078 4-8000 0.2 0.999Myricetin 12.09 319.0448 4-40000 0.3 0.997Quercetin 14.14 303.0499 4-8000 0.1 0.999

Kaempferol 16.13 287.0555 4-8000 0.1 0.999

14

Table S6. List of compounds with VIP value larger than 1.0 in GC-MS data

Compound Tr/s VIP value [O]/[G] p G-O [B]/[G] p G-B [B]/[O] p O-B

Fructose 1439 9.6 4.56 6.78×10-5 5.25 1.66×10-4 1.15 3.20×10-1

Caffeine 1431 3.0 0.75 2.76×10-4 1.02 8.87×10-1 1.37 6.47×10-4

Malic acid 1045 2.5 2.67 3.23×10-5 1.04 7.22×10-1 0.39 1.24×10-4

Quinic acid 1420 8.5 1.36 2.68×10-3 1.68 2.90×10-4 1.24 1.02×10-1

beta-Alanine 972 1.4 0.28 3.23×10-5 0.39 2.19×10-4 1.40 1.18×10-1

M167T2209 2209 2.0 0.13 8.64×10-5 0.40 1.90×10-2 3.13 3.93×10-2

M191T2108 2108 6.6 0.75 1.82×10-3 1.26 5.50×10-2 1.68 6.92×10-3

Galactinol 2266 2.8 11.54 3.23×10-5 0.94 7.76×10-1 0.08 1.24×10-4

Glycerol 784 2.3 0.41 2.76×10-4 2.77 2.90×10-4 6.77 1.24×10-4

Citric acid 1384 1.5 0.46 6.78×10-5 1.25 3.93×10-2 2.71 1.24×10-4

Phosphoric acid

7842.4

0.39 2.20×10-4 1.42 6.47×10-4 3.66 1.24×10-4

M355T2179 2179 4.4 1.87 2.20×10-4 0.27 2.24×10-3 0.14 2.90×10-4

M355T2232 2232 10.5 2.41 3.23×10-5 0.16 8.37×10-4 0.06 1.24×10-4

Sucrose 2032 3.0 2.01 5.32×10-4 0.81 7.22×10-1 0.41 3.57×10-3

Glucose 1452 14.0 4.02 5.32×10-4 3.22 1.08×10-3 0.80 2.27×10-1

Gallic acid 1511 7.9 0.48 6.58×10-4 2.44 1.66×10-4 5.06 1.24×10-4

Inositol 1621 5.3 2.53 5.31×10-5 2.24 2.90×10-4 0.89 2.27×10-1

Oxalic acid 601 8.7 0.47 9.37×10-3 2.70 2.90×10-4 5.74 1.24×10-4

Theanine 1083 4.6 0.28 3.23×10-5 0.37 1.66×10-4 1.29 7.56×10-2

Glutamic acid 1095 2.1 0.42 4.15×10-5 0.41 2.90×10-4 0.97 4.77×10-1

[O]/[G]. The ratio of mean value of one compound in oolong and green tea. [B]/[G]. The ratio of mean value of one compound in black and green tea.

15

[B]/[O]. The ratio of mean value of one compound in black and oolong tea.

Table S7. List of compounds with VIP value larger than 2.0 in LC-MS data

Compound m/z Tr/s VIP value

[O]/[G] p G-O[B]/[G]

p G-B[B]/[O]

P O-B

Epigallocatechin307.083

1 320 10.21.35 4.96×10-5 0.28 4.56×10-4 0.21 6.80×10-6

Theogallin345.078

2 154 9.30.20 7.40×10-7 0.50 2.44×10-3 2.43 1.18×10-2

Epigallocatechin gallate459.095

3 500 7.4 0.99 4.10×10-1 0.44 6.80×10-6 0.44 6.80×10-6

Theanine175.108

5 70 7.20.66 4.96×10-5 0.80 4.30×10-3 1.21 1.69×10-1

M579T423579.150

3 423 7.10.55 2.96×10-6 0.20 6.80×10-6 0.36 2.04×10-4

Epicatechin 291.089

1 433 6.71.10 2.42×10-2 0.38 1.31×10-3 0.34 1.80×10-3

Epicatechin gallate443.099

6 605 6.70.70 7.40×10-7 0.47 4.76×10-5 0.67 1.84×10-2

Caffeine195.089

4 489 6.60.88 2.96×10-6 1.22 2.72×10-5 1.39 6.80×10-6

Theobromine181.070

5 322 5.70.20 8.88×10-6 1.48 8.15×10-2 7.52 6.80×10-6

M466T818466.265

0 818 5.70.38 3.71×10-4 0.01 6.80×10-6 0.04 6.80×10-6

16

Gallocatechin 307.080

8 207 5.31.52 8.58×10-4 0.31 1.80×10-3 0.20 4.76×10-5

M652T384652.114

1 384 5.00.10 7.40×10-7 0.25 1.29×10-4 2.59 9.39×10-4

Pipecolic acid130.085

9 127 4.80.48 1.83×10-3 2.68 4.76×10-5 5.56 2.72×10-5

M261T518261.171

5 518 4.40.36 2.01×10-4 0.41 4.30×10-3 1.16 8.08×10-1

M763T426763.150

4 426 4.30.35 4.96×10-5 4.04 4.56×10-4 11.53 6.80×10-6

Apigenin-6,8-C-diglucoside595.169

6 613 4.33.32 8.88×10-6 2.27 1.84×10-2 0.68 4.91×10-2

M337T87337.160

4 87 4.2 0.88 2.66×10-1 1.76 5.62×10-3 2.01 9.39×10-4

LysoPC(18:2)520.339

9 1147 4.00.30 2.96×10-6 1.14 6.02×10-1 3.79 1.29×10-4

Glycerophosphocholine258.111

6 63 3.90.35 4.96×10-4 0.27 8.17×10-5 0.77 3.10×10-1

Gallocatechin gallate459.091

2 545 3.90.74 1.73×10-2 0.09 6.80×10-6 0.12 6.80×10-6

2-Benzofurancarboxaldehyde147.043

8 477 3.90.50 1.00×10-2 1.63 1.48×10-2 3.26 4.76×10-5

M289T501289.071

5 501 3.71.05 1.45×10-2 0.47 6.80×10-6 0.45 6.80×10-6

M482T628482.259

8 628 3.60.53 6.81×10-3 0.02 6.80×10-6 0.04 6.80×10-6

17

Catechin-4a-epicatechin 3-O-gallate731.165

6 556 3.60.34 7.40×10-7 0.25 6.80×10-6 0.73 1.48×10-1

M328T115328.137

7 115 3.3 1.21 1.78×10-1 6.62 6.80×10-6 5.48 6.80×10-6

5'-Deoxy-5'-(methylthio)adenosine298.096

2 323 3.30.60 4.96×10-5 0.41 1.80×10-3 0.69 6.93×10-2

LysoPC(18:3)518.320

6 1129 3.30.40 7.17×10-5 1.21 6.51×10-1 3.01 1.31×10-3

Adenine136.063

1 89 3.30.80 3.32×10-2 4.12 6.80×10-6 5.15 6.80×10-6

Myricetin 3-O-glucoside481.097

0 571 3.31.77 2.91×10-3 0.69 1.69×10-1 0.39 1.80×10-3

M458T331458.107

9 331 3.20.10 2.96×10-6 0.07 2.72×10-5 0.76 4.09×10-2

Choline104.108

4 61 3.2 1.04 2.91×10-1 1.43 1.36×10-5 1.37 8.17×10-5

M287T529287.055

2 529 3.20.42 1.11×10-3 3.90 8.17×10-5 9.34 6.80×10-6

Catechin 291.085

7 357 3.20.61 5.18×10-6 0.40 9.39×10-4 0.65 4.91×10-2

M579T643579.171

0 643 3.03.73 2.22×10-5 1.67 9.55×10-2 0.45 2.44×10-3

M130T78130.050

1 78 3.00.39 1.48×10-6 0.69 1.80×10-3 1.76 1.80×10-3

M434T462434.202

0 462 3.00.54 4.51×10-3 0.02 6.80×10-6 0.04 6.80×10-6

18

M793T1248792.561

8 1248 3.0 1.15 8.87×10-2 0.28 2.72×10-5 0.24 6.80×10-6

Epigallocatechin 3-O-(3-O-methylgallate)473.110

3 601 2.93.81 1.43×10-3 1.02 2.47×10-1 0.27 3.26×10-3

M427T693427.102

2 693 2.90.30 1.48×10-6 0.32 9.39×10-4 1.09 7.54×10-1

M747T487747.155

2 487 2.90.73 8.29×10-3 0.22 1.36×10-5 0.30 9.39×10-4

M595T454595.162

6 454 2.84.58 2.96×10-6 1.54 1.69×10-1 0.34 1.29×10-4

M611T282611.139

3 282 2.82.03 1.11×10-3 0.28 3.26×10-3 0.14 4.76×10-5

M535T1254535.270

2 1254 2.8 0.84 5.97×10-2 2.73 4.56×10-4 3.25 8.17×10-5

Epicatechin-4a-epicatechin 3,3'-digallate883.168

7 637 2.70.14 7.40×10-7 0.16 6.80×10-6 1.16 4.64×10-1

M549T157549.171

4 157 2.70.33 2.22×10-5 0.43 2.44×10-3 1.29 2.47×10-1

M275T571275.186

6 571 2.70.48 6.56×10-4 0.40 9.29×10-3 0.84 9.17×10-1

M568T1277568.426

4 1277 2.71.38 3.87×10-2 0.61 2.27×10-2 0.44 1.36×10-5

M381T64381.077

0 64 2.61.97 7.40×10-7 1.02 8.08×10-1 0.52 4.30×10-3

Leucine132.100

8 87 2.60.48 4.49×10-2 0.99 9.72×10-1 2.06 8.17×10-5

19

DG(18:4/18:3)611.465

7 1203 2.51.80 1.45×10-2 0.36 1.84×10-2 0.20 6.80×10-6

M654T552654.129

8 552 2.50.17 7.40×10-7 0.20 6.80×10-6 1.21 7.54×10-1

Kaempferol 3-O-glucoside449.110

2 701 2.50.42 2.74×10-4 1.18 3.45×10-1 2.85 8.17×10-5

Quercetin 3-O-glucosylrutinoside773.210

9 598 2.51.84 2.84×10-2 0.85 6.51×10-1 0.46 9.29×10-3

M110T52110.009

3 52 2.50.78 3.33×10-5 1.04 3.10×10-1 1.33 9.39×10-4

M467T941467.133

4 941 2.40.17 1.48×10-6 0.27 2.04×10-4 1.59 8.08×10-1

M147T351147.043

8 351 2.40.41 2.32×10-3 1.51 4.09×10-2 3.67 6.80×10-6

Digallocatechin-catechin899.166

4 572 2.40.20 7.40×10-7 0.53 5.62×10-3 2.64 2.72×10-5

M294T90294.153

6 90 2.4 1.02 5.51×10-1 5.48 1.36×10-5 5.37 6.80×10-6

M867T687867.176

0 687 2.40.15 7.40×10-7 0.16 2.72×10-5 1.12 9.72×10-1

M595T347595.144

4 347 2.3 0.99 7.99×10-1 0.32 2.44×10-3 0.33 1.31×10-3

M627T561627.155

1 561 2.32.94 6.56×10-4 0.55 5.85×10-2 0.19 1.29×10-4

Adenosine268.104

5 115 2.30.70 3.87×10-2 0.31 1.36×10-5 0.44 3.06×10-4

20

DG(18:3/18:3)613.479

3 1234 2.31.82 6.56×10-4 0.41 1.31×10-3 0.23 6.80×10-6

M579T466579.170

2 466 2.33.78 2.22×10-5 0.99 4.64×10-1 0.26 6.80×10-6

M544T156544.080

7 156 2.20.06 7.40×10-7 0.24 1.29×10-4 4.30 4.91×10-2

Proline116.069

9 65 2.20.36 6.56×10-4 1.16 2.47×10-1 3.20 6.80×10-6

M149T1168149.025

5 1168 2.20.86 4.96×10-4 1.11 1.29×10-1 1.29 2.04×10-4

M867T477867.212

6 477 2.10.50 2.22×10-5 0.16 6.80×10-6 0.32 2.72×10-5

M241T92241.152

3 92 2.10.57 5.18×10-6 0.99 8.62×10-1 1.74 4.76×10-5

M715T609715.165

5 609 2.00.27 7.40×10-7 0.30 1.36×10-5 1.11 5.08×10-1

M183T52182.962

4 52 2.00.59 3.33×10-5 1.07 2.47×10-1 1.81 3.06×10-4

M229T90229.151

8 90 2.00.65 2.74×10-4 0.88 2.77×10-1 1.35 1.80×10-3

[O]/[G]. The ratio of mean value of one compound in oolong and green tea. [B]/[G]. The ratio of mean value of one compound in black and green tea.[B]/[O]. The ratio of mean value of one compound in black and oolong tea.

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