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
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).
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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 difference (p<0.05) among them.
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Table S1. List of the identified compounds by using GC-MS
Compound / Tr/s / aI / bI / Similarity / ReverseEthylene glycol / 381.2 / 983 / 989 / 921 / 921
1,2-Propanediol / 402.4 / 998 / 1005 / 948 / 948 / a
Pyruvic acid / 477.4 / 1049 / 1049 / 864 / 864 / a
Phenol / 478.8 / 1050 / 1055 / 898 / 898
Lactic acid / 491.2 / 1059 / 1066 / 931 / 931 / a
Hexanoic acid / 512.2 / 1073 / 1073 / 899 / 899 / a
Glycolic acid / 516.2 / 1076 / 1080 / 934 / 934 / a
Valine 1 / 533.6 / 1088 / 1083 / 927 / 927 / a
Alanine / 552.6 / 1101 / 1093 / 943 / 943 / a
Hydroxylamine / 563.4 / 1108 / 1111 / 909 / 909
Oxalic acid / 600.8 / 1135 / 1131 / 954 / 954
3-Hydroxypropanoic acid / 613.4 / 1144 / 1144 / 953 / 953
Phenylmethyl alcohol / 624.0 / 1152 / 1156 / 929 / 940
Leucine 1 / 629.8 / 1156 / 1155 / 933 / 933 / a
2-Hydroxybutyric acid / 634.4 / 1159 / 1157 / 802 / 802 / a
2-Aminobutyric acid / 649.4 / 1170 / 1177 / 932 / 932 / a
Proline 1 / 655.0 / 1174 / 1178 / 938 / 938 / a
Isoleucine 1 / 658.0 / 1176 / 1178 / 959 / 959 / a
Malonic acid / 696.0 / 1203 / 1205 / 951 / 951 / a
Valine 2* / 707.6 / 1212 / 1221 / 922 / 951 / a
Phenylethyl alcohol / 723.0 / 1224 / 1223 / 881 / 903
Urea / 757.2 / 1250 / 1249 / 898 / 903 / a
Serine 1 / 764.2 / 1255 / 1252 / 914 / 914 / a
Ethanolamine / 772.6 / 1262 / 1265 / 928 / 928 / a
Pipecolic acid / 776.4 / 1264 / 1267 / 955 / 988
Leucine 2* / 781.8 / 1268 / 1275 / 829 / 829 / a
Phosphoric acid / 784.6 / 1271 / 1280 / 901 / 901 / a
Glycerol / 785.2 / 1271 / 1283 / 818 / 820 / a
Isoleucine 2* / 808.6 / 1289 / 1300 / 914 / 914 / a
Threonine 1 / 810.8 / 1290 / 1299 / 810 / 810 / a
Proline 2* / 812.6 / 1292 / 1302 / 851 / 895 / a
Nicotinic acid / 813.0 / 1292 / 1299 / 876 / 935
Phenylacetic acid / 817.2 / 1295 / 1302 / 946 / 946
Glycine / 823.4 / 1300 / 1310 / 906 / 921 / a
Succinic acid / 839.2 / 1313 / 1318 / 947 / 947 / a
2-Methyl succinic acid / 852.8 / 1324 / 1328 / 892 / 892
Glyceric acid / 856.0 / 1327 / 1335 / 890 / 890 / a
Uracil / 864.6 / 1333 / 1340 / 872 / 886 / a
Fumaric acid / 885.2 / 1350 / 1348 / 947 / 947 / a
Homoserine / 892.4 / 1356 / 1350 / 898 / 898 / a
Serine 2* / 893.0 / 1357 / 1368 / 903 / 965 / a
Threonine 2* / 923.0 / 1381 / 1367 / 838 / 838 / a
Hydroquinone / 943.0 / 1397 / 1408 / 877 / 887 / a
Glutaric acid / 951.0 / 1404 / 1412 / 862 / 876 / a
Aspartic acid 1 / 971.6 / 1422 / 1412 / 936 / 936 / a
beta-Alanine / 972.8 / 1423 / 1434 / 902 / 919 / a
Malic acid / 1045.0 / 1486 / 1483 / 945 / 945 / a
Threitol / 1063.6 / 1502 / 1507 / 915 / 926 / a
Salicyclic acid / 1065.4 / 1504 / 1508 / 892 / 892
Aspartic acid 2* / 1079.8 / 1517 / 1521 / 957 / 957 / a
Theanine / 1082.6 / 1519 / 1524 / 950 / 950 / a
4-Aminobutyric acid / 1088.6 / 1525 / 1542 / 829 / 915 / a
Glutamic acid 1 / 1095.6 / 1531 / 1518 / 871 / 903 / a
Pyrogallol / 1096.8 / 1532 / 1537 / 820 / 820
Threonic acid / 1102.2 / 1537 / 1523 / 898 / 903 / a
Phenylalanine / 1110.4 / 1545 / 1554 / 836 / 881 / a
Cinnamic acid / 1114.2 / 1548 / 1543 / 846 / 906 / a
2-Isopropylmalic acid / 1135.4 / 1568 / 1562 / 829 / 853
Asparagine / 1167.4 / 1597 / 1589 / 888 / 888 / a
Glutamic acid 2* / 1187.6 / 1616 / 1629 / 816 / 835 / a
Arabinonic acid-1,4-lactone / 1201.8 / 1630 / 1647 / 819 / 831
1,3,5-Benzenetriol / 1212.0 / 1640 / 1647 / 893 / 897
Xylose / 1220.4 / 1648 / 1646 / 879 / 879 / a
Arabinose / 1227.4 / 1655 / 1654 / 912 / 912 / a
Ribose / 1242.8 / 1670 / 1668 / 806 / 825 / a
Xylitol / 1261.2 / 1688 / 1682 / 887 / 887 / a
Arabinitol / 1284.4 / 1711 / 1710 / 861 / 861 / a
Ribitol / 1289.0 / 1715 / 1727 / 892 / 900 / a
Putrescine / 1301.6 / 1728 / 1719 / 875 / 935 / a
trans-Aconitic acid / 1319.8 / 1747 / 1745 / 846 / 884 / a
Glycerol 1-phosphate / 1330.4 / 1758 / 1744 / 805 / 805 / a
o-Phosphocolamine / 1349.2 / 1777 / 1768 / 822 / 841
Shikimic acid / 1377.6 / 1806 / 1794 / 898 / 898 / a
Citric acid / 1384.2 / 1814 / 1815 / 928 / 934 / a
Protocatechuic acid / 1385.2 / 1815 / 1828 / 826 / 874 / a
Quinic acid / 1420.8 / 1853 / 1849 / 852 / 855 / a
Fructose 1 / 1430.0 / 1863 / 1859 / 895 / 895 / a
Caffeine / 1430.8 / 1863 / 1848 / 855 / 937
Fructose 2* / 1438.8 / 1872 / 1868 / 901 / 932 / a
Mannose / 1442.6 / 1876 / 1885 / 828 / 936 / a
Galactose / 1446.4 / 1880 / 1882 / 850 / 899 / a
Tyrosine / 1449.4 / 1883 / 1901 / 849 / 849 / a
Glucose 1 / 1452.8 / 1887 / 1882 / 905 / 905 / a
Glucose 2* / 1469.6 / 1905 / 1900 / 947 / 947 / a
Mannitol / 1480.8 / 1918 / 1925 / 911 / 911 / a
p-Coumaric acid / 1498.4 / 1938 / 1943 / 879 / 879 / a
Gallic acid / 1510.8 / 1952 / 1962 / 806 / 824 / a
Gluconic acid / 1555.4 / 2002 / 1991 / 875 / 875 / a
Mucic acid / 1580.6 / 2032 / 2014 / 828 / 828 / a
n-Hexadecanoic acid / 1591.2 / 2045 / 2054 / 899 / 901
Inositol / 1621.4 / 2081 / 2083 / 908 / 908 / a
Phytol / 1695.4 / 2171 / 2179 / 824 / 874
Linoleic acid / 1726.4 / 2210 / 2208 / 886 / 901 / a
Linolenic acid / 1731.2 / 2216 / 2218 / 839 / 867 / a
Stearic acid / 1752.6 / 2244 / 2243 / 875 / 877 / a
Glucose-6-phosphate / 1804.2 / 2312 / 2320 / 822 / 841 / a
Sucrose / 2033.0 / 2631 / 2627 / 818 / 818 / a
Lactose / 2062.2 / 2674 / 2675 / 848 / 848 / a
Maltose / 2094.8 / 2721 / 2723 / 801 / 801 / a
Galactinol / 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.
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Table S2. List of the identified compounds by using LC-MS
Compound / Tr/min / m/z / ESI mode / Detected m/z / Mass accuracy/ppm / MS/MS Fragment / Metlin IDCholine / 1.02 / 104.1070 / M+H / 104.1078 / 7.7 / 60.0809, 58.0651 / 56 / b
Phosphocholine / 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,b
Proline / 1.07 / 116.0706 / M+H / 116.0699 / -6.0 / 70.0606 / 29 / a,b
Valine / 1.09 / 118.0863 / M+H / 118.0854 / -7.6 / 72.0782, 55.0547 / 35 / a,b
Betaine / 1.09 / 118.0863 / M+H / 118.0854 / -7.6 / 58.0623, 59.0704 / 287 / a,b
Theanine / 1.2 / 175.1076 / M+H / 175.1085 / 5.1 / 84.0454, 158.0808 / 44433 / a,b
Leucine / 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,b
Niacinamide / 1.6 / 123.0553 / M+H / 123.0543 / -8.1 / 80.0451, 78.0296, 53.0359 / 1497 / b
Guanine / 1.79 / 152.0567 / M+H / 152.0563 / -2.6 / 134.9958, 110.0074 / 315 / b
Phenylalanine / 1.79 / 166.0863 / M+H / 166.0865 / 1.2 / 120.0498, 103.0278, 93.0462 / 28 / a,b
Adenosine / 1.9 / 268.1043 / M+H / 268.1045 / 0.7 / 136.0738, 182.9767, 154.9758, 108.9675 / 86 / a,b
Pipecolic acid / 2.06 / 130.0863 / M+H / 130.0859 / -3.1 / 84.0817, 67.0547, 56.0501 / 58337 / a,b
Nipecotic acid / 2.06 / 130.0863 / M+H / 130.0859 / -3.1 / 112.0763, 84.0436, 56.0504 / 44223 / a,b
Theogallin / 2.47 / 345.0816 / M+H / 345.0782 / -9.9 / 153.0178 / 68616
Tryptophan / 2.58 / 205.0974 / M+H / 205.0963 / -5.4 / 146.05, 118.0567, 132.0716, 188.0591 / 33 / a,b
Gallocatechin / 3.48 / 307.0812 / M+H / 307.0808 / -1.3 / 139.0355, 163.0350, 195.0572 / 47219 / a
5-Caffeoylquinic acid / 4.34 / 355.1024 / M+H / 355.1032 / 2.3 / 163.0392, 145.0291 / 95165 / a
5'-Deoxy-5'-(methylthio)adenosine / 5.28 / 298.0968 / M+H / 298.0962 / -2.0 / 136.0564, 61.0077 / 3425 / b
Epigallocatechin / 5.32 / 307.0812 / M+H / 307.0831 / 6.2 / 139.0387, 163.0382 / 44010 / a
Theobromine / 5.38 / 181.0720 / M+H / 181.0705 / -8.3 / 138.0651, 110.0703 / 1456
Catechin / 5.95 / 291.0863 / M+H / 291.0857 / -2.1 / 139.0384, 207.0638, 123.0437, 165.0532 / 3419 / a,b
3-p-Coumaroylquinic acid / 5.98 / 339.1074 / M+H / 339.1091 / 5.0 / 147.0437, 119.0500 / 86421
3-Caffeoylquinic acid / 6.54 / 355.1024 / M+H / 355.1011 / -3.7 / 163.0392, 145.0290 / 3498 / a,b
Theophylline / 6.69 / 181.0720 / M+H / 181.0714 / -3.3 / 124.0501, 96.0554 / 1458 / a,b
4-Caffeoylquinic acid / 6.87 / 355.1024 / M+H / 355.1007 / -4.8 / 163.0392, 145.0292 / 3498 / a
Epicatechin / 7.2 / 291.0863 / M+H / 291.0891 / 9.6 / 139.0376, 123.0430, 161.0579, 207.0621 / 3420 / a,b
2-Benzofurancarboxaldehyde / 7.88 / 147.0441 / M+H / 147.0438 / -2.0 / 119.0363, 91.0446, 65.0325 / 89059
Caffeine / 8.1 / 195.0877 / M+H / 195.0894 / 8.7 / 138.0623, 110.0597, 83.0522, 69.0382 / 1455 / b
Epigallocatechin gallate / 8.34 / 459.0922 / M+H / 459.0955 / 7.2 / 139.0415, 153.0204, 151.0414 / 3550 / a,b
Gallocatechin 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 / 50838
Catechin-4a-epicatechin 3-O-gallate / 9.4 / 731.1607 / M+H / 731.1656 / 6.7 / 409.0836, 289.0646, 123.0413 / 92754
Myricetin 3-O-galactoside / 9.45 / 481.0977 / M+H / 481.1013 / 7.5 / 319.0536 / 50828
Myricetin 3-O-glucoside / 9.5 / 481.0977 / M+H / 481.0970 / -1.5 / 319.049 / 50836
Quercetin 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 / 86134
Quercetin 3-O-glucosylrutinoside / 9.98 / 773.2135 / M+H / 773.2109 / -3.4 / 465.0736, 303.0305, 611.1234 / 50523
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,b
Quercetin 3-O-rutinoside / 10.41 / 611.1607 / M+H / 611.1640 / 5.4 / 303.0594, 465.0655 / 50514 / a
Kaempferol 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