(ESI) an Untargeted Metabolomics Approach to Determine Component

Electronic Supplementary Material (ESI) for RSC Advances. This journal is © The Royal Society of Chemistry 2017

Electronic Supplementary Information (ESI)

An untargeted metabolomics approach to determine component differences and variation in their in vivo distribution between Kuqin and Ziqin, two commercial

specifications of Scutellaria Radix†

Zhi-Wei Yanga, Feng Xub,*, Xin Liuc, Yi Caoa, Qi Tanga, Qian-Yu Chena, Ming-Ying Shangb, Guang-Xue Liub, Xuan Wanga,*, Shao-Qing Caib

a Department of Chemical Biology, School of Pharmaceutical Sciences, Peking University, No. 38

Xueyuan Road, Beijing 100191, PR China.

b State Key Laboratory of Natural and Biomimetic Drugs, Peking University, No. 38 Xueyuan Road,

Beijing 100191, PR China.

c Technical Center, Beijing Entry-Exit Inspection and Quarantine Bureau, No. 6 Tianshuiyuan Street,

Beijing, 100026, PR China.

†Electronic supplementary information (ESI) available.

* Corresponding author:

Dr. Feng Xu. State Key Laboratory of Natural and Biomimetic Drugs, Peking University, No. 38

Xueyuan Road, Haidian District, Beijing 100191, PR China. Tel: +86-10-82802534; E-mail:

[email protected].

Dr. Xuan Wang (responsible for all correspondence during review and processing of the

manuscript), Department of Chemical Biology, School of Pharmaceutical Sciences, Peking University,

No. 38 Xueyuan Road, Haidian District, Beijing 100191, PR China. Tel: +86-10-82806818; E-mail:

[email protected].

1 Contents

Part A Pages

Table S1 Information of 51 Kuqin (KQ) and Ziqin (ZQ) samples 6

Table S2 Peak areas of the main active constituents in six batches of KQ and ZQ crude drug samples 8

Figure S1 Pattern analysis scores scatter plots between KQ and ZQ in colon and lungs 9

Figure S2 Pattern analysis scores scatter plots between KQ and ZQ crude drug samples 10

Figure S3 Extracted ion chromatograms of the constituents of Scutellariae Radix 11

Figure S4 Chemical difference between KQ and ZQ samples in negative ion modes for group one 12

Figure S5 Chemical difference between KQ and ZQ in positive ion modes for group one 13

Table S3 Characterization of constituents with content difference between KQ and ZQ 14

Literature reported biological activities of anti-inflammation, inhibiting of lungs and colon related 23 Table S4 diseases of 114 constituents in SR

Table S5 Peak area ratios of different constituents of KQ and ZQ samples 24

Peak areas of the main active constituents in colon calculated from extracted ion chromatograms in six 26 Table S6 repeated experiments

Peak areas of the main active constituents in lungs calculated from extracted ion chromatograms in six 27 Table S7 repeated experiments

2 Part B: MS2 and proposed fragmentation pathways of constituents in SR, colon and lungs tissues

S2...... 28

S3, and S4...... 29

S5...... 31

S6, S21, and S25...... 32

S7, S13, S17, S20, S29, and S39 ...... 35

S8...... 39

S9...... 40

S10...... 41

S11...... 42

S12, and S32...... 43

S14...... 44

S15...... 44

S16...... 45

S18...... 46

S19...... 46

S22...... 47

S23...... 48

S24...... 49

S26, S27, S36, and S37...... 50

S28...... 52

S30...... 53

S31, S44, S48, and S101...... 54

S32...... 57

S33...... 58

S34...... 59

S35...... 59

S38...... 60

S41, S42, and S43...... 61

S45...... 63

S47...... 64

S49...... 64

S50...... 65

S51, S53, S54, and S82...... 66

3 S52, S55, S61, S63, and S69 ...... 69

S56...... 73

S60, S62, S68, S74, S79, and S81 ...... 74

S64, S71 ...... 78

S65, S73, and S76...... 80

S66...... 83

S70...... 84

S72...... 85

S75...... 86

S77...... 87

S80...... 88

S83, S84 ...... 89

S85...... 91

S86...... 92

S87...... 93

S88...... 93

S89...... 94

S90...... 94

S91...... 95

S92...... 96

S93...... 97

S94...... 98

S95...... 99

S96...... 99

S57, S97 ...... 100

S98...... 102

S99...... 103

S100...... 104

S102...... 104

S103, and S106...... 105

S104, and S108...... 107

S105...... 108

S107...... 109

S108...... 109

4 S109...... 110

S110...... 110

S111...... 111

S112...... 111

S113...... 112

S114...... 113

M1 ...... 114

M3 ...... 115

M4 ...... 115

M5 ...... 116

M6 ...... 116

M7 ...... 117

M8 ...... 117

M9 ...... 118

M10 ...... 119

M11 ...... 120

M12 ...... 121

M13 ...... 122

M14 ...... 123

M15 ...... 124

M16 ...... 125

5 PART A

Table S1 Information of 51 Kuqin (KQ) and Ziqin (ZQ) samples

NO. Sample ID Specification Collection Date Region 1 KQ-6590 Kuqin 2010/10 Inner Mongolia 2 KQ-6613 Kuqin 2010/11 Hebei province 3 KQ-6616-1 Kuqin 2010/11 Hebei province 4 KQ-6616-2 Kuqin 2010/11 Hebei province 5 KQ-6618 Kuqin 2010/11 Hebei province 6 KQ-6620 Kuqin 2010/11 Hebei province 7 KQ-6626-1 Kuqin 2010/11 Hebei province 8 KQ-6626-2 Kuqin 2010/11 Hebei province 9 KQ-6628 Kuqin 2010/11 Hebei province 10 KQ-6629 Kuqin 2010/11 Hebei province 11 KQ-6697 Kuqin 2010/12 Shandong Province 12 KQ-70002 Kuqin 2014/10 Inner Mongolia 13 KQ-7486-1 Kuqin 2014/07 Inner Mongolia 14 KQ-7486-2 Kuqin 2014/07 Inner Mongolia 15 KQ-7486-3 Kuqin 2014/07 Inner Mongolia 16 KQ-7591 Kuqin 2014/09 Inner Mongolia 17 KQ-7591-1 Kuqin 2014/09 Inner Mongolia 18 KQ-7591-L1 Kuqin 2014/09 Inner Mongolia 19 KQ-7591-L2 Kuqin 2014/09 Inner Mongolia 20 KQ-7591-L3 Kuqin 2014/09 Inner Mongolia 21 KQ-7591-M1 Kuqin 2014/09 Inner Mongolia 22 KQ-7591-M2 Kuqin 2014/09 Inner Mongolia 23 KQ-7591-M3 Kuqin 2014/09 Inner Mongolia 24 KQ-7591-PS-1 Kuqin 2014/09 Inner Mongolia 25 KQ-7591-PS-2 Kuqin 2014/09 Inner Mongolia 26 KQ-7591-PS-3 Kuqin 2014/09 Inner Mongolia 27 KQ-7591-PS-4 Kuqin 2014/09 Inner Mongolia 28 KQ-7591-PS-5 Kuqin 2014/09 Inner Mongolia 29 ZQ-5773 Ziqin 2007/07 Shandong Province 30 ZQ-5797 Ziqin 2007/10 Gansu province 31 ZQ-6580 Ziqin 2010/10 Gansu province 32 ZQ-6596 Ziqin 2010/10 Inner Mongolia 33 ZQ-6614 Ziqin 2010/11 Hebei province 34 ZQ-6619 Ziqin 2010/11 Hebei province 35 ZQ-6624 Ziqin 2010/11 Hebei province 36 ZQ-6630 Ziqin 2010/11 Hebei province 37 ZQ-6633 Ziqin 2010/11 Yanqing County, Beijing 38 ZQ-6636 Ziqin 2010/11 Hebei Province 39 ZQ-6697 Ziqin 2010/12 Shandong Province 40 ZQ-6701 Ziqin 2010/01 Henan province 6 41 ZQ-70001 Ziqin 2014/10 Inner Mongolia 42 ZQ-7487-1 Ziqin 2014/07 Inner Mongolia 43 ZQ-7487-2 Ziqin 2014/07 Inner Mongolia 44 ZQ-7593 Ziqin 2014/09 Inner Mongolia 45 ZQ-7593-1 Ziqin 2014/09 Inner Mongolia 46 ZQ-7593-L1 Ziqin 2014/09 Inner Mongolia 47 ZQ-7593-L2 Ziqin 2014/09 Inner Mongolia 48 ZQ-7593-L3 Ziqin 2014/09 Inner Mongolia 49 ZQ-7593-M1 Ziqin 2014/09 Inner Mongolia 50 ZQ-7593-M2 Ziqin 2014/09 Inner Mongolia 51 ZQ-7593-S Ziqin 2014/09 Inner Mongolia

7 Table S2. Peak areas of the main active constituents in six batches of KQ and ZQ crude drug samples. (ZQ samples batch No. were 7593, 6616, 6620, 70002, and

7486; KQ samples batch No. were 7591, 6619, 6614, 70001, and 7487; Peak area unit, mAUs)

KQ-G1&G2 KQ-G3 KQ-G4 KQ-G5 KQ-G6 ZQ-G1&G2 ZQ-G3 ZQ-G4 ZQ-G5 ZQ-G6 ID Compounds No.7591 No.6616 No.6620 No.70002 No.7486 No.7593 No.6619 No.6614 No.70001 No.7487

S40 Chrysin 6-C-arabinoside 8-C-glucoside 3282.4 2896.8 2276.9 2156.7 3685.8 2531.3 3281.1 2512.8 2804.9 3720.7

S46 Chrysin 6-C-glucoside 8-C-arabinoside 2516.8 1688.9 1424.3 1285.6 2189.0 1760.9 2055.3 1511.7 1705.1 2300.9

S39 Baicalin 70110.8 46159.5 40624.6 46798.9 84945.1 54239.5 74453.6 56288.9 63557.1 89242.1

S25 Wogonoside 19619.0 12814.9 12765.8 11536.8 23661.9 14572.0 21983.8 15610.8 16614.7 22611.1

S21 Oroxylin A 7-O-glucuronide 8986.9 5781.5 1631.6 5036.8 8177.6 4828.2 8260.9 3953.5 8804.1 8475.2

S59 Baicalein 4599.4 7592.1 3430.1 4858.5 7286.8 3558.1 4160.2 4755.3 4121.5 5845.2

S60 Wogonin 1035.3 2841.9 2317.0 2559.1 2847.3 868.1 2470.3 2599.3 1903.1 2413.4

S62 Oroxylin A 657.1 947.2 591.0 1314.6 1183.5 321.4 999.1 806.9 1133.6 979.5

S78 Chrysin 211.4 113.4 246.0 158.4 234.2 126.0 111.8 289.0 143.5 144.3

8 Figure S1. Pattern analysis scores scatter plots between KQ (1) and ZQ (2) in colon and lungs. For lungs, PCA in negative (A) and positive (B) ion modes; For colon, PCA in negative (C) and positive (E) ion modes.

9 Figure S2. Pattern analysis scores scatter plots between KQ (1) and ZQ (2) crude drug samples: PCA in negative (A) and positive (D) ion modes; OPLS-DA in negative (B) and positive (E) ion modes. S-plot of OPLS-DA model both in negative (C) and positive (F) ion modes.

10 Figure S3. Extracted ion chromatograms of the constituents of Scutellariae Radix. (A) flavonoid aglycones, (B) flavonoid O-glycosides, (C) flavonoid C-glycosides, phenylethanoid glycosides, and other types in negative ion mode, and (D) flavonoid glycoside, flavonoid aglycones and other types in positive ion mode (samples No. 7593).

11 Figure S4. Chemical difference between KQ (SR sample No. 7591) and ZQ (SR sample No. 7593) in negative ion mode for group one. The heat map represented relative content of components in KQ (left) and ZQ (right); Sn, prototype components in SR, n = N; Down (Fold change < 0) = lower content in ZQ; Up (Fold Change > 0) = higher content in ZQ; * p ≤ 0.05, ** p ≤ 0.01.

12 Figure S5. Chemical difference between KQ (SR sample No. 7591) and ZQ (SR sample No. 7593) in positive ion mode for group one. The heat map represented relative content of components in KQ (left) and ZQ (right); Sn, prototype components in SR, n = N; Down (Fold Change < 0) = lower content in ZQ; Up (Fold Change > 0) = higher content in ZQ; * p ≤ 0.05, ** p ≤ 0.01.

13 Table S3. Characterization of constituents with content difference between KQ and ZQ t ion Predicted Diff ID R [M±H]± ESI-MS2 m/z（% Relative） Identification Stucture Type Note* (min) mode Formula (ppm)

S1 4.03 623.19869 − C29H36O15 0.877 461.16760(6),415.10431(27),179.03514(3),161.024 Acteoside Phenylethanoid / 52(100), 135.04463(8) glcosides S2 5.56 637.21439 − C30H38O15 0.936 461.16754(9),315.11038(5),193.05070(18),175.040 Leucosceptoside A Phenylethanoid / 05(100),160.01636(22),153.05603(10),135.04518(1 glcosides 7),113.02439(27) # S3 9.71 651.23014 − C31H40O15 1.069 636.66242(0.7),193.05060(24),175.03962(100),160. Isomartynoside Phenylethanoid F.I 01694(20),149.06090(5),134.03725(5),113.02420(1 glcosides 8) S4 8.84 651.23018 − C31H40O15 1.131 329.12497(1),299.05658(1),193.05080(13),175.040 Martynoside Phenylethanoid / 13(100),167.07126(3),160.01660(28),149.06087(3), glcosides 134.03743(8),119.03503(2),113.02441(15),101.024 48(2) S5 1.78 475.18188 − C21H32O12 −0.462 329.12436(2),311.11435(1),167.07141(2),149.0607 Darendoside A Phenylethanoid / 0(4),134.03731(4),113.02430(100),101.02428(17),9 glcosides 5.01369(9) S6 10.31 459.0938 − C22H20O11 1.123 283.06140(36),268.03796(100),113.02448(12),99.0 Isomer of S21 Flavone-O-glycosides / 1(7),99.0882.01(5),85.02940(13) S7 7.25 445.07798 − C21H18O11 0.776 269.04590(100) Isomer of S39 Flavone-O-glycosides /

S8 10.27 503.12007 − C24H24O12 1.134 459.13107(3),428.07468(4),299.05685(61),284.033 6''-O-acetyl Flavone-O-glycosides F.I 14(100),255.06674(33),211.04065(4),151.00386(3) homoplantaginin OR Ladanetin-6-O-β-(6''-O- acetyl)glucoside S9 7.86 907.19435 − C43H40O22 0.556 676.36243(4),547.01318(4),388.12686(4),345.1268 Isomer of Solanoflavone Flavone-O-glycosides F.I 6(4),299.05661(100),284.03271(9),269.04614(12),2 56.09375(4),267.03131(10) S10 6.61 731.12622 − C36H28O17 1.159 285.04032(0.6),269.04575(100),267.02943(0.4),251 5,7,4',5'',3''',4''''- Flavone-O-glycosides F.I .22560(2),113.02448(8). hexahydroxy-3''-O-β- glucosyl-3',7''-O-biflavone OR isomer S11 7.51 491.11986 − C23H24O12 0.734 329.06747(42),314.04388(100),299.02063(18),269. Trihydroxy- Flavone-O-glycosides / 04602(2) dimethoxyflavone O- glucoside S12 4.56 607.13127 − C27H28O16 1.338 431.09888(3),269.04596(100),251.03477(0.4),175.0 Trihydroxyflavone O- Flavone-O-glycosides F.I

14 2(1),113.02452(5),95.01376(1),85.02924(3) glucoside-(12)-O- glucuronide S13 9.88 445.07796 − C21H18O11 0.325 269.04587(100),251.03519(0.3),241.05064(0.1),225 Baicalein 6-O-glucuronide Flavone-O-glycosides / .05563(0.1),223.04022(0.3),113.02444(4),99.00870( 2),85.02940(4) S14 10.47 637.15677 − C32H30O14 0.771 283.06235(0.5),269.04596(100),251.03542(0.3),230 Isomer of chrysoeriol-7-O- Others F.I .95995(1),223.06(1),205.05(2) [2''-O-E-feruloyl]-β-D- glucoside S15 8.26 863.20450 − C42H40O20 0.56 271.06174(50),269.04608(100),211.07(2),165.62(0. Unknow / / 4),113.02454(5) S16 9.32 473.10911 − C23H22O11 0.371 283.06165(33),269.04611(100),268.03824(45),161. Baicalein 7-O- Flavone-O-glycosides / 00911(6) ethylglucuronide OR isomer S17 8.49 445.07793 − C21H18O11 0.295 269.04596(100),251.03575(0.1),241.05104(0.6),225 Norwogonin 7-O- Flavone-O-glycoside / .05591(2),197.06102(2),113.02441(4),99.00877(2), glucuronide 85.02941(4) S18 7.13 505.09920 − C23H22O13 0.864 329.06656(28),314.04343(100),299.02014(27),269. Isomer of viscidulin II 2'-O- Flavone-O-glycosides / 04565(5),196(3),113.02434(11),85.02942(13) glucuronide S19 9.21 431.09677 + C21H18O10 −1.167 271.05957(6),255.06471(100) Chrysin 7-O-glucuronide Flavone-O-glycoside /

S20 7.7 445.07795 − C21H18O11 0.709 269.04611(100) Isomer of S39 Flavone-O-glycosides /  S21 9.13 459.09374 − C22H20O11 0.992 283.06149(47),268.03806(100),239.07167(0.3),211. Oroxylin A 7-O- Flavone-O-glycosides RS 03976(0.1),175.02492(1.0),139.00372(0.4),129.019 glucuronide 33(2),117.01934(3),113.02438(17),99.00875(7),85. 02939(23),71.01373(7) S22 3.86 461.07327 − C21H18O12 1.564 371.07819(6),341.06790(20),299.05603(12),285.04 Tetrahydroxyflavone O- Flavone-O-glycosides / 077(100),271.06216(3),245.05(3),227.07204(4),211 glucuronide (Isomer of .04077(3) Scutellarin) S23 9.77 461.10910 − C22H22O11 0.359 299.05609(38),284.03268(83),283.02502(100),269. Trihydroxy- Flavone-O-glycosides / 04312(2),268.03726(1),253.05077(20),211.04008(9 methoxyflavone-O- ),173.06068(2) glucoside S24 4.61 477.10424 − C22H22O12 0.819 301.07242(70),286.04889(100),181.01442(21),165. 5,7,2'-Trihydroxy-6- Flavanone-O- / 99094(13) methoxyflavanone 7-O- glycosides glucuronide S25 9.84 459.09363 − C22H20O11 0.752 283.06149(75),268.03806(100),239.07164(0.3),175. Wogonoside Flavone-O-glycosides RS 02492(1),139.00372(0.4),129.01933(2),113.02438(2 4),99.00875(12),85.02939(22),71.01373(7) S26 5.27 475.08834 − C22H20O12 0.296 299.05655(58),284.03311(100) Isomer of 37 (trihydroxy- Flavone-O-glycosides / methoxyflavone O- glucuronide)

15 S27 9.47 475.08809 − C22H20O12 −0.23 299.05637(50),284.03305(100),270.04959(5) Isomer of 37 (trihydroxy- Flavone-O-glycosides / methoxyflavone O- glucuronide) S28 7.98 447.09353 − C21H20O11 0.549 271.06250(100),253.05099(8),243.06644(25) Dihydrobaicalin Flavanone-O- / glycosides S29 8.78 445.07795 − C21H18O11 0.709 269.04596(100),268.03815(3),267.03036(1),241.05 Norwogonin 8-O- Flavone-O-glycosides / 142(0.5),225.05623(1),197.06119(1),113.02449(3), glucuronide 99.00886(1),85.02956(3),71.01391(2) S30 4.89 621.14659 − C28H30O16 0.776 445.11441(70),430.09079(59),283.06143(49),268.0 Dihydroxy-methoxyflavone Flavone-O-glycosides F.I 3781(100),267.03018(93),239.03525(2),175.02502( O-glucuronide-(16)-O- 3),117.02(3),113.02444(25),103.00378(3),99.00882 glucoside (7),95.01390(7),85.02956(21) S31 9.61 415.10355 − C21H20O9 0.228 295.06122(3),269.04590(2),253.05075(100),224.04 Chrysin 7-O-glucoside or Flavone-O-glycosides F.I 839(0.2),209.06085(2) isomer S32 6.02 607.13129 − C27H28O16 1.371 445.18335(1),269.04572(100),113.02447(1) Trihydroxyflavone O- Flavone-O-glycosides F.I glucuronide-(12)-O- glucoside S33 10.27 489.10403 − C23H22O12 0.37 313.07257(24),298.04871(100),283.02521(29),281. 5,7-Dihydroxy-8,2'- Flavone-O-glycosides / 04529(4),269.04565(2),239.03593(2),211.04042(5) dimethoxyflavone 7-O- glucuronide S34 4.13 507.11461 − C23H24O13 0.387 492.09247(1),345.06189(15),330.03836(100),315.0 Viscidulin III 2'-O- Flavone-O-glycosides / 1505(14) glucoside S35 9.35 445.11423 − C22H22O10 0.472 285.07462(100),270.05118(17),241.04947(0.1) Wogonin 5-glucoside Flavone-O-glycosides /

S36 7.59 475.08836 − C22H20O12 0.339 299.05658(100),284.03305(59),270.10849(0.5) Isomer of 37 (trihydroxy- Flavone-O-glycosides / methoxyflavone O- glucuronide) S37 8.84 475.08832 − C22H20O12 0.254 299.05643(30),284.03299(100),267.02997(0.3),239. 5,7,2’-Trihydroxy-6- Flavone-O-glycosides / 03540(0.2),228.04262(0.4),200.04805(1),153.01936 methoxyflavone 7-O- (1),129.01955(1),113.02440(6),85.02940(7) glucuronide S38 10.95 551.13891 + C25H26O14 −1.128 375.10657(100),360.08340(9),345.05960(13),342.0 Dihydroxy- Flavone-O-glycoside / 7269(3),329.06488(0.3),327.04913(4),227.05461(3) tetramethoxyflavone O- ,177.05432(1) glucuronide S39 6.59 445.07991 − C21H18O11 2.275 269.04605(100),251.03560(1),241.05084(1),225.05 Baicalin Flavone-O-glycoside RS 608(0.4),197.06128(0.5),129.01952(1),117.01965(1 ),113.02452(6),99.00889(3),85.02959(7) S40 3.7 547.14611 − C26H28O13 0.724 547.14618(30),529.13562(3),487.12500(2),469.114 Chrysin 6-C-arabinoside 8- Flavone-C-glycosides RS 35(4),457.11453(40),439.10385(4),427.10352(66),4 C-glucoside 09.09323(4),397.09296(9),367.08243(64),349.0720 2(7),337.07214(100)

16 S41 3.87 565.15757 − C26H30O14 2.285 367.08337(1),337.07230(2),329.08737(8),299.0773 Isomer of Pinobanksin 8-C- Flavanonol-C- F.I 0(9),269.6674(40),239.05615(97),209.04556(100) arabinoside 6-C-glucoside glycosides S42 3.57 565.15700 − C26H30O14 1.276 329.08783(4),299.07840(10),269.06689(41),239.05 Isomer of Pinobanksin 8-C- Flavanone-C- F.I 627(100),209.04572(95) arabinoside 6-C-glucoside glycosides S43 3.24 565.15653 − C26H30O14 0.445 329.08795(7),299.07770(10),269.06622(43),239.05 Isomer of Pinobanksin 8-C- Flavanone-C- F.I 637(100),209.04559(89) arabinoside 6-C-glucoside glycosides S44 5.18 415.10373 − C21H20O9 0.662 325.07175(4),307.06094(2),295.06113(100),277.05 Isomer of S48 Flavone-C-glycosides / 060(1),267.06644(32),253.05106(0.5),227.07188(0. (Dihydroxyflavone C- 5),179.03456(0.6),149.02438(2) glucoside) S45 3.13 577.15683 − C27H30O14 0.955 577.15729(14),487.12531(11),457.11462(32),439.1 Chrysin 6,8-di-C- Flavone-C-glycosides / 0440(3),397.09293(6),367.08258(58),337.07224(10 glucopyranoside 0) S46 4.25 547.14609 − C26H28O13 0.687 547.14642(17),529.13593(3),487.12570(14),457.11 Chrysin 6-C-glucoside 8-C- Flavone-C-glycosides RS 465(22),427.10376(15),409.09360(10),397.09317(8 arabinoside ),367.08258(83),337.07224(100) S47 5.1 547.14620 − C26H28O13 0.888 547.14624(16),487.12512(17),457.11450(23),427.1 6-hexosyl-8-C-pentosyl Flavone-C-glycosides / 0364(40),397.09360(31),367.08234(100),337.07205 chrysin (70),309.07745(6) S48 8.03 417.11762 + C21H20O9 −0.932 325.07217(33),295.06152(100),267.06662(25),253. Chrysin 6-C-glucoside Flavone-C-glycoside / 05095(3),223.07791(0.5),151.05568(0.1) S49 11.52 343.08222 − C18H16O7 −0.309 328.06003(12),313.03540(100),298.01190(16),270. Skullcapflavone Flavones / 01706(2) S50 4.91 409.02370 − C17H14O10S 0.512 329.06705(100),314.04361(62),299.01993(27),195. 2',5,6-Trihydroxy-7,8- Flavones / 03003(2),180.00662(3),164.98241(1),133.02942(2) dimethoxyflavone 6-O- sulfate S51 10.23 329.06682 − C17H14O7 0.438 314.04337(49),299.01974(100),285.04105(2),271.0 Isomer of S54 (Trihydroxy- Flavones / 2505(2),255.02969(0.9),227.03496(0.3),180.00645( dimethoxyflavone) 9),164.98270(6),133.02942(7) S52 11.16 313.07190 − C17H14O6 0.443 298.04861(100),283.02521(85),255.03027(2),239.0 Isomer of S63 (Dihydroxy- Flavones / 3503(2),211.04025(19),173.06067(5) dimethoxyflavone) S53 12.95 329.06680 − C17H14O7 0.377 314.04309(61),299.01953(100),285.04083(3),271.0 5,8,2’-Trihydroxy-6,7- Flavones / 2472(2),255.02936(0.3),227.0.462(0.3),205.01410(0 dimethoxyflavone .8),180.00636(2),152.01122(2),133.02835(0.5) S54 11.7 329.06679 − C17H14O7 0.346 314.04349(100),299.01993(80),255.02878(0.7),180. 5,7,6’-Trihydroxy-8,2’- Flavones / 00696(2),165.99080(12),137.99586(6) dimethxoyflavone S55 10.26 313.07188 − C17H14O6 0.379 298.04871(100),283.02530(87),269.04614(78),255. Isomer of 6- Flavones / 12172(4),211.04001(18),167.04(5),145.02962(15),9 Methoxywogonin 1.02(28) (Dihydroxy- dimethoxyflavone)

17 S56 2.89 303.05117 − C15H12O7 0.475 285.04059(2),241.05075(2),217.05060(9),193.0555 5,7,3,2',6'- Flavanones / 1(4),177.01930(30),149.02429(10),125.02426(100) Pentahydroxyflavanone S57 6.95 347.07574 + C17H14O8 −1.164 347.07541(63),332.05203(100),314.04147(35),286. Viscidulin III Flavones RS 04645(2),183.02850(3),169.01292(7),142.02594(3) S58 5.62 285.04059 − C15H10O6 0.452 285.04077(100),267.03012(3),241.05083(20),217.0 Scutellarein Flavones RS 5066(10),199.04018(15),197.06(2),175.04(5),173.0 6079(2),169.01425(3),151.00365(80),133.02959(11 ),107.01385(8) S59 11.86 271.05975 + C15H10O5 −1.291 271.05942(100),253.04897(1),225.05417(0.2),169.0 Baicalein Flavones RS 1289(0.2),153.01797(4)

S60 13.72 283.06125 − C16H12O5 0.188 268.03809(100),240.04349(1),239.03520(1),224.04 Wogonin Flavones RS 802(1),212.04816(0.3),211.04041(0.3),198.03249(1 ),196.05321(1),184.05307(1),165.99049(1),163.003 72(2),137.02448(1),110.00012(0.4) S61 14.19 313.07224 − C17H14O6 0.479 298.04852(100),283.02515(87),269.04590(21),255. 5,8-Dihydroxy-6,7- Flavones / 03026(2),239.03487(0.3),211.04027(18),195.03015( dimethoxyflavone 0.3),180.00664(5),173.06090(0.3),164.98279(2),152 .01154(3),117.03396(0.2) S62 14.15 283.06129 − C16H12O5 0.33 268.03809(100),240.04308(0.4),239.03503(0.7),224 Oroxylin A Flavones RS .04767(0.4),212.04845(0.4),211.03987(0.2),198.032 33(1),196.05310(1),184.05318(1),165.99036(0.3),1 63.00372(2),137.02437(0.6),110.00023(0.4) S63 13.9 315.08592 + C17H14O6 −1.253 298.04868(68),283.02527(100),255.03012(2),211.0 Skullcapflavone I Flavones / 4028(2),183.04514(2),173.06091(4),164.98(2),155. 05032(3) S64 7.67 287.05625 − C15H12O6 0.483 287.05701(4),269.04599(3),225.05568(1),215.0351 Isomer of S71 Flavanones / 3(9),201.05588(9),177.06(2),173.06(1),161.02443(1 (Tetrahydroxyflavanone) 7),151.00369(3),133.02956(4),125.02438(100) S65 12.06 299.05618 − C16H12O6 0.23 284.03296(100),256.03872(2),255.03044(0.2),227.0 Trihydroxy- Flavones / 3548(0.1),200.04811(2),165.99077(8),137.99599(4) methoxyflavone ,110.00093 S66 14.5 373.09289 − C19H18O8 −0.002 358.06985(22),343.04617(100),328.02286(23),325. Scullcapflavone II Flavones / 03555(2),315.05099(1),313.03574(0.6),300.02783(5 ),285.00458(1),227.03514(4),194.99355(6),169.014 25(3),133.02936(1) S67 11.38 269.04552 − C15H10O5 −0.099 269.04584(100),241.05078(4),225.05591(8),213.05 Apigenin Flavones RS 597(3),197.06100(12),181.06610(2),169.06595(3) S68 14.75 283.06122 − C16H12O5 0.082 268.03796(100),240.04321(1),239.03526(1),224.04 Isomer of S60 (Dihydroxy- Flavones / 819(0.4),212.04845(0.4),211.04047(0.6),198.03242( methoxyflavone)

18 0.6),196.05336(0.4),184.05302(0.6),171.04515(0.2), 165.99080(0.5),137.02440(0.4) S69 10.5 313.0719 − C17H14O6 0.443 298.04874(100),283.02530(87),269.04593(21),255. Isomer of 6- Flavones F.I 03079(4),211.04013(18),173.06114(3),145.02940(3 Methoxywogonin ),91.02199(8) (Dihydroxy- dimethoxyflavone) S70 13.67 537.08295 − C30H18O10 0.428 391.04648(76),373.03580(10),347.05630(16),335.0 8,8'-Biapigenin Flavones / 5679(5),319.06134(7),291.06656(2),245.00926(100 ),239.03531(1),217.01433(3) S71 7.24 287.05622 − C15H12O6 0.379 269.04581(0.6),243.06630(0.1),225.05594(0.1),179. Eriodictyol Flavanone / 0350(0.1),161.02428(25),151.00359(1),135.04514(2 ),125.02432(100) S72 9.29 349.00236 − C15H10O8S −0.003 269.04593(100),241.05110(0.3),225.05605(1),225.0 Baicalein 6-O-sulfate Flavones / 5605(0.9),197.06(1),181.06602(0.2),139.00328(0.1) S73 11.61 299.05616 − C16H12O6 0.163 299.06(100),284.03290(49),267.03012(11),255.066 Trihydroxy- Flavones / 51(24),240.04300(12),231.07(7),227.07092(0.5),21 methoxyflavone (trihydoxy 2.04813(4),153.01930(0.2),151.00368(82),107.0138 and methoxy on A ring) 9(8) S74 10.27 283.06137 − C16H12O5 0.612 268.03815(100),255.03041(1),239.03531(1),224.04 Isomer of S60 (Dihydroxy- Flavones / 813(1),211.04037(1),198.03255(1),196.05328(1),18 methoxyflavone) 4.05304(1),183.04530(0.3),173.06088(1),163.00375 (2),137.02452(1),110.00090(0.3) S75 14.6 345.09647 + C18H16O7 −1.186 345.09631(100),330.07288(34),315.04938(92),312. Tenaxin I Flavones / 06241(18),297.03891(31) S76 10.72 299.05611 − C16H12O6 −0.004 284.03275(100),271.06204(6),255.06720(2),227.07 4'-hydroxy wogonin Flavones RS 127(9),212.04810(12),211.03995(17),183.02997(2), 165.01932(6),153.01926(36),133.02950(20) S77 10.47 315.05119 − C16H12O7 0.521 300.06476(69),284.02829(19),253.01425(30),227.0 Neptin Flavones F.I 3526(100),212.04431(7),165.99086(58),137.99605( 11),110.00083(9) S78 13.75 253.05057 − C15H10O4 −0.245 253.05109(100),209.15495(3),151.00400(0.2),143.0 Chrysin Flavones RS 5037(1),107.01380(1) S79 10.53 283.06165 − C16H12O5 1.601 268.03815(100),255.03064(0.1),224.04797(1),212.0 Isomer of S60 (Dihydroxy- Flavones / 4796(0.3),211.04030(1),198.03264(1),196.05330(1) methoxyflavone) ,184.05304(1),165.99068(0.4),163.00375(2),137.02 444(1),110.00021(0.3) S80 10.65 301.07175 − C16H14O6 −0.038 286.04865(100),283.02444(4),268.03766(),255.233 Trihydroxy- Flavanones F.I 23(10),185.06107(5),180.00667(16),165.99078(45), methoxyflavanone 152.01132(5),137.99594(9),119.05031(8)

19 S81 11.09 283.06149 − C16H12O5 1.036 268.04(100),255.03041(),224.04813(0.5),212.04037 Isomer of S60 (Dihydroxy- Flavones / (0.4),211.04037(0.2),198.03255(1),196.05328(1),18 methoxyflavone) 4.05(1),165.99072(1),163.00375(2),137.02438(1),1 10.00014(0.4) S82 10.87 329.06678 − C17H14O7 0.316 314.04358(62),299.01959(81)283.26471(26),268.03 Isomer of S54 (Trihydroxy- Flavones / 827(25) dimethoxyflavone) S83 0.81 191.0197 − C6H8O7 −0.135 173.00926(3),147.03001(1),129.01953(8),111.0088 D-Galactaric acid, 1,5- Others F.I 3(4),103.00378(4),85.03(100),72.99311(10) lactone OR isomer S84 1.04 191.01969 − C6H8O7 −0.135 173.00949(4),129.01956(8),117.01949(2),111.0088 Isomer of D-Galactaric Others F.I 2(100),87.00871(42),85.02947(34) acid, 1,5-lactone S85 1.27 503.14106 − C21H28O14 0.857 341.08823(),323.07770(13),281.06732(20),251.056 1-caffeyllaminaribiose Others F.I 49(10),223.97(2),221.04567(14),179.03532(44),161 .02457(100),135.04533(12) S86 8.29 417.11947 − C21H22O9 0.874 255.06686(10),211.07681(100),197.06166(0.2),169. Gaylussacin Stilbene (茋类) / 06604(5),112.98558(2) S87 22.48 255.23276 − C16H32O2 −0.758 255.23302(100),237.22174(0.2),211.20708(0.2) Isomer of Hexadecanoic Alkane F.I acid S88 17.94 295.22773 − C18H32O3 −0.468 277.21747(25),211.13409(1),195.13907(2),183.139 Isomer of 10- Alkane F.I 05(100) Hydroxyoctadecadienoic acid S89 6.12 301.07177 − C16H14O6 0.029 161.02446(23),139.04013(100),135.04533(22),133. 3-Hydroxy-4-O- Others F.I 00966(16),124.01660(11),107.05027(10) glucosylbenzyl alcohol OR isomer S90 19.97 324.28931 + C20H37O2N −1.221 306.27869(6),219.05690(6),147.11668(2),123.1167 Isomer of Linoleoyl Others F.I 8(5),109.10135(7),95.08574(14),81.07028(17),62.0 Ethanolamide 6064(100) S91 0.87 381.07891 + C17H16O10 −7.12 381.08(100),219.02664(30),201.01584(25) Isomer of 5-O-β-D- Others F.I glucopyranosyl-6- hydroxyangelicin S92 6.17 303.08598 + C16H14O6 −1.104 285.07507(15),267.06482(1),257.08026(32),242.05 3,4-Dihydroxy-7-O- Others F.I 684(8),229.08551(57),179.03380(2),167.03363(100 caffeoylbenzyl alcohol or ),163.03865(3),133.02831(24),123.04404(69),107.0 isomer 4928(44) S93 17.49 701.37151 + C35H56O14 −3.953 701.37067(100),539.31824(96),191.09856(1),105.0 Isomer of sileneoside H / / 3367(7) S94 4.17 445.07617 + C21H16O11 −0.826 427.06525(4),409.05493(9),381.05975(1),343.0446 Benzoic acid, 3,4,5- Others F.I 5(6),319.04428(23),287.05(10),275.05447(7),263.0 trihydroxy-,1,1'-(2- 5466(5),153.01807(100),141.01810(22) methoxy-1,4-phenylene) ester OR isomer

20 S95 5.67 339.10696 + C16H18O8 −1.427 321.07611(3),234.03915(37),177.05437(100),145.0 Unknown / F.I 2809(31),105.03366(13) S96 11.77 555.09167 + C30H18O11 −0.933 453.04468(11),435.03403(20),419.03882(10),269.0 Isomer of hegoflavone A Flavones / 3884(18),241.04912(12),121.02847(19),105.03368( 34) S97 10.39 347.07572 + C17H14O8 −1.221 347.07565(100),332.05206(26),317.02866(28),314. Isomer of S57 Flavones / 04156(37) (Tetrahydroxy- dimethoxyflavone) S98 14 375.10704 + C19H18O8 −1.077 360.08298(30),345.05960(100),342.07272(15),327. 5,6’-Dihydroxy-6,7,8,2’- Flavones / 04913(16),227.05446(8),213.03889(9) tetramethoxyflavone S99 11.14 563.13929 + C26H26O14 −0.429 315.08569(100),300.06229(19),285.03885(13),282. Dihydroxy- Flavone-O-glycoside F.I 05182(7) dimethoxyflavone O-6''- malonyl glucoside S100 10.35 549.12346 + C25H24O14 −0.768 301.06992(100),286.04651(16) Trihydroxy- Flavone-O-glycoside F.I methoxyflavone O-6''- malonyl glucoside S101 5.22 417.11739 + C21H20O9 −1.483 325.07217(5),295.06152(100),267.06662(31),245.0 Chrysin 8-C-glucoside Flavone-C-glycoside / 4578(1),223.07791(0.5),187.07007(0.5),149.02457( 2) S102 5.51 771.19748 + C33H38O21 −0.46 285.07526(21),271.05966(100),159.02872(0.8),127. Baicalein 7-O-β-D- Flavone-O-glycoside F.I 03899(3),85.02879(6) glucuronide-(1→3)[β-D- glucoside-(1→6)]-β-D- glucoside S103 10.93 519.11305 + C24H22O13 −0.515 343.08023(10),315.08505(69),311.05420(10),301.0 Trihydroxyflavone O-6''- Flavone-O-glycoside F.I 7013(20),283.05975(29),271.05951(100),231.06464 malonyl glucoside (Isomer (5),201.09091(7) of Apigenin 7-6''-malonyl glucoside) S104 9.49 433.11257 + C21H20O10 −0.816 271.05969(100) Isomer of Baicalein 7-O- Flavone-O-glycoside / glucoside (Trihydroxyflavone O- glucoside) S105 5.72 523.14417 + C24H26O13 −0.855 361.09100(100),346.06732(8),331.04391(8),328.05 Trihydroxy- Flavone-O-glycoside / 756(3),313.03406(3) trimethoxyflavone-O- glucoside S106 9.38 519.1129 + C24H22O13 −0.803 337.06061(2),297.07465(7),285.07510(10),271.059 Isomer of S103 Flavone-O-glycoside F.I 54(73),255.06462(10),239.06934(1),231.06471(2),2 (Trihydroxyflavone O-6''- 15.07065(1),174.55710(1),156.26376(1),105.03371( malonyl glucoside) 7),59.06100(100) S107 10.34 447.12802 + C22H22O10 −1.237 285.07468(100),270.05124(15) Oroxylin A 7-O-glucoside Flavanone-O- RS glycoside

21 S108 5.77 433.11249 + C21H20O10 −1 271.05957(100),169.01288(0.1) Isomer of Baicalein 7-O- Flavone-O-glycoside / glucoside (Trihydroxyflavone O- glucoside) S109 5.41 595.16536 + C27H30O15 −0.649 271.05954(100),127.03880(1) Isomer of Apigenin 7-O- Flavone-O-glycoside F.I sophoroside S110 10.63 533.12852 + C25H24O13 −0.839 285.07535(100),270.05191(18),267.06497(0.3),253. Dihydroxy-methoxyflavone Flavone-O-glycoside F.I 04749(0.1),239.06937(0.1) O-6''-malonyl glucoside S111 5.97 623.12372 + C27H26O17 −0.892 285.07532(100),271.05948(68),270.05182(15) Isomer of Clerodendrin Flavone-O-glycoside F.I

S112 5.36 609.18105 + C28H32O15 −0.569 285.07538(100),271.05981(15),270.05107(6) Isomer of Acacetin 7-O-β- Flavone-O-glycoside F.I sophoroside S113 12.17 489.13876 + C24H24O11 −0.773 285.07523(100),270.05176(18),175.07506(1),165.0 Dihydroxy-methoxyflavone Flavone-O-glycoside / 9137(0.2),105.03358(2) O-glucuronide ethyl ester S114 12.57 539.09695 + C30H18O10 −0.599 521.08783(3),503.0761(1),493.09171(4),465.0969(2 8,8'-Bibaicalein Flavones / ),449.1020(1),437.04977(100),419.03888(71),401.0 2802(10),391.04047(5),375.05029(8),363.0499(3),3 47.0550(2),323.05453(50),297.03854(6),271.05960( 58),270.04407(24),269.04407(70),241.04915(62),22 5.05426(4) #, F.I, represented as first report of compound in SR. , RS, represented as identification result obtained by comparing the retention time, UV spectra, and MS data with authentic standards.

22 Table S4. Literature reported biological activities of anti-inflammation, inhibiting of lungs and colon related diseases of 114 constituents in SR. (UP, ZQ group was higher than KQ group; DOWN, KQ group was higher than ZQ group)

anti-inflammatory anti-colitis anti-pneumonia ID Identification Up-Down Ref. in vitro in vivo in vivo

S1 Acteoside UP    1, 2 3, 4 S2 Leucosceptoside A DOWN  / / 5 S3 Isomartynoside DOWN  / / 6 S4 Martynoside DOWN  / / 5, 7 S5 Darendoside A DOWN  / / 8-11 S17 Norwogonoside UP  / / 12 S19 Chrysin 7-O-glucuronide UP  / / 13 S21 Oroxylin A 7-O-glucuronide UP  / / 14, 15 S22 Scutellarin UP  /  16, 17 S23 Dinatin 7 O-glucoside UP  / / 18 S24 5,7,2'-Trihydroxy-8-methoxyflavanone DOWN  / / 19, 20 7-O-glucuronide S25 Wogonoside UP    21-24 S39 Baicalin UP    25-29 27 30 S40 Chrysin-6-C-arabinoside-8-C-glucoside UP  / / 12 31 S45 Chrysin 6,8-di-C- glucoside UP  / / 31 S46 Chrysin-6-C- glucoside-8-C- UP  / / 12 arabinoside S56 5,7,3,2',6'-Pentahydroxyflavanone UP  / / 32 S57 Viscidulin III UP  / / 33 S58 Scutellarein UP  /  34, 35 S59 Baicalein UP    36-42, [419-421 S60 Wogonin UP    43, 44 45-47

S62 Oroxylin A DOWN    48-51 S63 Skullcapflavone I DOWN  / / 52 S66 Scullcapflavone II DOWN  / / 33 S67 Apigenin DOWN    53, 54 S71 Eriodictyol DOWN  / / 55 S77 Nepetin DOWN  /  56, 57 S78 Chrysin DOWN    58 S104 Apigenin 7-O-glucoside UP  / / 59 S114 8,8''-Bibaicalein DOWN  / / 60

23 Table S5. Peak area ratios of different constituents of KQ and ZQ samples Recognition rate for known samples Prediction accuracy and false negative rate for unknown samples** Ratio EIC peak area ratio KQ recognition ZQ recognition KQ prediction KQ false negative ZQ prediction ZQ false negative range rate（%）* rate（%）* accuracy（%）** rate（%）** accuracy（%）** rate（%）** S40/S78#  1.0 75.0 95.5 24.1  1.0 95.7 75.9 4.5 S78/S46  1.4 75.0 91.3 25.0  1.4 91.3 75.0 8.7 （S46+S40）/S78  1.6 75.0 100.0 23.3  1.6 100.0 76.7 0.0 S39/S59  1.1 82.1 88.5 20.0  1.1 87.0 80.0 11.5 S25/S60  0.9 89.3 78.1 23.8  0.9 69.6 76.2 21.9 S21/S62  1.6 82.1 85.2 22.7  1.6 82.6 77.3 14.8 （S25+S46+S40）/（S60+S78）  1.1 82.1 85.2 20.8  1.1 82.6 79.2 14.8 S13/S67  0.6 71.4 71.4 34.8  0.6 65.2 65.2 28.6 S59/S28  5.1 89.3 89.3 13.0  5.1 87.0 87.0 10.7 （S39+S28）/S59  1.4 85.7 85.7 17.4  1.4 82.6 82.6 14.3 （S17+S25）/S60  1.3 75.0 84.0 26.9  1.3 82.6 73.1 16.0

24 S25/S71  6.5 92.9 89.7 9.1  6.5 87.0 90.9 10.3 S39/S71  9.0 96.4 96.4 4.3  9.0 95.7 95.7 3.6 （S25+S39）/（S60+S71）  1.8 85.7 96.0 15.4  1.8 95.7 84.6 4.0 S28/S71  2.0 96.4 93.1 4.5  2.0 91.3 95.5 6.9 S13/S71  1.0 89.3 89.3 13.0  1.0 87.0 87.0 10.7 S27/S71  1.4 92.9 96.3 8.3  1.4 95.7 91.7 3.7 S29/S71  1.0 89.3 89.3 13.0  1.0 87.0 87.0 10.7 S27/S5  30.0 85.7 88.9 16.7  30.0 87.0 83.3 11.1 *, KQ recognition rate (%)=Identified amount of KQ samples/28 KQ samples; ZQ recognition rate (%)=Identified amount of ZQ samples/23 ZQ samples. **, KQ prediction accuracy (%)=Actual amount of KQ samples in unknown samples/identified amount of unknown samples; ZQ prediction accuracy (%)=Actual amount of ZQ samples in unknown samples/identified amount of unknown samples; KQ false negative rate (%)=1−ZQ prediction accuracy; ZQ false negative rate (%)=1−KQ prediction accuracy.

25 Table S6. Peak areas of the main active constituents in colon calculated from extracted ion chromatograms in six repeated experiments. Avg1, Avg2, Avg3, Avg4,

Avg5, and Avg6 was the average content in G1, G2, G3, G4, G5, and G6 (n=6 in each group). KQAvg1~6, ZQAvg1~6, SEMKQ, SEMZQ represented mean ± SEM in KQ groups (n=36) and ZQ groups (n=36). KQ-G1 KQ-G2 KQ-G3 KQ-G4 KQ-G5 KQ-G6 ZQ-G1 ZQ-G2 ZQ-G3 ZQ-G4 ZQ-G5 ZQ-G6 ID KQAvg1~6 SEMKQ ZQAvg1~6 SEMZQ KQAvg1 KQAvg2 KQAvg3 KQAvg4 KQAvg5 KQAvg6 ZQAvg1 ZQAvg2 ZQAvg3 ZQAvg4 ZQAvg5 ZQAvg6 S13# 1.33E+06 1.10E+06 3.00E+06 5.21E+05 2.23E+06 2.78E+06 9.85E+05 6.57E+05 3.23E+06 1.60E+06 3.36E+06 3.34E+06 1.83E+06 3.06E+05 2.19E+06 2.75E+05

S21 3.94E+06 4.36E+06 1.26E+07 1.34E+06 8.22E+06 6.82E+06 1.67E+06 1.68E+06 1.09E+07 5.19E+06 1.18E+07 1.05E+07 6.22E+06 1.13E+06 6.95E+06 1.00E+06

S25 1.98E+06 4.66E+06 1.86E+07 4.33E+06 8.71E+06 1.02E+07 5.16E+05 1.32E+06 1.34E+07 9.63E+06 1.20E+07 1.66E+07 8.09E+06 1.76E+06 8.89E+06 8.08E+05

S39 8.35E+05 4.78E+06 1.58E+07 3.03E+06 9.46E+06 9.76E+06 5.19E+05 2.04E+06 1.40E+07 7.79E+06 1.17E+07 1.49E+07 7.29E+06 1.55E+06 8.48E+06 2.21E+08

S40 1.47E+07 1.96E+06 6.61E+06 2.25E+06 5.71E+06 6.50E+06 1.04E+07 2.63E+06 1.07E+07 5.08E+06 7.13E+06 4.59E+06 6.29E+06 1.50E+06 6.76E+06 1.55E+07

S46 7.47E+06 9.71E+05 4.45E+06 1.17E+06 3.94E+06 4.53E+06 7.47E+06 1.53E+06 8.02E+06 4.53E+06 4.62E+06 3.54E+06 3.76E+06 8.26E+05 4.95E+06 4.92E+05

S59 1.95E+08 8.30E+07 4.70E+08 1.14E+08 4.65E+08 7.45E+08 1.32E+08 8.92E+07 8.62E+08 5.59E+08 8.77E+08 1.95E+09 3.45E+08 6.48E+07 7.45E+08 7.91E+06

S60 1.25E+08 2.98E+07 1.14E+08 3.01E+07 1.13E+08 1.35E+08 4.73E+07 1.88E+07 1.85E+08 9.07E+07 1.65E+08 1.80E+08 9.12E+07 1.55E+07 1.14E+08 9.04E+06

S61 1.47E+06 8.61E+05 2.86E+06 3.69E+05 5.77E+06 8.64E+06 1.05E+06 4.05E+05 4.27E+06 3.24E+06 6.35E+06 5.47E+06 3.33E+06 7.97E+05 3.46E+06 2.63E+06

S62 5.38E+07 9.45E+06 5.75E+07 6.57E+06 5.14E+07 4.76E+07 1.72E+07 6.52E+06 9.51E+07 2.98E+07 1.02E+08 7.48E+07 3.77E+07 6.44E+06 5.42E+07 1.53E+07

S65 1.67E+07 4.17E+06 2.50E+07 5.08E+06 2.41E+07 3.94E+07 7.25E+06 4.10E+06 5.91E+07 2.47E+07 3.93E+07 1.44E+08 1.91E+07 3.68E+06 4.64E+07 1.60E+06

S66 7.47E+06 2.77E+06 2.57E+07 5.23E+06 1.26E+07 4.56E+07 4.72E+06 2.98E+06 3.84E+07 1.65E+07 2.06E+07 2.24E+07 1.66E+07 3.40E+06 1.76E+07 1.01E+06

S67 5.09E+07 2.00E+07 9.81E+07 3.15E+07 9.19E+07 1.47E+08 3.96E+07 2.89E+07 2.42E+08 9.37E+07 1.55E+08 1.33E+08 7.32E+07 1.22E+07 1.15E+08 1.38E+06

M2 2.90E+06 2.05E+06 1.07E+07 1.76E+05 7.52E+06 7.37E+06 4.67E+06 1.96E+06 1.26E+07 4.56E+06 1.04E+07 9.36E+06 5.11E+06 1.04E+06 7.24E+06 1.09E+06

M3 1.92E+07 4.05E+06 2.03E+07 2.43E+06 1.00E+07 1.54E+07 1.73E+07 1.51E+07 1.73E+07 9.69E+06 1.89E+07 1.88E+07 1.19E+07 1.76E+06 1.62E+07 2.18E+06

M9 1.76E+06 3.69E+05 6.87E+06 4.97E+05 8.55E+06 4.97E+06 1.78E+06 1.04E+06 1.66E+07 5.12E+06 1.37E+07 6.90E+06 3.84E+06 9.47E+05 7.53E+06 1.32E+06

M10 3.21E+06 7.11E+05 2.12E+06 1.47E+05 2.87E+06 7.46E+06 9.61E+05 5.82E+05 4.53E+06 1.72E+06 4.62E+06 3.88E+06 2.75E+06 6.17E+05 2.72E+06 4.04E+05

M12 1.68E+07 6.89E+05 3.33E+06 1.20E+06 6.74E+06 1.27E+06 5.61E+06 9.64E+05 1.27E+07 2.57E+06 1.01E+07 1.06E+06 5.00E+06 1.52E+06 5.50E+06 1.04E+06

M14 1.53E+06 1.77E+05 7.76E+05 1.47E+05 6.17E+05 6.19E+05 1.58E+06 1.52E+05 1.86E+06 5.27E+05 1.20E+06 4.97E+05 6.45E+05 1.64E+05 9.70E+05 2.15E+05

26 Table S7. Peak areas of the main active constituents in lungs calculated from extracted ion chromatograms in six repeated experiments. Avg1, Avg2, Avg3, Avg4,

Avg5, and Avg6 was the average content in G1, G2, G3, G4, G5, and G6 (n=6 in each group). KQAvg1~6/ ZQAvg1~6 and SEMKQ/ SEMZQ represented mean ± SEM in KQ groups (n=36) and ZQ groups (n=36). KQ-G1 KQ-G2 KQ-G3 KQ-G4 KQ-G5 KQ-G6 ZQ-G1 ZQ-G2 ZQ-G3 ZQ-G4 ZQ-G5 ZQ-G6 ID KQAvg1~6 SEMKQ ZQAvg1~6 SEMZQ KQAvg1 KQAvg2 KQAvg3 KQAvg4 KQAvg5 KQAvg6 ZQAvg1 ZQAvg2 ZQAvg3 ZQAvg4 ZQAvg5 ZQAvg6

S13# 1.65E+06 1.31E+06 1.16E+06 2.95E+05 1.00E+06 1.21E+06 9.18E+05 7.78E+05 1.51E+06 7.33E+05 1.27E+06 1.34E+06 1.10E+06 1.05E+05 1.09E+06 2.88E+05

S21 2.30E+06 1.47E+06 1.16E+06 2.58E+05 1.19E+06 1.71E+06 7.12E+05 6.67E+05 1.39E+06 7.84E+05 4.29E+06 8.49E+05 1.35E+06 1.60E+05 1.45E+06 1.08E+05

S25 2.76E+06 2.18E+06 2.05E+06 6.91E+05 1.71E+06 3.06E+06 8.02E+05 8.86E+05 2.45E+06 1.37E+06 4.07E+06 1.48E+06 2.08E+06 2.10E+05 1.84E+06 2.46E+05

S39 2.50E+06 1.20E+06 1.09E+06 8.94E+04 9.26E+05 8.50E+05 1.42E+06 5.10E+05 1.16E+06 3.78E+05 1.49E+06 9.05E+05 1.11E+06 1.55E+05 9.78E+05 1.00E+05

S59 1.71E+06 1.68E+06 1.21E+06 3.77E+05 1.62E+06 1.64E+06 9.51E+05 1.89E+06 1.14E+06 4.41E+05 3.20E+06 6.26E+06 1.37E+06 2.01E+05 2.31E+06 6.35E+05

S60 1.05E+07 1.57E+06 9.08E+05 3.10E+05 1.47E+06 2.14E+06 3.35E+06 1.43E+06 1.22E+06 4.84E+05 2.86E+06 1.92E+06 2.82E+06 6.95E+05 1.88E+06 2.64E+05

S62 2.63E+06 5.35E+05 3.96E+05 8.07E+04 6.04E+05 7.66E+05 1.21E+06 6.54E+05 4.53E+05 1.36E+05 1.53E+06 6.59E+05 8.35E+05 1.73E+05 7.74E+05 1.35E+05

S67 4.85E+05 1.75E+05 5.05E+04 1.26E+05 1.82E+05 8.40E+05 2.93E+05 3.98E+05 1.61E+05 1.02E+05 5.57E+05 1.14E+06 3.10E+05 7.48E+04 4.41E+05 1.47E+05

S78 2.41E+06 5.66E+05 6.76E+05 2.44E+05 1.16E+06 9.80E+05 1.27E+06 5.87E+05 1.40E+06 4.81E+05 1.57E+06 1.40E+06 1.01E+06 1.52E+05 1.12E+06 1.58E+05

M1 4.14E+06 1.12E+06 5.77E+05 2.21E+05 6.82E+05 1.48E+06 9.64E+05 5.80E+05 2.44E+06 1.28E+06 2.14E+06 7.90E+05 1.37E+06 2.82E+05 1.37E+06 2.48E+05

M2 3.18E+06 9.73E+05 9.58E+05 2.24E+05 8.12E+05 1.48E+06 1.19E+06 6.95E+05 1.28E+06 5.57E+05 4.77E+06 1.21E+06 1.27E+06 1.96E+05 1.62E+06 3.41E+05

M3 3.75E+06 5.76E+05 7.95E+05 3.74E+05 5.86E+05 2.36E+06 1.08E+06 4.69E+05 1.59E+06 6.18E+05 4.79E+06 1.04E+06 1.41E+06 2.98E+05 1.60E+06 3.39E+05

M4 8.08E+07 2.10E+07 1.49E+07 7.36E+06 1.67E+07 3.27E+07 1.36E+07 1.50E+07 3.13E+07 1.78E+07 6.90E+07 1.35E+07 2.89E+07 5.30E+06 2.67E+07 4.35E+06

27 Part B: MS2 and proposed fragmentation pathways of constituents in SR, colon and lungs tissues

61 Leucosceptoside A (tR=5.63 min) MS1(−): 637.2141 MS2(−): 461.16754(9),315.11038(5),193.05070(18),175.04005(100),160.01636(22),153.05603(10),135.04 518(17),113.02439(27)

7591 #1054 RT: 5.63 AV: 1 NL: 1.07E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-670.00] 175.04005 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

25 113.02439

20 160.01636 193.05070 15 461.16754 10 89.02442 315.11038 5 71.01383 208.30823 293.97531 345.47891 548.43372 598.84204 0 50 100 150 200 250 300 350 400 450 500 550 600 650 m/z

OH HO

O OH HO -H O O

O OH HO OH OH HO OH - Chemical Formula: C20H29O12 Exact Mass: 461.1664 HO O O O -H -H O OH HO HO O -H O O O O - •- O Chemical Formula: C10H7O3 Chemical Formula: C9H4O3 HO O Exact Mass: 175.0401 Exact Mass: 160.0166 OH O OH -H HO OH - Chemical Formula: C30H37O15 HO O Exact Mass: 637.2138 - Chemical Formula: C10H9O4 Exact Mass: 193.0506

HO HO -H -H

HO OH O - - Chemical Formula: C8H9O3 Chemical Formula: C8H7O2 Exact Mass: 153.0557 Exact Mass: 135.0452

28 S3, and S4

RT: 0.00 - 30.00 8.91 NL: 6.03E7 100 m/z= 651.22688- 95 651.23340 F: FTMS - p ESI Full 90 ms [150.00-1000.00] 85 MS 7591

60 e c n

a 55 d n u b

A 50

e v i

t 9.72

a 45 l e R 40

5 3.58 4.89 6.43 8.15 11.08 15.42 17.76 0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 Time (min) 62 S3 Isomartynoside (tR=9.74 min) MS1(−):651.23014 MS2(−):636.66242(0.7),193.05060(24),175.03962(100),160.01694(20),149.06090(5),134.03725(5), 113.02420(18)

7593-neg #1916 RT: 9.77 AV: 1 NL: 2.57E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-685.00] 175.03993 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

25 193.05060 20 113.02433 160.01648

10 71.01373 134.03740 298.04871 5 265.07147 313.07205 505.17175 222.30096 401.76944 439.68298 605.05969 651.22803 0 50 100 150 200 250 300 350 400 450 500 550 600 650 m/z

O -H -H HO HO -H OH HO O O O

- Chemical Formula: C H O - Chemical Formula: C H O •- Chemical Formula: C10H9O4 9 9 2 8 6 2 Exact Mass: 134.0373 O OH OH -H Exact Mass: 193.0506 Exact Mass: 149.0608 HO O OH O -H O -H O OH -H O O OH HO O OH O HO O O O O O Chemical Formula: C H O - - Chemical Formula: C H O •- 5 5 3 Chemical Formula: C10H7O3 9 4 3 HO Exact Mass: 113.0244 Exact Mass: 175.0401 Exact Mass: 160.0166 - Chemical Formula: C31H39O15 Exact Mass: 651.2294 O OH OH -H HO O OH O O O O OH OH O O

HO •- Chemical Formula: C30H36O15 Exact Mass: 636.2060

29 62 S4 Martynoside (tR=8.91 min) MS1(−): 651.23018 MS2(−): 329.12497(1),299.05658(1),193.05080(13),175.04013(100),167.07126(3),160.01660(28),149.060 87(3),134.03743(8),119.03503(2),113.02441(15),101.02448(2)

7591 #1705 RT: 8.82 AV: 1 NL: 6.10E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-685.00] 175.04013 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

25 160.01660

20 113.02441 15 193.05080

10 103.03986 134.03743 71.01379 5 299.05658 207.06789 329.12497 425.97375 494.35999 0 50 100 150 200 250 300 350 400 450 500 550 600 650 m/z

30 S5

Darendoside A62 MS1(−): 475.18188 MS2(−): 329.12436(2),311.11435(1),167.07141(2),149.06070(4),134.03731(4),113.02430(100),101.02428 (17),95.01369(9)

7591-neg2_150921204157 #296 RT: 1.85 AV: 1 NL: 1.63E6 F: FTMS - p ESI d Full ms2 [email protected] [50.00-505.00] 113.02430 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

35 59.01373 89.02428 30

15 134.03731 10 149.06070 5 161.04558 329.12436 207.28134 261.04102 297.77417 362.53690 395.03900 475.18167 0 50 100 150 200 250 300 350 400 450 500 m/z

-H O O O -H O O HO HO -H O O O HO HO OH O HO OH O OH OH - - HO OH O Chemical Formula: C15H21O8 Chemical Formula: C15H19O7 Exact Mass: 329.1242 Exact Mass: 311.1136 O O -H -H HO OH O -H O HO OH OH O O O - - •- - Chemical Formula: C H O Chemical Formula: C9H9O2 Chemical Formula: C8H6O2 Chemical Formula: C21H31O12 9 11 3 Exact Mass: 134.0373 Exact Mass: 475.1821 Exact Mass: 167.0714 Exact Mass: 149.0608 O HO -H

- Chemical Formula: C5H5O3 Exact Mass: 113.0244

31 S6, S21, and S25

RT: 0.00 - 30.00 10.00 NL: 1.86E9 100 m/z= 459.09150- 95 459.09610 F: FTMS - p ESI Full 90 ms [150.00-1000.00] 85 MS 7591

65 9.32 60 e c n

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e v i t

a 45 l e R 40

5 10.84 0.91 1.75 3.63 4.58 6.00 7.97 11.37 13.71 14.39 15.78 17.70 19.68 21.86 22.45 23.52 24.45 27.36 28.00 0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 Time (min)

S6 Isomer of S21 (tR=10.31 min) MS1(−): 459.0938 MS2(−): 283.06140(36),268.03796(100),113.02448(12),99.01(7),99.0882.01(5),85.02940(13)

7591 #2031 RT: 10.30 AV: 1 NL: 4.00E6 F: FTMS - p ESI d Full ms2 [email protected] [50.00-485.00] 268.03796 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

35 283.06140 30

20 85.02940 113.02448 15

10 59.01375 99.00882 5 159.40805 189.41518 221.27060 299.39957 394.62454 475.03687 0 50 100 150 200 250 300 350 400 450 m/z

32 S21 Oroxylin A 7-glucuronide (tR=9.32 min) MS1(−): 459.09374 MS2(−): 283.06149(47),268.03806(100),239.07167(0.3),211.03976(0.1),175.02492(1.0),139.00372(0.4),12 9.01933(2),117.01934(3),113.02438(17),99.00875(7),85.02939(23),71.01373(7)

7591 #1772 RT: 9.13 AV: 1 NL: 2.47E6 F: FTMS - p ESI d Full ms2 [email protected] [50.00-485.00] 268.03806 100

60 e c n

a 55 d n u b 283.06149

A 50

e v i t

a 45 l e R 40

25 85.02939 20 113.02438 15 254.17509 10 59.01377 99.00875

5 129.01933 175.02492 211.03976 239.07164 299.05698 341.96295 378.47791 406.95578 445.69559 478.31711 0 50 100 150 200 250 300 350 400 450 m/z

-H -H -H HO O HO O HO O

O O O OH OH OH O OH O

HO OH -H - •- 2•- Chemical Formula: C16H11O5 Chemical Formula: C15H8O5 Chemical Formula: C6H3O4 Exact Mass: 283.0612 Exact Mass: 139.0037 HO Exact Mass: 268.0377 O O O -H O -H -H O HO O HO OH O Chemical Formula: C H O - 22 19 11 O Exact Mass: 459.0933 O O OH OH OH Chemical Formula: C H O - - Chemical Formula: C H O - 15 11 4 Chemical Formula: C15H11O3 14 11 2 Exact Mass: 255.0663 Exact Mass: 239.0714 Exact Mass: 211.0765

OH -H OH -H HO OH HO OH HO O O O - - Chemical Formula: C6H7O6 Chemical Formula: C5H5O4 Exact Mass: 175.0248 Exact Mass: 129.0193

-H -H OH HO OH HO OH

HO - - Chemical Formula: C5H5O3 Chemical Formula: C4H3O3 Exact Mass: 113.0244 Exact Mass: 99.0088

-H HO OH

- Chemical Formula: C4H5O2 Exact Mass: 85.0295

33 S25 Wogonoside (tR=10.00 min) MS1(−): 459.09363 MS2(−): 283.06149(75),268.03806(100),239.07164(0.3),175.02492(1),139.00372(0.4),129.01933(2),113.0 2438(24),99.00875(12),85.02939(22),71.01373(7)

7591 #1772 RT: 9.13 AV: 1 NL: 2.47E6 F: FTMS - p ESI d Full ms2 [email protected] [50.00-485.00] 268.03806 100

60 e c n

a 55 d n u b 283.06149

A 50

e v i t

a 45 l e R 40

25 85.02939 20 113.02438 15 254.17509 10 59.01377 99.00875

5 129.01933 175.02492 211.03976 239.07164 299.05698 341.96295 378.47791 406.95578 445.69559 478.31711 0 50 100 150 200 250 300 350 400 450 m/z

-H -H O -H O O HO O HO O HO O

OH OH O OH O

- •- 2•- Chemical Formula: C16H11O5 Chemical Formula: C15H8O5 Chemical Formula: C6H3O4 Exact Mass: 283.0612 Exact Mass: 268.0377 Exact Mass: 139.0037

-H -H -H O O O O O O O HO O HO HO

HO OH

OH OH O OH OH Chemical Formula: C H O - Chemical Formula: C H O - - 22 19 11 15 11 4 Chemical Formula: C15H11O3 Exact Mass: 459.0933 Exact Mass: 255.0663 Exact Mass: 239.0714

OH -H OH -H HO OH HO OH HO O O O - - Chemical Formula: C6H7O6 Chemical Formula: C5H5O4 Exact Mass: 175.0248 Exact Mass: 129.0193

-H -H OH HO OH HO OH

HO - - Chemical Formula: C5H5O3 Chemical Formula: C4H3O3 Exact Mass: 113.0244 Exact Mass: 99.0088

-H HO OH

- Chemical Formula: C4H5O2 Exact Mass: 85.0295

34 S7, S13, S17, S20, S29, and S39

RT: 0.00 - 30.00 6.77 NL: 1.23E9 100 Base Peak m/z= 445.07575- 95 445.08021 F: FTMS - p ESI Full ms 90 [150.00-1000.00] MS 7591 85 6.97 80

65 8.49 60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

25 8.93 20 9.88

5 0.91 2.53 3.40 4.76 6.22 10.21 11.87 13.71 15.77 17.67 19.85 21.17 21.89 22.55 23.92 25.33 27.51 28.25 0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 Time (min)

S7 Isomer of S39 (tR=7.25 min) MS1(−):445.07798 MS2(−):269.04590(100)

61 S13 Baicalein 6-O-glucuronide (tR=9.88 min) MS1(−): 445.07796 MS2(−): 269.04587(100),251.03519(0.3),241.05064(0.1),225.05563(0.1),223.04022(0.3),113.02444(4),99. 00870(2),85.02940(4)

-H -H HO O -H -H HO O HO HO O HO OH O HO HO O OH OH O OH HO - - - Chemical Formula: C14H9O4 Chemical Formula: C14H9O3 Chemical Formula: C13H9O2 OH OH Exact Mass: 241.0506 Exact Mass: 225.0557 Exact Mass: 197.0608 - Chemical Formula: C21H17O11 Exact Mass: 445.0776 -H -H

-H O O O O HO O

OH O OH HO Chemical Formula: C H O - Chemical Formula: C H O - OH O 15 7 4 14 7 3 - Exact Mass: 251.0350 Exact Mass: 223.0401 Chemical Formula: C15H9O5 Exact Mass: 269.0455 -H OH -H HO OH HO OH

HO - Chemical Formula: C5H5O3 - Chemical Formula: C4H3O3 Exact Mass: 113.0244 Exact Mass: 99.0088

-H HO OH

- Chemical Formula: C4H5O2 Exact Mass: 85.0295 61 S17 Norwogonin 7-O-glucuronide(norwogonoside) (tR=8.49 min) 35 MS1(−): 445.07793 MS2(−): 269.04596(100),251.03575(0.1),241.05104(0.6),225.05591(2),197.06102(2),113.02441(4),99.008 77(2),85.02941(4)

7591 #1627 RT: 8.42 AV: 1 NL: 2.28E8 F: FTMS - p ESI d Full ms2 [email protected] [50.00-470.00] 269.04596 50 48 46 44 42 40 38 36 34 32 30 e c n

a 28 d n

u 26 b A

e 24 v i t a l 22 e R 20 18 16 14 12 10 8 6 85.02941 113.02441 4 59.01380 2 99.00877 197.06102 225.05591 129.01944 171.04520 241.05104 0 50 100 150 200 250 300 350 400 450 m/z

OH OH -H -H -H OH OH -H OH HO O O HO O HO O HO OH O HO O OH OH OH

- Chemical Formula: C H O - - Chemical Formula: C H O - Chemical Formula: C21H17O11 14 9 4 Chemical Formula: C14H9O3 13 9 2 Exact Mass: 445.0776 Exact Mass: 241.0506 Exact Mass: 225.0557 Exact Mass: 197.0608

-H -H -H OH O O O O HO O

OH O OH OH O - Chemical Formula: C H O - Chemical Formula: C14H7O3 - 15 7 4 Chemical Formula: C15H9O5 Exact Mass: 251.0350 Exact Mass: 223.0401 Exact Mass: 269.0455

-H OH -H HO OH HO OH

HO - Chemical Formula: C5H5O3 - Chemical Formula: C4H3O3 Exact Mass: 113.0244 Exact Mass: 99.0088

-H HO OH

- Chemical Formula: C4H5O2 Exact Mass: 85.0295

S20 Isomer of S39 (tR 7.70) MS1(−): 445.07795 MS2(−): 269.04611(100)

36 61 S29 Norwogonin 8-O-glucuronide (tR=8.93 min) MS1(−): 445.07795 MS2(−): 269.04596(100),268.03815(3),267.03036(1),241.05142(0.5),225.05623(1),197.06119(1),113.0244 9(3),99.00886(1),85.02956(3),71.01391(2)

7591 #1743 RT: 9.00 AV: 1 NL: 3.98E7 F: FTMS - p ESI d Full ms2 [email protected] [50.00-470.00] 269.04596 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

10 59.01389 5 85.02956 113.02449 197.06119 225.05623 129.01939 165.01932 325.07178 383.07596 0 50 100 150 200 250 300 350 400 450 m/z OH HO OH -H -H OH OH -H OH HO -H HO O HO O O O HO O

OH OH OH

- - - Chemical Formula: C14H9O4 Chemical Formula: C14H9O3 Chemical Formula: C13H9O2 OH O Exact Mass: 241.0506 Exact Mass: 225.0557 Exact Mass: 197.0608 - Chemical Formula: C21H17O11 Exact Mass: 445.0776 -H -H O O -H O O OH HO O

OH O OH - Chemical Formula: C H O - Chemical Formula: C15H7O4 14 7 3 OH O Exact Mass: 223.0401 - Exact Mass: 251.0350 Chemical Formula: C15H9O5 Exact Mass: 269.0455 -H OH -H HO OH HO OH

HO - Chemical Formula: C5H5O3 - Chemical Formula: C4H3O3 Exact Mass: 113.0244 Exact Mass: 99.0088

-H HO OH

- Chemical Formula: C4H5O2 Exact Mass: 85.0295

37 S39 Baicalin (tR=6.77 min) MS1(−): 445.07991 MS2(−): 269.04605(100),251.03560(1),241.05084(1),225.05608(0.4),197.06128(0.5),129.01952(1),117.01 965(1),113.02452(6),99.00889(3),85.02959(7)

7591 #1235 RT: 6.59 AV: 1 NL: 9.71E6 F: FTMS - p ESI d Full ms2 [email protected] [50.00-470.00] 269.04581 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

10 85.02938 113.02437 5 59.01376 99.00869 283.06180 129.01939 169.06613 197.06111 223.04050 251.03528 311.05701 386.32507 440.09186 0 50 100 150 200 250 300 350 400 450 m/z

OH -H -H -H -H HO O O HO O HO HO O HO HO HO HO OH O HO O OH OH OH

Chemical Formula: C H O - - - - 21 17 11 Chemical Formula: C14H9O4 Chemical Formula: C14H9O3 Chemical Formula: C13H9O2 Exact Mass: 445.0776 Exact Mass: 241.0506 Exact Mass: 225.0557 Exact Mass: 197.0608

-H -H -H

HO O O O O O HO OH O OH O OH Chemical Formula: C H O - - - 15 9 5 Chemical Formula: C15H7O4 Chemical Formula: C14H7O3 Exact Mass: 269.0455 Exact Mass: 251.0350 Exact Mass: 223.0401

-H OH -H HO OH HO OH

- - Chemical Formula: C5H5O3 Chemical Formula: C4H3O3 Exact Mass: 113.0244 Exact Mass: 99.0088

-H HO OH

- Chemical Formula: C4H5O2 Exact Mass: 85.0295

38 S8

63 6''-O-acetyl homoplantaginin OR Ladanetin-6-O-β-(6''-O-acetyl)glucoside (tR=10.39 min) MS1(−): 503.12007 MS2(−): 459.13107(3),428.07468(4),299.05685(61),284.03314(100),255.06674(33),211.04065(4),151.003 86(3)

7591 #2024 RT: 10.27 AV: 1 NL: 2.33E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-530.00] 284.03314 100

70 299.05658 65

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

25 255.06674 20

5 211.04065 428.07468 91.99551 151.00386 488.09641 201.05592 239.03508 459.13107 0 50 100 150 200 250 300 350 400 450 500 m/z

OH -H OH -H HO O O OH OH O HO O O HO O OH O O O HO O OH O O •- •- Chemical Formula: C21H16O10 Chemical Formula: C23H20O12 -H Exact Mass: 428.0749 OH Exact Mass: 488.0960 OH OH -H OH HO O O HO O O HO O O HO O OH OH O -H O OH O HO O O - O Chemical Formula: C24H23O12 - O Exact Mass: 503.1195 Chemical Formula: C23H23O10 Exact Mass: 459.1297 OH O -H •- OH Chemical Formula: C15H8O6 Exact Mass: 284.0326 HO O O O -H

O O OH O O - Chemical Formula: C16H11O6 Chemical Formula: C H O 2•- Exact Mass: 299.0561 9 5 4 Exact Mass: 177.01933 -H OH O -H

HO O OH O O 2•- Chemical Formula: C7H3O4 OH Exact Mass: 151.00368 - Chemical Formula: C15H11O4 Exact Mass: 255.0663 -H -H OH OH

O O

O OH OH 2•- - Chemical Formula: C14H7O4 Chemical Formula: C13H7O3 Exact Mass: 239.03498 Exact Mass: 211.0401

39 S9

64 Isomer of Solanoflavone (tR=7.81 min) MS1(−): 907.19435 MS2(−): 676.36243(4),547.01318(4),388.12686(4),345.12686(4),299.05661(100),284.03271(9),269.04614 (12),256.09375(4),267.03131(10)

7591 #1494 RT: 7.81 AV: 1 NL: 4.34E4 F: FTMS - p ESI d Full ms2 [email protected] [63.00-945.00] 299.05661 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 91.99572 267.03131

15 113.02458

5 167.94878 252.43759 345.21329 388.12686 547.01318 676.36243

0 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 m/z

O O OH O -H -H -H

HO O HO O HO O O O OH OH O O OH O OH O O O O O Chemical Formula: C H O - Chemical Formula: C H O •- HO O OH 16 11 6 15 8 6 Exact Mass: 299.0561 Exact Mass: 284.0326 O HO OH HO OH -H OH OH O OH - Chemical Formula: C44H41O21 Exact Mass: 905.2146 HO O OH •- Chemical Formula: C15H8O6 Exact Mass: 284.0326

40 S10

65 5,7,4',5'',3''',4''''-hexahydroxy-3''-O-β-glucosyl-3',7''-O-biflavone OR isomer (tR=6.62 min) MS1(−): 731.12622 MS2(−): 285.04032(0.6),269.04575(100),267.02943(0.4),251.22560(2),113.02448(8).

7591 #1242 RT: 6.62 AV: 1 NL: 7.15E4 F: FTMS - p ESI d Full ms2 [email protected] [51.00-765.00] 269.04575 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

10 113.02448 5 168.12543 251.22560 387.19846 447.95267 644.86310 0 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 m/z

OH -H -H OH O -H HO O HO O HO O OH O

OH O OH O - Chemical Formula: C H O - OH O Chemical Formula: C15H9O6 15 7 5 HO O Exact Mass: 285.0405 Exact Mass: 267.0299 OH OH -H O -H O OH O O HO OH O O HO OH OH Chemical Formula: C H O - 36 27 17 OH O OH O Exact Mass: 731.1254 - - Chemical Formula: C15H9O5 Chemical Formula: C15H7O4 Exact Mass: 269.0455 Exact Mass: 251.0350

41 S11

61 Trihydroxy-dimethoxyflavone O-glucoside (tR=7.51 min) MS1(−): 491.11986 MS2(−): 329.06747(42),314.04388(100),299.02063(18),269.04602(2)

7591-2 #1429 RT: 7.47 AV: 1 NL: 3.25E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-520.00] 314.04388 100

65 329.06747

60 e c n

a 55 d 269.04602 n u b

A 50

e v i t

a 45 l e R 40

25 299.02063 20

10 61.98824 91.99557 5 125.02483 164.28314 225.05611 493.43002

0 50 100 150 200 250 300 350 400 450 500 m/z

OH HO -H HO OH HO -H O O O HO O O OH O O OH OH O O O O - Chemical Formula: C17H13O7 OH O Exact Mass: 329.0667 2•- OH Chemical Formula: C15H7O7 O Exact Mass: 299.0197 OH O HO -H HO -H - Chemical Formula: C23H23O12 Exact Mass: 491.1195 O O O

OH OH O O OH O O •- •- Chemical Formula: C16H10O7 Chemical Formula: C15H9O5 Exact Mass: 314.0432 Exact Mass: 269.0455

42 S12, and S32

RT: 0.00 - 30.00 3.28 NL: 8.49E6 100 m/z= 607.12627- 95 607.13627 F: FTMS - p ESI Full 90 ms [150.00-1000.00] 85 MS 7591

60 e 3.21 c n

a 55 d n u b

A 50

e v i

t 4.64

a 45 l e R 40

15 6.13 6.44 6.59 10 7.28 9.81 5 8.74 13.56 2.07 10.35 11.55 15.46 16.58 16.81 20.26 20.89 27.49 0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 Time (min) 66 S12 Trihydroxyflavone O-glucoside-(12)-O-glucuronide (tR=4.56 min) MS1(−): 607.13127 MS2(−): 431.09888(3),269.04596(100),251.03477(0.4),175.02(1),113.02452(5),95.01376(1),85.02924(3)

7591 #822 RT: 4.49 AV: 1 NL: 5.88E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-640.00] 269.04596 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

5 71.01377 113.02452 431.09888 179.55910 251.03477 297.56854 337.07663 365.26581 524.95111 599.69965 0 50 100 150 200 250 300 350 400 450 500 550 600 m/z

OH OH OH HO OH OH -H O O HO -H -H O O -H O O HO HO HO O O O O O HO O HO HO HO OH O OH O OH O HO OH O - - - Chemical Formula: C H O - Chemical Formula: C15H7O4 Chemical Formula: C27H27O16 Chemical Formula: C21H19O10 15 9 5 Exact Mass: 251.0350 Exact Mass: 607.1305 Exact Mass: 431.0984 Exact Mass: 269.0455

43 S14

Isomer of chrysoeriol-7-O-[2''-O-E-feruloyl]-β-D-glucoside (tR=10.39 min) MS1(−): 637.15677 MS2(−): 283.06235(0.5),269.04596(100),251.03542(0.3),230.95995(1),223.06(1),205.05(2)

7591 #2049 RT: 10.38 AV: 1 NL: 7.03E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-670.00] 269.04596 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

25 230.95995 20

10 91.99541 283.06235 123.25819 5 388.95328 59.33638 147.36299 216.42105 359.14587 449.38727 0 50 100 150 200 250 300 350 400 450 500 550 600 650 m/z

S15

Unknow (tR=8.17 min) MS1(−): 863.20450 MS2(−): 271.06174(50),269.04608(100),211.07(2),165.62(0.4),113.02454(5)

7591 #1572 RT: 8.17 AV: 1 NL: 1.48E5 F: FTMS - p ESI d Full ms2 [email protected] [60.00-900.00] 269.04608 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 295.06180

10 113.02454 5 91.99390 175.02475 243.06673 325.07346 394.49838 460.24826 513.93640 770.94501 0 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 m/z

44 S16

67, 68 Baicalein 7-O-ethylglucuronide OR isomer (tR=9.32 min) MS1(−): 473.10911 MS2(−): 283.06165(33),269.04611(100),268.03824(45),161.00911(6) 7591-2 #1822 RT: 9.35 AV: 1 NL: 3.27E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-500.00] 269.04611 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

15 101.02451

10 87.00854 283.06165

5 72.99301 161.00958 189.00441 115.00383 225.54617 251.03438 438.38098 491.55972 0 50 100 150 200 250 300 350 400 450 500 m/z

OH OH -H HO OH -H -H

O O HO O O O O O

O HO HO HO OH OH O OH O - - - Chemical Formula: C16H11O5 Chemical Formula: C15H9O5 Chemical Formula: C23H21O11 Exact Mass: 283.0612 Exact Mass: 269.0455 Exact Mass: 473.1089

45 S18

Isomer of viscidulin II 2'-O-glucuronide (tR=7.13 min) MS1(−): 505.09920 MS2(−): 329.06656(28),314.04343(100),299.02014(27),269.04565(5),196(3),113.02434(11),85.02942(13)

7591 #1328 RT: 7.02 AV: 1 NL: 3.17E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-535.00] 269.04565 100 314.04343

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

35 299.02014 329.06656 30

25 113.02434 20 85.02942

15 235.00482

10 141.01965 285.04141 5 91.99612 149.57576 210.00473 245.22394 380.10315 406.57953 475.85806

0 100 150 200 250 300 350 400 450 500 m/z

HO O -H -H -H -H HO HO HO O O O O O O O O O O O O O O OH OH OH OH OH O HO OH OH O OH O OH O OH •- 2•- - - Chemical Formula: C H O Chemical Formula: C15H7O7 Chemical Formula: C23H21O13 Chemical Formula: C17H13O7 16 10 7 Exact Mass: 505.0988 Exact Mass: 329.0667 Exact Mass: 314.0432 Exact Mass: 299.0197

S19

61, 62 Chrysin 7-O-glucuronide (tR=9.21 min) MS1(+):431.09677 MS2(+):271.05957(6),255.06471(100)

7591-pos #1782 RT: 9.07 AV: 1 NL: 7.07E5 F: FTMS + p ESI d Full ms2 [email protected] [50.00-460.00] 255.06471 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

10 271.05957 5 55.56884 105.03375 137.19731 158.68146 282.07556 350.00165 449.28256 0 50 100 150 200 250 300 350 400 450 m/z

46 S22

Scutellarin (tR=3.86 min)61 MS1(−): 461.07327 MS2(−): 371.07819(6),341.06790(20),299.05603(12),285.04077(100),271.06216(3),245.05(3),227.07204( 4),211.04077(3)

7591 #692 RT: 3.85 AV: 1 NL: 1.57E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-490.00] 285.04 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

15 139.00

10 299.06 113.02 59.01 85.03 341.07 5 125.02 164.98 227.07 211.04 271.06 71.01 111.01 161.02 175.03 256.04 320.62 371.08 428.25 0 50 100 150 200 250 300 350 400 450 m/z

-H OH -H OH OH HO O O -H HO O HO O O HO HO HO HO OH O HO O OH O OH

- - - Chemical Formula: C21H17O12 Chemical Formula: C15H9O6 Chemical Formula: C6H3O4 Exact Mass: 461.0725 Exact Mass: 285.0405 Exact Mass: 139.0037

47 S23

61 Trihydroxy-methoxyflavone-O-glucoside (tR=9.77 min) MS1(−): 461.1091 MS2(−): 299.05609(38),284.03268(83),283.02502(100),269.04312(2),268.03726(1),253.05077(20),211.04 008(9),173.06068(2)

7591-neg2_150921204157 #1748 RT: 9.77 AV: 1 NL: 6.00E6 F: FTMS - p ESI d Full ms2 [email protected] [50.00-490.00] 283.02502 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40 299.05609

25 253.05077 20

10 211.04008 199.03928 461.10941 446.08630 5 173.06068 239.03493 269.04312 70.88451 113.02409 145.02820 0 50 100 150 200 250 300 350 400 450 m/z

OH OH -H -H -H HO OH OH O OH OH HO O HO O O O

O O O OH O OH O OH O - Chemical Formula: C H O •- - Chemical Formula: C16H11O6 15 8 6 Chemical Formula: C22H21O11 Exact Mass: 299.0561 Exact Mass: 284.0326 Exact Mass: 461.1089 -H -H -H OH OH OH

O O O O O

O O O O OH O OH O •- 2•- 2•- Chemical Formula: C16H10O6 Chemical Formula: C15H7O6 Chemical Formula: C15H9O4 Exact Mass: 298.04829 Exact Mass: 283.02481 Exact Mass: 253.05063 -H OH

O O •- Chemical Formula: C13H7O3 Exact Mass: 211.0401

48 S24

61 5,7,2'-Trihydroxy-6-methoxyflavanone 7-O-glucuronide (tR=4.60 min) MS1(−): 477.10424 MS2(−): 301.07242(70),286.04889(100),181.01442(21),165.99094(13)

7591-2 #840 RT: 4.60 AV: 1 NL: 5.84E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-505.00] 286.04889 100

65 301.07242 60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

35 113.02441 30

25 85.02942 20 181.01442

15 154.99901 10 71.01376 99.00883 139.04012 5 200.27242 251.84570 315.05127 375.38110 465.40866 0 50 100 150 200 250 300 350 400 450 500 m/z

-H -H -H HO HO HO O O O O O O O HO O HO O HO

HO OH OH OH O OH O OH O

- - Chemical Formula: C H O •- Chemical Formula: C22H21O12 Chemical Formula: C16H13O6 15 10 6 Exact Mass: 477.1038 Exact Mass: 301.0718 Exact Mass: 286.0483

O O -H -H HO HO O O

O O OH OH

- •- Chemical Formula: C8H5O5 Chemical Formula: C7H2O5 Exact Mass: 181.0142 Exact Mass: 165.9908

49 S26, S27, S36, and S37

RT: 0.00 - 30.00 9.63 NL: 100 5.30E8 m/z= 95 474.58-475.58 F: FTMS - p ESI Full 90 ms [150.00-1000.00] 85 MS 7591-2

75 8.97 70

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

10 5.44 0.88

5 5.28 7.84 10.61 1.77 3.32 5.02 7.53 11.58 12.55 14.49 15.51 16.66 19.03 21.24 21.86 22.59 25.17 27.58 28.35 0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 Time (min)

S26 Isomer of 37 (trihydroxy-methoxyflavone O-glucuronide) (tR=5.27 min) MS1(−): 475.08834 MS2(−): 299.05655(58),284.03311(100)

S27 Isomer of 37 (trihydroxy-methoxyflavone O-glucuronide) (tR=9.47 min) MS1(−): 475.08809 MS2(−): 299.05637(50),284.03305(100),270.04959(5)

S36 Isomer of 37 (trihydroxy-methoxyflavone O-glucuronide) (tR=7.59 min) MS1(−): 475.08836 MS2(−): 299.05658(100),284.03305(59),270.10849(0.5)

50 61 S37 5,7,2’-Trihydroxy-6-methoxyflavone 7-O-glucuronide (tR=8.84 min) MS1(−): 475.08832 MS2(−): 299.05643(30),284.03299(100),267.02997(0.3),239.03540(0.2),228.04262(0.4),200.04805(1),153. 01936(1),129.01955(1),113.02440(6),85.02940(7)

7591-2 #1736 RT: 8.95 AV: 1 NL: 1.18E8 F: FTMS - p ESI d Full ms2 [email protected] [50.00-505.00] 284.03299 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

35 299.05643 30

10 85.02940 113.02440 5 59.01378 99.00875 153.01936 200.04805 228.04262 267.02997 340.94260 392.52316 500.90985 0 50 100 150 200 250 300 350 400 450 500 m/z

O OH OH HO -H HO -H HO -H HO -H O HO OH HO O HO O O O O O O O O OH O OH O OH O OH O •- - - - Chemical Formula: C H O Chemical Formula: C15H7O5 Chemical Formula: C22H19O12 Chemical Formula: C16H11O6 15 8 6 Exact Mass: 267.0299 Exact Mass: 475.0882 Exact Mass: 299.0561 Exact Mass: 284.0326 HO -H -H O O O O O

OH OH Chemical Formula: C H O 2•- - 7 5 4 Chemical Formula: C14H7O4 Exact Mass: 153.01933 Exact Mass: 239.0350

51 S28

Dihydrobaicalin (tR 7.98)61, 62 MS1(−): 447.07795 MS2(−): 271.06250(100),253.05099(8),243.06644(25)

7591-2 #1504 RT: 7.83 AV: 1 NL: 2.95E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-475.00] 271.06250 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

25 243.06644

20 113.02449 85.02942 15

10 59.01383 99.00884 5 166.99866 227.07170 139.00378 193.01477 323.30975 393.30203 0 50 100 150 200 250 300 350 400 450 m/z

-H

HO O

HO OH - Chemical Formula: C14H11O4 Exact Mass: 243.0663

-H

-H O -H OH HO O O OH O HO O Chemical Formula: C H O - O 15 9 4 HO HO Exact Mass: 253.0506 HO OH O HO O OH O -H - - HO O Chemical Formula: C21H19O11 Chemical Formula: C15H11O5 Exact Mass: 447.0933 Exact Mass: 271.0612 HO OH O

- Chemical Formula: C7H3O5 Exact Mass: 166.9986

HO -H O HO OH

- Chemical Formula: C6H3O4 Exact Mass: 139.0037

52 S30

Dihydroxy-methoxyflavone O-glucuronide-(16)-O-glucoside (tR=4.91 min) MS1(−): 621.14659 MS2(−): 445.11441(70),430.09079(59),283.06143(49),268.03781(100),267.03018(93),239.03525(2),175.0 2502(3),117.02(3),113.02444(25),103.00378(3),99.00882(7),95.01390(7),85.02956(21)

7591-2 #906 RT: 4.91 AV: 1 NL: 9.31E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-650.00] 268.03781 100

80 445.11441 75

70 430.09079 65

60 e c n

a 55 d n u

b 283.06143

A 50

e v i t

a 45 l e R 40 113.02444 35

25 85.02956

5 129.01958 325.07193 175.02502 239.03525 193.03554 354.25461 400.64301 583.92432 613.93140 0 50 100 150 200 250 300 350 400 450 500 550 600 650 m/z

HO O

HO -H O -H O OH -H O O OH O OH HO O O HO HO O OH O HO O O HO O HO O O OH OH OH

OH O OH O OH O Chemical Formula: C H O - - •- 28 29 16 Chemical Formula: C22H21O10 Chemical Formula: C21H18O10 Exact Mass: 621.1461 Exact Mass: 445.1140 Exact Mass: 430.0905

-H -H -H -H -H O HO O O O O

HO O HO HO HO O O O O

HO OH O OH OH OH O OH O - •- 2•- Chemical Formula: C H O - - Chemical Formula: C H O Chemical Formula: C15H7O5 6 7 6 Chemical Formula: C15H11O3 Chemical Formula: C16H11O5 15 8 5 Exact Mass: 175.0248 Exact Mass: 239.0714 Exact Mass: 283.0612 Exact Mass: 268.0377 Exact Mass: 267.02990

53 S31, S44, S48, and S101

RT: 0.00 - 30.00 5.25 NL: 5.72E7 100 m/z= 415.10147- 95 415.10563 F: FTMS - p ESI Full 90 ms [150.00-1000.00] 85 MS 7591-2

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

35 9.63

25 8.06 20

15 4.91 10

5 1.64 4.05 4.22 5.51 7.78 9.08 9.88 11.01 11.58 14.49 15.90 17.77 19.03 19.98 22.50 24.79 26.02 26.84 0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 Time (min) 69, 70 S31 Chrysin 7-O-glucoside OR isomer (Trihydroxyflavone O- glucoside) (tR=9.61 min) MS1(−): 415.10355 MS2(−): 295.06122(3),269.04590(2),253.05075(100),224.04839(0.2),209.06085(2)

7593-neg2 #1891 RT: 9.67 AV: 1 NL: 5.88E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-440.00] 253.05075 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

10 415.10373 5 295.06122 209.06085 269.04590 65.88356 96.96002 141.06993 242.26855 369.78830 401.00290 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 m/z

-H

-H -H OH - Chemical Formula: C14H9O2 O O O HO O Exact Mass: 209.0608 HO -H

HO OH O OH OH O OH O - - Chemical Formula: C21H19O9 Chemical Formula: C15H9O4 Exact Mass: 415.1035 Exact Mass: 253.0506 OH O •- Chemical Formula: C14H8O3 Exact Mass: 224.0479

S44 Isomer of S48 (Dihydroxyflavone C-glucoside) (tR=5.12 min) MS1(−):415.10373 MS2(−):325.07175(4),307.06094(2),295.06113(100),277.05060(1),267.06644(32),253.05106(0.5), 227.07188(0.5),179.03456(0.6),149.02438(2)

54 7591-2 #951 RT: 5.13 AV: 1 NL: 1.97E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-440.00] 295.06152 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

35 267.06662

10 307.06140 325.07217 415.10431 5 277.05096 149.02457 77.88606 112.98559 187.04007 223.07791 245.04578 338.05563 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 m/z 61 S48 Chrysin 6-C-glucoside (tR=8.03 min) MS1(+): 415.10413 (positive) MS2(+): 325.07217(33),295.06152(100),267.06662(25),253.05095(3),223.07791(0.5),151.05568(0.1)

7593-neg2 #1523 RT: 7.91 AV: 1 NL: 1.85E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-440.00] 295.06140 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

30 325.07199 25 267.06653

277.05206 10 307.06189 91.99550 5 415.10483 70.24506 107.85503 163.51932 227.10291 253.05124 337.07294 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 m/z

-H -H

HO O HO O

O HO O O HO O O OH OH - - Chemical Formula: C21H17O8 Chemical Formula: C18H11O5 Exact Mass: 397.0929 Exact Mass: 307.0612 -H

HO O -H

HO O OH O -H OH OH HO O - O Chemical Formula: C18H13O6 O Chemical Formula: C H O - O Exact Mass: 325.0718 17 9 4 HO -H Exact Mass: 277.0506 -H -H OH O HO OH HO O HO O OH

- Chemical Formula: C21H19O9 Exact Mass: 415.1035 OH O OH OH OH OH OH - - - Chemical Formula: C17H11O5 Chemical Formula: C16H11O4 Chemical Formula: C15H11O2 Exact Mass: 295.0612 Exact Mass: 267.0663 Exact Mass: 223.0765 -H

HO O

OH O - Chemical Formula: C15H9O4 Exact Mass: 253.0506 55 61 S101 Chrysin 8-C-glucoside (tR=5.22 min) MS1(+): 415.10431 MS2(+): 325.07217(5),295.06152(100),267.06662(31),245.04578(1),223.07791(0.5),187.07007(0.5),149.0 2457(2)

7593-neg #989 RT: 5.30 AV: 1 NL: 2.32E7 F: FTMS - p ESI d Full ms2 [email protected] [50.00-440.00] 295.06110 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

35 267.06628 30

10 307.06110 5 325.07172 415.10358 59.01359 149.02428 277.05029 77.68641 121.02912 187.04002 227.07147 253.05058 337.07257 361.07098 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 m/z

OH OH HO HO -H -H O O O O O

OH O OH O - - OH OH Chemical Formula: C21H17O8 Chemical Formula: C18H11O5 OH Exact Mass: 397.0929 Exact Mass: 307.0612 OH -H O -H -H OH OH HO O HO O O O

OH O OH O OH O - - - Chemical Formula: C18H13O6 Chemical Formula: C17H9O4 Chemical Formula: C21H19O9 Exact Mass: 415.1035 Exact Mass: 325.0718 Exact Mass: 277.0506 -H -H -H OH OH OH HO O HO O

OH OH O OH - - - Chemical Formula: C15H11O2 Chemical Formula: C17H11O5 Chemical Formula: C16H11O4 Exact Mass: 295.0612 Exact Mass: 267.0663 Exact Mass: 223.0765

56 S32

66 Trihydroxyflavone O-glucuronide-(12)-O-glucoside (tR=6.02 min) MS1(−): 607.13129 MS2(−): 445.18335(1),269.04572(100),113.02447(1)

7591 #1104 RT: 5.89 AV: 1 NL: 1.88E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-640.00] 269.04572 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

5 91.99635 195.04332 226.39609 280.65921 361.28253 445.18335 527.49866 622.38263 0 50 100 150 200 250 300 350 400 450 500 550 600 m/z

57 S33

61, 62 5,7-Dihydroxy-8,2'-dimethoxyflavone 7-O-glucuronide (tR=10.27 min) MS1(−): 489.10400 MS2(−): 313.07257(24),298.04871(100),283.02521(29),281.04529(4),269.04565(2),239.03593(2),211.040 42(5)

7591-neg #2010 RT: 10.12 AV: 1 NL: 8.27E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-515.00] 298.04871 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

35 283.02521 30 313.07257 25

15 85.02943 111.00878 10 99.00874 59.01373 211.04080 5 126.76942 161.26450 191.27446 239.03593 269.04565 339.27301 359.00381 411.99783 439.95370 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 m/z

-H O -H O -H O -H O O O O O O O O O HO O HO HO

HO OH OH OH O OH O OH OH - 2•- 2•- 2•- Chemical Formula: C23H21O12 Chemical Formula: C15H7O6 Chemical Formula: C14H7O4 Chemical Formula: C13H7O3 Exact Mass: 489.1038 Exact Mass: 283.0248 Exact Mass: 239.0350 Exact Mass: 211.0401 O -H O O -H O O HO O

O -H OH O O Chemical Formula: C H O - HO O 16 9 5 OH O Exact Mass: 281.0455 - Chemical Formula: C17H13O6 O -H Exact Mass: 313.0718 O OH O O O •- Chemical Formula: C16H10O6 Exact Mass: 298.0483

OH 2•- Chemical Formula: C15H9O5 Exact Mass: 269.04555

58 S34

61 Viscidulin III 6'-O-glucoside (tR=4.13 min) MS1(−): 507.11461 MS2(−): 492.09247(1),345.06189(15),330.03836(100),315.01505(14)

7591 #738 RT: 4.07 AV: 1 NL: 2.56E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-535.00] 330.03836 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 345.06189

15 315.01505

5 223.02840 64.26513 91.99663 125.02412 165.04082 186.35643 394.52908 430.96545 0 50 100 150 200 250 300 350 400 450 m/z

OH -H O -H -H -H O OH OH OH O O HO O O O O O HO O O O HO O HO O OH OH O OH OH OH HO OH OH O OH OH O OH O •- 2•- - - Chemical Formula: C H O Chemical Formula: C15H7O8 Chemical Formula: C23H23O13 Chemical Formula: C17H13O8 16 10 8 Exact Mass: 315.0146 Exact Mass: 507.1144 Exact Mass: 345.0616 Exact Mass: 330.0381

S35

61 Wogonin 5-glucoside (tR=9.35 min) MS1(+):447.12802 MS2(+):285.07462(100),270.05118(17),241.04947(0.1)

7591-pos_150921221703 #1662 RT: 9.46 AV: 1 NL: 4.56E7 F: FTMS + p ESI d Full ms2 [email protected] [50.00-475.00] 285.07462 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 270.05118 15

5 85.02859 69.03390 127.03877 167.12489 194.09413 241.04947 297.07480 327.08514 0 50 100 150 200 250 300 350 400 450 m/z

59 S38

Dihydroxy-tetramethoxyflavone O-glucuronide (tR=10.95 min) MS1(+): 551.13891 MS2(+): 375.10657(100),360.08340(9),345.05960(13),342.07269(3),329.06488(0.3),327.04913(4),227.054 61(3),177.05432(1)

7591-pos #2173 RT: 10.88 AV: 1 NL: 2.00E6 F: FTMS + p ESI d Full ms2 [email protected] [50.00-580.00] 375.10657 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

15 345.05960

5 227.05461 327.04913 85.02872 145.02803 177.05432 254.14893 314.07800 385.09122 458.09760 550.85754 0 50 100 150 200 250 300 350 400 450 500 550 m/z

O O +H O +H +H O O O O O O O O O O O O O O O HO HO HO OH O OH O OH O HO OH •+ 2•+ Chemical Formula: C18H16O8 Chemical Formula: C17H13O8 OH Exact Mass: 360.0840 Exact Mass: 345.0605 + Chemical Formula: C25H27O14 Exact Mass: 551.1395 O +H O +H O O O +H O O O O O O O O O O +H O O O 2•+ HO O 2•+ Chemical Formula: C16H11O5 O Chemical Formula: C17H11O7 Exact Mass: 283.0601 OH O Exact Mass: 327.0499 + O Chemical Formula: C19H19O8 O O O +H Exact Mass: 375.1074 +H O O O O O O •+ O O Chemical Formula: C18H14O7 O O Exact Mass: 342.0734

O O •+ Chemical Formula: C H O 2•+ Chemical Formula: C17H14O6 16 11 6 Exact Mass: 314.0785 Exact Mass: 299.0550

60 S41, S42, and S43

RT: 0.30 - 14.57 3.25 NL: 1.69E6 100 m/z= 565.15474- 95 565.16040 F: FTMS - p ESI Full 90 ms [150.00-1000.00] 85 MS 7591-2 3.28 80

60 e

c 10.61 n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 3.59 3.83 15 0.88 10.85 10 11.37 4.35 4.49 3.10 5 2.81 4.54 12.60 1.77 4.76 5.51 7.84 12.79 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Time (min)

S41 Isomer of Pinobanksin 8-C-arabinoside 6-C-glucoside (Containing C-glycosides) (tR=3.87 min) MS1(−): 565.15757 MS2(−): 367.08337(1),337.07230(2),329.08737(8),299.07730(9),269.6674(40),239.05615(97),209.04556( 100)

7593-neg #674 RT: 3.81 AV: 1 NL: 1.37E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-595.00] 239.05598 100 209.04544

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l

e 269.06668 R 40

35 167.03482 30

20 197.04546 15

10 125.02424 299.07669 329.08737

5 70.34653 97.02943 137.02454 367.08252 0 50 100 150 200 250 300 350 400 450 500 550 m/z

S42 Isomer of Pinobanksin 8-C-arabinoside 6-C-glucoside (containing C-glycosides) (tR=3.57 min) MS1(−): 565.15700 MS2(−): 329.08783(4),299.07840(10),269.06689(41),239.05627(100),209.04572(95)

61 7591-2 #634 RT: 3.62 AV: 1 NL: 4.66E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-595.00] 239.05627 100

85 209.04572

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

35 269.06689 30 153.01945 25

15 197.04620

10 299.07840 311.07858 5 91.99670 125.02467 367.08463 0 50 100 150 200 250 300 350 400 450 500 550 m/z

S43 Isomer of Pinobanksin 8-C-arabinoside 6-C-glucoside (Containing C-glycosides) (tR=3.24 min) MS1(−): 565.15653 MS2(−): 329.08795(7),299.07770(10),269.06622(43),239.05637(100),209.04559(89)

7591-2 #538 RT: 3.13 AV: 1 NL: 2.09E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-595.00] 239.05637 100

75 209.04559 70

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e

R 269.06622 40

30 167.03532 25 384.08221 197.04626 20 125.02459

15 281.06793 10 61.98832 91.99532 354.07117 329.08795 412.30261 539.90698 5 143.48375

0 50 100 150 200 250 300 350 400 450 500 550 m/z HO

-H HO HO OH OH OH HO HO -H -H OH O O OH HO HO OH HO O HO OH - Chemical Formula: C12H13O7 O Exact Mass: 269.0667 HO OH

OH O OH HO -H HO OH OH HO OH HO -H OH OH HO OH - - Chemical Formula: C26H29O14 Chemical Formula: C14H17O9 Exact Mass: 565.1563 Exact Mass: 329.0878 OH OH OH OH OH

- - Chemical Formula: C11H11O6 Chemical Formula: C10H9O5 Exact Mass: 239.0561 Exact Mass: 209.0455

62 S45

71 Chrysin 6,8-di-C-glucopyranoside (tR=3.13 min) MS1(−): 577.15683 MS2(−): 577.15729(14),487.12531(11),457.11462(32),439.10440(3),397.09293(6),367.08258(58),337.072 24(100)

7591-2 #521 RT: 3.05 AV: 1 NL: 3.53E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-605.00] 337.07224 100

60 367.08258 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

35 457.11462 30

15 487.12531 577.15729 10 379.08252 309.07767 5 281.08218 439.10440 191.03468 517.13611 87.90216 149.02388 218.91542 559.14807 0 50 100 150 200 250 300 350 400 450 500 550 600 m/z

-H HO -H HO O HO HO O O HO OH O HO OH OH O OH OH - - Chemical Formula: C23H21O10 Chemical Formula: C19H13O6 Exact Mass: 457.1140 Exact Mass: 337.0718 OH -H OH -H HO HO HO O OH HO O HO O OH HO -H O OH O HO HO OH OH O HO O OH OH - - Chemical Formula: C20H15O7 Chemical Formula: C24H23O11 O Exact Mass: 487.1246 Exact Mass: 367.0823 HO OH -H OH O HO OH HO OH HO O - Chemical Formula: C27H29O14 Exact Mass: 577.1563 HO OH O OH - Chemical Formula: C21H17O8 Exact Mass: 397.0929 HO -H HO HO O

OH O OH

- Chemical Formula: C20H15O7 Exact Mass: 367.0823

63 S47

61 6-hexosyl-8-C-pentosyl chrysin (tR=5.10 min) MS1(−):547.1462 MS2(−):547.14624(16),487.12512(17),457.11450(23),427.10364(40),397.09360(31),367.08234(1 00),337.07205(70),309.07745(6)

7591-2 #913 RT: 4.94 AV: 1 NL: 3.42E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-575.00] 337.07205 100

90 367.08234 85

60 e

c 427.10364 n

a 55 d n u

b 457.11450

A 50 547.14624

e v i t

a 45 l e R 40

15 397.09360 10 309.07745

5 91.99556 487.12512 154.49739 191.03539 221.04578 271.55316 529.03442 0 50 100 150 200 250 300 350 400 450 500 550 m/z

S49

61 Skullcapflavone (tR=14.60 min) MS1(−):343.08222 MS2(−):328.06003(12),313.03540(100),298.01190(16),270.01706(2)

7593-neg_150921211339 #2054 RT: 11.49 AV: 1 NL: 3.94E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-370.00] 313.03540 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 298.01190 15 328.06003 10 343.15549

5 91.99581 266.05365 69.42751 117.08619 140.97705 159.58257 180.08965 218.53777 240.70897 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 m/z

O -H O -H O -H O O O O O O O O O

OH OH OH

OH O OH O OH Chemical Formula: C H O - Chemical Formula: C H O 2•- 3•- 18 15 7 16 9 7 Chemical Formula: C14H6O6 Exact Mass: 343.0823 Exact Mass: 313.0354 Exact Mass: 270.0170 O -H O O -H O O O O O OH OH OH O •- OH O Chemical Formula: C17H12O7 3•- Chemical Formula: C15H6O7 Exact Mass: 328.0589 Exact Mass: 298.0119

64 S50

70 2',5,6-Trihydroxy-7,8-dimethoxyflavone 6-O-sulfate (tR=4.91 min) MS1(−):409.0237 MS2(−):329.06705(100),314.04361(62),299.01993(27),195.03003(2),180.00662(3),164.98241(1), 133.02942(2)

7591-2 #905 RT: 4.90 AV: 1 NL: 1.11E6 F: FTMS - p ESI d Full ms2 [email protected] [50.00-435.00] 329.06705 100

60 e

c 314.04361 n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

30 299.01993 25

5 133.02942 180.00662 199.02472 285.04071 80.35626 96.95981 261.04071 345.18527 382.67203 402.94427 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 m/z

HO -H -H -H O HO -H HO HO O O O O O O O O O O O

O O S HO HO HO HO OH O O OH O OH O OH O - •- 2•- Chemical Formula: C17H13O7 Chemical Formula: C H O Chemical Formula: C15H7O7 Chemical Formula: C H O S- 16 10 7 17 13 10 Exact Mass: 329.0667 Exact Mass: 314.0432 Exact Mass: 299.0197 Exact Mass: 409.0235 O O O -H -H -H O O O O O O HO HO HO OH OH OH - •- Chemical Formula: C HO 2•- Chemical Formula: C9H7O5 Chemical Formula: C8H4O5 7 5 Exact Mass: 195.0299 Exact Mass: 180.0064 Exact Mass: 164.9829

65 S51, S53, S54, and S82

RT: 5.87 - 21.67 12.21 NL: 3.32E7 100 11.84 m/z= 329.06517- 95 329.06847 F: FTMS - p ESI Full 90 ms [150.00-1000.00] 85 MS 7591-2

60 e c n

a 55 d n u b

A 50 11.69

e v i t

a 45 l e R 40 10.96

35 10.21 30

10 12.92

5 9.69 13.43 6.67 7.20 7.60 8.69 13.90 14.49 15.15 15.83 16.95 18.34 18.82 19.31 20.20 21.58 0 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 Time (min)

S51 Isomer of S54 (Trihydroxy-dimethoxyflavone) (tR=10.23 min) MS1(−):329.06682 MS2(−):314.04337(49),299.01974(100),285.04105(2),271.02505(2),255.02969(0.9),227.03496(0. 3),180.00645(9),164.98270(6),133.02942(7)

7593-neg #2001 RT: 10.15 AV: 1 NL: 6.88E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-355.00] 299.01974 100

60 e c n

a 55 d n u

b 314.04337

A 50

e v i t

a 45 l e R 40

20 329.06671 15

10 180.00645 133.02942 164.98270 285.04105 5 111.00857 195.02982 271.02505 76.60100 152.01076 227.03496 255.02969 346.43387 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 m/z

S82 Isomer of S54 (Trihydroxy-dimethoxyflavone) (tR=10.87 min) MS1(−):329.06778 MS2(−):314.04358(62),299.01959(81)283.26471(26),268.03827(25)

7593-neg #2157 RT: 10.86 AV: 1 NL: 1.46E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-355.00] 299.01959 100

85 314.04358

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

30 268.03827 25 111.00884

15 125.02429 283.26471 257.08197 329.06760 10 91.99467 187.09744 227.44994 78.09958 145.05112 170.84331 5

0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 m/z

66 61 S53 5,8,2’-Trihydroxy-6,7-dimethoxyflavone (tR=12.95 min) MS1(−):329.06680 MS2(−):314.04309(61),299.01953(100),285.04083(3),271.02472(2),255.02936(0.3),227.0.462(0.3), 205.01410(0.8),180.00636(2),152.01122(2),133.02835(0.5)

7593-neg #2596 RT: 13.00 AV: 1 NL: 3.62E6 F: FTMS - p ESI d Full ms2 [email protected] [50.00-355.00] 299.01953 100

65 314.04309 60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 329.06650 15

5 285.04083 152.01122 180.00636 268.03751 72.97884 91.99448 111.00817 133.02835 205.01410 227.03462 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 m/z

HO -H HO -H OH OH O O O O

O O OH O OH 2•- 2•- Chemical Formula: C15H7O7 Chemical Formula: C14H7O6 Exact Mass: 299.0197 Exact Mass: 271.0248 HO -H OH OH O -H O

-H HO HO O O OH OH OH OH O O •- 2•- O O Chemical Formula: C7H4O4 Chemical Formula: C14H7O5 Exact Mass: 152.0115 Exact Mass: 255.0299 HO -H O O OH OH O O OH O O -H - Chemical Formula: C H O •- Chemical Formula: C17H13O7 16 10 7 Exact Mass: 329.0667 Exact Mass: 314.0432 O O O OH OH •- 2•- Chemical Formula: C8H4O5 Chemical Formula: C13H7O4 Exact Mass: 180.0064 Exact Mass: 227.0350 HO -H OH O O

O O •- Chemical Formula: C15H9O6 Exact Mass: 285.0405

67 61 S54 5,7,6’-Trihydroxy-8,2’-dimethxoyflavone (tR=11.74 min) MS1(−): 329.06679 MS2(−): 314.04349(100),299.01993(80),255.02878(0.7),180.00696(2),165.99080(12),137.99586(6)

7593-neg #2313 RT: 11.61 AV: 1 NL: 1.91E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-355.00] 314.04349 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

35 299.01993

15 165.99080 10 212.13744 110.00072 137.99586 329.06732 230.14795 5 207.24657 283.26465 97.06593 180.00696 268.03732 57.03448 83.05012 125.02424 151.00311 240.13289 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 m/z

-H -H -H -H O O O O O O O O HO O HO O HO O HO O

OH OH OH OH

OH O OH O OH - OH O 2•- Chemical Formula: C H O •- 2•- Chemical Formula: C14H7O6 17 13 7 Chemical Formula: C16H10O7 Chemical Formula: C15H7O7 Exact Mass: 329.0667 Exact Mass: 314.0432 Exact Mass: 299.0197 Exact Mass: 271.0248 -H O O O -H -H O O O -H HO HO O O O

OH O O O OH OH OH OH •- •- •- 2•- Chemical Formula: C8H4O5 Chemical Formula: C6H2O4 Chemical Formula: C7H2O5 Chemical Formula: C14H7O5 Exact Mass: 180.00642 Exact Mass: 137.9959 Exact Mass: 165.9908 Exact Mass: 255.0299

68 S52, S55, S61, S63, and S69

RT: 0.00 - 30.00 13.91 NL: 1.87E8 100 m/z= 313.07033- 95 313.07347 F: FTMS - p ESI Full 90 ms [150.00-1000.00] 85 MS 7591-2

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

35 14.16

15 10.27 11.15 10

5 13.80 14.49 0.98 3.15 3.68 4.73 6.19 6.82 7.94 8.88 15.14 16.39 18.23 19.63 20.79 22.10 23.96 27.42 27.61 28.24 0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 Time (min)

S52 Isomer of S63 (Dihydroxy-dimethoxyflavone) (tR=11.16 min) MS1(−): 313.07190 MS2(−): 298.04861(100),283.02521(85),255.03027(2),239.03503(2),211.04025(19),173.06067(5)

7591-2 #2226 RT: 11.19 AV: 1 NL: 2.58E6 F: FTMS - p ESI d Full ms2 [email protected] [50.00-340.00] 298.04861 100

80 283.02521

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 211.04025

10 201.05632 5 173.06075 217.05032 269.04605 313.07227 183.04538 239.03503 255.03027 72.59841 91.02206 127.05502 155.05023 331.92194 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 m/z

S55 Isomer of 6-Methoxywogonin (Dihydroxy-dimethoxyflavone) (tR=10.27 min) MS1(−): 313.07188 MS2(−): 298.04871(100),283.02530(87),269.04614(78),255.12172(4),211.04001(18),167.04(5),145.02962 (15),91.02(28)

69 7591-2 #1991 RT: 10.12 AV: 1 NL: 3.92E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-340.00] 298.04871 100

95 283.02530

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40 91.02212 35 269.04614

30 313.23892

20 145.02962 211.04001 15 229.05109 10 101.82377 159.97330 255.12172 80.91671 5 173.06104 241.21863 65.63998 112.01554 196.29350 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 m/z

O HO O

O O OH O O - - Chemical Formula: C17H13O6 Chemical Formula: C9H5O2 Exact Mass: 313.0718 Exact Mass: 145.0295

61, 62 S61 5,8-Dihydroxy-6,7-dimethoxyflavone (tR=14.19) MS1(−): 313.07224 MS2(−): 298.04852(100),283.02515(87),269.04590(21),255.03026(2),239.03487(0.3),211.04027(18),195.0 3015(0.3),180.00664(5),173.06090(0.3),164.98279(2),152.01154(3),117.03396(0.2)

7591-2 #2820 RT: 14.18 AV: 1 NL: 1.44E7 F: FTMS - p ESI d Full ms2 [email protected] [50.00-340.00] 283.02515 100

65 298.04852

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

15 313.07220

10 180.00664 5 152.01154 269.04590 211.04027 255.03026 65.00288 91.02194 117.03396 136.98767 195.03015 227.03522 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 m/z

70 -H -H -H OH OH OH O O O O O O

O O O OH O OH O OH •- 2•- 2•- Chemical Formula: C16H10O6 Chemical Formula: C15H7O6 Chemical Formula: C14H7O5 Exact Mass: 298.0483 Exact Mass: 283.0248 Exact Mass: 255.0299 -H O O -H OH -H O O O -H OH O O O O O O O O O OH 2• 2•- 2•- Chemical Formula: C9H8O5 Chemical Formula: C7HO5 Chemical Formula: C14H7O4 O Exact Mass: 196.03717 Exact Mass: 164.98295 Exact Mass: 239.0350 -H OH O O O -H - -H O Chemical Formula: C17H13O6 Exact Mass: 313.0718 O O O O O OH - •- 2•- Chemical Formula: C8H5O Chemical Formula: C8H4O5 Chemical Formula: C13H7O3 Exact Mass: 117.0346 Exact Mass: 180.00642 Exact Mass: 211.0401

-H OH O O -H

O O OH O O Chemical Formula: C H O - •- 16 13 4 Chemical Formula: C7H4O4 Exact Mass: 269.0819 Exact Mass: 152.01151

62 S63 Skullcapflavone I (tR=13.90 min) MS1(−): 313.07211 MS2(−): 298.04868(68),283.02527(100),255.03012(2),211.04028(2),183.04514(2),173.06091(4),164.98(2),1 55.05032(3)

7591-2 #2779 RT: 13.99 AV: 1 NL: 3.92E6 F: FTMS - p ESI d Full ms2 [email protected] [50.00-340.00] 298.04868 100

80 283.02527 75

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 211.04028

173.06091 201.05606 217.05136 269.04565 5 313.07211 183.04514 239.03534 255.03012 72.59839 91.99577 127.05514 155.05032 331.92163 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 m/z

71 -H -H -H HO HO HO HO -H O O O O O O O O O O O O

OH O OH O OH O OH - •- 2•- Chemical Formula: C H O 2•- Chemical Formula: C17H13O6 Chemical Formula: C16H10O6 Chemical Formula: C15H7O6 14 7 5 Exact Mass: 313.0718 Exact Mass: 298.0483 Exact Mass: 283.0248 Exact Mass: 255.0299

HO -H -H HO -H O HO -H HO -H HO O O O O O O

HO OH Chemical Formula: C H O- - 11 7 Chemical Formula: C12H7O2 Chemical Formula: C H O 2•- 2•- 2•- 13 7 3 Chemical Formula: C14H7O4 Chemical Formula: C13H7O4 Exact Mass: 155.0502 Exact Mass: 183.0452 Exact Mass: 211.0401 Exact Mass: 239.0350 Exact Mass: 227.0350

72 S69 Isomer of 6-Methoxywogonin (Dihydroxy-dimethoxyflavone) (tR=10.50 min) MS1(−): 313.07190 MS2(−): 298.04874(100),283.02530(87),269.04593(21),255.03079(4),211.04013(18),173.06114(3),145.02 940(3),91.02199(8)

7591-2 #2074 RT: 10.49 AV: 1 NL: 7.91E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-340.00] 298.04874 100

75 283.02530 70

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 91.02199 211.04013 269.04593 15 313.23914 10 145.02940 80.91679 173.06114 5 96.96017 226.02757 255.03079 75.00855 111.00853 161.80220 183.04544 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 m/z

O HO O

O O OH O O - - Chemical Formula: C17H13O6 Chemical Formula: C9H5O2 Exact Mass: 313.0718 Exact Mass: 145.0295

72 S56

61 5,7,3,2',6'-Pentahydroxyflavanone (tR=2.89 min) MS1(−): 303.05117 MS2(−): 285.04059(2),241.05075(2),217.05060(9),193.05551(4),177.01930(30),149.02429(10),125.02426 (100)

7593-neg #490 RT: 2.89 AV: 1 NL: 1.04E8 F: FTMS - p ESI d Full ms2 [email protected] [50.00-330.00] 125.02426 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

30 177.01930

149.02429 10 217.05060 231.06642 5 57.03443 193.05069 83.01366 165.05562 199.04015 241.05075 285.04059 303.05109 65.00309 107.01375 133.02937 259.06152 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 m/z

-H HO

HO O

OH OH O - Chemical Formula: C15H9O6 Exact Mass: 285.0405 HO -H HO -H

HO HO

OH OH OH OH OH - - Chemical Formula: C14H11O5 Chemical Formula: C14H9O4 Exact Mass: 259.0612 Exact Mass: 241.0506 -H HO HO -H HO -H HO O O OH OH O OH O OH - - Chemical Formula: C H O Chemical Formula: C8H5O3 OH O 9 5 4 - Exact Mass: 177.0193 Exact Mass: 149.0244 Chemical Formula: C15H11O7 -H Exact Mass: 303.0510 HO OH

OH - Chemical Formula: C6H5O3 Exact Mass: 125.0244 HO -H -H HO HO O O OH OH OH OH OH - - Chemical Formula: C14H11O6 Chemical Formula: C12H9O4 Exact Mass: 275.0561 Exact Mass: 217.0506

73 S60, S62, S68, S74, S79, and S81

RT: 0.00 - 30.00 13.71 NL: 1.94E9 100 m/z= 283.05983- 95 283.06267 F: FTMS - p ESI Full 90 ms [150.00-1000.00] 85 MS 7591-2

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

35 14.13

5 9.98 14.49 9.29 10.64 15.35 0.98 2.37 3.32 4.79 6.74 8.60 12.62 16.48 17.80 19.61 20.88 22.01 23.76 25.17 27.68 28.35 0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 Time (min)

S60 Wogonin (tR=13.71 min) MS1(−): 283.06125 MS2(−):268.03809(100),240.04349(1),239.03520(1),224.04802(1),212.04816(0.3),211.04041(0.3),1 98.03249(1),196.05321(1),184.05307(1),165.99049(1),163.00372(2),137.02448(1),110.00012(0.4)

7591-2 #2737 RT: 13.79 AV: 1 NL: 1.02E8 F: FTMS - p ESI d Full ms2 [email protected] [50.00-305.00] 268.03809 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

5 283.06152 163.00372 66.88620 82.00525 110.00012 137.02448 184.05307 198.03249 224.04802 239.03520 251.03458 0 60 80 100 120 140 160 180 200 220 240 260 280 300 m/z

74 O -H O -H HO O OH

OH O O -H •- •- O Chemical Formula: C7H2O5 Chemical Formula: C5H2O3 Exact Mass: 165.9908 Exact Mass: 110.00094 HO -H -H O O O -H HO O O

OH - Chemical Formula: C15H11O3 O Exact Mass: 239.0714 OH OH O •- •- •- Chemical Formula: C8H3O4 Chemical Formula: C13H8O3 Chemical Formula: C13H7O3 Exact Mass: 163.0037 Exact Mass: 212.0479 Exact Mass: 211.0401 -H O -H O -H O HO O HO -H O O O O OH O OH •- OH - Chemical Formula: C14H8O4 •- Chemical Formula: C H O •- Chemical Formula: C16H11O5 Chemical Formula: C13H8O3 12 8 2 Exact Mass: 240.0428 Exact Mass: 283.0612 Exact Mass: 212.0479 Exact Mass: 184.0530 -H O -H -H O O HO O HO

OH O OH OH Chemical Formula: C H O •- •- Chemical Formula: C H O •- 15 8 5 Chemical Formula: C14H8O3 13 8 2 Exact Mass: 268.0377 Exact Mass: 224.0479 Exact Mass: 196.0530 -H -H O O -H HO O O O O

OH O OH O O •- •- Chemical Formula: C H O •- Chemical Formula: C15H8O5 Chemical Formula: C14H8O4 12 6 3 Exact Mass: 268.0377 Exact Mass: 240.0428 Exact Mass: 198.0322

S62 Oroxylin A (tR=13.91 min) MS1(−): 283.06129 MS2(−): 268.03809(100),240.04308(0.4),239.03503(0.7),224.04767(0.4),212.04845(0.4),211.03987(0.2),1 98.03233(1),196.05310(1),184.05318(1),165.99036(0.3),163.00372(2),137.02437(0.6),110.00023 (0.4)

7591-2 #2792 RT: 14.05 AV: 1 NL: 2.39E7 F: FTMS - p ESI d Full ms2 [email protected] [50.00-305.00] 268.03809 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

5 283.06158 163.00372 66.88603 95.78077 110.00023 137.02437 184.05318 198.03233 224.04767 240.04308 263.64731 304.44189 0 60 80 100 120 140 160 180 200 220 240 260 280 300 m/z

S68 Isomer of S60 (Dihydroxy-methoxyflavone) (tR=14.75 min) MS1(−): 283.06122 MS2(−): 268.03796(100),240.04321(1),239.03526(1),224.04819(0.4),212.04845(0.4),211.04047(0.6),198.0 3242(0.6),196.05336(0.4),184.05302(0.6),171.04515(0.2),165.99080(0.5),137.02440(0.4)

75 7591-neg #2973 RT: 14.80 AV: 1 NL: 2.23E7 F: FTMS - p ESI d Full ms2 [email protected] [50.00-305.00] 268.03796 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

10 283.06143 5 163.00354 239.03526 65.00277 82.00543 110.00026 137.02440 184.05302 198.03242 211.04047 260.25568 0 60 80 100 120 140 160 180 200 220 240 260 280 300 m/z

S74 Isomer of S60 (Dihydroxy-methoxyflavone) (tR=10.27 min) MS1(−):283.06137 MS2(−): 268.03815(100),255.03041(1),239.03531(1),224.04813(1),211.04037(1),198.03255(1),196.05328 (1),184.05304(1),183.04530(0.3),173.06088(1),163.00375(2),137.02452(1),110.00090(0.3)

7591-2 #2024 RT: 10.26 AV: 1 NL: 3.38E6 F: FTMS - p ESI d Full ms2 [email protected] [50.00-305.00] 268.03815 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

5 283.06155 163.00375 66.88657 91.99442 110.00090 137.02452 198.03255 211.04037 239.03531 255.03041 0 60 80 100 120 140 160 180 200 220 240 260 280 300 m/z

S79 Isomer of S60 (Dihydroxy-methoxyflavone) (tR=10.53 min) MS1: 283.06165 MS2: 268.03815(100),255.03064(0.1),224.04797(1),212.04796(0.3),211.04030(1),198.03264(1),196.05 330(1),184.05304(1),165.99068(0.4),163.00375(2),137.02444(1),110.00021(0.3)

7591-2 #2081 RT: 10.52 AV: 1 NL: 3.56E6 F: FTMS - p ESI d Full ms2 [email protected] [50.00-305.00] 268.03815 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

5 283.06161 163.00375 66.88632 91.99492 110.00021 137.02444 184.05304 198.03264 224.04797 239.03528 255.03064 295.76309 0 60 80 100 120 140 160 180 200 220 240 260 280 300 m/z

76 S81 Isomer of S60 (Dihydroxy-methoxyflavone) (tR=11.09 min) MS1(−): 283.06149 MS2(−): 268.04(100),255.03041(0.2),224.04813(0.5),212.04037(0.4),211.04037(0.2),198.03255(1),196.05 328(1),184.05(1),165.99072(1),163.00375(2),137.02438(1),110.00014(0.4)

7591-2 #2186 RT: 11.01 AV: 1 NL: 3.10E6 F: FTMS - p ESI d Full ms2 [email protected] [50.00-305.00] 268.03802 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

5 283.06146 163.00368 65.00327 91.99554 110.00014 137.02438 184.05318 198.03247 224.04770 239.03519 255.03030 289.26392 0 60 80 100 120 140 160 180 200 220 240 260 280 300 m/z

77 S64, S71

RT: 0.10 - 19.13 7.32 NL: 1.19E8 100 m/z= 287.05481- 95 287.05769 F: FTMS - p ESI Full ms 90 [150.00-1000.00] MS 7593-neg 85

60 e c n

a 55 d n u b

A 50

e 7.69 v i t

a 45 l e R 40

20 6.58 15

5 5.57 3.41 0.67 1.32 2.62 3.34 3.72 4.68 8.09 8.68 10.36 10.89 11.72 13.16 14.16 14.59 16.05 16.72 18.22 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 Time (min)

S64 Isomer of S71 (Tetrahydroxyflavanone) (tR=7.67 min) MS1(−): 287.05625 MS2(−): 287.05701(4),269.04599(3),225.05568(1),215.03513(9),201.05588(9),177.06(2),173.06(1),161.02 443(17),151.00369(3),133.02956(4),125.02438(100)

7591-neg #1459 RT: 7.55 AV: 1 NL: 1.25E6 F: FTMS - p ESI d Full ms2 [email protected] [50.00-310.00] 125.02438 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 161.02443 15 165.01971

10 201.05588 215.03513

5 112.98556 133.02956 287.05701 57.03449 68.99568 151.00369 177.05577 269.04599 107.05025 183.04572 225.05568 243.06636 0 60 80 100 120 140 160 180 200 220 240 260 280 300 m/z 62, 73 S71 Eriodictyol (tR=7.24 min) MS1(−): 287.05622 MS2(−): 269.04581(0.6),243.06630(0.1),225.05594(0.1),179.0350(0.1),161.02428(25),151.00359(1),135.0 4514(2),125.02432(100)

78 7591-neg #1395 RT: 7.24 AV: 1 NL: 1.88E7 F: FTMS - p ESI d Full ms2 [email protected] [50.00-310.00] 125.02432 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

25 161.02428

15 165.01953

10 57.03444 151.00359 5 109.02930 135.04514 153.01944 177.01936 287.05640 65.00311 81.03446 201.05576 215.03497 243.06630 269.04581 0 60 80 100 120 140 160 180 200 220 240 260 280 300 m/z

-H O HO O

OH O - Chemical Formula: C15H9O5 Exact Mass: 269.0455 -H -H OH O HO HO OH

OH OH - - Chemical Formula: C14H11O4 Chemical Formula: C14H9O3 Exact Mass: 243.0663 Exact Mass: 225.0557

-H HO OH -H OH

HO O OH OH - Chemical Formula: C6H5O3 Exact Mass: 125.0244 -H OH O OH O - Chemical Formula: C15H11O6 O OH O Exact Mass: 287.0561

O O - Chemical Formula: C H O - Chemical Formula: C9H7O4 9 5 3 Exact Mass: 179.0350 Exact Mass: 161.0244

OH -H

- Chemical Formula: C8H7O2 Exact Mass: 135.0452

HO -H O

O OH - Chemical Formula: C7H3O4 Exact Mass: 151.0037

79 S65, S73, and S76

RT: 6.62 - 17.66 11.74 NL: 2.15E8 100 m/z= 299.05466- 95 299.05766 F: FTMS - p ESI Full ms 90 [150.00-1000.00] MS 7591-neg 85 11.06 80

60 e c n

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A 50

e v i t

a 45 l e R 40

35 12.06

20 10.82 15 11.62

10 9.63 5 8.94 13.73 7.06 7.42 7.81 8.42 9.88 12.25 12.51 14.06 14.45 15.23 15.82 16.16 16.82 17.61 0 7 8 9 10 11 12 13 14 15 16 17 Time (min)

S65 Trihydroxy-methoxyflavone (tR=12.06 min) MS1(−): 299.05618 MS2(−): 284.03296(100),256.03872(2),255.03044(0.2),227.03548(0.1),200.04811(2),165.99077(8),137.99 599(4),110.00093

7591-neg #2435 RT: 12.11 AV: 1 NL: 1.42E7 F: FTMS - p ESI d Full ms2 [email protected] [50.00-325.00] 284.03296 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

15 299.05643 10 165.99077

5 110.00093 137.99599 212.04813 65.00328 82.00556 117.03376 187.04007 227.03548 256.03827 270.07797 321.76727 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 m/z S73 5,6,7-Trihydroxy-8-methoxyflavone OR isomer (trihydoxy and methoxy on A ring)

(tR=11.61 min) MS1(−): 299.05616 MS2(−): 299.06(100),284.03290(49),267.03012(11),255.06651(24),240.04300(12),231.07(7),227.07092(0. 5),212.04813(4),153.01930(0.2),151.00368(82),107.01389(8)

80 7591-neg #2328 RT: 11.61 AV: 1 NL: 4.54E6 F: FTMS - p ESI d Full ms2 [email protected] [50.00-325.00] 299.05630 100

85 151.00368 80

60 e c n

a 55 d

n 284.03290 u b

A 50

e v i t

a 45 l e R 40

25 255.06651

15 156.76505 240.04300 267.03012 10 107.01389 231.06631 94.00584 136.98796 5 65.00340 212.04813 83.01394 125.02441 169.01428 189.05588 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 m/z

-H O HO O

HO OH O •- Chemical Formula: C15H8O6 Exact Mass: 284.0326 -H O -H O

HO O O O

HO OH - OH O Chemical Formula: C7H3O4 Chemical Formula: Exact Mass: 151.0037 -H - -H C16H11O6 O O Exact Mass: 299.0561 HO HO

HO HO OH OH •- - Chemical Formula: C14H8O4 Chemical Formula: C15H11O4 Exact Mass: 255.0663 Exact Mass: 240.0428

S76 4’-hydroxy wogonin (tR=10.72 min) MS1(−): 299.05611 MS2(−): 284.03275(100),271.06204(6),255.06720(2),227.07127(9),212.04810(12),211.03995(17),183.029 97(2),165.01932(6),153.01926(36),133.02950(20)

7591-neg #2141 RT: 10.72 AV: 1 NL: 8.60E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-325.00] 284.03275 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40 153.01926 35

25 253.21741 20 133.02950 211.03995 15 299.05637 10 227.07127 165.01932 271.06204 5 111.00878 139.04033 183.02997 56.74940 93.03460 124.98764 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 m/z

81 -H -H OH OH O O HO O HO

OH O OH •- •- Chemical Formula: C14H8O4 Chemical Formula: C15H8O6 Exact Mass: 240.0428 Exact Mass: 284.0326 -H -H -H OH OH OH O O O HO O HO

OH OH OH Chemical Formula: C H O - - - 15 11 5 Chemical Formula: C15H11O4 Chemical Formula: C14H11O3 Exact Mass: 271.0612 Exact Mass: 255.0663 Exact Mass: 227.0714 O -H -H -H OH OH HO OH O O -H OH O HO O OH O - Chemical Formula: C8H7O5 Exact Mass: 183.0299 OH O •- •- Chemical Formula: C13H8O3 Chemical Formula: C H O O -H 13 7 3 OH O Exact Mass: 212.0479 Exact Mass: 211.0401 HO - Chemical Formula: C16H11O6 O Exact Mass: 299.0561

OH - Chemical Formula: C7H5O4 Exact Mass: 153.0193 -H OH

- Chemical Formula: C8H5O2 Exact Mass: 133.0295 O -H HO O

OH - Chemical Formula: C8H5O4 Exact Mass: 165.0193

82 S66

61 Scullcapflavone II (tR=14.50 min) MS1(−): 373.09289 MS2(−): 358.06985(22),343.04617(100),328.02286(23),325.03555(2),315.05099(1),313.03574(0.6),300.02 783(5),285.00458(1),227.03514(4),194.99355(6),169.01425(3),133.02936(1)

7591-neg #2913 RT: 14.51 AV: 1 NL: 7.14E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-400.00] 343.04617 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

25 328.02286 358.06985

10 194.99355 227.03514 300.02783 5 151.97484 169.01425 373.09338 61.98830 285.00458 315.05099 83.85269 133.02936 181.01466 209.00970 249.04039 381.19702 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 m/z

O -H O -H O -H O O O O O O O O O

OH OH OH O O O OH O OH O OH O •- - 3•- Chemical Formula: C18H14O8 Chemical Formula: C17H11O8 Chemical Formula: C16H8O8 Exact Mass: 358.0694 Exact Mass: 343.0459 Exact Mass: 328.0225 O -H O -H O O O O -H O O O O O OH OH O O O O OH O O -H OH OH 2•- 3•- Chemical Formula: C H O 4•- O Chemical Formula: C8H3O6 Chemical Formula: C15H8O7 15 5 8 Exact Mass: 312.9990 O O Exact Mass: 194.9935 Exact Mass: 300.0276 O - O -H O -H H OH O O O OH O OH O O OH O Chemical Formula: C H O - OH 19 17 8 O O O Exact Mass: 373.0929 OH OH OH - 2•- 4•- Chemical Formula: C9H11O5 Chemical Formula: C7H5O5 Chemical Formula: C14H5O7 Exact Mass: 199.0612 Exact Mass: 169.0142 Exact Mass: 285.0041 O -H

O •- Chemical Formula: C8H5O2 Exact Mass: 133.0295

83 S70

62 8,8'-Biapigenin (tR=13.67 min) MS1(−): 537.08295 MS2(−):391.04648(76),373.03580(10),347.05630(16),335.05679(5),319.06134(7),291.06656(2),2 45.00926(100),239.03531(1),217.01433(3)

7591-neg #2705 RT: 13.52 AV: 1 NL: 4.01E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-565.00] 245.00926 100

80 391.04648

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 347.05630 15 537.08368 10 373.03580 267.03012 319.06134 5 217.01433 417.02603 291.06656 76.33808 104.14204 145.02925 187.04085 449.10300 475.08267 519.07367 547.75348 0 50 100 150 200 250 300 350 400 450 500 550 m/z

OH OH

-H -H O O OH OH OH OH HO O HO

OH OH - - Chemical Formula: C20H11O7 Chemical Formula: C20H11O6 Exact Mass: 363.0510 Exact Mass: 347.0561 OH O OH OH

-H OH -H -H O O OH OH OH -H O OH OH O O O OH HO O HO O OH HO HO

OH O OH O OH O - - Chemical Formula: C21H9O7 Chemical Formula: C19H11O5 Chemical Formula: C H O - Chemical Formula: C H O - Exact Mass: 373.0354 Exact Mass: 319.0612 30 17 10 21 11 8 OH Exact Mass: 537.0827 Exact Mass: 391.0459 OH -H -H O O OH OH HO O O

OH OH - Chemical Formula: C H O - Chemical Formula: C12H5O6 11 5 5 Exact Mass: 245.0092 Exact Mass: 217.0142

84 S72

70 Baicalein 6-O-sulfate (tR=9.29 min) MS1(−): 349.00236 MS2(−): 269.04593(100),241.05110(0.3),225.05605(1),225.05605(0.9),197.06(1),181.06602(0.2),139.0032 8(0.1)

7591-neg #1824 RT: 9.29 AV: 1 NL: 6.80E7 F: FTMS - p ESI d Full ms2 [email protected] [50.00-375.00] 269.04593 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

5 60.40955 79.95751 95.01342 139.00328 171.04509 197.06104 225.05605 241.05110 349.00262 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 m/z

-H -H -H -H

HO O HO O HO O HO O HO S O HO HO HO O OH O OH O OH OH - - - Chemical Formula: C H O - Chemical Formula: C15H9O8S Chemical Formula: C15H9O5 Chemical Formula: C14H9O4 14 9 3 Exact Mass: 349.0024 Exact Mass: 269.0455 Exact Mass: 241.0506 Exact Mass: 225.0557 -H -H -H HO -H HO O HO O O HO OH OH OH OH - - - - Chemical Formula: C6H3O4 Chemical Formula: C12H7O2 Chemical Formula: C13H9O3 Chemical Formula: C13H9O2 Exact Mass: 139.0037 Exact Mass: 183.0452 Exact Mass: 213.0557 Exact Mass: 197.0608

85 S75

61 Tenaxin I (tR=14.60 min) MS1(+): 345.09647 MS2(+): 345.09631(100),330.07288(34),315.04938(92),312.06241(18),297.03891(31)

7591-pos #2937 RT: 14.68 AV: 1 NL: 1.48E7 F: FTMS + p ESI d Full ms2 [email protected] [50.00-370.00] 345.09631 100

95 315.04938 90

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

35 330.07288 297.03891 30

15 350.40247 10 284.06738 5 82.38966 227.05452 59.78812 121.02805 138.03096 169.01289 212.03122 251.64114 277.23355 367.72034 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 m/z

+H +H +H O O O O O O O O O

OH OH OH O O O OH O OH O OH O + •+ 2•+ Chemical Formula: C18H17O7 Chemical Formula: C17H14O7 Chemical Formula: C16H11O7 Exact Mass: 345.0969 Exact Mass: 330.0734 Exact Mass: 315.0499 +H O O +H O O O O

O O OH O OH O •+ 2•+ Chemical Formula: C17H12O6 Chemical Formula: C16H9O6 Exact Mass: 312.0628 Exact Mass: 297.0394

86 S77

72 Neptin (tR=10.47 min) MS1(−): 315.05119 MS2(−): 300.06476(69),284.02829(19),253.01425(30),227.03526(100),212.04431(7),165.99086(58),137.9 9605(11),110.00083(9)

7591-2 #2047 RT: 10.37 AV: 1 NL: 4.78E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-340.00] 300.06476 100

75 165.99086 70

60 e c n

a 55 d n

u 227.03526 b

A 50

e v i t

a 45 l e R 40

35 284.02829 30

20 315.08755 110.00083 15 253.01425 137.99605 269.24930 10 91.02206 212.04431 178.57605 5 73.67879 97.02964 128.61873 190.75917 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 m/z

-H -H OH OH -H -H HO O HO O HO O HO O OH OH

O O O O OH O OH O OH O O - •- Chemical Formula: C H O •- Chemical Formula: C H O • Chemical Formula: C16H11O7 Chemical Formula: C15H8O7 7 2 5 6 3 4 Exact Mass: 315.0510 Exact Mass: 300.0276 Exact Mass: 165.99077 Exact Mass: 139.00313 O -H -H OH -H O OH O HO O OH O O HO O •- 2•- •- Chemical Formula: C5H3O3 Chemical Formula: C14H5O5 Chemical Formula: C13H7O4 Exact Mass: 253.0142 Exact Mass: 227.0350 Exact Mass: 111.0088

87 S80

Trihydroxy-methoxyflavanone (dihydroxy and methoxy on A ring, monhydroxy on B ring)

(tR=10.65 min) MS1(−): 301.07175 MS2(−): 286.04865(100),283.02444(4),268.03766(),255.23323(10),185.06107(5),180.00667(16),165.9907 8(45),152.01132(5),137.99594(9),119.05031(8)

7591-neg2 #2137 RT: 10.66 AV: 1 NL: 1.54E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-325.00] 286.04865 100

60 e c n

a 55 d n u

b 165.99078

A 50

e v i t

a 45 l e R 40

20 180.00667 15 255.23323 119.05031 137.99594 10 110.00092 301.07211 152.01132 241.01488 5 91.99541 185.06107 229.05090 124.01682 64.99074 84.65604 97.25957 207.03067 268.03766 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 m/z

-H -H OH OH

O O O O

O O O O •- Chemical Formula: C H O - Chemical Formula: C15H8O5 -H 16 11 5 Exact Mass: 283.0612 Exact Mass: 268.0377 OH -H OH -H O O O O O O HO HO HO OH O OH O •- OH O Chemical Formula: C8H4O5 Chemical Formula: C H O - 16 13 6 Chemical Formula: C H O •- Exact Mass: 180.0064 Exact Mass: 301.0718 15 10 6 Exact Mass: 286.0483 O -H O -H O -H O O

HO O HO O OH OH OH O •- Chemical Formula: C H O •- Chemical Formula: C H O •- Chemical Formula: C7H4O4 7 2 5 6 2 4 Exact Mass: 152.0115 Exact Mass: 165.9908 Exact Mass: 137.9959

88 S83, S84

RT: 0.00 - 30.00 0.88 NL: 1.93E7 100 m/z= 191.01874- 95 191.02066 F: FTMS - p ESI Full 90 ms [150.00-1000.00] 85 MS 7591-2

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

15 1.12

5 1.33 11.87 3.46 8.05 1.72 3.74 5.44 6.73 8.99 10.27 13.75 14.49 16.22 17.67 18.46 19.70 22.50 24.46 25.58 27.33 29.70 0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 Time (min)

S83 D-Galactaric acid, 1,5-lactone OR isomer (tR=0.81 min) MS1(−): 191.01970 MS2(−): 173.00926(3),147.03001(1),129.01953(8),111.00883(4),103.00378(4),85.03(100),72.99311(10)

7591-2 #100 RT: 0.82 AV: 1 NL: 6.79E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-215.00] 85.02953 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

25 111.00883 20

15 87.00877 72.99311 191.02002 10 59.01385

71.01389 103.00378 5 129.01953 147.03001 83.01392 89.02447 120.04559 68.99822 133.01439 164.03572 173.00926 185.05525 0 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 m/z

S84 Isomer of D-Galactaric acid, 1,5-lactone (tR=1.04 min) MS1(−): 191.01969 MS2(−): 173.00949(4),129.01956(8),117.01949(2),111.00882(100),87.00871(42),85.02947(34)

89 7591-2 #149 RT: 1.04 AV: 1 NL: 5.59E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-215.00] 111.00882 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l

e 102.94885 R 40 87.00871

35 85.02947 30

10 129.01956 191.02026 117.01949 81.37997 146.93889 5 57.03450 123.94654 75.00872 154.99881 173.00949 58.95897 93.24155 134.38223 164.03560 203.82991 0 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 m/z

O -H O -H -H -H O O O O O O O O -H OH OH O O

HO HO OH HO OH HO HO OH OH OH OH - - - - - Chemical Formula: C6H5O6 Chemical Formula: C6H7O7 Chemical Formula: C5H7O5 Chemical Formula: C5H5O4 Chemical Formula: C5H3O3 Exact Mass: 173.0092 Exact Mass: 191.0197 Exact Mass: 147.0299 Exact Mass: 129.0193 Exact Mass: 111.0088

-H O -H O -H HO HO HO OH OH - - OH Chemical Formula: C3H3O3 Chemical Formula: C4H5O2 Chemical Formula: C H O - 4 5 3 Exact Mass: 87.0088 Exact Mass: 85.0295 Exact Mass: 101.0244

90 S85

74 1-caffeyllaminaribiose (tR=1.29 min) MS1(−): 503.14106 MS2(−): 341.08823(2),323.07770(13),281.06732(20),251.05649(10),223.97(2),221.04567(14),179.03532( 44),161.02457(100),135.04533(12)

7591-2 #199 RT: 1.29 AV: 1 NL: 6.50E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-530.00] 161.02457 100

60 e c n

a 55 d n u b

A 50

e 179.03523 v i t

a 45 l e R 40

25 281.06732

20 251.05649 15 323.07770 135.04533 221.04567 10 89.02451

5 59.01374 119.03519 341.08823 503.14050 202.25432 302.98846 0 50 100 150 200 250 300 350 400 450 500 m/z

-H OH -H O O O O O HO OH HO O O HO OH HO OH OH OH - Chemical Formula: C H O - Chemical Formula: C15H17O9 15 15 8 Exact Mass: 323.0772 Exact Mass: 341.0878 -H OH

O OH O HO OH OH - Chemical Formula: C13H13O7 -H Exact Mass: 281.0667 -H OH OH

O O O HO OH OH O O HO OH OH O O OH - HO Chemical Formula: C12H11O6 Exact Mass: 251.0561 -H HO OH OH OH O - OH Chemical Formula: C21H27O14 O Exact Mass: 503.1406 OH

- Chemical Formula: C11H9O5 Exact Mass: 221.0455 -H -H OH O HO HO OH O O - - Chemical Formula: C9H7O4 Chemical Formula: C9H5O3 Exact Mass: 179.0350 Exact Mass: 161.0244 -H OH

- Chemical Formula: C8H7O2 Exact Mass: 135.0452

91 S86

75 Gaylussacin (tR=8.29 min) MS1(−): 417.11947 MS2(−): 255.06686(10),211.07681(100),197.06166(0.2),169.06604(5),112.98558(2)

7591-2 #1599 RT: 8.28 AV: 1 NL: 4.36E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-445.00] 211.07681 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

10 255.06686

5 169.06604 56.32799 86.98617 112.98558 197.06166 236.52243 263.30334 296.06522 328.08337 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 m/z

-H

-H OH HO O - Chemical Formula: C14H11O2 -H HO Exact Mass: 211.0765

HO O -H

O O HO HO HO - -H Chemical Formula: C12H9O HO O HO OH Exact Mass: 169.0659 -H OH OH O - - Chemical Formula: C21H21O9 Chemical Formula: C15H11O4 Exact Mass: 417.1191 Exact Mass: 255.0663 HO OH - - Chemical Formula: C13H9O2 Chemical Formula: C14H11O3 Exact Mass: 227.0714 Exact Mass: 197.0608

92 S87

76 Isomer of Hexadecanoic acid (tR=22.48 min) MS1(−):255.23276 MS2(−):255.23302(100),237.22174(0.2),211.20708(0.2)

7591-neg2 #4351-4487 RT: 22.39-22.58 AV: 2 NL: 7.08E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-280.00] 255.23311 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

5 143.05016 65.00313 80.91665 211.03988 94.98070 119.39329 137.31817 160.01827 171.04475 193.15942 227.03513 240.03709 279.72899 0 60 80 100 120 140 160 180 200 220 240 260 280 m/z

S88

Isomer of 10-Hydroxyoctadecadienoic acid (tR=17.94 min) MS1(−): 295.22773 MS2(−): 277.21747(25),211.13409(1),195.13907(2),183.13905(100)

7591-neg2 #3565 RT: 17.86 AV: 1 NL: 1.95E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-320.00] 183.13905 100

60 e c n

a 55 d 295.22803 n u b

A 50

e v i t

a 45 l e R 40

30 277.21747 25

15 171.10265 10 195.13907 5 111.08132 268.06210 61.98816 96.95983 130.98360 166.47346 211.13409 253.05901 313.29715 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 m/z

O -H

OH - Chemical Formula: C12H19O2 -H Exact Mass: 195.1391 O O -H

OH OH Chemical Formula: C H O - OH 11 19 2 Exact Mass: 183.1391 - -H Chemical Formula: C18H31O3 O Exact Mass: 295.2279 OH - Chemical Formula: C18H29O2 Exact Mass: 277.2173

93 S89

Isomer of 3-Hydroxy-4-O-glucosylbenzyl alcohol (tR=6.12 min) MS1(−): 301.03561 MS2(−): 161.02446(23),139.04013(100),135.04533(22),133.00966(16),124.01660(11),107.05027(10)

7591-neg2 #1163 RT: 6.08 AV: 1 NL: 4.94E6 F: FTMS - p ESI d Full ms2 [email protected] [50.00-325.00] 139.04013 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 133.02966 161.02446 301.03561 15 124.01660 10 107.05027

5 165.01932 151.00366 269.04578 283.06143 65.00323 97.02951 201.05611 225.05591 241.05095 312.97992 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 m/z

S90

Isomer of Linoleoyl Ethanolamide (LEA) (tR=19.97 min) MS1(−): 324.12268 (positive) MS2(−): 306.27869(6),219.05690(6),147.11668(2),123.11678(5),109.10135(7),95.08574(14),81.07028(17),6 2.06064(100)

7591-pos #3894 RT: 19.91 AV: 1 NL: 8.77E4 F: FTMS + p ESI d Full ms2 [email protected] [50.00-350.00] 62.06064 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 81.07028 15 95.08574

10 67.05475 109.10135 219.05690 123.11678 306.27869 324.12268 5 133.10149 149.13257 173.20901 195.84442 263.33090 278.77411 342.32510 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 m/z

94 S91

77 Isomer of 5-O-β-D-glucopyranosyl-6-hydroxyangelicin (tR=0.87 min) MS1(+): 381.07891 MS2(+): 381.08(100),219.02664(30),201.01584(25)

7591-pos #102 RT: 0.82 AV: 1 NL: 6.33E5 F: FTMS + p ESI d Full ms2 [email protected] [50.00-405.00] 381.07898 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

30 219.02635 201.01579 25

5 91.99839 62.96750 116.25042 175.11911 248.01599 288.95691 317.33939 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 m/z

O O O

+H +H OH O O O O O O O O HO

HO OH OH O OH OH

+ + Chemical Formula: C H O + Chemical Formula: C11H5O4 Chemical Formula: C17H17O10 11 7 5 Exact Mass: 201.0182 Exact Mass: 381.0816 Exact Mass: 219.0288

95 S92

78 3,4-Dihydroxy-7-O-caffeoylbenzyl alcohol OR isomer (tR=6.17 min) MS1(+): 303.08598 MS2(+): 285.07507(15),267.06482(1),257.08026(32),242.05684(8),229.08551(57),179.03380(2),167.0336 3(100),163.03865(3),133.02831(24),123.04404(69),107.04928(44)

7591-pos #1205 RT: 6.23 AV: 1 NL: 5.09E6 F: FTMS + p ESI d Full ms2 [email protected] [50.00-330.00] 167.03363 100

70 123.04404

60 229.08551 e c n

a 55 d n u b

A 50

e 107.04928 v i t

a 45 l e R 40

35 257.08026 102.76474 30 133.02831 25

20 285.07507 15 91.05452

10 242.05684 153.05444 5 141.05431 179.03380 215.06967 267.06482 62.81287 79.05477 303.08514 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 m/z

O O +H +H OH O O O O O OH + Chemical Formula: C H O + Chemical Formula: C16H13O5 16 11 4 Exact Mass: 285.0757 Exact Mass: 267.0652 O +H

O O +H O +H O Chemical Formula: C H O + HO OH 14 13 3 O O Exact Mass: 229.0859 O HO OH OH O +H

Chemical Formula: C H O + + 16 15 6 Chemical Formula: C15H13O4 OH Exact Mass: 303.0863 Exact Mass: 257.0808 O

+ Chemical Formula: C9H7O3 Exact Mass: 163.0390 +H OH +H O OH

O OH OH

+ + Chemical Formula: C8H7O4 Chemical Formula: C7H7O2 Exact Mass: 167.0339 Exact Mass: 123.0441

HO +H

HO O O

+ Chemical Formula: C9H7O4 Exact Mass: 179.0339

96 S93

Unknown (tR=17.44 min) MS1(+): 701.37151 MS2(+): 701.37067(100),539.31824(96),191.09856(1),105.03367(7)

7591-pos #3443 RT: 17.44 AV: 1 NL: 1.56E5 F: FTMS + p ESI d Full ms2 [email protected] [50.00-735.00] 701.37067 100

95 539.31824

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

10 105.03367 5 91.99885 277.08926 347.09415 125.98358 191.09856 321.35818 409.60461 0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 m/z

97 S94

Benzoic acid, 3,4,5-trihydroxy-,1,1'-(2-methoxy-1,4-phenylene) ester OR isomer (tR=4.17 min) MS1(+): 445.07617 MS2(+): 427.06525(4),409.05493(9),381.05975(1),343.04465(6),319.04428(23),287.05(10),275.05447(7), 263.05466(5),153.01807(100),141.01810(22)

7591-pos #747 RT: 4.09 AV: 1 NL: 4.30E5 F: FTMS + p ESI d Full ms2 [email protected] [50.00-470.00] 153.01807 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

25 141.01810 319.04428 20

10 287.05447 409.05493 171.02858 343.04465 263.05466 427.06525 5 129.01817 73.02888 203.03360 381.05975 0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 m/z

+H O O O O HO HO O O

O O HO O O O OH OH HO O O + + Chemical Formula: C21H13O9 Chemical Formula: C21H15O10 Exact Mass: 409.0554 +H Exact Mass: 427.0660 OH O +H O OH +H HO O O O O OH HO O HO OH HO OH HO OH OH O + + Chemical Formula: C7H5O4 Chemical Formula: C7H7O5 + Exact Mass: 153.0182 Chemical Formula: C21H17O11 Exact Mass: 171.0288 Exact Mass: 445.0765 O HO +H O HO O

HO O O + Chemical Formula: C15H11O8 Exact Mass: 319.0448

98 S95

Unknown (tR=5.67 min) MS1(+): 339.10696 MS2(+): 321.07611(3),234.03915(37),177.05437(100),145.02809(31),105.03366(13)

7591-pos #1062 RT: 5.55 AV: 1 NL: 4.27E4 F: FTMS + p ESI d Full ms2 [email protected] [50.00-365.00] 177.05437 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40 234.03915 35 145.02809 30

15 105.03366

10 81.03384 120.12451 5 190.25932 321.07611 339.14130 69.03388 91.99683 135.53558 156.89761 203.40045 242.90579 279.91760 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 m/z

S96

Isomer of hegoflavone A (tR=11.70 min) MS1(+): 555.09167 MS2(+): 453.04468(11),435.03403(20),419.03882(10),269.03884(18),241.04912(12),121.02847(19),105.0 3368(34)

7591-pos #2344 RT: 11.70 AV: 1 NL: 2.63E5 F: FTMS + p ESI d Full ms2 [email protected] [50.00-585.00] 555.09137 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

35 105.03368

20 121.02847 435.03403 269.04388 15 241.04912 419.03882 453.04468 10 287.05460 391.04416 363.04916 5 95.04947 139.00253 225.05406 339.04953 174.98849 481.08725 509.08936 0 50 100 150 200 250 300 350 400 450 500 550 m/z

99 S57, S97

RT: 0.00 - 30.00 6.96 NL: 1.64E8 100 m/z= 347.07400- 95 347.07748 F: FTMS + p ESI Full ms 90 [150.00-1000.00] MS 7591-pos 85

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

25 6.19

15 10.40

10 3.28

5 7.24 10.13 1.48 2.08 4.28 4.96 11.13 12.21 13.91 15.40 17.26 18.37 20.53 21.81 22.55 23.97 25.19 27.48 28.19 0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 Time (min) 61 S57 Viscidulin III (tR=6.95 min) MS1(+): 347.07574 MS2(+): 347.07541(63),332.05203(100),314.04147(35),286.04645(2),183.02850(3),169.01292(7),142.025 94(3)

7591-pos #1331 RT: 6.85 AV: 1 NL: 1.18E6 F: FTMS + p ESI d Full ms2 [email protected] [50.00-375.00] 332.05203 100

65 347.07541 60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40 314.04147 35

10 169.01292 5 142.02594 304.22998 93.03692 183.02850 286.04645 71.08599 117.07313 150.03105 199.02382 243.02837 267.76981 368.03992 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 m/z

100 +H OH +H +H O O O O O O OH HO O OH HO O HO O

OH OH OH O OH O •+ •+ Chemical Formula: C H O •+ Chemical Formula: C16H12O8 Chemical Formula: C16H10O7 15 10 6 Exact Mass: 332.0527 Exact Mass: 314.0421 Exact Mass: 286.0472 OH +H O +H O O +H O O HO HO OH HO O

OH O OH OH + •+ OH O Chemical Formula: C7H5O5 Chemical Formula: C6H6O4 + Chemical Formula: C17H15O8 Exact Mass: 169.0131 Exact Mass: 142.0261 Exact Mass: 347.0761 O +H HO O

O OH + Chemical Formula: C8H7O5 Exact Mass: 183.0288

S97 Isomer of S57 (Tetrahydroxy-dimethoxyflavone) (tR=10.39 min) MS1(+): 347.07572 MS2(+): 347.07565(100),332.05206(26),317.02866(28),314.04156(37)

7591-pos #2086 RT: 10.47 AV: 1 NL: 6.65E5 F: FTMS + p ESI d Full ms2 [email protected] [50.00-375.00] 347.07565 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40 314.04156

30 332.05206 25

93.03695 131.04910 5 213.03883 229.08524 283.16864 304.22946 60.04501 82.48460 117.07310 163.07526 179.03355 259.41010 363.13242 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 m/z

HO O +H O O

+H HO +H HO OH O O HO O O O O OH O

2•+ OH OH Chemical Formula: C15H9O8 HO HO Exact Mass: 317.0292 OH O OH O HO +H O + •+ Chemical Formula: C17H15O8 Chemical Formula: C16H12O8 O O Exact Mass: 347.0761 Exact Mass: 332.0527 OH O O •+ Chemical Formula: C16H10O7 Exact Mass: 314.0421

101 S98

61 5,6’-Dihydroxy-6,7,8,2’-tetramethoxyflavone (tR=14.00 min) MS1(+): 375.10704 MS2(+): 360.08298(30),345.05960(100),342.07272(15),327.04913(16),227.05446(8),213.03889(9)

7591-pos #2799 RT: 14.00 AV: 1 NL: 2.57E6 F: FTMS + p ESI d Full ms2 [email protected] [50.00-400.00] 345.05960 100

85 375.10641

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

30 360.08298

20 327.04913 15 54.63952 10 213.03889 230.04192

5 199.02328 162.06717 314.07764 71.01311 89.90285 107.04927 135.08034 250.46713 283.05969 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 m/z

+H +H +H O O O O O O O O O O O O

OH OH OH O O O OH O OH O OH O + •+ 2•+ Chemical Formula: C19H19O8 Chemical Formula: C18H16O8 Chemical Formula: C17H13O8 Exact Mass: 375.1074 Exact Mass: 360.0840 Exact Mass: 345.0605 +H O O O O O O +H +H +H O O O O O O O O

O O O O O OH OH O OH O OH O + •+ Chemical Formula: C H O •+ Chemical Formula: C H O 2•+ Chemical Formula: C10H11O6 Chemical Formula: C9H9O6 18 14 7 17 11 7 Exact Mass: 227.0550 Exact Mass: 213.0394 Exact Mass: 342.0734 Exact Mass: 327.0499

102 S99

79 Dihydroxy-dimethoxyflavone O-6''-malonylglucoside (tR=11.14 min) MS1(+): 563.13929 MS2(+): 315.08569(100),300.06229(19),285.03885(13),282.05182(7)

7591-pos #2205 RT: 11.03 AV: 1 NL: 7.51E5 F: FTMS + p ESI d Full ms2 [email protected] [50.00-595.00] 315.08569 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 300.06229

15 285.03885

5 89.05997 133.08595 188.98331 218.79251 271.05948 331.25803 369.14578 416.53088 464.79083 594.57397 0 50 100 150 200 250 300 350 400 450 500 550 m/z

+H +H O O O O O O +H O HO HO O O +H OH O OH O •+ 2•+ O O O Chemical Formula: C16H12O6 Chemical Formula: C15H9O6 Exact Mass: 300.0628 Exact Mass: 285.0394 O O O O HO O OH O +H O HO OH HO O O OH O +H OH O + + Chemical Formula: C26H27O14 Chemical Formula: C17H15O6 Exact Mass: 315.0863 O Exact Mass: 563.1395 O O

HO •+ Chemical Formula: C16H10O5 OH Exact Mass: 282.0523 + Chemical Formula: C16H15O4 Exact Mass: 271.0965

103 S100

Trihydroxy-methoxyflavone O-6''-malonylglucoside (tR=10.35 min) MS1(+): 549.12346 (positive) MS2(+): 301.06992(100),286.04651(16)

7591-pos #2039 RT: 10.25 AV: 1 NL: 4.15E6 F: FTMS + p ESI d Full ms2 [email protected] [50.00-580.00] 301.06992 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 286.04651 15

10 59.06098

5 85.02869 127.03883 159.02838 202.01057 271.05936 315.08551 384.76010 414.55685 559.99207 0 50 100 150 200 250 300 350 400 450 500 550 m/z

+H +H +H O O O O O O O O HO O HO O HO O OH OH OH

HO OH OH O OH OH O OH O + •+ + Chemical Formula: C16H13O6 Chemical Formula: C15H10O6 Chemical Formula: C25H25O14 Exact Mass: 549.1239 Exact Mass: 301.0707 Exact Mass: 286.0472

S102

80 Baicalein 7-O-β-D-glucuronide-(1→3)[β-D-glucoside-(1→6)]-β-D-glucoside (tR 5.51) MS1(+):771.19748 MS2(+):285.07526(21),271.05966(100),159.02872(0.8),127.03899(3),85.02879(6)

7591-pos #1025 RT: 5.38 AV: 1 NL: 1.46E6 F: FTMS + p ESI d Full ms2 [email protected] [53.67-805.00] 271.05966 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

25 285.07526 20

10 85.02879 5 127.03899 258.04755 145.04930 213.03908 361.09082 637.62964 0 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 m/z

104 S103, and S106

RT: 0.00 - 30.00 9.38 NL: 1.85E7 100 m/z= 519.11045- 95 519.11565 F: FTMS + p ESI Full ms 90 [150.00-1000.00] MS 7591-pos 85

65 10.92

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

30 10.19

15 3.92 9.12 10

5 9.02 0.90 2.91 5.79 6.60 8.06 11.22 13.29 14.50 0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 Time (min) S103 Trihydroxyflavone O-(6''-malonylglucoside) (Isomer of apigenin 7-(6''-

malonylglucoside)) (tR=10.93 min) MS1(+): 519.11305 MS2(+): 343.08023(10),315.08505(69),311.05420(10),301.07013(20),283.05975(29),271.05951(100),231. 06464(5),201.09091(7)

7591-pos #2152 RT: 10.79 AV: 1 NL: 2.03E4 F: FTMS + p ESI d Full ms2 [email protected] [50.00-550.00] 271.05951 100

75 315.08505 70

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40 89.05999

35 105.03373 283.05975 30

15 343.08023 10 133.08589 201.09091 83.04946 143.07758 231.06464 462.86960 5

0 50 100 150 200 250 300 350 400 450 500 550 m/z

OH +H

HO O

OH O + Chemical Formula: C15H11O5 Exact Mass: 271.0601 +H +H +H OH OH OH O O O O O O O O O HO HO O HO

OH OH HO OH OH O OH OH OH O Chemical Formula: C H O + + 18 15 7 Chemical Formula: C17H15O6 Chemical Formula: C H O + 24 23 13 Exact Mass: 343.0812 Exact Mass: 315.0863 Exact Mass: 519.1133 +H +H OH OH

O O O O O O

OH OH OH + Chemical Formula: C H O + Chemical Formula: C16H13O6 16 11 5 Exact Mass: 301.0707 Exact Mass: 283.0601

105 S106 Isomer of S103 (Trihydroxyflavone O-(6''-malonylglucoside)) (tR=9.38 min) MS1(+): 519.1129 MS2(+): 337.06061(2),297.07465(7),285.07510(10),271.05954(73),255.06462(10),239.06934(1),231.0647 1(2),215.07065(1),174.55710(1),156.26376(1),105.03371(7),59.06100(100)

7591-pos #1828 RT: 9.28 AV: 1 NL: 8.73E4 F: FTMS + p ESI d Full ms2 [email protected] [50.00-550.00] 59.06100 100

75 271.05954 70

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

15 255.06462 285.07510 10 105.03371 297.07465 5 91.99796 231.06471 79.25175 125.31502 156.26376 337.06061 0 50 100 150 200 250 300 350 400 450 500 550 m/z

106 S104, and S108

RT: 0.00 - 30.00 7.97 NL: 1.05E9 100 m/z= 433.11040- 95 433.11474 F: FTMS + p ESI Full ms 90 [150.00-1000.00] MS 7591-pos 85

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

10 9.81 10.49 5 5.76 4.05 5.38 9.19 1.24 2.76 3.50 7.43 10.66 12.88 13.66 16.66 17.94 20.19 21.79 22.45 23.38 24.63 27.29 27.98 0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 Time (min) 61 S104 Isomer of Baicalein 7-O-glucoside (Trihydroxyflavone O-glucoside) (tR=9.49 min) MS1(+): 433.11257 MS2(+): 271.05969(100)

7593-pos #1905 RT: 9.66 AV: 1 NL: 1.54E6 F: FTMS + p ESI d Full ms2 [email protected] [50.00-460.00] 271.05969 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

5 301.07025 85.02872 127.03910 181.04944 207.06500 256.06851 286.04553 0 50 100 150 200 250 300 350 400 450 m/z

107 S105

62 Trihydroxy-trimethoxyflavone-O-glucoside (tR=5.72 min) MS1(+): 523.14417 MS2(+): 361.09100(100),346.06732(8),331.04391(8),328.05756(3),313.03406(3)

7593-pos #1073 RT: 5.61 AV: 1 NL: 1.55E5 F: FTMS + p ESI d Full ms2 [email protected] [50.00-550.00] 361.09100 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

15 331.04391 10

5 91.99793 139.34229 164.34729 227.05455 275.04022 313.03406 0 50 100 150 200 250 300 350 400 450 500 550 m/z

HO O +H +H +H +H O O HO HO HO O O O O O O O O O O O O OH OH O OH OH OH HO OH O O O OH OH O OH O OH O Chemical Formula: C H O + + •+ Chemical Formula: C H O 2•+ 24 27 13 Chemical Formula: C18H17O8 Chemical Formula: C17H14O8 16 11 8 Exact Mass: 523.1446 Exact Mass: 361.0918 Exact Mass: 346.0683 Exact Mass: 331.0448

+H +H HO HO O O O O O O

O O OH O OH O

•+ 2•+ Chemical Formula: C17H12O7 Chemical Formula: C16H9O7 Exact Mass: 328.0578 Exact Mass: 313.0343

108 S107

61 Oroxylin A 7-O-glucoside (tR=10.34 min) MS1(+):447.12802 MS2(+):285.07468(100),270.05124(15)

7591-pos_150921221703 #1840 RT: 10.36 AV: 1 NL: 5.38E7 F: FTMS + p ESI d Full ms2 [email protected] [50.00-475.00] 285.07468 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 270.05124 15

5 85.02852 105.03332 150.71942 180.30341 319.21375 351.39066 385.21460 0 50 100 150 200 250 300 350 400 450 m/z

OH OH HO O +H +H +H OH O O HO O HO O

O O O OH O OH O OH O + + Chemical Formula: C H O •+ Chemical Formula: C22H23O10 Chemical Formula: C16H13O5 15 10 5 Exact Mass: 447.1286 Exact Mass: 285.0757 Exact Mass: 270.0523

S108

61 Isomer of Baicalein 7-O-glucoside (Trihydroxyflavone O-glucoside) (tR=9.49 min) (tR 5.77) MS1(+):433.11249 MS2(+):271.05957(100),169.01288(0.1)

7591-pos #1106 RT: 5.75 AV: 1 NL: 2.20E7 F: FTMS + p ESI d Full ms2 [email protected] [50.00-460.00] 271.05957 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

5 85.02877 105.03391 139.89957 169.01288 203.75960 238.45053 0 50 100 150 200 250 300 350 400 450 m/z

109 S109

81 Isomer of Apigenin 7-O-sophoroside (tR=5.41 min) MS1(+):595.16536 MS2(+):271.05954(100),127.03880(1)

7593-pos #1008 RT: 5.30 AV: 1 NL: 6.34E5 F: FTMS + p ESI d Full ms2 [email protected] [50.00-625.00] 271.05954 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

5 85.02875 251.79031 127.03880 191.91168 230.59056 298.26987 360.30774 389.78976 465.54022 498.99936 0 50 100 150 200 250 300 350 400 450 500 550 600 m/z

S110

Dihydroxy-methoxyflavone O-(6''-malonylglucoside) (tR=10.63 min) MS1(+):533.12852 MS2(+):285.07535(100),270.05191(18),267.06497(0.3),253.04749(0.1),239.06937(0.1)

7593-pos #2124 RT: 10.69 AV: 1 NL: 2.34E6 F: FTMS + p ESI d Full ms2 [email protected] [50.00-560.00] 285.07535 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 270.05191

5 69.35287 91.99615 127.03886 239.06937 386.38687 415.55042 521.05493 0 50 100 150 200 250 300 350 400 450 500 550 m/z

+H +H +H O O O O O O O O O O HO O OH O HO HO HO OH OH O OH O + Chemical Formula: C H O •+ OH Chemical Formula: C16H13O5 15 10 5 + Chemical Formula: C25H25O13 Exact Mass: 285.0757 Exact Mass: 270.0523 Exact Mass: 533.1290 +H +H

O O O O

O O O + + Chemical Formula: C16H11O4 Chemical Formula: C15H11O3 Exact Mass: 267.0652 Exact Mass: 239.0703

110 S111

66 Isomer of Clerodendrin (tR=5.97 min) MS1(+): 623.12372 MS2(+): 285.07532(100),271.05948(68),270.05182(15)

7593-pos #1145 RT: 5.96 AV: 1 NL: 5.90E4 F: FTMS + p ESI d Full ms2 [email protected] [50.00-655.00] 285.07532 100

75 271.05948 70

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

5 91.99860 141.02406 205.04706 234.49225 301.29153 390.01279 428.60361 498.96866 553.52496 0 50 100 150 200 250 300 350 400 450 500 550 600 650 m/z

S112

Isomer of Acacetin 7-O-β-sophoroside (tR=5.36 min) MS1(+): 609.18105 MS2(+): 285.07538(100),271.05981(15),270.05107(6)

7591-pos2 #1005 RT: 5.27 AV: 1 NL: 1.27E6 F: FTMS + p ESI d Full ms2 [email protected] [50.00-640.00] 285.07538 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 271.05981 15

5 85.02874 127.03933 164.33060 239.09558 300.20081 418.99335 0 50 100 150 200 250 300 350 400 450 500 550 600 m/z

111 S113

67 Dihydroxy-methoxyflavone O-glucuronide ethyl ester (tR=12.13 min) MS1(+): 489.13876 MS2(+): 285.07523(100),270.05176(18),175.07506(1),165.09137(0.2),105.03358(2)

7591-pos #2436 RT: 12.13 AV: 1 NL: 5.12E5 F: FTMS + p ESI d Full ms2 [email protected] [50.00-515.00] 285.07523 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 270.05176

5 105.03358 69.35271 131.74422 175.07506 209.67088 301.38116 437.83514 489.16592 0 50 100 150 200 250 300 350 400 450 500 m/z

O OH OH O +H +H +H O OH O O HO O HO O

O O O OH O OH O OH O + + •+ Chemical Formula: C24H25O11 Chemical Formula: C16H13O5 Chemical Formula: C15H10O5 Exact Mass: 489.1391 Exact Mass: 285.0757 Exact Mass: 270.0523

112 S114

61 8,8'-Bibaicalein (tR=12.57 min) MS1(+):539.09695 (positive) MS2(+):521.08783(3),503.0761(1),493.09171(4),465.0969(2),449.1020(1),437.04977(100),419.03 888(71),401.02802(10),391.04047(5),375.05029(8),363.0499(3),347.0550(2),323.05453(50),297. 03854(6),271.05960(58),270.04407(24),269.04407(70),241.04915(62),225.05426(4)

7591-pos #2511 RT: 12.48 AV: 1 NL: 1.28E5 F: FTMS + p ESI d Full ms2 [email protected] [50.00-570.00] 437.04977 100

75 419.03888 269.04407 70

65 241.04915 105.03371 60 e c n

a 55 d n

u 323.05453 b

A 50

e v i t

a 45 l e R 40

20 89.06012 15 173.05959 401.02802 10 375.05029 539.09656 152.10056 297.03854 5 133.08601 225.05426 363.04892 493.09171 73.02896 191.52141 465.09579 0 50 100 150 200 250 300 350 400 450 500 550 m/z

O O +H

O HO O +H

O O O +H O HO O

HO O HO O OH O + Chemical Formula: C30H15O8 HO O Exact Mass: 503.0761 HO O OH +H + Chemical Formula: C28H17O7 HO Exact Mass: 465.0969 OH O HO O

+ Chemical Formula: C30H17O9 HO O O Exact Mass: 521.0867 +H OH HO +H OH O HO O

Chemical Formula: C H O + HO O O 29 17 8 Exact Mass: 493.0918 O HO O OH + Chemical Formula: C28H17O6 Exact Mass: 449.1020 OH + Chemical Formula: C18H11O6 Exact Mass: 323.0550 OH O O O HO +H +H

HO O HO O OH O HO +H O O OH O O O HO +H HO O O O OH OH HO O + + HO O Chemical Formula: C22H11O9 Chemical Formula: C22H9O8 Exact Mass: 419.0398 Exact Mass: 401.0292 HO HO O OH OH OH O HO +H +H + HO Chemical Formula: C30H19O10 O Exact Mass: 539.0973 OH + HO O HO O Chemical Formula: C22H13O10 Exact Mass: 437.0503 O O O O

O O OH OH + + Chemical Formula: C21H11O8 Chemical Formula: C20H11O7 Exact Mass: 391.0448 Exact Mass: 363.0499

OH OH HO +H +H

HO HO

O O O O

O O OH OH + Chemical Formula: C H O + Chemical Formula: C21H11O7 20 11 6 Exact Mass: 375.0499 Exact Mass: 347.0550

OH O OH OH2 +H HO HO +H HO +H

O O O O O

Chemical Formula: C H O + + + 15 9 5 Chemical Formula: C14H9O4 Chemical Formula: C14H9O3 Exact Mass: 269.0444 Exact Mass: 241.0495 Exact Mass: 225.0546

113 M1

Chrysin O-sulfate (tR=11.1 min) MS1(−):333.00798 MS2(−):253.05118(100)

zq-plasma-neg_151203090408 #1338 RT: 11.08 AV: 1 NL: 1.51E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-360.00] 253.05118 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

5 275.09042 63.72383 91.99595 146.01122 183.37045 230.02995 353.52884 0 50 100 150 200 250 300 350 400 450 m/z

M2 Apigenin O-sulfate (tR=9.50 min) MS1(−):349.00297 MS2(−):269.04642(100),225.05632(1)

ZQ-Colon-neg_151203111055 #1307 RT: 9.44 AV: 1 NL: 1.70E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-375.00] 269.04642 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

5 64.93980 91.99540 111.23693 142.63882 225.05632 247.61958 292.56140 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 m/z

114 M3

Baicalein O-sulfate (tR=10.06 min) MS1(−):349.00301 MS2(−):269.04636(100),251.03532(0.3),197.06163(0.1)

ZQ-Colon-neg_151203111055 #1400 RT: 9.98 AV: 1 NL: 7.47E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-375.00] 269.05 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

5 50.38 66.32 92.00 112.29 132.77 169.07 197.06 212.93 224.51 251.04 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 m/z

-H

O O -H -H

O OH O HO O O O Chemical Formula: C H O - S 15 7 4 HO Exact Mass: 251.0350 O -H HO HO OH O OH O - - Chemical Formula: C15H9O8S Chemical Formula: C15H9O5 HO Exact Mass: 349.0024 Exact Mass: 269.0455

OH - Chemical Formula: C13H9O2 Exact Mass: 197.0608

Wogonin O-sulfate (tR=11.10 min) MS1(−): 363.01881 MS2(−):283.06204(96),268.03854(100)

ZQ-Lung-neg_151203131740 #1092 RT: 11.07 AV: 1 NL: 5.63E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-390.00] 268.04 283.06 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

10 99.93 5 115.92 56.23 92.00 141.23 152.99 189.18 202.93 229.65 255.41 331.45 348.12 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 m/z

115 M5

6,7-Dehydrobaicalein (tR=11.90 min) MS1(−): 267.03054 MS2(−):239.03534(100),211.04114(1.14),136.98807(13.85)

ZQ-Colon-neg_151203111055 #1766 RT: 11.86 AV: 1 NL: 1.10E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-290.00] 239.03534 100

60 e

c 267.03070 n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

136.98807 15 271.98865 10

5 65.00315 131.43944 61.08945 77.62045 99.03600 114.96834 146.67157 171.04532 211.04114 282.51569 0 60 80 100 120 140 160 180 200 220 240 260 280 m/z

-H -H -H

O O O O O O

O O OH O OH OH Chemical Formula: C H O - - - 15 7 5 Chemical Formula: C14H7O4 Chemical Formula: C13H7O3 Exact Mass: 267.0299 Exact Mass: 239.0350 Exact Mass: 211.0401

O -H O O OH - Chemical Formula: C6HO4 Exact Mass: 136.9880

Isomer of hydroxylation of baicalin (Tetrahydroxyflavone) (tR=6.90 min) MS1(−):285.04126 MS2(−):285.04123(100),151.08276(1)

ZQ-Colon-neg_151203111055 #873 RT: 6.71 AV: 1 NL: 7.78E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-310.00] 285.04123 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

10 269.04169 5 242.01799 63.82799 78.95646 91.99567 117.03458 151.08276 166.99870 189.37268 219.87454 297.49527 0 60 80 100 120 140 160 180 200 220 240 260 280 300 m/z

116 M7

Hydroxylation of baicalin (Tetrahydroxyflavone) (tR=5.80 min) MS1(−):285.04125 MS2(−):285.04132(100),241.05148(20),199.04099(15),151.00395(66),133.02989(6)

ZQ-Colon-neg_151203111055 #732 RT: 5.64 AV: 1 NL: 2.59E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-310.00] 285.04132 100

70 151.00395 65

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

20 241.05148 199.04099 269.04260 15

10 133.02989 107.01420 289.39224 5 91.99642 208.88702 53.56080 78.18829 183.93765 225.15257 0 60 80 100 120 140 160 180 200 220 240 260 280 300 m/z

-H -H OH OH

HO O HO

HO HO OH O OH - Chemical Formula: C H O - Chemical Formula: C15H9O6 14 9 4 Exact Mass: 285.0405 Exact Mass: 241.0506 -H -H OH HO -H OH O O HO O HO OH - - - Chemical Formula: C7H3O4 Chemical Formula: C8H5O2 Chemical Formula: C12H7O3 Exact Mass: 133.0295 Exact Mass: 199.0401 Exact Mass: 151.0037

Isomer of kanzakiflavone I (tR=10.87 min) MS1(−): 327.05179

117 M9

Trihydroxy-dimethoxyflavone (tR=11.80 min) MS1(−):329.06732 MS2(−): 329.06747(5),314.04416(97),299.02051(100),271.02548(4),227.03551(11),199.04102(4)

ZQ-Colon-neg_151203111055 #1773 RT: 11.89 AV: 1 NL: 7.87E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-355.00] 299.02051 100 314.04416

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

15 227.03551 10 271.02548 329.06747 5 199.04102 183.04594 240.04349 65.17336 91.99586 109.47387 139.05576 215.03581 284.01636 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 m/z

-H -H -H O O -H O O

O O O O O O O O

OH OH OH OH HO HO HO HO OH O OH O OH O OH 2•- - •- Chemical Formula: C H O 2•- Chemical Formula: C14H7O6 Chemical Formula: C17H13O7 Chemical Formula: C16H10O7 15 7 7 Exact Mass: 299.0197 Exact Mass: 271.0248 Exact Mass: 329.0667 Exact Mass: 314.0432 -H O -H O

O O

OH OH 2•- Chemical Formula: C H O 2•- Chemical Formula: C12H7O3 13 7 4 Exact Mass: 199.0401 Exact Mass: 227.0350

118 M10

Dihydroxy-trimethoxyflavone (tR=14.60 min) MS1(−): 343.08295 MS2(−): 328.05975(27),313.03641(100),298.01288(14),271.01740(2),209.00899(0.5),194.99405(2)

ZQ-Colon-neg_151203111055 #2258 RT: 14.54 AV: 1 NL: 1.76E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-370.00] 313.03641 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

30 328.05975 25

20 298.01288 15

5 343.08325 194.99405 270.01740 59.12871 84.82619 103.92030 138.24275 158.96260 224.73453 248.19002 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 m/z

-H -H -H -H O O O O O O O O O O O O

OH OH OH OH O O O O OH O OH O OH O OH O - •- 2•- Chemical Formula: C H O 2•- Chemical Formula: C18H15O7 Chemical Formula: C17H12O7 Chemical Formula: C16H9O7 16 9 7 Exact Mass: 343.0823 Exact Mass: 328.0589 Exact Mass: 313.0354 Exact Mass: 313.0354 -H O O -H O O O O

OH O O OH O OH O 2•- 3•- Chemical Formula: C9H5O6 Chemical Formula: C15H6O7 Exact Mass: 209.0092 Exact Mass: 298.0119

119 M11

Trihydroxy-trimethoxyflavone (tR=11.80 min) MS1(−): 359.07789 MS2(−):344.05469(60),329.03140(100),314.00830(2),311.02087(2),301.03745(6),297.00381(2),2 85.04218(1),242.02234(1),198.03300(3),154.99925(2)

ZQ-Colon-neg_151203111055 #1752 RT: 11.79 AV: 1 NL: 7.49E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-385.00] 329.03140 100

65 344.05469 60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

15 359.15128 10 301.03745 5 58.58427 91.99622 198.03300 311.02087 75.12537 135.12566 154.99925 242.02234 285.04218 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 m/z

-H -H -H -H O O O O O O O O O O O O O O O O

OH OH OH OH HO HO HO HO OH O OH O OH O OH O - •- 2•- Chemical Formula: C H O 3•- Chemical Formula: C18H15O8 Chemical Formula: C17H12O8 Chemical Formula: C16H9O8 15 6 8 Exact Mass: 359.0772 Exact Mass: 344.0538 Exact Mass: 329.0303 Exact Mass: 314.0068

-H O -H O O -H O O O O O O O

OH OH HO HO OH OH OH 2• 2•- Chemical Formula: C H O 3•- Chemical Formula: C6H3O5 Chemical Formula: C15H9O7 13 6 5 Exact Mass: 154.9980 Exact Mass: 301.0354 Exact Mass: 242.0221

120 M12

2,5-Dihydroxyflavonone 6-C-arabinoside (tR=11.40 min) MS1(−): 387.10951 MS2(−):369.09869(0.4),351.08817(1),327.08862(4),309.08862(3),297.07758(100),269.08313(5),2 55.06735(2),191.03568(5)

ZQ-Colon-neg_151203111055 #1680 RT: 11.43 AV: 1 NL: 3.54E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-415.00] 297.07758 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

30 387.10968 25

10 309.07800 191.03568 5 269.08313 327.08862 369.09869 255.06735 279.06726 83.01355 100.31537 125.02435 159.85773 227.07217 351.08817 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 m/z

-H -H

O O

O O OH O O O O HO HO OH OH - - Chemical Formula: C20H17O7 Chemical Formula: C20H15O6 Exact Mass: 369.0980 Exact Mass: 351.0874 -H

OH -H -H OH O O OH O OH Chemical Formula: C H O - OH O 18 15 6 OH Exact Mass: 327.0874 OH -H OH OH O Chemical Formula: C H O - HO OH 16 13 4 O Exact Mass: 269.0819 OH - Chemical Formula: C20H19O8 OH -H Exact Mass: 387.1085 OH OH O OH O - Chemical Formula: C17H13O5 OH OH Exact Mass: 297.0768 - Chemical Formula: C10H7O4 Exact Mass: 191.0350 -H -H

O O

O O OH OH OH O OH - Chemical Formula: C H O - Chemical Formula: C16H11O5 15 11 4 Exact Mass: 283.0612 Exact Mass: 255.0663

121 M13

Trihydroxy-tetramethoxyflavone (tR=12.9 min) MS1(−): 389.08871 MS2(−): 374.06497(100),359.04156(84),344.01788(25),316.02380(4),300.02774(7),285.00543(1),183.030 52(1)

ZQ-Colon-neg_151203111055 #1955 RT: 12.86 AV: 1 NL: 9.77E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-415.00] 374.06497 100

85 359.04156

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

30 344.01788 25

10 300.02774 5 64.77271 316.02380 80.36687 126.23843 149.02472 183.03052 210.78844 264.10730 285.00543 409.36142 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 m/z

-H -H -H - OH OH OH OH H O O O O O O O O O O O O O O O O

O OH O OH O OH O OH OH O OH O OH O OH O - •- Chemical Formula: C H O 2•- Chemical Formula: C H O 3•- Chemical Formula: C19H17O9 Chemical Formula: C18H14O9 17 11 9 16 8 9 Exact Mass: 389.0878 Exact Mass: 374.0643 Exact Mass: 359.0409 Exact Mass: 344.0174 -H -H -H O OH OH OH -H O O O O O O O O O O O O O O OH O OH O OH OH •- OH OH OH Chemical Formula: C8H7O5 Chemical Formula: C H O 4•- Chemical Formula: C H O 3•- Chemical Formula: C H O 3•- Exact Mass: 183.0299 14 5 7 15 8 7 15 8 8 Exact Mass: 285.0041 Exact Mass: 300.0276 Exact Mass: 316.0225

122 M14

Phlorizin (tR=10.50 min) MS1(−): 419.13573 MS2(−): 329.10379(17),299.09293(100),257.08221(32),197.04630(9),195.77(2),167.03508(55)

ZQ-Colon-neg_151203111055 #1495 RT: 10.49 AV: 1 NL: 5.51E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-445.00] 299.09293 100

60 e c n

a 55 167.03508 d n u b

A 50

e v i t

a 45 l e R 40

35 257.08221 30

20 329.10379 15 125.02445 269.08310 10 197.04630 109.05239 227.10867 5 91.99698 59.14502 143.67535 173.94289 213.09340 244.56577 276.47879 311.09244 368.06134 413.10999 0 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 m/z

HO OH -H

OH O OH - Chemical Formula: C17H15O5 Exact Mass: 299.0925

-H HO OH HO OH -H

-H OH O HO OH OH OH OH OH - Chemical Formula: C H O - O Chemical Formula: C18H17O6 8 7 4 HO Exact Mass: 329.1031 Exact Mass: 167.0350 OH O -H -H HO OH HO OH HO OH OH - O Chemical Formula: C21H23O9 HO Exact Mass: 419.1348 OH OH HO OH OH OH OH Chemical Formula: C H O - Chemical Formula: C H O - 9 9 5 12 15 8 Exact Mass: 197.0455 Exact Mass: 287.0772 -H -H

HO OH OH

O O

OH O OH O - - Chemical Formula: C16H13O5 Chemical Formula: C15H13O4 Exact Mass: 285.0768 Exact Mass: 257.0819

123 M15

Trihydroxyflavone O-glucuronide (tR=8.80 min) MS1(−): 445.07863 MS2(−): 269.04626(100),197.06091(0.6),171.04570(0.7),113.02453(2)

ZQ-Colon-neg_151203111055 #1208 RT: 8.82 AV: 1 NL: 1.94E5 F: FTMS - p ESI d Full ms2 [email protected] [50.00-475.00] 269.04626 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

5 85.02943 113.02453 171.04570 197.06091 222.00302 278.58078 311.22076 372.60107 470.89581 0 50 100 150 200 250 300 350 400 450 m/z

OH HO OH -H -H -H HO O O O HO O O HO HO HO OH O OH O OH - - Chemical Formula: C H O - Chemical Formula: C21H17O11 Chemical Formula: C15H9O5 13 9 2 Exact Mass: 445.0776 Exact Mass: 269.0455 Exact Mass: 197.0608

124 M16

Trihydroxy-tetramethoxyflavone O-sulfate (tR=11.50 min) MS1(−): 469.04555 MS2(−): 389.08881(19),374.06531(100),359.04163(25)

ZQ-Colon-neg_151203111055 #1700 RT: 11.52 AV: 1 NL: 7.79E4 F: FTMS - p ESI d Full ms2 [email protected] [50.00-495.00] 374.06531 100

60 e c n

a 55 d n u b

A 50

e v i t

a 45 l e R 40

30 359.04163 25

20 389.08881

10 469.22751 91.99629 5 423.27652 74.09719 127.68891 191.23946 257.38675 455.31415 0 50 100 150 200 250 300 350 400 450 m/z

OH -H O S O -H -H - O OH OH OH H O O O O O O O O O O O O O O O O

O OH O OH O OH O OH OH O OH O OH O OH O Chemical Formula: C H O S- - •- 2•- 19 17 12 Chemical Formula: C19H17O9 Chemical Formula: C18H14O9 Chemical Formula: C17H11O9 Exact Mass: 469.0446 Exact Mass: 389.0878 Exact Mass: 374.0643 Exact Mass: 359.0409

125 Reference

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