S1B
Electronic Supplementary Information for
First Synthesis, Full Characterization, and Evidence for the Presence in Human Biological Fluids, of Hydroxycinnamic acid Sulphate and Glucuronide Conjugates, as a Result of Coffee Consumption.
René Fumeaux,† Candice Menozzi-Smarrito,† Angelique Stalmach,‡ Caroline Munari,† Karin Kraehenbuehl,† Heike Steiling,† Alan Crozier,‡ Gary Williamson,† and Denis Barron*,†
† Nestlé Research Center, PO Box 44, CH-1000 Lausanne 26, Switzerland. ‡Plant Products and Human Nutrition Group, Graham Kerr Building, Division of Ecology and Evolutionary Biology, Faculty of Biomedical and Life Sciences, University of Glasgow, Glasgow G12 8QQ, UK.
Part B: Purity control data
Abstract - A systematic investigation of the human metabolism of hydroxycinnamic acid conjugates was carried out. A set of 24 potential human metabolites of coffee polyphenols has been chemically prepared, and used as analytical standards for unequivocal identifications. These included glucuronide conjugates and sulphate esters of caffeic, ferulic, isoferulic, m-coumaric and p-coumaric acids as well as their dihydro derivatives. A particular focus has been made on caffeic and 3,4- dihydroxyphenylpropionic acid derivatives, especially the sulphate conjugates, for which regioselective preparation was particularly challenging, and have so far never been identified as human metabolites. Ten, out of the 24 synthesized conjugates have been identified in human plasma and/or urine after coffee consumption. A number of these conjugates were synthesized, characterized and detected as hydroxycinnamic acid metabolites for the first time. This was the case of dihydroisoferulic acid 3’-O- glucuronide, caffeic acid 3’-sulphate, as well as the sulphate and glucuronide derivatives of 3,4-dihydroxyphenylpropionic acid.
*To whom correspondence should be addressed. Nestlé Research Center, PO Box 44, CH-1000 Lausanne 26, Switzerland. Phone: + 41 21 785 9497. Fax: + 41 21 785 8554. e-mail: [email protected]
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S2B
Table of contents
1. Purity control data of analytical standards 1-24 ...... S4B 2. HPLC control of analytical standards 1-24 (Method A) ...... S5B Figure S1: (E)-p-Coumaric acid 4’-O- β -D-glucuronide 1a (280 nm)...... S5B Figure S2: (E)-m-Coumaric acid 3’-O- β -D-glucuronide 2a (280 nm)...... S5B Figure S3: (E)-Ferulic acid 4’-O- β -D-glucuronide 3a (280 nm)...... S6B Figure S4: (E)- and (Z)-Isoferulic acid 3’-O- β -D-glucuronides 4a + 4b (280 nm)...... S6B Figure S5: (E)- and (Z)-Caffeic acid 3’-O- β -D-glucuronides 5a + 5b (280 nm)...... S7B Figure S6: (E)- and (Z)-Caffeic acid 4’-O-β-D-glucuronides 6a + 6b (280 nm). S7B Figure S7: (E)-p-Coumaric acid 4’-sulphate 7 (280 nm)...... S8B Figure S8: (E)-m-Coumaric acid 3’-sulphate 8 (280 nm)...... S8B Figure S9: (E)-Ferulic acid 4’-sulphate 9 (280 nm)...... S9B Figure S10: (E)-Isoferulic acid 3’-sulphate 10 (280 nm)...... S9B Figure S11: (E)- and (Z)-Caffeic acid 3’-sulphates 11a + 11b (280 nm)...... S10B Figure S12: (E)- and (Z)-Caffeic acid 4’-sulphates 12a + 12b (280 nm)...... S10B Figure S13: Dihydro-p-coumaric acid 4’-O- β -D-glucuronide 13 (280 nm). .... S11B Figure S14: Dihydro-m-coumaric acid 3’-O- β -D-glucuronide 14 (210 nm). ... S11B Figure S15: Dihydroferulic acid 4’-O- β -D-glucuronide 15 (280 nm)...... S12B Figure S16: Dihydroisoferulic acid 3’-O- β -D-glucuronide 16 (280 nm)...... S12B Figure S17: Dihydrocaffeic acid 3’-O- β -D-glucuronide 17 (280 nm)...... S13B Figure S18: Dihydrocaffeic acid 4’-O- β -D-glucuronide 18 (280 nm)...... S13B Figure S19: Dihydro-p-coumaric acid 4’-sulphate 19 (210 nm)...... S14B Figure S20: Dihydro-m-coumaric acid 3’-sulphate 20 (210 nm)...... S14B Figure S21: Dihydroferulic acid 4’-sulphate 21 (280 nm)...... S15B Figure S22: Dihydroisoferulic acid 3’-sulphate 22 (280 nm)...... S15B Figure S23: Dihydrocaffeic acid 3’-sulphate 23 (280 nm)...... S16B Figure S24: Dihydrocaffeic acid 4’-sulphate 24 (280 nm)...... S16B 3. 1H and 13C NMR spectra of analytical standards 1-24 ...... S17B Figure S25: (E)-p-Coumaric acid 4’-O- β -D-glucuronide 1a ...... S17B Figure S26: (E)-m-Coumaric acid 3’-O- β -D-glucuronide 2a...... S18B Figure S27: (E)-Ferulic acid 4’-O- β -D-glucuronide 3a...... S19B Figure S28: (E)- and (Z)-Isofeulic acid 3’-O- β -D- glucuronides 4a + 4b...... S20B Figure S29: (E)- and (Z)-Caffeic acid 3’-O- β -D- glucuronides 5a + 5b...... S21B Figure S30: (E)- and (Z)-Caffeic acid 4’-O- β -D- glucuronides 6a + 6b...... S22B Figure S31: (E)-p-Coumaric acid 4’-sulphate 7...... S23B Figure S32: (E)-m-Coumaric acid 3’-sulphate 8...... S24B Figure S33: (E)-Ferulic acid 4’-sulphate 9...... S25B Figure S34: (E)-Isoferulic acid 3’-sulphate 10...... S26B Figure S35: (E)- and (Z)-Caffeic acid 3’- sulphates 11a + 11b...... S27B Figure S36: (E)- and (Z)-Caffeic acid 4’- sulphates 12a + 12b...... S28B Figure S37: Dihydro-p-coumaric acid 4’-O- β -D-glucuronide 13...... S29B Figure S38: Dihydro-m-coumaric acid 3’-O- β -D-glucuronide 14...... S30B Figure S39: Dihydroferulic acid 4’-O- β -D-glucuronide 15...... S31B Figure S40: Dihydroisoferulic acid 3’-O- β -D-glucuronide 16...... S32B Figure S41: Dihydrocaffeic acid 3’-O- β -D-glucuronide 17...... S33B Figure S42: Dihydrocaffeic acid 4’-O- β -D-glucuronide 18...... S34B Figure S43: Dihydro-p-coumaric acid 4’-sulphate 19...... S35B
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S3B
Figure S44: Dihydro-m-coumaric acid 3’-sulphate 20...... S36B Figure S45: Dihydroferulic acid 4’-sulphate 21...... S37B Figure S46: Dihydroisoferulic acid 3’-sulphate 22...... S38B Figure S47: Dihydrocaffeic acid 3’-sulphate 23...... S39B Figure S48: Dihydrocaffeic acid 4’-sulphate 24...... S40B
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S4B
1. Purity control data of analytical standards 1-24
Table S1: Purity control of analytical standards 1-24. No Compound LC-HRMS data HPLC % Quantification purity data of sulphate (nm) ester content - 1a (E)-p-Coumaric acid 4’-O- [M-H] Calc for C15H15O9: 99 (280) - β-D-glucuronide 339.0716; found: 339.0721. - 2a (E)-m-Coumaric acid 3’-O- [M-H] calc for C15H15O9: 97 (280) - β-D-glucuronide 339.0716; found: 339.0719. - 3a (E)-Ferulic acid 4’-O-β-D- [M-H] calc for C16H17O10: 99 (280) - glucuronide 369.0821; found: 369.0834. - 4a + (E)- and (Z)-Isoferulic acid [M-H] calc for C16H17O10: 99 (280) - 4b 3’-O-β-D-glucuronides 369.0821; found: 369.0825. - 13 Dihydro-p-coumaric acid [M-H] calc for C15H17O9: 99 (280) - 4’-O-β-D-glucuronide 341.0872; found: 341.0882. - 14 Dihydro-m-coumaric acid [M-H] calc for C15H17O9: 99 (210) - 3’-O-β-D-glucuronide 341.0872; found: 341.0878. - 15 Dihydroferulic acid 4’-O-β- [2M-H] calc for C32H39O20: 99 (280) - D-glucuronide 743.2040; found: 743.2019. - 16 Dihydroisoferulic acid 3’-O- [M-H] calc for C16H19O10: 98 (280) - β-D-glucuronide 371.0978; found: 371.0974. - 5a + (E)- and (Z)-Caffeic acid 3’- [M-H] calc for C15H15O10: 94 (280) - 5b O-β-D-glucuronides 355.0665; found: 355.0653. - 6a + (E)- and (Z)-Caffeic acid 4’- [M-H] calc for C15H15O10: 99 (280) - 6b O-β-D-glucuronides 355.0665; found: 355.0664. - 17 Dihydrocaffeic acid 3’-O-β- [M-H] calc for C15H17O10: 99 (280) - D-glucuronide 357.0821; found: 357.0816. - 18 Dihydrocaffeic acid 4’-O-β- [M-H] calc for C15H17O10: 98 (280) - D-glucuronide 357.0821; found: 357.0824. - 7 (E)-p-Coumaric acid 4’- [M-H] calc for C9H7O6S: 98 (280) 2.81 μmol/mg sulphate 242.9963; found: 242.9994 - 8 (E)-m-Coumaric acid 3’- [M-H] calc for C9H7O6S: 98 (280) 2.70 μmol/mg sulphate 242.9963; found: 243.0001 - 9 (E)-Ferulic acid 4’-sulphate [M-H] calc for C10H9O7S: 98 (280) 1.93 μmol/mg 273.0069; found: 273.0099 - 10 (E)-Isoferulic acid 3’- [M-H] calc for C10H9O7S: 98 (280) 1.57 μmol/mg sulphate 273.0069; found: 273.0112 - 11a (E)- and (Z)-Caffeic acid 3'- [M-H] calc for C9H7O7S: 97 (280) 2.30 μmol/mg + sulphates 258.9912; found: 258.9960 11b - 12a (E)- and (Z)-Caffeic acid 4'- [M-H] calc for C9H7O7S: 95 (280) 1.91 μmol/mg + sulphates 258.9912; found: 258.9955 12b - 19 Dihydro-p-coumaric acid [M-H] calc for C9H9O6S: 98 (210) 2.22 μmol/mg 4’-sulphate 245.0119; found: 245.0164 - 20 Dihydro-m-coumaric acid [M-H] calc for C9H9O6S: 98 (210) 2.10 μmol/mg 3’-sulphate 245.0119; found: 245.0161 - 21 Dihydroferulic acid 4’- [M-H] calc for C10H11O7S: 97 (280) 1.57 μmol/mg sulphate 275.0225; found: 275.0270 - 22 Dihydroisoferulic acid 3’- [M-H] calc for C10H11O7S: 98 (280) 2.15 μmol/mg sulphate 275.0225; found: 275.0270 - 23 Dihydrocaffeic acid 3'- [M-H] calc for C9H9O7S: 98 (280) 1.75 μmol/mg sulphate 261.0069; found: 261.0115 - 24 Dihydrocaffeic acid 4'- [M-H] calc for C9H9O7S: 98 (280) 1.55 μmol/mg sulphate 261.0069; found: 261.0108
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S5B
2. HPLC control of analytical standards 1-24 (Method A)
DAD1 A, Sig=280,10 Ref=550,100 (LFO\LFO00299.D) mA U 5.419
800
600
400
200
0
2.5 5 7.5 10 12.5 15 17.5 20 min
Figure S1: (E)-p-Coumaric acid 4’-O- β -D-glucuronide 1a (280 nm).
mA U
600 6.179
500
400
300
200
100 6.065
0
4 6 8 10 12 14 16 18 20 22 min
Figure S2: (E)-m-Coumaric acid 3’-O- β -D-glucuronide 2a (280 nm).
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S6B
mA U
500 5.832
400
300
200
100
0
4 6 8 10 12 14 16 18 20 min
Figure S3: (E)-Ferulic acid 4’-O- β -D-glucuronide 3a (280 nm).
mA U 6.531
350
300
250
200
150
100
50
0
4 6 8 10 12 14 16 18 20 22 min
Figure S4: (E)- and (Z)-Isoferulic acid 3’-O-β-D-glucuronides 4a + 4b (280 nm).
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S7B
mA U 5.882
300
250
200
150
100
50 5.987
0
4 6 8 10 12 14 16 18 20 22 min
Figure S5: (E)- and (Z)-Caffeic acid 3’-O- β -D-glucuronides 5a + 5b (280 nm).
mA U 5.281 500
400
300
200
100
0
4 6 8 10 12 14 16 18 20 22 min
Figure S6: (E)- and (Z)-Caffeic acid 4’-O-β-D-glucuronides 6a + 6b (280 nm).
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S8B
mA U 5.556
700
600
500
400
300
200
100
0
4 6 8 10 12 14 16 18 20 22 min
Figure S7: (E)-p-Coumaric acid 4’-sulphate 7 (280 nm).
mA U 5.855
1000
800
600
400
200
0
4 6 8 10 12 14 16 18 20 22 min
Figure S8: (E)-m-Coumaric acid 3’-sulphate 8 (280 nm).
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S9B
mA U 5.633
1000
800
600
400
200
0
4 6 8 10 12 14 16 18 20 22 min
Figure S9: (E)-Ferulic acid 4’-sulphate 9 (280 nm).
mA U 6.085 1000
800
600
400
200
0
4 6 8 10 12 14 16 18 20 22 min
Figure S10: (E)-Isoferulic acid 3’-sulphate 10 (280 nm).
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S10B
mA U 5.495
400
300
200
100
0
4 6 8 10 12 14 16 18 20 22 min
Figure S11: (E)- and (Z)-Caffeic acid 3’-sulphates 11a + 11b (280 nm).
mA U 5.291 1000
800
600
400
200 5.178
0
4 6 8 10 12 14 16 18 20 22 min
Figure S12: (E)- and (Z)-Caffeic acid 4’-sulphates 12a + 12b (280 nm).
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S11B
mA U 5.418
40
35
30
25
20
15
10
5
0 5.766
4 6 8 10 12 14 16 18 20 22 min
Figure S13: Dihydro-p-coumaric acid 4’-O- β -D-glucuronide 13 (280 nm).
mA U 5.934
300
200
100
0
-100
-200
-300
4 6 8 10 12 14 16 18 20 22 min
Figure S14: Dihydro-m-coumaric acid 3’-O- β -D-glucuronide 14 (210 nm).
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S12B
mA U 5.781
40
30
20
10
0
4 6 8 10 12 14 16 18 20 22 min
Figure S15: Dihydroferulic acid 4’-O- β -D-glucuronide 15 (280 nm).
mA U 6.322
60
50
40
30
20
10
0 5.916 6.171
4 6 8 10 12 14 16 18 20 22 min
Figure S16: Dihydroisoferulic acid 3’-O- β -D-glucuronide 16 (280 nm).
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S13B
mA U 5.463 60
50
40
30
20
10
0
4 6 8 10 12 14 16 18 20 22 min
Figure S17: Dihydrocaffeic acid 3’-O- β -D-glucuronide 17 (280 nm).
DAD1 A, Sig=280,10 Ref=550,100 (LFO\LFO00252.D) mA U 5.229
70
60
50
40
30
20
10 5.414 0
4 6 8 10 12 14 16 18 20 22 min
Figure S18: Dihydrocaffeic acid 4’-O- β -D-glucuronide 18 (280 nm).
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S14B
mA U 5.082
200
100
0
-100
-200
-300
4 6 8 10 12 14 16 18 20 22 min
Figure S19: Dihydro-p-coumaric acid 4’-sulphate 19 (210 nm).
mA U
300 5.339
200
100
0
-100
-200
-300
5 7.5 10 12.5 15 17.5 20 22.5 25 min
Figure S20: Dihydro-m-coumaric acid 3’-sulphate 20 (210 nm).
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S15B
mA U 5.253
35
30
25
20
15
10
5 5.824 0
4 6 8 10 12 14 16 18 20 22 min
Figure S21: Dihydroferulic acid 4’-sulphate 21 (280 nm).
mA U 5.601
100
80
60
40
20
0
4 6 8 10 12 14 16 18 20 22 min
Figure S22: Dihydroisoferulic acid 3’-sulphate 22 (280 nm).
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S16B
mA U 4.818
200
175
150
125
100
75
50
25
0
4 6 8 10 12 14 16 18 20 22 min
Figure S23: Dihydrocaffeic acid 3’-sulphate 23 (280 nm).
mA U 4.701
140
120
100
80
60
40
20
0
4 6 8 10 12 14 16 18 20 22 min
Figure S24: Dihydrocaffeic acid 4’-sulphate 24 (280 nm).
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3. 1H and 13C NMR spectra of analytical standards 1-24
O O COOH HO OH OH
HO
O
Figure S25: (E)-p-Coumaric acid 4’-O- β -D-glucuronide 1a.
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Figure S26: (E)-m-Coumaric acid 3’-O- β -D-glucuronide 2a.
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OCH3 O O COOH HO OH OH
HO
O
Figure S27: (E)-Ferulic acid 4’-O- β -D-glucuronide 3a.
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OCH3
O O COOH HO OH HO OH 4a:Major O + OCH3
O O COOH HO OH OH OH O 4b:Minor
Figure S28: (E)- and (Z)-Isoferulic acid 3’-O- β -D-glucuronides 4a + 4b.
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S21B
OH
O O COOH HO OH HO OH 5a:Major O + OH
O O COOH HO OH OH OH O 5b:Minor
Figure S29: (E)- and (Z)-Caffeic acid 3’-O- β -D-glucuronide 5a + 5b.
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OH O O COOH HO OH OH
HO 6a:Major O + OH O O COOH HO OH OH
OH 6b:Minor O
Figure S30: (E)- and (Z)-Caffeic acid 4’-O- β -D-glucuronide 6a + 6b.
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- OSO3
-O
O
Figure S31: (E)-p-Coumaric acid 4’-sulphate 7.
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- OSO3 -O
O
Figure S32: (E)-m-Coumaric acid 3’-sulphate 8.
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- OSO3
OCH3 -O
O
Figure S33: (E)-Ferulic acid 4’-sulphate 9.
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OCH3
- OSO3 -O
O
Figure S34: (E)-Isoferulic acid 3’-sulphate 10.
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Figure S35: (E)- and (Z)-Caffeic acid 3’-sulphates 11a + 11b.
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Figure S36: (E)- and (Z)-Caffeic acid 4’-sulphates 12a + 12b.
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O O COOH HO OH OH
HO
O
Figure S37: Dihydro-p-coumaric acid 4’-O- β -D-glucuronide 13.
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S30B
O O COOH HO OH HO OH O
Figure S38: Dihydro-m-coumaric acid 3’-O- β -D-glucuronide 14.
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S31B
OCH3 O O COOH HO OH OH
HO
O
Figure S39: Dihydroferulic acid 4’-O- β -D-glucuronide 15.
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S32B
OCH3
O O COOH HO OH HO OH O
Figure S40: Dihydroisoferulic acid 3’-O- β -D-glucuronide 16.
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S33B
OH
O O COOH HO OH HO OH O
Figure S41: Dihydrocaffeic acid 3’-O- β -D-glucuronide 17.
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S34B
OH O O COOH HO OH OH
HO
O
Figure S42: Dihydrocaffeic acid 4’-O- β -D-glucuronide 18.
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S35B
- OSO3
-O
O
Figure S43: Dihydro-p-coumaric acid 4’-sulphate 19.
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S36B
- OSO3 -O
O
Figure S44: Dihydro-m-coumaric acid 3’-sulphate 20.
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S37B
- OSO3
OCH3 -O
O
Figure S45: Dihydroferulic acid 4’-sulphate 21.
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OCH3
- OSO3 -O
O
Figure S46: Dihydroisoferulic acid 3’-sulphate 22.
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OH
- OSO3 -O
O
Figure S47: Dihydrocaffeic acid 3’-sulphate 23.
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 S40B
- OSO3
OH -O
O
Figure S48: Dihydrocaffeic acid 4’-sulphate 24.
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010