Hydroxycinnamoyl Amino Acids Conjugates: A Chiral Pool to Distinguish Commercially Exploited Coffea spp.
Abstract
:1. Introduction
2. Results and Discussion
3. Materials and Methods
3.1. Chemicals
3.2. Instrumentation
3.3. Samples
3.4. General Procedure for the Preparation of the Hydroxycinnamoyl Amides Esters 1a–5a
3.5. General Procedure for the Preparation of the Hydroxycinnamoyl Amides 1b–5b
3.6. Extraction of Hydroxycinnamoyl Amides and Sample Preparation
3.7. Quantitative Analyses
4. Conclusions
Author Contributions
Funding
Conflicts of Interest
Abbreviations
CD | Circular Dichroism |
5-CQA | 5-caffeoylquinic acid |
DCC | N,N′-Dicyclohexylcarbodiimide |
DW | Dry weight |
FA | Formic acid |
HCA | Hydroxycinnamoyl amide |
References
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Sample Availability: Samples of the compounds are not available from the authors. |
Compound | tR (min) | [M + H] (m/z) Exp. | Dimer + Na (m/z) Exp. | Specific Rotation |
---|---|---|---|---|
p-coumaroyl-N-tyrosine 1b | 26.9 | 328.1 | 677.1 (positive mode) | −39.9 (c 0.1 MeOH) (lit. −26.9 (MeOH) [11] and −17.7 (c 0.1 MeOH) [7]) |
caffeoyl-N-phenylalanine 2b | 30.6 | 328.0 | 677.2 (positive mode) | −48.8 (c 0.1 MeOH) |
caffeoyl-N-tyrosine 3b | 24.6 | 344.1 | 709.2 (positive mode) | −41.7 (c 0.1, MeOH) (lit. −35.6 [11]) |
p-coumaroyl-N-tryptophan 4b | 33.0 | 351.0 | 723.2 (positive mode) | −27.8 (c 0.1, MeOH) |
caffeoyl-N-tryptophan 5b | 31.1 | 367.1 | 731.1 (negative mode) | −33.2 (c 1.0, MeOH) |
Sample | Species | 1b | 2b | 3b | 4b | 5b | Total |
---|---|---|---|---|---|---|---|
1 | C. arabica Nicaragua | <LOD | <LOD | <LOD | <LOD | 117 (2) | 117 (2) |
2 | C. arabica Peru | <LOD | <LOD | <LOD | <LOD | <LOD | - |
3 | C. arabica Rwanda | <LOD | <LOD | <LOD | <LOD | 51 (1) | 51 (1) |
4 | C. arabica El Salvador | <LOD | <LOD | <LOD | <LOD | <LOD | - |
5 | C. arabica India | <LOD | <LOD | <LOD | <LOD | 125 (3) | 125 (3) |
6 | C. arabica Brazil | <LOD | <LOD | <LOD | <LOD | 37 (1) | 37 (1) |
7 | C. arabica Guatemala | <LOD | <LOD | <LOD | <LOD | 97 (2) | 97 (2) |
8 | C. arabica – lot 1 Ethiopia | <LOD | <LOD | <LOD | <LOD | 59 (1) | 59 (1) |
9 | C. arabica – lot 2 Ethiopia | <LOD | <LOD | <LOD | <LOD | 75 (2) | 75 (2) |
10 | C. arabica Burundi | <LOD | <LOD | <LOD | <LOD | 40 (1) | 40 (1) |
11 | C. canephora Cameroon | n.q. a | n.q. b | <LOD | 119 (4) | 878 (26) | 997 (30) |
12 | C. canephora Ivory Coast | <LOD | n.q. b | <LOD | 116 (4) | 712 (21) | 828 (25) |
13 | C. canephora Tanzania | n.q. a | n.q. b | 348 (5) | 319 (3) | 1042 (14) | 1709 (22) |
14 | C. canephora Indonesia | <LOD | <LOD | <LOD | 113 (2) | 590 (12) | 703 (14) |
15 | C. canephora – lot 1 India | <LOD | n.q. b | <LOD | 103 (3) | 790 (24) | 893 (27) |
16 | C. canephora – lot 2 India | <LOD | n.q. b | <LOD | 212 (6) | 1205 (48) | 1417 (54) |
17 | C. canephora – lot 3 India | <LOD | n.q. b | <LOD | 128 (4) | 780 (23) | 908 (27) |
18 | C. canephora Brazil var. Conilon | n.q. a | 47 (1) | 182 (4) | <LOD | 470 (9) | 699 (14) |
19 | C. canephora Uganda | n.q. a | n.q. b | 140 (3) | 195 (5) | 717 (21) | 1052 (29) |
20 | C. canephora Vietnam | <LOD | n.q. b | <LOD | 136 (3) | 702 (20) | 838 (23) |
21 | C. liberica – lot 1 | <LOD | <LOD | <LOD | <LOD | <LOD | - |
22 | C. liberica – lot 2 | <LOD | <LOD | <LOD | <LOD | <LOD | - |
23 | C. liberica – lot 3 | <LOD | <LOD | <LOD | <LOD | <LOD | - |
% A (H2O + 0.1% FA) | % B (CH3CN + 0.1% FA) | Time (min) |
---|---|---|
97 | 3 | 0 |
85 | 15 | 10 |
60 | 40 | 30 |
60 | 40 | 40 |
97 | 3 | 45 |
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Berti, F.; Navarini, L.; Colomban, S.; Forzato, C. Hydroxycinnamoyl Amino Acids Conjugates: A Chiral Pool to Distinguish Commercially Exploited Coffea spp. Molecules 2020, 25, 1704. https://doi.org/10.3390/molecules25071704
Berti F, Navarini L, Colomban S, Forzato C. Hydroxycinnamoyl Amino Acids Conjugates: A Chiral Pool to Distinguish Commercially Exploited Coffea spp. Molecules. 2020; 25(7):1704. https://doi.org/10.3390/molecules25071704
Chicago/Turabian StyleBerti, Federico, Luciano Navarini, Silvia Colomban, and Cristina Forzato. 2020. "Hydroxycinnamoyl Amino Acids Conjugates: A Chiral Pool to Distinguish Commercially Exploited Coffea spp." Molecules 25, no. 7: 1704. https://doi.org/10.3390/molecules25071704