LC-MS and Spectrophotometric Approaches for Evaluation of Bioactive Compounds from Peru Cocoa By-Products for Commercial Applications
Abstract
:1. Introduction
2. Results and Discussion
2.1. Characterization of Cocoa Husk and Bean Extracts by HPLC-ESI-TOF
2.1.1. Phenolic Acid Derivatives
2.1.2. Flavonoids
2.1.3. Amino Acid Derivatives
2.1.4. Other Compounds
2.1.5. Hierarchical Clustering Analysis
2.2. Total Phenol and Flavan-3-ol Contents and Antioxidant Capacities
3. Materials and Methods
3.1. Chemicals
3.2. Plant Collection and Extract Preparation
3.3. HPLC-ESI-TOF-MS Analysis
3.4. Total Phenolic and Flavan-3-ol Content
3.5. Antioxidant Capacity Measurements
3.6. Data Processing and Statistics
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Sample Availability: Samples of the compounds are available from the authors. |
Peak | RT (min) | m/z exp | m/z cal | Error (ppm) | mSigma | Molecular Formula | Proposed Compound | H1 | H2 | H3 | H4 | H5 | H6 | H7 | H8 | B1 | B2 | B3 | B4 | B5 | B6 | B7 | B8 |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
1 | 3.1 | 195.0516 | 195.0510 | 2.9 | 2.6 | C6 H12 O7 | Gluconic acid | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
2 | 3.5 | 341.1086 | 341.1089 | 0.8 | 29.5 | C12 H22 O11 | Sacarose | X | X | X | X | X | X | X | X | X | X | X | X | X | X | ||
3 | 6.6 | 191.0198 | 191.0197 | 0.1 | 0.6 | C6 H8 O7 | Citric acid | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
4 | 7.9 | 180.0670 | 180.0666 | 2.1 | 0.6 | C9 H11 NO3 | Tyrosine | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
5 | 8.4 | 292.1405 | 292.1402 | 0.9 | 15.4 | C12 H23 NO7 | Fructose-leucine | X | X | X | X | X | X | ||||||||||
6 | 8.6 | 265.0935 | 265.0929 | 2.2 | 2.0 | C10 H18 O8 | Unknown 1 | X | X | X | X | X | X | X | X | ||||||||
7 | 9.0 | 282.0872 | 282.0884 | 4.2 | 25.7 | C15 H13 N3 O3 | Hydroxy-triaminoflavone | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
8 | 9.5 | 383.1559 | 383.1559 | 0.0 | 11.1 | C15 H28 O11 | Tri-O-methylsacarose | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
9 | 9.8 | 442.1566 | 442.1566 | 0.0 | 0.0 | C16 H29 NO13 | Fructofuranosyl-treonyl-glucopyranoside | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
10 | 10.2 | 164.0718 | 164.0717 | 0.6 | 2.3 | C9 H11 NO2 | Phenylalanine | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
11 | 10.9 | 179.0580 | 179.0574 | 3.1 | 2.2 | C7 H8 N4 O2 | Theobromine | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
12 | 11.3 | 451.1245 | 451.1246 | 0.1 | 5.6 | C21 H24 O11 | Aspalathin isomer 1 | X | X | X | X | X | X | ||||||||||
13 | 11.3 | 294.0626 | 294.0619 | 2.2 | 6.9 | C13 H13 NO7 | N-caffeoyl-l-aspartate isomer 1 | X | X | X | X | X | X | X | X | ||||||||
14 | 11.7 | 865.1971 | 865.1985 | 1.6 | 23.1 | C45 H38 O18 | Procyanidin C isomer 1 | X | X | X | X | X | X | X | X | X | X | X | X | ||||
15 | 11.7 | 153.0202 | 153.0193 | 5.7 | 1.1 | C7 H6 O4 | Protocatechuic acid | X | X | X | X | X | X | X | X | X | |||||||
16 | 12.0 | 576.1274 | 576.1273 | 0.3 | 159.7 | C60 H50 O24 | (Epi)catechin tetramer isomer 1 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
17 | 12.4 | 451.1254 | 451.1246 | 1.7 | 3.1 | C21 H24 O11 | Aspalathin isomer 2 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
18 | 12.8 | 369.028 | 369.0252 | 7.6 | 18.9 | C18 H10 O9 | Phlorotannin | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
19 | 12.9 | 181.0514 | 181.0506 | 4.2 | 9.8 | C9 H10 O4 | Homovanillic acid | X | X | X | X | X | X | X | X | ||||||||
20 | 13.0 | 294.0622 | 294.0619 | 0.8 | 3.1 | C13 H13 NO7 | N-caffeoyl-l-aspartate isomer 2 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
21 | 13.3 | 577.1353 | 577.1351 | 0.2 | 1.7 | C30 H26 O12 | Procyanidin dimer type B isomer 1 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
22 | 13.4 | 329.0893 | 329.0878 | 4.6 | 40.8 | C14 H18 O9 | Vanillic acid glycoside isomer 1 | X | X | X | X | X | X | X | X | ||||||||
23 | 13.9 | 451.1233 | 451.1246 | 2.9 | 9.0 | C21 H24 O11 | Aspalathin isomer 3 | X | X | X | X | X | X | X | X | ||||||||
24 | 14.1 | 329.0896 | 329.0878 | 5.5 | 30.0 | C14 H18 O9 | Vanillic acid glycoside isomer 2 | X | X | X | X | X | X | X | X | ||||||||
25 | 14.3 | 577.1343 | 577.1351 | 1.4 | 34.5 | C30 H26 O12 | Procyanidin dimer type B isomer 2 | X | X | X | X | X | X | X | X | X | X | X | X | ||||
26 | 14.6 | 305.0675 | 305.0667 | 2.7 | 26.3 | C15 H14 O7 | (Epi)gallocatechin | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
27 | 15.6 | 278.0668 | 278.0670 | 0.9 | 1.7 | C13 H13 NO6 | l-aspartic acid N-[3-(4-hydroxyphenyl)-1-oxo-2-propenyl] | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
28 | 16.0 | 177.0200 | 177.0193 | 3.8 | 3.6 | C9 H6 O4 | Aesculetin | X | X | X | X | X | X | ||||||||||
29 | 16.3 | 407.1552 | 407.1559 | 1.7 | 30.5 | C17 H28 O11 | Unknown 2 | X | X | X | X | X | X | X | X | X | X | ||||||
30 | 16.8 | 289.0726 | 289.0718 | 2.8 | 5.8 | C15 H14 O6 | Catechin | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
31 | 19.3 | 358.0927 | 358.0932 | 1.5 | 4.8 | C18 H17 NO7 | Trans-clovamide (N-[(2E)-3-(3.4-dihydroxyphenyl)-1-oxo-2-propen-1-yl] -3-hydroxy-l-tyrosine) | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
32 | 19.5 | 381.1760 | 381.1766 | 1.7 | 1.8 | C16 H30 O10 | Everlastoside C isomer 1 | X | X | X | X | X | X | X | X | X | |||||||
33 | 20.3 | 381.1760 | 381.1766 | 1.2 | 6.4 | C16 H30 O10 | Everlastoside C isomer 2 | X | X | X | X | X | X | X | |||||||||
34 | 20.4 | 737.1735 | 737.1723 | 1.6 | 10.3 | C36 H34 O17 | (Epi)catechin dimer hexose | X | X | X | X | X | X | X | X | X | X | X | X | X | X | ||
35 | 21.0 | 707.1641 | 707.1618 | 3.4 | 4.1 | C35 H32 O16 | Arabinopyranosyl-(epi)catechin-(epi)catechin | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
36 | 21.3 | 415.1589 | 415.1610 | 5.0 | 31.9 | C19 H28 O10 | β-d-Glucopyranoside, 2-phenylethyl 6-O-β-d-xylopyranose | X | X | X | X | X | X | X | |||||||||
37 | 21.6 | 577.1339 | 577.1351 | 2.2 | 4.1 | C30 H26 O12 | Procyanidin dimer type B isomer 3 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
38 | 22.1 | 165.0560 | 165.0557 | 1.6 | 4.4 | C9 H10 O3 | Paeonol | X | X | X | X | X | X | X | X | X | X | ||||||
39 | 23.1 | 605.1679 | 605.1664 | 2.4 | 4.7 | C32 H30 O12 | (Epi)catechin methyl dimer isomer 1 | X | X | X | X | X | X | X | X | X | X | X | X | X | |||
40 | 24.0 | 575.1181 | 575.1195 | 2.3 | 126.2 | C30 H24 O12 | Procyanidin dimer type A isomer 1 | X | X | X | X | X | X | X | X | ||||||||
41 | 25.5 | 576.1296 | 576.1273 | 3.9 | 29.1 | C60 H50 O24 | (Epi)catechin tetramer isomer 2 | X | X | X | X | X | X | X | X | X | X | ||||||
42 | 26.8 | 326.1039 | 326.1034 | 1.4 | 12.1 | C18 H17 NO5 | Deoxyclovamide (N-[(2E)-3-(3.4-dihydroxyphenyl)-1-oxo-2-propen-1-yl]-l-tyrosine) | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
43 | 28.4 | 463.0878 | 463.0882 | 0.9 | 3.2 | C21 H20 O12 | Quercetin glucoside | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
44 | 28.8 | 393.1778 | 393.1766 | 3.1 | 9.5 | C17 H30 O10 | Hexenyl primeveroside | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
45 | 29.5 | 433.0774 | 433.0776 | 0.5 | 12.4 | C20 H18 O11 | Quercetin arabinofuranoside | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
46 | 30.3 | 605.1643 | 605.1664 | 3.6 | 7.8 | C32 H30 O12 | (Epi)catechin methyl dimer isomer 3 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | ||
47 | 30.9 | 516.2475 | 516.2450 | 4.8 | 13.4 | C24 H39 NO11 | Unknown 3 | X | X | X | X | X | X | ||||||||||
48 | 31.3 | 575.1190 | 575.1195 | 1.0 | 35.6 | C30 H24 O12 | Procyanidin dimer type A isomer 2 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | ||
49 | 31.6 | 605.1664 | 605.1671 | 1.1 | 10.3 | C32 H30 O12 | (Epi)catechin methyl dimer isomer 4 | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
Sample | Yield (%) | Folin–Ciocalteau (µg GAE/mg Dry Extract) | Vanillin (µg CE/mg Dry Extract) | FRAP (µg eq. FeSO4/mg Dry Extract) | TEAC (µg eq. Trolox/mg Dry Extract) |
---|---|---|---|---|---|
H1 | 19.3 | 9.3 ± 0.8 | 22 ± 2 | 0.073 ± 0.003 | 0.9 ± 0.1 |
H2 | 20.9 | 14.8 ± 0.7 | 32 ± 9 | 0.11 ± 0.01 | 0.96 ± 0.02 |
H3 | 17.9 | 22.2 ± 0.7 | 36 ± 2 | 0.131 ± 0.003 | 1.048 ± 0.001 |
H4 | 23.3 | 11.4 ± 0.2 | 33 ± 1 | 0.096 ± 0.006 | 1.1 ± 0.1 |
H5 | 16.0 | 7.8 ± 0.4 | 24.9 ± 0.5 | 0.069 ± 0.003 | 0.618 ± 0.005 |
H6 | 17.4 | 4.9 ± 0.2 | 16.1 ± 0.8 | 0.044 ± 0.004 | 0.5 ± 0.1 |
H7 | 8.6 | 10.7 ± 0.1 | 27 ± 6 | 0.078 ± 0.003 | 0.3 ± 0.1 |
H8 | 7.9 | 8.6 ± 0.1 | 16 ± 1 | 0.065 ± 0.008 | 0.44 ± 0.02 |
B1 | 10.6 | 29.8 ± 0.7 | 96 ± 8 | 0.195 ± 0.005 | 1.54 ± 0.04 |
B2 | 10.3 | 28.1 ± 0.4 | 99 ± 2 | 0.23 ± 0.01 | 1.4 ± 0.3 |
B3 | 7.9 | 20.9 ± 0.1 | 74 ± 8 | 0.157 ± 0.008 | 1.1 ± 0.4 |
B4 | 11.0 | 31.3 ± 0.1 | 130 ± 2 | 0.266 ± 0.008 | 1.0 ± 0.1 |
B5 | 8.7 | 15.0 ± 0.1 | 50.6 ± 0.5 | 0.128 ± 0.005 | 1.03 ± 0.01 |
B6 | 10.0 | 29.5 ± 0.5 | 118 ± 16 | 0.216 ± 0.002 | 2.2 ± 0.1 |
B7 | 15.8 | 11.4 ± 0.1 | 19 ± 2 | 0.095 ± 0.003 | 1.07 ± 0.02 |
B8 | 8.0 | 13.7 ± 0.2 | 34.6 ± 0.2 | 0.116 ± 0.001 | 1.4 ± 0.1 |
Origin | La Convención | Zarumilla | Leoncio Prado | |||||
---|---|---|---|---|---|---|---|---|
Genotype | CHUNCHO | TRINITARIO | CCN51 | |||||
N° samples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
Crop locus | Quillabamba | Papayal | Km. 51 | Huayranga | Pumahuasi | Cadena | La Victoria | Las Vegas |
Altitude (m.a.s.l.) | 950 | 42 | 710 | 670 | 720 | 700 | 830 | 900 |
Type of fermentation & days | Wooden boxes (6 days) | Polypropylene bags with wooden platform (7 days) | Polypropylene bags (5 days) | Polypropylene bags (5 days) | Polypropylene bags (4 days) | Polypropylene bags (5 days) | Polypropylene bags (5 days) | Polypropylene bags (4 days) |
Drying methods | Sun-dried with plastic film cover (Agro Films) | Sun-dried with plastic film cover (Agro Films) | Drying by direct sunlight | Drying by direct sunlight | Drying by direct sunlight | Drying by direct sunlight | Drying by direct sunlight | Drying by direct sunlight |
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Cádiz-Gurrea, M.d.l.L.; Fernández-Ochoa, Á.; Leyva-Jiménez, F.J.; Guerrero-Muñoz, N.; Villegas-Aguilar, M.d.C.; Pimentel-Moral, S.; Ramos-Escudero, F.; Segura-Carretero, A. LC-MS and Spectrophotometric Approaches for Evaluation of Bioactive Compounds from Peru Cocoa By-Products for Commercial Applications. Molecules 2020, 25, 3177. https://doi.org/10.3390/molecules25143177
Cádiz-Gurrea MdlL, Fernández-Ochoa Á, Leyva-Jiménez FJ, Guerrero-Muñoz N, Villegas-Aguilar MdC, Pimentel-Moral S, Ramos-Escudero F, Segura-Carretero A. LC-MS and Spectrophotometric Approaches for Evaluation of Bioactive Compounds from Peru Cocoa By-Products for Commercial Applications. Molecules. 2020; 25(14):3177. https://doi.org/10.3390/molecules25143177
Chicago/Turabian StyleCádiz-Gurrea, María de la Luz, Álvaro Fernández-Ochoa, Francisco Javier Leyva-Jiménez, Noelia Guerrero-Muñoz, María del Carmen Villegas-Aguilar, Sandra Pimentel-Moral, Fernando Ramos-Escudero, and Antonio Segura-Carretero. 2020. "LC-MS and Spectrophotometric Approaches for Evaluation of Bioactive Compounds from Peru Cocoa By-Products for Commercial Applications" Molecules 25, no. 14: 3177. https://doi.org/10.3390/molecules25143177