Rapid and Simultaneous Determination of Free Aromatic Carboxylic Acids and Phenols in Commercial Juices by GC-MS after Ethyl Chloroformate Derivatization
Abstract
:1. Introduction
2. Materials and Methods
2.1. Reagents and Standards
2.2. Extraction/Derivatization Procedure
2.3. Gas Chromatography–Mass Spectrometry
2.4. Method Validation
2.5. Fruit Juice Analysis
3. Results and Discussion
3.1. GC-MS Characterization of ECF Derivatives
3.2. Optimization of the Method
3.3. Method Validation
3.4. Fruit Juice Analysis
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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No. | Compound | RT (min) | RI | M+∙ | Ions, m/z (% Relative Abundance) |
---|---|---|---|---|---|
1 | Benzoic acid | 5.95 | 1179.1 | 150 (6) | 105 (100); 122 (50); 77 (49); 51 (17) |
2 | Trans-cinnamic acid | 8.66 | 1480.2 | 176 (32) | 131 (100); 103 (48); 77 (29); 147 (16) |
3 | 3-(dimethylamino)benzoic acid | 9.82 | 1622.4 | 193 (97) | 164 (100); 165 (40); 192 (32); 120 (26) |
4 | 3,4-dimethoxybenzoic acid | 10.18 | 1670.7 | 210 (75) | 165 (100); 182 (25); 79 (14); 166 (12) |
5 | Resorcinol | 10.95 | 1774.0 | 254 (3) | 110 (100); 82 (10); 111 (8); 81 (8); 182 (8) |
6 | 2-hydroxybenzyl alcohol | 11.16 | 1802.4 | 268 (1) | 106 (100); 78 (55); 107 (27); 77 (16); 196 (11) |
7 | 4-(diethylamino)benzoic acid | 11.63 | 1872.0 | 221 (31) | 206 (100); 178 (27); 176 (19); 150 (14) |
8 | Vanillic acid | 11.89 | 1910.5 | 268 (7) | 151 (100); 196 (50); 168 (36); 152 (15); 123 (12) |
9 | Phloretic acid | 11.99 | 1925.3 | 266 (11) | 120 (100); 107 (96); 123 (32); 135 (30); 194 (21) |
10 | Homovanillic acid | 12.37 | 1981.5 | 282 (8) | 137 (100); 210 (29); 138 (11); 165 (8) |
11 | Tyrosol | 12.51 | 2002.4 | 282 (1) | 120 (100); 107 (18); 121 (18); 192 (14); 91 (11) |
12 | P-coumaric acid | 12.81 | 2051.3 | 264 (16) | 147 (100); 120 (45); 192 (44); 164 (20); 91 (18) |
13 | Syringic acid | 13.05 | 2090.4 | 298 (5) | 226 (100); 181 (73); 198 (31); 225 (15); 211 (14) |
14 | Gentisic acid | 13.55 | 2171.7 | 326 (1) | 136 (100); 164 (36); 182 (28); 135 (22); 137 (18) |
15 | Homoprotocatechuic acid | 13.80 | 2213.3 | 340 (2) | 123 (100); 196 (43); 151 (27); 224 (13); 122 (12) |
16 | Ferulic acid | 13.90 | 2230.9 | 294 (21) | 222 (100); 177 (59); 150 (53); 145 (34) |
17 | Isoferulic acid | 14.06 | 2258.9 | 294 (48) | 222 (100); 177 (93); 150 (52); 147 (28) |
18 | Dihydrocaffeic acid | 14.45 | 2327.3 | 354 (4) | 136 (100); 123 (65); 210 (48); 135 (47); 164 (32) |
19 | Caffeic acid | 15.19 | 2462.0 | 352 (5) | 208 (100); 163 (90); 136 (56); 180 (52); 134 (44) |
Compound | Range (ng/mL) | Slope | Intercept | R2 | LOQ (LOD) (ng/mL) | Concentration (ng/mL) | Accuracy (Recovery %) | Precision (RSD %) |
---|---|---|---|---|---|---|---|---|
Benzoic acid | 25–3000 | 0.0001 | 0.0575 | 0.9952 | 25 (12.5) | 200 | 103.91 | 7.16 |
2000 | 101.05 | 8.96 | ||||||
Trans-cinnamic acid | 50–3000 | 0.0003 | −0.0097 | 0.9985 | 50 (25) | 200 | 102.87 | 2.97 |
2000 | 104.05 | 8.44 | ||||||
3-(dimethylamino) benzoic acid | 25–3000 | 0.0003 | −0.0018 | 0.9968 | 25 (12.5) | 200 | 98.89 | 6.38 |
2000 | 97.76 | 7.04 | ||||||
3,4-dimethoxybenzoic acid | 25–3000 | 0.0003 | 0.0031 | 0.9993 | 25 (12.5) | 200 | 101.82 | 8.90 |
2000 | 97.51 | 7.43 | ||||||
Resorcinol | 25–3000 | 0.0018 | 0.0076 | 0.9997 | 25 (12.5) | 200 | 100.94 | 4.53 |
2000 | 99.87 | 2.75 | ||||||
2-hydroxybenzyl alcohol | 25–3000 | 0.0012 | 0.0252 | 0.9994 | 25 (12.5) | 200 | 99.86 | 7.41 |
2000 | 101.60 | 8.20 | ||||||
4-(dimethylamino) benzoic acid | 50–3000 | 0.0006 | −0.0200 | 0.9987 | 50 (50) | 200 | 96.25 | 8.47 |
2000 | 97.67 | 5.04 | ||||||
Vanillic acid | 50–3000 | 0.0004 | −0.0075 | 0.9997 | 50 (50) | 200 | 101.30 | 6.25 |
2000 | 100.13 | 7.95 | ||||||
Phloretic acid | 50–3000 | 0.0004 | −0.0346 | 0.9965 | 50 (50) | 200 | 96.56 | 9.33 |
2000 | 95.16 | 1.74 | ||||||
Homovanillic acid | 50–3000 | 0.0010 | −0.0366 | 0.9984 | 50 (25) | 200 | 99.34 | 5.39 |
2000 | 95.13 | 2.44 | ||||||
Tyrosol | 50–3000 | 0.0006 | −0.0654 | 0.9958 | 50 (50) | 200 | 86.97 | 7.94 |
2000 | 85.12 | 7.46 | ||||||
P-coumaric acid | 100–3000 | 0.0003 | −0.0561 | 0.9932 | 100 (50) | 200 | 102.85 | 8.35 |
2000 | 98.78 | 3.64 | ||||||
Syringic acid | 25–3000 | 0.0002 | 0.0015 | 0.9999 | 25 (12.5) | 200 | 102.24 | 4.13 |
2000 | 104.65 | 3.46 | ||||||
Gentisic acid | 50–3000 | 0.0004 | −0.0320 | 0.9976 | 50 (25) | 200 | 102.64 | 8.42 |
2000 | 103.96 | 9.09 | ||||||
Homoprotocatechuic acid | 50–3000 | 0.0004 | −0.0425 | 0.9951 | 50 (50) | 200 | 98.45 | 5.44 |
2000 | 100.68 | 5.12 | ||||||
Ferulic acid | 50–3000 | 0.0001 | −0.0136 | 0.9967 | 50 (50) | 200 | 98.13 | 3.41 |
2000 | 102.14 | 2.90 | ||||||
Isoferulic acid | 50–3000 | 0.0001 | −0.0098 | 0.9966 | 50 (50) | 200 | 99.68 | 5.62 |
2000 | 102.16 | 3.86 | ||||||
Dihydrocaffeic acid | 50–3000 | 0.0002 | −0.0262 | 0.9933 | 50 (50) | 200 | 101.05 | 4.49 |
2000 | 98.90 | 6.32 | ||||||
Caffeic acid | 25–3000 | 0.0003 | −0.0186 | 0.9972 | 25 (12.5) | 200 | 98.71 | 5.80 |
2000 | 98.49 | 2.24 |
Fruit Juices | ||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
Number | #1 | #2 | #3 | #4 | #5 | #6 | #7 | #8 | #9 | #10 | #11 | #12 |
Fruit Content (%) | 40 | 100 | 40 | 50 | 100 | 25 | 50 | 100 | 100 | 100 | 100 | 100 |
Composition (%) | 100% Blueberry | 48% Red Grape 32% Blueberry 20% Cranberry | 100% Blueberry | 51% Pomegranate 49% Apple | 100% Pomegranate | 84% Red Grape 8.4% Raspberry 4% Strawberry 3.6% Elder | 100% Red Grape | 100% Apple | 66% Red Grape 24% Cranberry 10% Goji | 100% Apple | 100% White Grape | 74% Pomegranate 23% Apple 3% Red Grape |
Benzoic acid | 1334 | 48976 | 864 | 542 | 869 | 645 | 947 | 2105 | 63763 | 2101 | 1469 | 1220 |
3,4-dimethoxy benzoic acid | 121 | 99 | nd | 45 | 80 | 88 | nd | 48 | nd | nd | 58 | nd |
Resorcinol | nd | nd | nd | nd | nd | nd | nd | nd | nd | nd | 84 | 40 |
4-(dimethylamino) benzoic acid | nd | 188 | nd | nd | nd | 106 | 290 | 98 | 247 | 105 | 793 | nd |
Vanillic acid | 450 | 1160 | 199 | 199 | 305 | 360 | 183 | 199 | 1250 | 97 | 167 | 114 |
Phloretic acid | nd | 408 | nd | nd | nd | 240 | 492 | 230 | 514 | 198 | 1223 | nd |
Homovanillic acid | nd | nd | nd | nd | nd | nd | nd | 98 | nd | 96 | nd | nd |
Tyrosol | 305 | 323 | 282 | 300 | 336 | 328 | 289 | 256 | 335 | 274 | nd | nd |
P-coumaric acid | 799 | 3631 | 837 | 784 | 733 | 730 | 980 | 722 | 5550 | 599 | nd | 578 |
Syringic acid | 2016 | 1576 | 675 | 74 | 117 | 546 | 389 | 123 | 901 | 109 | 35 | 86 |
Homoprotocatechuic acid | 365 | 385 | 351 | 334 | 379 | nd | 368 | 361 | 479 | 334 | 589 | 365 |
Ferulic acid | nd | nd | nd | nd | nd | nd | nd | 463 | 810 | 435 | 474 | nd |
Isoferulic acid | 392 | 597 | 459 | 328 | 385 | nd | 279 | nd | 1112 | nd | 302 | 396 |
Caffeic acid | 642 | 1022 | 661 | 403 | 236 | 347 | 465 | 302 | 1180 | 256 | 626 | 258 |
Total (ng/mL) | 6424 | 58365 | 4328 | 3009 | 3440 | 3390 | 4682 | 5005 | 76141 | 4604 | 5820 | 3057 |
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Incocciati, A.; Di Fabio, E.; Boffi, A.; Bonamore, A.; Macone, A. Rapid and Simultaneous Determination of Free Aromatic Carboxylic Acids and Phenols in Commercial Juices by GC-MS after Ethyl Chloroformate Derivatization. Separations 2022, 9, 9. https://doi.org/10.3390/separations9010009
Incocciati A, Di Fabio E, Boffi A, Bonamore A, Macone A. Rapid and Simultaneous Determination of Free Aromatic Carboxylic Acids and Phenols in Commercial Juices by GC-MS after Ethyl Chloroformate Derivatization. Separations. 2022; 9(1):9. https://doi.org/10.3390/separations9010009
Chicago/Turabian StyleIncocciati, Alessio, Elisa Di Fabio, Alberto Boffi, Alessandra Bonamore, and Alberto Macone. 2022. "Rapid and Simultaneous Determination of Free Aromatic Carboxylic Acids and Phenols in Commercial Juices by GC-MS after Ethyl Chloroformate Derivatization" Separations 9, no. 1: 9. https://doi.org/10.3390/separations9010009