Structural Study on Hypochlorous Acid-Mediated Chlorination of Betanin and Its Decarboxylated Derivatives from an Anti-Inflammatory Beta vulgaris L. Extract
Abstract
:1. Introduction
2. Results and Discussion
2.1. High-Resolution Mass Spectrometric Study on Mono-Chlorinated Betanin and Its Decarboxylated Derivatives
2.2. NMR Structural Elucidation of 18-Chloro-Betanin and Its Decarboxylated Derivatives
3. Materials and Methods
3.1. Reagents
3.2. Preparation of Betalains from Beta vulgaris L. Extracts
3.3. Chromatographic and Mass Spectrometric Determination of the Identity of the Generated Chlorinated Betacyanins in the Chemical (NaOCl) and Enzymatic Systems (MPO)
3.4. Preparative Chlorination of Betanin and Its Decarboxylated Derivatives
3.5. Chromatographic Analysis by LC-DAD-ESI-MS/MS System
3.6. NMR Experiments
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Sample Availability: Samples of the compounds are not available from the authors. |
No. | Compound | λmax [nm] | m/z [M + H]+ | m/z from MS/MS of [M + H]+ |
---|---|---|---|---|
1 | betanin | 538 | 551 | 389 |
1a | 18-chloro-betanin | 522 | 585 | 423 |
2 | 17-decarboxy-betanin | 505 | 507 | 345 |
2a | 18-chloro-17-decarboxy-betanin | 524 | 541 | 379 |
3 | 15-decarboxy-betanin | 528 | 507 | 345 |
3a | 18-chloro-15-decarboxy-betanin | 514 | 541 | 379 |
4 | 2-decarboxy-betanin | 533 | 507 | 345 |
4a | 18-chloro-2-decarboxy-betanin | 525 | 541 | 379 |
5 | betanidin | 540 | 389 | 345 |
5a | 18-chloro-betanidin | 528 | 423 | 377 |
6/6’ | 2,17-bidecarboxy-betanin/-isobetanin | 507 | 463 | 301 |
6a | 18-chloro-2,17-bidecarboxy-betanin | 519 | 497 | 335 |
7 | neobetanin | 466 | 549 | 387; 343; 299 |
Pigment and Fragmentation Ions a | [M + H]+ Molecular Formula | [M + H]+ Observed | [M + H]+ Predicted | Error [mDa] | Error [ppm] | MS2 Ions |
---|---|---|---|---|---|---|
18-chloro-betanin (1a) | C24H26ClN2O13 | 585.1127 | 585.1118 | 0.9 | 1.54 | 423; 377; 341; 295 |
nl: -Glc | C18H16ClN2O8 | 423.0599 | 423.0590 | 0.9 | 2.13 | 387; 377; 341; 331; 297; 295; 287; 253; 251; 150 |
18-chloro-17-decarboxy- -betanin (2a) | C23H26ClN2O11 | 541.1211 | 541.1220 | −0.9 | −1.66 | 379; 343; 333; 297; 253 |
nl: -Glc | C17H16ClN2O6 | 379.0687 | 379.0691 | −0.4 | −1.06 | 343; 333; 299; 297; 287; 255; 253; 150; 132 |
18-chloro-15-decarboxy- -betanin (3a) | C23H26ClN2O11 | 541.1234 | 541.1220 | 1.4 | 2.59 | 379; 333; 297; 251 |
nl: -Glc | C17H16ClN2O6 | 379.0680 | 379.0691 | −1.1 | −2.90 | 343; 333; 297; 287; 253; 251; 150; 132 |
18-chloro-2-decarboxy- -betanin (4a) | C23H26ClN2O11 | 541.1239 | 541.1220 | 1.9 | 3.51 | 379; 333; 297; 253 |
nl: -Glc | C17H16ClN2O6 | 379.0697 | 379.0691 | 0.6 | 1.58 | 343; 333; 297; 253; 150; 132 |
18-chloro-2,17-bidecarboxy--betanin (6a) | C22H26ClN2O9 | 497.1339 | 497.1321 | 1.8 | 3.62 | 335; 299; 253 |
nl: -Glc | C16H16ClN2O4 | 335.0785 | 335.0793 | −0.8 | −2.39 | 299; 289; 255; 253; 150 |
18-Chloro-Betanin (1a) | 18-Chloro-17-Decarboxy-Betanin (2a) | 18-Chloro-2,17-Bidecarboxy-Betanin (6a) | ||||
---|---|---|---|---|---|---|
No. | 1H NMR a | 13C NMR b,c | 1H NMR a | 13C NMR b,c | 1H NMR a | 13C NMR b,c |
2 or 2a/b | 4.90, dd, 2.1; 8.4 | 68.0 | 4.72, dd, 3.1, 10.5 | 67.8 | 4.04, bt | 53.1 |
3a/b | 3.60 (overlap) 3.19, dd, 2.5; 16.4 | 36.2 | 3.61 (overlap) 3.18, dd, 3.4, 16.9 | 35.6 | 3.09, bt | 29.5 |
4 | 7.12, s | 116.7 | 7.09, s | 115.9 | 6.97, s | 115.9 |
5 | 147.1 | 147.2 | 146.1 | |||
6 | 149.4 | 148.7 | 147.8 | |||
7 | 7.00, s | 102.9 | 7.02, s | 102.6 | 6.82, s | 102.5 |
8 | 140.2 | 139.7 | 138.6 | |||
9 | 127.3 | 126.8 | 128.5 | |||
10 | 178.4 | 177.9 | - | |||
11 | 8.29, d, 12.4 | 147.6 | 8.21, d, 12.5 | 146.9 | 8.02, d, 11.9 | 146.7 |
12 | 5.97, d, 12.4 | 105.7 | 5.83, d, 12.6 | 104.4 | 5.83, d, 12.0 | 104.7 |
13 | 163.8 | 156.8 | 156.1 | |||
14a/b | 3.37, bm | 30.8 | 3.22, bm, | 30.2 | 3.18, bm | 30.4 |
15a/b | 4.48, t, 7.5 | 55.7 | 4.22, t, 8.5 | 56.3 | 4.22, t, 7.1 | 56.7 |
17 | 158.9 | 7.73, s | 156.3 | 7.65, s | 156.2 | |
18 | 105.6 | 108.2 | 109.0 | |||
19 | 176.7 | 177.1 | 177.8 | |||
20 | 169.7 d | - | - | |||
1’ | 5.05, d, 6.8 | 104.5 | 5.04, d, 7.2 | 104.2 | 5.05, d, 6.9 | 103.9 |
2’ | 3.59 (overlap) | 79.2 | 3.56 (overlap) | 79.1 | 3.58 (overlap) | 79.2 |
3’ | 3.52 | 72.3 | 3.49 | 72.2 | 3.51 | 72.6 |
4’ | 3.61 (overlap) | 75.8 | 3.58 (overlap) | 75.9 | 3.55 (overlap) | 75.6 |
5’ | 3.61 (overlap) | 78.6 | 3.59 (overlap) | 78.4 | 3.60 (overlap) | 78.4 |
6’a/b | 3.92, dd, 2.1, 12.5 3.77, dd, 5.4, 12.5 | 63.4 | 3.92, dd, 2.2, 12.5 3.76, dd, 5.4, 12.6 | 63.3 | 3.94, dd, 2,6; 12.3 3.76, dd, 5.3; 12.3 | 63.6 |
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Kumorkiewicz-Jamro, A.; Starzak, K.; Sutor, K.; Nemzer, B.; Pietrzkowski, Z.; Popenda, Ł.; Wybraniec, S. Structural Study on Hypochlorous Acid-Mediated Chlorination of Betanin and Its Decarboxylated Derivatives from an Anti-Inflammatory Beta vulgaris L. Extract. Molecules 2020, 25, 378. https://doi.org/10.3390/molecules25020378
Kumorkiewicz-Jamro A, Starzak K, Sutor K, Nemzer B, Pietrzkowski Z, Popenda Ł, Wybraniec S. Structural Study on Hypochlorous Acid-Mediated Chlorination of Betanin and Its Decarboxylated Derivatives from an Anti-Inflammatory Beta vulgaris L. Extract. Molecules. 2020; 25(2):378. https://doi.org/10.3390/molecules25020378
Chicago/Turabian StyleKumorkiewicz-Jamro, Agnieszka, Karolina Starzak, Katarzyna Sutor, Boris Nemzer, Zbigniew Pietrzkowski, Łukasz Popenda, and Sławomir Wybraniec. 2020. "Structural Study on Hypochlorous Acid-Mediated Chlorination of Betanin and Its Decarboxylated Derivatives from an Anti-Inflammatory Beta vulgaris L. Extract" Molecules 25, no. 2: 378. https://doi.org/10.3390/molecules25020378