Structural Effects on the Antioxidant Properties of Amino Acid Betaxanthins
Betaxanthins are natural products with high antioxidant and anti-inflammatory properties. Here, we describe the semisynthesis of twenty-one betaxanthins derived from proteinogenic amino acids, including the elusive betaxanthin of <span style="font-variant: small-caps;">l</span>...
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-11-01
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| Series: | Antioxidants |
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| Online Access: | https://www.mdpi.com/2076-3921/11/11/2259 |
| _version_ | 1797466053357338624 |
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| author | Larissa Cerrato Esteves Caroline Oliveira Machado Letícia Christina Pires Gonçalves Victor Fernandes Cavalcante Guilherme Obeid Thiago Carita Correra Erick Leite Bastos |
| author_facet | Larissa Cerrato Esteves Caroline Oliveira Machado Letícia Christina Pires Gonçalves Victor Fernandes Cavalcante Guilherme Obeid Thiago Carita Correra Erick Leite Bastos |
| author_sort | Larissa Cerrato Esteves |
| collection | DOAJ |
| description | Betaxanthins are natural products with high antioxidant and anti-inflammatory properties. Here, we describe the semisynthesis of twenty-one betaxanthins derived from proteinogenic amino acids, including the elusive betaxanthin of <span style="font-variant: small-caps;">l</span>-cysteine and two betaxanthins derived from <span style="font-variant: small-caps;">l</span>-lysine, and rationalize their antioxidant properties in mechanistic terms. The antioxidant capacity and redox potential of these betaxanthins were compared to those of model betaxanthins derived from dopamine, <span style="font-variant: small-caps;">l</span>-DOPA (L-3,4-dihydroxyphenylalanine), and pyrrolidine and structure–property relationships were established by using matched molecular pair analysis and a model developed using a genetic algorithm. Either a phenol or indole moiety enhance the antioxidant capacity of betaxanthins, which is overall much higher than that of their amino acid precursors and standard antioxidants, except for the cysteine-betaxanthin. The one-electron oxidation of amino acid betaxanthins produces radicals stabilized in multiple centers, as demonstrated by quantum chemical calculations. |
| first_indexed | 2024-03-09T18:31:29Z |
| format | Article |
| id | doaj.art-a2bb1ab6558141da88637d72283ec0ca |
| institution | Directory Open Access Journal |
| issn | 2076-3921 |
| language | English |
| last_indexed | 2024-03-09T18:31:29Z |
| publishDate | 2022-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Antioxidants |
| spelling | doaj.art-a2bb1ab6558141da88637d72283ec0ca2023-11-24T07:32:18ZengMDPI AGAntioxidants2076-39212022-11-011111225910.3390/antiox11112259Structural Effects on the Antioxidant Properties of Amino Acid BetaxanthinsLarissa Cerrato Esteves0Caroline Oliveira Machado1Letícia Christina Pires Gonçalves2Victor Fernandes Cavalcante3Guilherme Obeid4Thiago Carita Correra5Erick Leite Bastos6Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, São Paulo 05508-000, SP, BrazilDepartamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, São Paulo 05508-000, SP, BrazilDepartamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, São Paulo 05508-000, SP, BrazilDepartamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, São Paulo 05508-000, SP, BrazilDepartamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, São Paulo 05508-000, SP, BrazilDepartamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, São Paulo 05508-000, SP, BrazilDepartamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, São Paulo 05508-000, SP, BrazilBetaxanthins are natural products with high antioxidant and anti-inflammatory properties. Here, we describe the semisynthesis of twenty-one betaxanthins derived from proteinogenic amino acids, including the elusive betaxanthin of <span style="font-variant: small-caps;">l</span>-cysteine and two betaxanthins derived from <span style="font-variant: small-caps;">l</span>-lysine, and rationalize their antioxidant properties in mechanistic terms. The antioxidant capacity and redox potential of these betaxanthins were compared to those of model betaxanthins derived from dopamine, <span style="font-variant: small-caps;">l</span>-DOPA (L-3,4-dihydroxyphenylalanine), and pyrrolidine and structure–property relationships were established by using matched molecular pair analysis and a model developed using a genetic algorithm. Either a phenol or indole moiety enhance the antioxidant capacity of betaxanthins, which is overall much higher than that of their amino acid precursors and standard antioxidants, except for the cysteine-betaxanthin. The one-electron oxidation of amino acid betaxanthins produces radicals stabilized in multiple centers, as demonstrated by quantum chemical calculations.https://www.mdpi.com/2076-3921/11/11/2259betalainsbetaxanthinsamino acidssemisynthesisplant pigments |
| spellingShingle | Larissa Cerrato Esteves Caroline Oliveira Machado Letícia Christina Pires Gonçalves Victor Fernandes Cavalcante Guilherme Obeid Thiago Carita Correra Erick Leite Bastos Structural Effects on the Antioxidant Properties of Amino Acid Betaxanthins Antioxidants betalains betaxanthins amino acids semisynthesis plant pigments |
| title | Structural Effects on the Antioxidant Properties of Amino Acid Betaxanthins |
| title_full | Structural Effects on the Antioxidant Properties of Amino Acid Betaxanthins |
| title_fullStr | Structural Effects on the Antioxidant Properties of Amino Acid Betaxanthins |
| title_full_unstemmed | Structural Effects on the Antioxidant Properties of Amino Acid Betaxanthins |
| title_short | Structural Effects on the Antioxidant Properties of Amino Acid Betaxanthins |
| title_sort | structural effects on the antioxidant properties of amino acid betaxanthins |
| topic | betalains betaxanthins amino acids semisynthesis plant pigments |
| url | https://www.mdpi.com/2076-3921/11/11/2259 |
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