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Revisiting the HO^●-initiated oxidation of L-proline amino acid in the aqueous phase: influence of transition metal ions.

ABSTRACT: The oxidation of L-proline (Pro) by HO^● radical in water and the influence of transition metal ions on this process has been revisited by using the density functional theory (DFT) method at the M05-2X/6-311 + + G(3df,3pd)//M05-2X/6-311 + + G(d,p) level of theory at the temperature of 298.15 K. The main reactive sites of the HO^●-initiated oxidation of Pro via hydrogen atom transfer (HAT) reactions are at the β- and γ-carbon, with the branching ratios being 44.6% and 39.5%, respectively. The overall rate constant at 298.15 K is 6.04 × 10⁸ M^-1 s^-1. In addition, Pro tends to form stable complexes with both Fe and Cu ions via the -COO functional group of dipole-salt form. The most stable Cu(II)-Pro complexes have high oxidant risks in enhancing the HO^● formation in the presence of reducing agents. Besides this, the high oxidation state metal complexes, i.e. Fe(III)-Pro and Cu(II)-Pro, may be oxidized by HO^● radical via HAT reactions but with a lower rate constant than that of free-Pro. By contrast, the low oxidation state metal complexes (i.e. Fe(II)-Pro and Cu(I)-Pro) have higher oxidation risks than the free ligands, and thus, the complexation enhances the oxidation of Pro amino acid.

SUBMITTER: Truong DH

PROVIDER: S-EPMC10245202 | biostudies-literature | 2023 Jun

REPOSITORIES: biostudies-literature

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Revisiting the HO●-initiated oxidation of L-proline amino acid in the aqueous phase: influence of transition metal ions.

Truong Dinh Hieu DH Lan Nguyen Thi Huong TH Dao Duy Quang DQ

Royal Society open science 20230607 6

The oxidation of L-proline (Pro) by HO● radical in water and the influence of transition metal ions on this process has been revisited by using the density functional theory (DFT) method at the M05-2X/6-311 + + G(3df,3pd)//M05-2X/6-311 + + G(d,p) level of theory at the temperature of 298.15 K. The main reactive sites of the HO●-initiated oxidation of Pro via hydrogen atom transfer (HAT) reactions are at the β- and γ-carbon, with the branching ratios being 44.6% and 39.5%, r ...[more]

PMID: 37293362

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Dataset Information

Revisiting the HO^●-initiated oxidation of L-proline amino acid in the aqueous phase: influence of transition metal ions.

Publications

Revisiting the HO<sup>●</sup>-initiated oxidation of L-proline amino acid in the aqueous phase: influence of transition metal ions.

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