Pro(anti)oxidant Properties of Amino Acids and Their Derivatives in The Presence of Fe2+ and Cu2+ Ions

Milach, O. A.; Мельситова, Инна Владимировна; Yurkova, Irina

doi:10.1134/s1070363220060080

Cited by 6 publications

(5 citation statements)

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“…However, these metal complexes may enhance the production of reactive HO ● radicals [ 21 , 22 ]. Milach et al [ 21 ] found that L-glutamic acid (Glu), Ala, His and L-cysteine (Cys) and its derivatives favour the HO ● formation in the presence of cupric ion – Cu(II). Furthermore, Cys also enhances the HO ● production in the Fe(II)/EDTA system.…”

Section: Introductionmentioning

confidence: 99%

“…electron transfer, catalysis, structural support and protein folding/unfolding [15][16][17][18][19][20]. However, these metal complexes may enhance the production of reactive HO • radicals [21,22]. Milach et al [21] found that L-glutamic acid (Glu), Ala, His and L-cysteine (Cys) and its derivatives favour the HO • formation in the presence of cupric ion -Cu(II).…”

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confidence: 99%

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

2023

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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 × 10 8 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.

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Section: Introductionmentioning

confidence: 99%

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confidence: 99%

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

2023

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“…Milach et al . [ 12 ] investigated the pro-oxidant properties of amino acids and their derivatives in the presence of Fe(II) and Cu(II) ions and illustrated the pro-oxidant activity of cysteine in the Fe(II)/EDTA system.…”

Section: Introductionmentioning

confidence: 99%

“…Besides, amino acids have also proven their pro-oxidant risks when transition metal ions are available in the environment. Milach et al [12] investigated the pro-oxidant properties of amino acids and their derivatives in the presence of Fe(II) and Cu(II) ions and illustrated the pro-oxidant activity of cysteine in the Fe(II)/EDTA system. L(-)-Leucine (Leu), a branched-chain amino acid, is an essential amino acid that cannot be synthesized from scratch by the organism fast enough to supply its demand, and it must therefore be obtained from the diet [3,[13][14][15].…”

Section: Introductionmentioning

confidence: 99%

Oxidation of l -leucine amino acid initiated by hydroxyl radical: are transition metal ions an enhancement factor?

et al. 2022

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Hydroxyl radical (HO·) formation initiated by the Fenton-type reactions of Fe and Cu complexes of l -leucine (Leu) amino acid as well as its oxidation reaction by HO· was computationally investigated by using the density functional theory method at the M05-2X/6-311++G(3df,2pd)//M05-2X/6-311++G(d,p) level of theory in the aqueous phase. The results showed that dipole-salt is the main form of Leu in the physiological condition. Leu exhibits high chelating potential towards both Fe(III)/Fe(II) and Cu(II)/Cu(I) ions with the most favourable coordinating positions at two oxygen atoms of the –COO functional group. Furthermore, the Leu-ions complexes show a high risk of HO· formation via Fenton-like reactions, especially when ascorbate anion exists in the environment as a reducing agent. Finally, the oxidation reaction of l -leucine by HO· demonstrated a relatively high overall apparent reaction rate, k overall , being 1.18 × 10 9 M −1 s −1 , in which formal hydrogen transfer reactions of the dipole-salt form occur as the primary mechanism. Consequently, the Leu oxidation by HO· radical can be promoted by the Fenton reaction enhancement of its transition metal complexes.

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“…[15][16][17][18][19][20] Abdel-Mottaleb et al 20 However, the chelation of natural amino acids toward transition metal ions may enhance the formation of reactive HO • radicals. 21,22 Milach et al 21 studied the amino acids and their derivatives using a fluorescent probe to assess their ability to accept and promote the HO • radicals' formation.…”

Section: Introductionmentioning

confidence: 99%

Influence of transition metal ions on the oxidation of L-proline amino acid initiated by HO● radical in the aqueous phase

Dao

Truong

Nguyen

2022

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The oxidation of L-proline (Pro) amino acid by HO • radical and the influence of transition metal ions on this process have been investigated 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 in the aqueous phase. The results show that Pro can be oxidized by HO • radical via formal hydrogen transfer (FHT) reactions at multiple sites, with the highest branching ratio found at hydrogen atoms H10 (30.04%) and H12 (25.60%). The overall rate constant at 298.15K is determined as 6.04 × 10 8 M -1 s -1 , and its expression from 250 to 400K is k=1.634×T 2.990 ×exp[1.591(kcal mol -1 )/RT] M -1 s -1 . In addition, Pro tends to form the stable mono-and bidentate complexes with both Fe and Cu ions via the-COO functional group of dipole-salt form, which significantly increases when the concentration of Pro doubles. The most stable Cu(II)-Pro complexes have high potential oxidant risks by enhancing the HO • radical formation when reducing agents such as superoxide anion, or ascorbate anion are available. Besides, the oxidant reaction of the high oxidation state complexes, including Fe(III)-Pro and Cu(II)-Pro, by HO • radical as FHT reactions have a lower rate constant than that of free-ligand, while the ones for SET reactions is extremely low even though they are higher than that of free-ligand. As a result, the Pro's oxidation enhancement of these complexes is negligible. In contrast, the rate constants of SET reactions of low oxidation state complexes (i.e., Fe(II)-Pro and Cu(I)-Pro) are likely to be many times faster than the oxidation rate of free ligand, and thus, these complexes promote the oxidation of Pro. Finally, the FHT chemical nature of HO-initiated oxidation for free Pro, Fe(III)-Pro, and Cu(II)-Pro complexes are evaluated to determine whether these processes occur via hydrogen atom transfer (HAT) or proton-coupled electron transfer (PCET).

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Pro(anti)oxidant Properties of Amino Acids and Their Derivatives in The Presence of Fe2+ and Cu2+ Ions

Cited by 6 publications

References 24 publications

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

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

Oxidation of l -leucine amino acid initiated by hydroxyl radical: are transition metal ions an enhancement factor?

Influence of transition metal ions on the oxidation of L-proline amino acid initiated by HO● radical in the aqueous phase

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Pro(anti)oxidant Properties of Amino Acids and Their Derivatives in The Presence of Fe2+ and Cu2+ Ions

Cited by 6 publications

References 24 publications

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

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

Oxidation of l -leucine amino acid initiated by hydroxyl radical: are transition metal ions an enhancement factor?

Influence of transition metal ions on the oxidation of L-proline amino acid initiated by HO● radical in the aqueous phase

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

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