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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Mechanistic aspects of alloxan diabetogenic activity: A key role of keto-enol inversion of dialuric acid on ionization
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Mechanistic aspects of alloxan diabetogenic activity: A key role of keto-enol inversion of dialuric acid on ionization

机译：四氧嘧啶致糖尿病活性的机理方面：乙醛酸的酮-烯醇转化对电离的关键作用

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摘要

The inversion of the keto-enol stability order of dialuric acid on ionization was calculated and verified experimentally. The radical cations in both forms were characterized. The spectrum of the keto form was observed upon direct ionization of dialuric acid under matrix conditions, whereas the enol form was formed upon a sequential electron-proton-proton attachment to alloxan under acidic aqueous condition. Facilitation of the one-electron oxidation of dialuric acid upon its enolization can result in a more effective formation of superoxide radical anion in the process of its auto-oxidation. This process is discussed in reference to the alloxan diabetogenic action. Both neutral keto and enol forms are energetically close, and under favorable conditions, the auto-oxidation of dialuric acid could involve participation of the enol form.
机译：计算并通过实验验证了二硬脂酸在电离时酮-烯醇稳定顺序的反演。对两种形式的自由基阳离子进行了表征。酮形式的光谱在基质条件下直接电离二乙酸时观察到，而烯醇形式是在酸性水溶液条件下依序将电子-质子-质子连接到四氧嘧啶上而形成的。二烯酸在烯醇化时促进单电子氧化可导致超氧自由基阴离子在其自氧化过程中更有效地形成。参照四氧嘧啶的致糖尿病作用讨论了该过程。中性酮和烯醇形式在能量上都接近，并且在有利条件下，透析酸的自氧化可涉及烯醇形式的参与。

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