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铜(I)-菲咯啉对甘油-2-磷酸衍生自由基中磷酸根β-消除速率的增强作用。脉冲辐解研究。

Enhancement of the rate of the beta-elimination of phosphate from radicals derived from glycerol-2-phosphate by Cu(I)-phenanthroline. A pulse radiolysis study.

作者信息

Goldstein S, Czapski G, Cohen H, Meyerstein D

机构信息

Department of Physical Chemistry, Hebrew University of Jerusalem, Israel.

出版信息

Free Radic Biol Med. 1990;9(5):371-9. doi: 10.1016/0891-5849(90)90014-a.

Abstract

Hydroxyl radicals abstract hydrogen atoms from glycerol-2-phosphate with a specific rate constant of (7.0 +/- 1.5) x 10(8) M-1s-1 forming the beta-phospho radical as the major product. At physiological pH this radical undergoes a beta-phosphate elimination with a rate constant less than or equal to 1 x 10(3) s-1. The beta-phospho radical reacts with Cu(I)-phenanthroline to produce an unstable transient with a metal-carbon sigma-bond which has an absorbance similar to that of the cuprous phenanthroline complex in the visible region. This intermediate decomposes via a beta-elimination of phosphate with a rate constant of (1.0 +/- 1.5) x 10(4) s-1, which was independent of the acidity in the pH range 4-9.

摘要

羟基自由基从甘油 - 2 - 磷酸中提取氢原子,其特定速率常数为(7.0 ± 1.5)×10⁸ M⁻¹s⁻¹,形成β - 磷酸自由基作为主要产物。在生理pH值下,该自由基进行β - 磷酸消除反应,速率常数小于或等于1×10³ s⁻¹。β - 磷酸自由基与Cu(I) - 菲罗啉反应生成一种具有金属 - 碳σ键的不稳定瞬态物质,其在可见光区域的吸光度与亚铜菲罗啉配合物相似。该中间体通过β - 磷酸消除反应分解,速率常数为(1.0 ± 1.5)×10⁴ s⁻¹,在pH值4 - 9范围内与酸度无关。

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