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柔红霉素氧化还原反应的脉冲辐解研究:氧化还原循环还是糖苷键裂解?

Pulse radiolysis study of daunorubicin redox reactions: redox cycles or glycosidic cleavage?

作者信息

Houée-Levin C, Gardès-Albert M, Ferradini C

出版信息

J Free Radic Biol Med. 1986;2(2):89-97. doi: 10.1016/s0748-5514(86)80056-3.

DOI:10.1016/s0748-5514(86)80056-3
PMID:3029211
Abstract

Two aspects of daunorubicin reactivity were investigated by pulse radiolysis. The reactions of O2 and O2- with the semiquinone and the hydroquinone transients of daunorubicin were determined and their rate constants measured. Although O2- can reduce the drug and its semiquinone form, it is a more powerful oxidant towards the two reduced transients. The hydroquinone daunorubicin glycosidic cleavage in aqueous solution was studied. Three intermediates were seen and characterized by their absorption spectra, their formation and decay kinetics. The competition between these two main processes was evaluated in the conditions of pulse radiolysis. Even under low O2 partial pressures the redox cycles are much more rapid than the glycosidic cleavage and a relatively high O2- steady state is settled. Biological implications are discussed.

摘要

通过脉冲辐解研究了柔红霉素反应性的两个方面。测定了O₂和O₂⁻与柔红霉素半醌和对苯二酚瞬态的反应,并测量了它们的速率常数。虽然O₂⁻可以还原药物及其半醌形式,但它对这两种还原瞬态是更强的氧化剂。研究了柔红霉素对苯二酚糖苷在水溶液中的裂解。观察到三种中间体,并通过它们的吸收光谱、形成和衰减动力学对其进行了表征。在脉冲辐解条件下评估了这两个主要过程之间的竞争。即使在低O₂分压下,氧化还原循环也比对糖苷裂解快得多,并且建立了相对较高的O₂⁻稳态。讨论了其生物学意义。

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