Transient kinetics of electron-transfer reactions of flavodoxins.

Transient kinetics of electron-transfer reactions of flavodoxins.
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黄素氧还蛋白电子转移反应的瞬态动力学。

DOI:
10.1021/bi00521a005
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发表时间:
1981
期刊:
影响因子:
2.9
通讯作者:
Tollin,G
Tollin,G
中科院分区:
生物学3区
文献类型:
--
作者:
Jung,J;Tollin,G

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Jin Jung* 1和Gordon Tollin* 摘要:采用停流法和激光光解法研究了完全还原的核黄素的电子转移反应速率和巴氏梭菌核黄素氧还蛋白的三种氧化态。研究了正常和7,8-二氯黄素类似物。氧化还原试剂包括氧、铁氰化物、EDTA铁和几种C型细胞色素作为氧化剂,5-脱氮核黄素的半醌作为还原剂。二氯类似物黄氧还蛋白的半醌形式的氧化速率对氧化剂浓度的依赖性为反应途径中存在络合物提供了明确的证据。速率常数的比较表明,二氯取代降低了黄素氧还蛋白半醌氧化的速率至少1-2个数量级。已发现限制性一级速率常数取决于对黄素多辛进行的高分辨率X射线晶体结构测定(Burnett等人,1974; Mayhew & Ludwig,1975; Smith等人,1977)为研究黄素性质与结合辅酶的蛋白质环境之间的关系提供了极好的机会。通过X射线分析所阐明的结构特征如下:(a)FMN辅因子的二甲苯环部分暴露于溶剂中,(B)黄素的N5-C4 a-C10 a-N1区,即分子中最明显的氧化还原活性部分,被蛋白质结构所屏蔽;(c)黄素的异咯嗪环在氧化态(PF)、半还原态(PFH·)和完全还原态(PFH”)的所有三种氧化还原态中被限制为平面。在下文所述的工作中,我们解决了以下问题:
Jin Jung* 1 and Gordon Tollin* abstract: Stopped-flow and laser photolysis methodshave been used to investigate the rates of electron-transfer reactions of fully reduced riboflavin and the threeoxidation states of Clostridium pasteurianumflavodoxin. Both normal and 7, 8-dichloroflavin analogues were studied. Redox reagents included oxygen, ferricyanide, ferric EDTA, and several c-type cytochromes as oxidants and the semiquinone of 5-deaza-riboflavin as a reductant. The dependence of the rate of oxidation of the semiquinone form of the dichloro analogue flavodoxin upon oxidant concentration has provided clear evidence for the existence of a complex in the reaction pathway. Rate constant comparisons demonstrate that dichloro substitution decreases the rate of flavodoxin semiquinone oxidation byat least 1-2 orders of magnitude. The limiting first-order rate constants were found to be dependent on theThe high-resolution X-ray crystal structure determinations which have been carried out on the flavodoxins (Burnett et al., 1974; Mayhew & Ludwig, 1975; Smith et al., 1977) provide an excellent opportunity to investigate the relationships which exist between flavin properties and the protein envi-ronment of the bound coenzyme. Among the structural features which have been elucidated by the X-ray analysis are the following:(a) the dimethylbenzene ring of the FMN cofactor is partially exposed to the solvent;(b) the N5-C4a-C10a-Nl region1 of the flavin, ie, the most obviously re-dox-active part of the molecule, is shielded by the protein structure;(c) the isoalloxazine ring of the flavin is constrained to be planar in all three redoxstates, oxidized (PF), half-re-duced (PFH·), and fully reduced (PFH"). In the work to be described below, we have addressed the following questions:
通过化学和同位素取代衍生物的电子自旋共振光谱揭示中性黄素自由基的化学和电子结构。
DOI: --
发表时间: 1970
期刊: European Journal of Biochemistry
影响因子: --
作者:
F. Müller;P. Hemmerich;A. Ehrenberg;G. Palmer;V. Massey
通讯作者: V. Massey
黄素类似物的一种电子还原产物:氰基异恶嗪和脱氮异恶嗪
DOI: --
发表时间: 1979
期刊:
影响因子: --
作者:
G. Tollin;R. Chan;Thomas R. Malefyt;T. C. Bruice
通讯作者: T. C. Bruice
2 黄素氧还蛋白和电子传递黄素蛋白
DOI: --
发表时间: 1975
期刊:
影响因子: --
作者:
S. Mayhew;M. Ludwig
通讯作者: M. Ludwig
黄素氧还蛋白中黄素结合的研究。
DOI: --
发表时间: 1971
期刊: Biochimica et Biophysica Acta
影响因子: --
作者:
S. Mayhew
通讯作者: S. Mayhew