关于二氢烟酰胺还原过程中的电子转移：氧化黄素和黄素自由基与N-苄基-1,5-二氢烟酰胺的反应
Concerning 1e- transfer in reduction by dihydronicotinamide: reaction of oxidized flavin and flavin radical with N-benzyl-1,5-dihydronicotinamide.
作者信息
Powell M F, Wong W H, Bruice T C
出版信息
Proc Natl Acad Sci U S A. 1982 Aug;79(15):4604-8. doi: 10.1073/pnas.79.15.4604.
Abstract
The rates of reaction of 5-ethyl-3-methyllumiflavinium perchlorate and 5-ethyl-3-methyllumiflavinyl radical with a NADH analogue, N-benzyl-1,4-dihydronicotinamide, were measured anaerobically in tert-butanol and 5% acetonitrile/95% tert-butanol solutions at 30 degrees C. The biphasic kinetics observed for the reaction of flavin radical with dihydronicotinamide were interpreted in terms of both a 1e- and a 2e- mechanism; the former was found to be inadequate based on experimental requirements of the mechanism. The dihydronicotinamide reacts preferentially with oxidized flavin rather than flavin radical, even when the concentration of oxidized flavin is at a concentration 5 orders of magnitude less than that of radical. These studies show that the "hydride" reduction of oxidized flavin by BNAH is more facile than is the 1e- reduction of flavin radical by BNAH.
摘要
在30℃下，于叔丁醇以及5%乙腈/95%叔丁醇溶液中，对高氯酸5-乙基-3-甲基荧光黄素鎓与5-乙基-3-甲基荧光黄素基与NADH类似物N-苄基-1,4-二氢烟酰胺的反应速率进行了厌氧测定。观察到的黄素基与二氢烟酰胺反应的双相动力学可根据单电子和双电子机制来解释；基于该机制的实验要求，发现前者并不充分。即使氧化型黄素的浓度比自由基的浓度低5个数量级，二氢烟酰胺仍优先与氧化型黄素而非黄素基发生反应。这些研究表明，BNAH对氧化型黄素的“氢化物”还原比BNAH对黄素基的单电子还原更容易。
相似文献
1
Concerning 1e- transfer in reduction by dihydronicotinamide: reaction of oxidized flavin and flavin radical with N-benzyl-1,5-dihydronicotinamide.关于二氢烟酰胺还原过程中的电子转移：氧化黄素和黄素自由基与N-苄基-1,5-二氢烟酰胺的反应
Proc Natl Acad Sci U S A. 1982 Aug;79(15):4604-8. doi: 10.1073/pnas.79.15.4604.
2
Nicotinamide-dependent one-electron and two-electron (flavin) oxidoreduction: thermodynamics, kinetics, and mechanism.烟酰胺依赖性单电子和双电子（黄素）氧化还原：热力学、动力学及机制
Eur J Biochem. 1976 Aug 1;67(1):67-80. doi: 10.1111/j.1432-1033.1976.tb10634.x.
3
Intermolecular complexes between N-methyl-1,4-dihydronicotinamide and flavines. The influence of steric and electronic factors on complex formation and the rate of flavine-dependent dihydronicotinamide dehydrogenation.
Biochemistry. 1975 Jul 15;14(14):3172-6. doi: 10.1021/bi00685a021.
4
Negative kinetic temperature effect on the hydride transfer from NADH analogue BNAH to the radical cation of N-benzylphenothiazine in acetonitrile.在乙腈中，负动力学温度对从NADH类似物BNAH到N-苄基吩噻嗪自由基阳离子的氢化物转移的影响。
J Org Chem. 2006 Sep 1;71(18):7007-15. doi: 10.1021/jo061145c.
5
Mechanisms of electron-transfer oxidation of NADH analogues and chemiluminescence. Detection of the keto and enol radical cations.NADH类似物的电子转移氧化机制与化学发光。酮基和烯醇自由基阳离子的检测。
J Am Chem Soc. 2003 Apr 23;125(16):4808-16. doi: 10.1021/ja029623y.
6
Flavin-nicotinamide biscoenzymes: models for the interaction between NADH (NADPH) and flavin in flavoenzymes. Reaction rates and physicochemical properties of intermediate species.
Eur J Biochem. 1975 Jan 2;50(2):351-6. doi: 10.1111/j.1432-1033.1975.tb09810.x.
7
Structure and properties of 5-deazaflavin radicals as compared to natural flavosemiquinones.与天然黄素半醌相比，5-脱氮黄素自由基的结构与性质
Biochim Biophys Acta. 1981 Apr 3;673(4):570-93. doi: 10.1016/0304-4165(81)90487-6.
8
Sequential electron-transfer and proton-transfer pathways in hydride-transfer reactions from dihydronicotinamide adenine dinucleotide analogues to non-heme oxoiron(IV) complexes and p-chloranil. Detection of radical cations of NADH analogues in acid-promoted hydride-transfer reactions.从二氢烟酰胺腺嘌呤二核苷酸类似物到非血红素氧代铁（IV）配合物和对苯醌的氢化物转移反应中的顺序电子转移和质子转移途径。在酸促进的氢化物转移反应中检测NADH类似物的自由基阳离子。
J Am Chem Soc. 2008 Nov 12;130(45):15134-42. doi: 10.1021/ja804969k. Epub 2008 Oct 21.
9
Coenzyme models. 10. Rapid oxidation of NADH by a flavin immobilized in cationic polyelectrolytes.
Macromolecules. 1978 Jan-Feb;11(1):65-8. doi: 10.1021/ma60061a012.
10
Radical mechanisms for 1,5-dihydroflavin reduction of carbonyl compounds.羰基化合物1,5-二氢黄素还原的自由基机制。
Proc Natl Acad Sci U S A. 1975 May;72(5):1763-7. doi: 10.1073/pnas.72.5.1763.
引用本文的文献
1
Asymmetric azidohydroxylation of styrene derivatives mediated by a biomimetic styrene monooxygenase enzymatic cascade.由仿生苯乙烯单加氧酶酶促级联介导的苯乙烯衍生物的不对称叠氮羟基化反应。
Catal Sci Technol. 2021 Jun 14;11(15):5077-5085. doi: 10.1039/d1cy00855b. eCollection 2021 Aug 2.
2
The mechanism of the quinone reductase reaction of pig heart lipoamide dehydrogenase.猪心脂酰胺脱氢酶醌还原酶反应的机制。
Biochem J. 1990 Jul 1;269(1):101-5. doi: 10.1042/bj2690101.
本文引用的文献
1
CHEMICAL AND PHOTOCHEMICAL REDUCTIONS OF FLAVIN NUCLEOTIDES AND ANALOGS.黄素核苷酸及其类似物的化学还原和光化学还原
Biochemistry. 1964 Mar;3:384-93. doi: 10.1021/bi00891a014.
2
Kinetics and mechanism of oxidation-reduction reactions between pyridine nucleotides and flavins.吡啶核苷酸与黄素之间氧化还原反应的动力学及机制
Biochemistry. 1970 May 26;9(11):2219-24. doi: 10.1021/bi00813a001.
3
The kinetics of lumiflavin reduction by N-methyl-1,4-dihydronicotinamide: direct evidence for a preequilibrium complex between oxidized lumiflavin and N-methyl-1,4-dihydronicotinamide.
Biochem Biophys Res Commun. 1973 May 15;52(2):447-52. doi: 10.1016/0006-291x(73)90732-8.
4
Demonstration of a direct hydrogen transfer between NADH and a deazaflavin.
J Am Chem Soc. 1972 Sep 6;94(8):6548-9. doi: 10.1021/ja00773a052.
5
The chemistry of flavins and flavoproteins. 3. The reaction of dihydrolipoic acid with flavins.黄素与黄素蛋白的化学。3. 二氢硫辛酸与黄素的反应。
Biochim Biophys Acta. 1967 May 9;131(3):498-507. doi: 10.1016/0005-2728(67)90009-6.
6
Reactions of dihydronicotinamides. I. Evidence for an intermediate in the reduction of trifluoroacetophenone by 1-substituted dihydronicotinamides.
J Am Chem Soc. 1971 Dec;93(24):6694-6. doi: 10.1021/ja00753a072.
7
Studies on the mechanism of action of the flavoenzyme lactate oxidase. Oxidation and elimination with beta-chlorolactate.黄素酶乳酸氧化酶作用机制的研究。β-氯乳酸的氧化与消除
J Biol Chem. 1973 Oct 25;248(20):7049-54.
8
9
Intermolecular complexes between N-methyl-1,4-dihydronicotinamide and flavines. The influence of steric and electronic factors on complex formation and the rate of flavine-dependent dihydronicotinamide dehydrogenation.
Biochemistry. 1975 Jul 15;14(14):3172-6. doi: 10.1021/bi00685a021.
10
Flavin-nicotinamide biscoenzymes: models for the interaction between NADH (NADPH) and flavin in flavoenzymes. Reaction rates and physicochemical properties of intermediate species.
Eur J Biochem. 1975 Jan 2;50(2):351-6. doi: 10.1111/j.1432-1033.1975.tb09810.x.
Zotero 插件