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烷基钴胺素自由基对中磁场依赖性重组的起源。

The origin of magnetic field dependent recombination in alkylcobalamin radical pairs.

作者信息

Natarajan E, Grissom C B

机构信息

Department of Chemistry, University of Utah, Salt Lake City 84112, USA.

出版信息

Photochem Photobiol. 1996 Aug;64(2):286-95. doi: 10.1111/j.1751-1097.1996.tb02460.x.


DOI:10.1111/j.1751-1097.1996.tb02460.x
PMID:8760570
Abstract

Magnetic field effect studies of alkylcobalamin photolysis provide evidence for the formation of a reactive radical pair that is born in the singlet spin state. The radical pair recombination process that is responsible for the magnetic field dependence of the continuous-wave (CW) quantum yield is limited to the diffusive radical pair. Although the geminate radical pair of adenosylcob(III)alamin also undergoes magnetic field dependent recombination (A.M. Chagovetz and C. B. Grissom, J. Am. Chem. soc. 115, 12152-12157, 1993), this process does not account for the magnetic field dependence of the CW quantum yield that is only observed in viscous solvents. Glycerol and ethylene glycol increase the microviscosity of the solution and thereby increase the lifetime of the spin-correlated diffusive radical pair. This enables magnetic field dependent recombination among spin-correlated diffusive radical pairs in the solvent cage. Magnetic field dependent recombination is not observed in the presence of nonviscosigenic alcohols such as isopropanol, thereby indicating the importance of the increased microviscosity of the medium. Paramagnetic radical scavengers that trap alkyl radicals that escape the solvent cage do not diminish the magnetic field effect on the CW quantum yield, thereby ruling out radical pair recombination among randomly diffusing radical pairs, as well as excluding the involvement of solvent-derived radicals. Magnetic field dependent recombination among alkylcobalamin radical pairs has been simulated by a semi-classical model of radical pair dynamics and recombination. These calculations support the existence of a singlet radical pair precursor.

摘要

烷基钴胺素光解的磁场效应研究为单重态自旋态下产生的反应性自由基对的形成提供了证据。导致连续波(CW)量子产率磁场依赖性的自由基对复合过程仅限于扩散性自由基对。尽管腺苷钴胺(III)的偕偶自由基对也会发生磁场依赖性复合(A.M.查戈韦茨和C.B.格里森姆,《美国化学会志》115,12152 - 12157,1993),但该过程并不能解释仅在粘性溶剂中观察到的CW量子产率的磁场依赖性。甘油和乙二醇会增加溶液的微观粘度,从而延长自旋相关扩散自由基对的寿命。这使得溶剂笼中自旋相关扩散自由基对之间能够发生磁场依赖性复合。在存在异丙醇等非粘性醇的情况下未观察到磁场依赖性复合,从而表明介质微观粘度增加的重要性。捕获逸出溶剂笼的烷基自由基的顺磁性自由基清除剂不会减弱磁场对CW量子产率的影响,从而排除了随机扩散自由基对之间的自由基对复合,也排除了溶剂衍生自由基的参与。烷基钴胺素自由基对之间的磁场依赖性复合已通过自由基对动力学和复合的半经典模型进行了模拟。这些计算支持单重态自由基对前体的存在。

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引用本文的文献

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TD-DFT insight into photodissociation of the Co-C bond in coenzyme B12.

Front Chem. 2014-2-5

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