硫醇基-钴胺素（III）的荧光团辅助光解
Fluorophore Assisted Photolysis of Thiolato-Cob(III)alamins.
作者信息
Rodgers Zachary L, Shell Thomas A, Brugh Alexander M, Nowotarski Hannah L, Forbes Malcolm D E, Lawrence David S
机构信息
Department of Chemistry, ‡Division of Chemical Biology and Medicinal Chemistry, and §Department of Pharmacology, University of North Carolina , Chapel Hill, North Carolina 27599, United States.
出版信息
Inorg Chem. 2016 Mar 7;55(5):1962-9. doi: 10.1021/acs.inorgchem.5b02036. Epub 2016 Feb 5.
Cobalamins are known to react with thiols to yield stable β-axial Co(III)-S bonded thiolato-cobalamin complexes. However, in stark contrast to the Co-C bond in alkylcobalamins, the photolability of the Co-S bond in thiolato-cobalamins remains undetermined. We have investigated the photolysis of N-acetylcysteinyl cob(III)alamin at several wavelengths within the ultraviolet and visible spectrum. To aid in photolysis, we show that attaching fluorophore "antennae" to the cobalamin scaffold can improve photolytic efficiency by up to an order of magnitude. Additionally, electron paramagnetic resonance confirms previous conjectures that the photolysis of thiolato-cobalamins at wavelengths as long as 546 nm produces thiyl radicals.
已知钴胺素与硫醇反应生成稳定的β-轴向Co(III)-S键合硫醇钴胺素配合物。然而，与烷基钴胺素中的Co-C键形成鲜明对比的是，硫醇钴胺素中Co-S键的光解稳定性仍未确定。我们研究了N-乙酰半胱氨酸钴胺(III)在紫外和可见光谱的几个波长下的光解情况。为了辅助光解，我们发现将荧光团“天线”连接到钴胺素支架上可以将光解效率提高一个数量级。此外，电子顺磁共振证实了之前的推测，即硫醇钴胺素在长达546 nm的波长下光解会产生硫自由基。
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