Department of Chemistry and Biochemistry, University of California, Santa Barbara, Santa Barbara, California 93106-9510, USA.
Inorg Chem. 2011 May 16;50(10):4453-62. doi: 10.1021/ic200094x. Epub 2011 Apr 8.
Experimental and density functional theory (DFT) studies are described that are focused on outlining the reactivity of the known photochemical nitric oxide precursor trans-Cr(cyclam)(ONO)(2)(+) ("CrONO", cyclam = 1,4,8,11-tetrazacycltetradecane). Studies in both aerated and deaerated aqueous media are described as are the roles of both the oxidant O(2) and a reductant such as glutathione in trapping the apparent Cr(IV) photoreaction intermediate trans-Cr(cyclam)(O)(ONO)(+). Also reported and characterized structurally is the Cr(V) product of long-term photolysis in the absence of reducing agents, the trans-dioxo species trans-Cr(cyclam)(O)(2). Photosensitization experiments indicate that at least a significant fraction of the reaction occurs from the lowest energy doublet excited state(s). Lastly, cell culture experiments demonstrate that CrONO has little or no acute toxicity either before or after photolysis.
实验和密度泛函理论（DFT）研究集中于概述已知光化学反应一氧化氮前体反式-Cr（环戊烷）（ONO）（2）（+）（“CrONO”，环戊烷= 1,4,8,11-四氮杂环十四烷）的反应性。描述了在充气和脱氧水介质中的研究，以及氧化剂 O（2）和还原剂（如谷胱甘肽）在捕获明显的 Cr（IV）光反应中间体反式-Cr（环戊烷）（O）（ONO）（+）中的作用。还报道并结构表征了在没有还原剂的情况下长时间光解的 Cr（V）产物，即反式-二氧物种[反式-Cr（环戊烷）（O）（2）]（ClO4）。光敏化实验表明，至少有一部分反应是从最低能量的双重激发态发生的。最后，细胞培养实验表明，CrONO 在光解前后几乎没有或没有急性毒性。
