Hydrogen Peroxide Disproportionation with Manganese Macrocyclic Complexes of Cyclen and Pyclen.
Hydrogen Peroxide Disproportionation with Manganese Macrocyclic Complexes of Cyclen and Pyclen.
复制标题
Cyclen 和 Pyclen 的锰大环配合物的过氧化氢歧化。
DOI：
10.1039/c9qi01509d
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发表时间：
2020
影响因子：
7
通讯作者：
Green,KaylaN
中科院分区：
文献类型：
--
作者：
Freire,DavidM;Beeri,Debora;Pota,Kristof;Johnston,HannahM;Palacios,Philip;Pierce,BradS;Sherman,BenjaminD;Green,KaylaN
过氧化氢酶家族包括具有双核锰活性位点的各种酶，通过促进过氧化氢转化为分子氧和水来减轻活性氧的风险。在这项工作中，使用锰和cyclen或pyclen之间形成的络合物的过氧化氢分解进行了研究，由于与天然MnCAT酶的光谱相似性。电位滴定法被用来构建形态图，确定在不同的pH值的锰络合物组合物。每个复合物的行为作为过氧化氢酶的功能模拟。紫外-可见光谱的H2 O2分解反应的调查产生的信息的初始催化剂和中间体，包括单体和二聚体物种的结构。结果表明，由pyclen的吡啶环赋予的刚性是与cyclen相比测量的TON和TOF值增加的关键因素。
The catalase family of enzymes, which include a variety with a binuclear manganese active site, mitigate the risk from reactive oxygen species by facilitating the disproportionation of hydrogen peroxide into molecular oxygen and water. In this work, hydrogen peroxide disproportionation using complexes formed between manganese and cyclen or pyclen were investigated due to the spectroscopic similarities with the native MnCAT enzyme. Potentiometric titrations were used to construct speciation diagrams that identify the manganese complex compositions at different pH values. Each complex behaves as a functional mimic of catalase enzymes. UV-visible spectroscopic investigations of the H2O2 decomposition reaction yielded information about the structure of the initial catalyst and intermediates that include monomeric and dimeric species. The results indicate that rigidity imparted by the pyridine ring of pyclen is a key factor in increased TON and TOF values measured compared to cyclen.