Spectroscopic and computational studies of nitrite reductase: proton induced electron transfer and backbonding contributions to reactivity.
Spectroscopic and computational studies of nitrite reductase: proton induced electron transfer and backbonding contributions to reactivity.
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DOI：
10.1021/ja806873e
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发表时间：
2009-01-14
影响因子：
15
通讯作者：
Solomon, Edward I.
中科院分区：
文献类型：
--
作者：
Ghosh, Somdatta;Dey, Abhishek;Sun, Yan;Scholes, Charles P.;Solomon, Edward I.
光谱学和 DFT 计算相结合，用于定义球形红杆菌亚硝酸盐还原酶在高和低 pH 条件下亚硝酸盐结合 2 型 (T2) 铜位点的几何和电子结构。在高 pH 值下，没有电子从还原型 1 (T1) 转移到亚硝酸盐结合的 T2 铜，而质子化会触发 T1 → T2 电子转移并生成 NO。 DFT 计算出还原 T2 铜还原亚硝酸盐时 N-O 键断裂的反应坐标，表明该过程最好描述为质子转移触发电子转移。据计算，与铜结合的二齿亚硝酸盐在通过反向键合以及通过与 Cu2+ 配位来稳定 -OH 产物来激活亚硝酸盐键的还原断裂方面发挥着主要作用。
A combination of spectroscopy and DFT calculations has been used to define the geometric and electronic structure of the nitrite bound type 2 (T2) copper site at high and low pH in nitrite reductase from Rhodobacter sphaeroides. At high pH there is no electron transfer from reduced type 1 (T1) to the nitrite bound T2 copper, while protonation triggers T1 → T2 electron transfer and generation of NO. The DFT calculated reaction coordinate for the N-O bond cleavage in nitrite reduction by the reduced T2 copper suggests that the process is best described as proton transfer triggering electron transfer. Bidentate nitrite binding to copper is calculated to play a major role in activating the reductive cleavage of the nitrite bond through backbonding combined with stabilization of the −OH product by coordination to the Cu2+.
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影响因子：
4.8
作者：
ADMAN, ET;GODDEN, JW;TURLEY, S
通讯作者：
TURLEY, S
DOI：
10.1073/pnas.0504207102
发表时间：
2005-08-23
影响因子：
11.1
作者：
Antonyuk, SV;Strange, RW;Hasnain, SS
通讯作者：
Hasnain, SS
影响因子：
5.6
作者：
Dodd, FE;Van Beeumen, J;Hasnain, SS
通讯作者：
Hasnain, SS
影响因子：
15
作者：
Kujime, Masato;Izumi, Chiemi;Fujii, Hiroshi
通讯作者：
Fujii, Hiroshi
影响因子：
5.6
作者：
Ellis, MJ;Prudêncio, M;Hasnain, SS
通讯作者：
Hasnain, SS