Nature of the copper-nitrosyl intermediates of copper nitrite reductases during catalysis.
Nature of the copper-nitrosyl intermediates of copper nitrite reductases during catalysis.
复制标题
DOI：
10.1039/d0sc04797j
复制
发表时间：
2020-10-20
期刊：
影响因子：
8.4
通讯作者：
Hasnain SS
中科院分区：
文献类型：
--
作者：
Hough MA;Conradie J;Strange RW;Antonyuk SV;Eady RR;Ghosh A;Hasnain SS
设计和合成能够将亚硝酸根还原为NO的铜配合物引起了人们极大的兴趣。他们一直在指导广泛的酶铜亚硝酸还原酶的催化铜中心的结构信息，但在所有这些酶的晶体学研究中观察到的NO的化学新颖的侧结合已被质疑的功能相关性。我们显示NO2−转化为NO在晶体中保持在170 K和目前的“分子电影”定义的事件在酶营业额，包括形成侧的Cu-NO中间体。DFT建模表明，真正的{CuNO}11和正式的{CuNO}10状态可能会发生侧上的形式在酶活性位点的稳定性的{CuNO}10侧上的形式由组氨酸配体的质子化状态。因此，铜-亚硝酰基中间体的形成需要在未来的功能性合成Cu-NiR络合物的设计模板中被容纳。亚硝酸铜还原酶催化过程中亚硝酰基铜中间体的观察及其密度泛函理论的证实。
The design and synthesis of copper complexes that can reduce nitrite to NO has attracted considerable interest. They have been guided by the structural information on the catalytic Cu centre of the widespread enzymes Cu nitrite reductases but the chemically novel side-on binding of NO observed in all crystallographic studies of these enzymes has been questioned in terms of its functional relevance. We show conversion of NO2− to NO in the crystal maintained at 170 K and present ‘molecular movies’ defining events during enzyme turnover including the formation of side-on Cu-NO intermediate. DFT modelling suggests that both true {CuNO}11 and formal {CuNO}10 states may occur as side-on forms in an enzymatic active site with the stability of the {CuNO}10 side-on form governed by the protonation state of the histidine ligands. Formation of a copper-nitrosyl intermediate thus needs to be accommodated in future design templates for functional synthetic Cu-NiR complexes. Observation of side-on copper-nitrosyl intermediate and its confirmation by DFT during catalysis of copper nitrite reductases.
登录
查看更多内容
DOI：
10.1107/s0907444905036693
发表时间：
2006-01-01
影响因子：
2.2
作者：
Evans, P
通讯作者：
Evans, P
系列晶体学以原子分辨率从一个晶体捕获亚硝酸铜还原酶的酶催化作用。
影响因子：
3.9
作者：
Horrell S;Antonyuk SV;Eady RR;Hasnain SS;Hough MA;Strange RW
通讯作者：
Strange RW
影响因子：
3.9
作者：
Dong J;Sasaki D;Eady RR;Antonyuk SV;Hasnain SS
通讯作者：
Hasnain SS
DOI：
10.1007/978-1-4939-7000-1_26
发表时间：
2017
期刊：
Methods in molecular biology (Clifton, N.J.)
影响因子：
--
作者：
Burley SK;Berman HM;Kleywegt GJ;Markley JL;Nakamura H;Velankar S
通讯作者：
Velankar 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