Journal of Inorganic Biochemistry ( IF 3.8 ) Pub Date : 2020-10-28 , DOI: 10.1016/j.jinorgbio.2020.111299 Kye-Ryong Sin 1 , Sun-Gyong Ko 1 , Chol-Jin Kim 1 , Tae-Won Maeng 1 , Sung-Jub Choe 1 , Kum-Ryong Ri 1
The AEOL series of manganoporphyrins (MnP; AEOL compounds were named by US Aeolus pharmaceuticals) designed as superoxide dismutase mimic are well-known for their powerful catalytic activity to neutralize reactive oxygen and nitrogen species. Reductive oxygen atom cleavage from peroxynitrite (ONOO−) to form NO2 in aqueous solution by some AEOL compounds (AEOL-10113, AEOL-10150, AEOL-11114 and AEOL-11203) was studied by DFT/M06-2X computations with D3 dispersion correction and gCP (geometrical counterpoise correction) for basis set superposition error. DFT computation showed that AEOL-10150 can form the most stable association complex {MnP…OONO} among four AEOL models. AEOL-10150 complex with ONOO− has the lowest deformation energy. In AEOL compounds and their association complexes with ONOO−, Mn atom prefered the high spin state (S = 2) to the intermediate spin state (S = 1). Natural bond orbital analysis showed that electron transfer from the most negative oxygen atom in ONOO− to Mn atom in MnP has the biggest interaction energy among all kinds of donor-acceptor interactions between ONOO− and MnP.
中文翻译:
通过 AEOL 系列的一些锰卟啉减少过亚硝酸盐:具有色散校正和 NBO 分析的 DFT 方法
AEOL 系列锰卟啉(MnP;AEOL 化合物由美国 Aeolus 制药公司命名)设计为超氧化物歧化酶模拟物,以其强大的催化活性而闻名,可中和活性氧和氮物种。使用 D3 分散体通过 DFT/M06-2X 计算研究了一些 AEOL 化合物(AEOL-10113、AEOL-10150、AEOL-11114 和 AEOL-11203)从过氧亚硝酸盐 (ONOO - ) 中还原氧原子裂解形成水溶液中的NO 2基组叠加误差的校正和 gCP(几何平衡校正)。DFT 计算表明 AEOL-10150 可以形成四种 AEOL 模型中最稳定的结合复合物 {MnP ... OONO}。AEOL-10150 复杂与 ONOO -具有最低的变形能。在AEOL化合物及其与ONOO -的缔合复合物中,Mn原子更喜欢高自旋态(S = 2)而不是中间自旋态(S = 1)。自然键轨道分析表明从最负的氧原子在ONOO该电子转移-在锰过氧化物酶与Mn原子已ONOO之间各种供体-受体相互作用的中最大的相互作用能-和锰过氧化物酶。