Comparison of Experimental and Broken Symmetry Density Functional Theory Calculated Electron Paramagnetic Resonance Parameters for the Manganese Catalase Active Site in the Superoxidized MnIII/MnIV State.
Comparison of Experimental and Broken Symmetry Density Functional Theory Calculated Electron Paramagnetic Resonance Parameters for the Manganese Catalase Active Site in the Superoxidized MnIII/MnIV State.
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超氧化 MnIII/MnIV 态锰过氧化氢酶活性位点的实验与破缺对称密度泛函理论计算的电子顺磁共振参数的比较。
DOI：
10.1021/acs.jpcb.7b11649
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发表时间：
2018
期刊：
影响因子：
--
通讯作者：
Beal NJ
中科院分区：
文献类型：
--
作者：
Beal NJ
用破缺对称密度泛函理论计算了超氧化MnIII/MnIV型过氧化氢酶天然形式和叠氮抑制形式的活性中心模型的张量、55Mn、14N和17O超精细耦合。虽然在所有模型中，计算的和实验的G张量和55Mn超精细耦合很好地吻合，但只有通过14N叠氮化物和17O HFC的计算和实验的比较，才能很容易地区分活性位几何和Mn离子的氧化态。这一比较表明，只有包含Jahn-Teller扭曲的5坐标(MnIII)2位和6坐标(MnIV)1位的模型才能满意地再现实验中的14N和17O超精细耦合。
Broken symmetry density functional theory has been used to calculateg-tensor,55Mn,14N, and17O hyperfine couplings for active site models of superoxidized MnIII/MnIVmanganese catalase both in its native and azide-inhibited form. While a good agreement is found between the calculated and experimentalg-tensor and55Mn hyperfine couplings for all models, the active site geometry and Mn ion oxidation state can only be readily distinguished based on a comparison of the calculated and experimental14N azide and17O HFCs. This comparison shows that only models containing a Jahn–Teller distorted 5-coordinate (MnIII)2site and a 6-coordinate (MnIV)1site can satisfactorily reproduce the experimental14N and17O hyperfine couplings.