Theoretical Studies on Tyrosinase Models
Theoretical Studies on Tyrosinase Models
复制标题
酪氨酸酶模型的理论研究
DOI：
10.1002/9781119951438.eibc2249
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
S. Herres-Pawlis
中科院分区：
文献类型：
--
作者：
A. Hoffmann;S. Herres-Pawlis
铜-二氧化学和相应的酪氨酸酶激发的反应性被认为是计算化学的折磨轨迹，因为结果强烈依赖于精确交换的包含量、基集大小和经验弥散的包含。近年来，密度泛函理论已成为研究这一领域反应机理的主力。纯官能团和杂化官能团可用于研究同分异构体侧对过氧化二铜（II）种(P)和双（μ -氧）二铜（III）种(O)之间的平衡。此外，有几个研究小组研究了酚酸盐与Cu2O2core的配位以及随后的羟基化步骤。在这里，O - O键断裂是发生在酚酸盐配位之前还是之后的结果取决于所考虑的体系的大小，并且aPor anOcore是否执行关键的C-H激活步骤仍然是开放的。进一步的研究还集中在从铜(I)和二氧开始的cu2o2物种形成过程以及配体羟基化上，由于计算能力的提高，这些研究总是着眼于实验研究。因此，重点从研究相当小的NH3稳定体系转移到现实的，有时甚至是催化活性的配合物。方法论基准转向耦合聚类方法，并最终转向实验确定平衡的能量基准。结合势能表面（PES）扫描、电荷分解分析（CDA）和自然键轨道（NBO）分析，对酪氨酸酶的反应机理有了重要的认识，更多的研究将有助于解决酪氨酸酶的完整催化循环。
Copper–dioxygen chemistry and the corresponding tyrosinase‐inspired reactivity are regarded as a torture track for computational chemistry, since a strong dependence of the results from the included amount of exact exchange, the basis set size and inclusion of empirical dispersion has been found. In the last years, density functional theory has become the workhorse for the investigation of reaction mechanisms in this area. Pure and hybrid functionals have been found to be useful to investigate the equilibrium between isomeric side‐on peroxide dicopper(II) species (P) and bis(μ‐oxo) dicopper(III) species (O). Moreover, the coordination of the phenolate to the Cu2O2core with subsequent hydroxylation step has been studied by several groups. Here, the results of whether the OO bond scission occurs before or after phenolate coordination depend on the size of the regarded system, and the question is still open whether aPor anOcore performs the crucial C–H activation step. Further studies also focused on the Cu2O2species formation process starting with copper(I) and dioxygen and also on the ligand hydroxylation—always with view to experimental studies owing to the increasing computational power. Hence, the focus shifted from the study of rather small NH3‐stabilized systems to realistic and sometimes even catalytically active complexes. Methodology benchmarking moved to coupled‐cluster methods and finally toward benchmarking of energies of experimentally determined equilibria. Together with potential energy surface (PES) scans, charge decomposition analyses (CDA), and natural bonding orbital (NBO) analyses, important insights into the reaction mechanisms have been obtained and many more will be awaited to resolve the full catalytic cycle of tyrosinase.
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影响因子：
15
作者：
Ottenwaelder,Xavier;Rudd,DeanneJackson;Corbett,MaryC;Hodgson,KeithO;Hedman,Britt;Stack,TDanielP
通讯作者：
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影响因子：
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作者：
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DOI：
--
发表时间：
2015
期刊：
影响因子：
--
作者：
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通讯作者：
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影响因子：
1.7
作者：
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通讯作者：
L. Cavallo
DOI：
--
发表时间：
2016
期刊：
影响因子：
--
作者：
Yohta Fukuda;Eiichi Mizohata;Tsuyoshi Inoue
通讯作者：
Tsuyoshi Inoue