配体复杂性对1型铜位光谱性质影响的理论研究

IF 3.4 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Umut Ozuguzel, Serzat Safaltin, S. Pamir Alpay, Kenda Alkadry, Reed Nieman, Carol Korzeniewski, Adelia J. A. Aquino
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引用次数: 0

摘要

多铜氧化酶(MCOs)是生物技术中备受关注的酶类,因为它们能高效催化氧气还原成水,在可持续能源生产和生物电化学应用中具有重要价值。本研究采用时间相关密度泛函理论(TDDFT)研究了 Azurin 中 1 型(T1)铜位点的电子结构和光谱特性,该位点可作为 MCOs 中类似位点的模型。从 T1 位点导出了四个复杂程度不同的模型复合物,包括三个三配位模型和一个带有轴向蛋氨酸连接的四配位模型,以探索分子分支和轴向配位的影响。使用 ωB97X-D3 函数、def2-TZVP 基集和类导体极化连续模型 (CPCM) 溶解模型进行的计算重现了关键的实验光谱特征,模型复杂度的增加提高了计算结果的一致性,尤其是共振拉曼光谱中约 400 cm-1 的波段分裂。这项工作增强了我们对 T1 铜位点的电子特性和光谱的理解,缩小了简化模型与复杂蛋白质之间的差距。这些发现有助于解释蓝铜蛋白的光谱数据,并可为今后类似生物系统的研究提供参考。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Influence of Ligand Complexity on the Spectroscopic Properties of Type 1 Copper Sites: A Theoretical Study

Influence of Ligand Complexity on the Spectroscopic Properties of Type 1 Copper Sites: A Theoretical Study

Multi-copper oxidases (MCOs) are enzymes of significant interest in biotechnology due to their efficient catalysis of oxygen reduction to water, making them valuable in sustainable energy production and bio-electrochemical applications. This study employs time-dependent density functional theory (TDDFT) to investigate the electronic structure and spectroscopic properties of the Type 1 (T1) copper site in Azurin, which serves as a model for similar sites in MCOs. Four model complexes of varying complexity were derived from the T1 site, including 3 three-coordinate models and 1 four-coordinate model with axial methionine ligation, to explore the impact of molecular branches and axial coordination. Calculations using ωB97X-D3 functional, def2-TZVP basis set, and conductor-like polarizable continuum model (CPCM) solvation model reproduced key experimental spectral features, with increased model complexity improving agreement, particularly for the ~400 cm−1 band splitting in resonance Raman spectra. This work enhances our understanding of T1 copper sites' electronic properties and spectra, bridging the gap between simplified models and complex proteins. The findings contribute to the interpretation of spectroscopic data in blue copper proteins and may inform future studies on similar biological systems.

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来源期刊
CiteScore
6.60
自引率
3.30%
发文量
247
审稿时长
1.7 months
期刊介绍: This distinguished journal publishes articles concerned with all aspects of computational chemistry: analytical, biological, inorganic, organic, physical, and materials. The Journal of Computational Chemistry presents original research, contemporary developments in theory and methodology, and state-of-the-art applications. Computational areas that are featured in the journal include ab initio and semiempirical quantum mechanics, density functional theory, molecular mechanics, molecular dynamics, statistical mechanics, cheminformatics, biomolecular structure prediction, molecular design, and bioinformatics.
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