HNO-Binding in Heme Proteins: Effects of Iron Oxidation State, Axial Ligand, and Protein Environment.
HNO-Binding in Heme Proteins: Effects of Iron Oxidation State, Axial Ligand, and Protein Environment.
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DOI：
10.1002/anie.201608539
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发表时间：
2016-11-21
影响因子：
16.6
通讯作者：
Zhang, Yong
中科院分区：
文献类型：
--
作者：
Khade, Rahul L.;Yang, Yuwei;Shi, Yelu;Zhang, Yong
HNO在许多生物过程中起着重要作用。许多血红素蛋白结合HNO，这是其生物学功能的重要步骤。进行了系统的计算研究，以提供铁氧化态，轴向配体和蛋白质环境对HNO结合影响的第一个详细趋势和起源。结果表明，HNO与铁卟啉的结合弱于相应的铁体系，为实验观察到的还原亚硝基化提供了强大的热力学驱动力。轴向配体通过反式效应和电荷给予效应影响HNO的结合。蛋白质环境对HNO氢键结构和性质有显著影响。预测的核磁共振和振动数据与实验结果吻合良好。这些新颖和广泛的结果将有助于研究HNO在许多血红素蛋白、模型和相关金属蛋白中的结合。HNO结合是其发挥生物学功能的重要步骤。我们的研究结果首次直接表明：1)HNO与含铁卟啉的结合优于相应的铁卟啉体系，因为它具有更好的金属配体背给性；2)轴向配体通过反式效应和电荷给予效应强烈影响HNO的结合；3)血红素蛋白环境对不同蛋白的HNO氢键结构和性质有显著影响。
HNO plays significant roles in many biological processes. Numerous heme proteins bind HNO, an important step for its biological functions. A systematic computational study was performed to provide the first detailed trends and origins of the effects of iron oxidation state, axial ligand, and protein environment on HNO binding. Results show that HNO binds much weaker with ferric porphyrins than corresponding ferrous systems, offering strong thermodynamic driving force for experimentally observed reductive nitrosylation. Axial ligand was found to influence HNO binding through its trans effect and charge donation effect. The protein environment significantly affects the HNO hydrogen bonding structures and properties. The predicted NMR and vibrational data are in excellent agreement with experiment. These novel and broad range of results shall facilitate studies of HNO binding in many heme proteins, models, and related metalloproteins. HNO binding is an important step for its biological functions. Our results for the first time directly show that 1) HNO preferably binds with ferrous porphyrins than corresponding ferric systems due to better metal to ligand back-donation; 2) Axial ligand can strongly influence HNO binding through its trans effect and charge donation effect; 3) The heme protein environment has a significant effect on HNO hydrogen bonding structures and properties in different proteins.
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影响因子：
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