一种功能[NiFe]-酶模型化合物,经历了生物学相关的可逆的酸盐质子化
Katharina Weber1, Tobias Krämer, Hannah S Shafaat
1Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany.
Journal of the American Chemical Society
|December 1, 2012
概括
这项研究报告了新的[NiFe]-酶活性位点模型,具有独特的硫--铁协调. 这些模型的质子化影响铁中心.
科学领域:
- 生物有机化学 生物有机化学
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
背景情况:
- [NiFe]-基酶是催化氧化和生产的关键酶.
- [NiFe]-基酶的活性部位具有独特的异金属[NiFe]中心.
- 了解这些酶的电子结构和催化机制对于生物启发的能源应用至关重要.
研究的目的:
- 合成和描述模仿[NiFe]-酶活性位点的新型双核-铁模型化合物.
- 为了研究质子化对这些模型化合物的电子结构和催化活性的影响.
- 为原生[NiFe]-化酶中拟议的催化中间体提供实验证据.
主要方法:
- 使用X射线晶体学,NMR,FTIR, (57) Fe-Mössbauer,电子吸收和共振拉曼光谱学合成和表征双核铁复合体.
- 密度函数理论 (DFT) 计算以支持光谱数据解释和探测电子结构.
- 电化学实验用于评估减少质子的电催化活性.
主要成果:
- 成功合成和表征了两个具有异常{S(2) Ni(μ-S) ((μ-CO) Fe(CO) ((2) S}协调环境的模型化合物.
- 在结合的硫酸硫酸盐中证明可逆质子化,从而产生了第一个质子化中间体的双核[NiFe]模型.
- 光谱和计算数据显示,在铁中心在质子化时发生了显著的电子结构变化,尽管在位发生质子化.
- 这两种模型化合物都表现出电催化质子还原中的活性.
结论:
- 合成的双核[NiFe]复合体作为[NiFe]-酶活性位点的有价值模型.
- 位上的质子会显著影响铁中心的电子结构,这与原生酶中提出的机制相一致.
- 这些模型提供了对催化中间体和[NiFe]-化中金属中心之间的电子通信的实验性见解.
- 这些模型的电催化活性凸显了它们在开发人工生产系统方面的潜力.
相关概念视频
Preparation and Reactions of Thiols
Thiols are prepared using the hydrosulfide anion as a nucleophile in a nucleophilic substitution reaction with alkyl halides. For instance, bromobutane reacts with sodium hydrosulfide to give butanethiol.
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
Nitriles to Carboxylic Acids: Hydrolysis
Nitriles undergo acid-catalyzed hydrolysis or base-catalyzed hydrolysis to form a carboxylic acid. These reactions proceed via an amide intermediate.
Phase II Reactions: Glutathione Conjugation and Mercapturic Acid Formation
Glutathione, a tripeptide made up of glutamate, cysteine, and glycine, is a critical player in the detoxification of drugs and xenobiotics via a process known as glutathione conjugation or mercapturic acid formation. This phase II biotransformation reaction involves the covalent binding of glutathione to a drug or its metabolite, enhancing the compound's water solubility and enabling its excretion.
Several distinctive characteristics distinguish glutathione conjugation from other phase II...
Several distinctive characteristics distinguish glutathione conjugation from other phase II...
Structure and Nomenclature of Thiols and Sulfides
Thiols and sulfides are sulfur analogs of alcohols and ethers, respectively, where the sulfur atom takes the place of the oxygen atom. Thus, thiols are generally represented as RSH, where R is an alkyl substituent and —SH is the functional group. On the other hand, in sulfides, the central sulfur atom is bonded to two hydrocarbon groups on either side. Depending upon the type of group, sulfides can be either symmetrical or asymmetrical. Both thiols and sulfides display a bent geometry, similar...
Oxidation of Phenols to Quinones
In the presence of oxidizing agents, phenols are oxidized to quinones. Quinones can be easily reduced back to phenols using mild reducing agents. The electron-donating hydroxyl group enhances the reactivity of the aromatic ring, enabling oxidation of the ring even in the absence of an α hydrogen.
o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox property is crucial in...
o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox property is crucial in...
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