由基酶催化的乙烯还原的立体特异性
P M Benton1, J Christiansen, D R Dean
1Department of Chemistry and Biochemistry, Utah State University, Logan, UT 84322, USA.
Journal of the American Chemical Society
|July 18, 2001
概括
基酶酶酶酶酶酶酶酶酶酶酶酶酶酶酶酶酶酶酶酶酶酶酶
科学领域:
- 生物化学 生物化学
- 酶动力学 酶动力学
- 生物有机化学 生物有机化学
背景情况:
- 酶催化氨基合成和替代基质的减少.
- 乙烯还原立体化学探测了酶机制.
- 修改MoFe蛋白活性部位改变了酶的功能.
研究的目的:
- 通过修改的酶酶来研究乙烯还原的立体化学.
- 检查活性部位氨基酸替代对基质结合和质子化的影响.
- 提出通过基酶进行乙烯还原的修订机制.
主要方法:
- 福里埃变换红外光谱法 (FTIR) 用于分析C(2) D(2) 减少产物.
- 局部定向突变生成以产生改变的MoFe蛋白质.
- 乙烯还原的动力分析 (K (m) 确定).
主要成果:
- 降解C(2) D(2) 的立体化学独立于K(m) 和C(2) H(6) 的形成.
- 电子流量显著影响 cis-到 trans-1,2-C(2) H(2) D(2) 的比率.
- 观察到的产品分布与之前的酶结合中间模型相矛盾.
结论:
- 在酶中活性位点残留物的替代改变了催化结果.
- 涉及eta(2) - 乙烯基中间体的分支反应途径解释了观察到的立体化学.
- 了解酶机制对于氨生产和固定研究至关重要.
相关概念视频
Induced-fit Model
Most chemical reactions in cells require enzymes—biological catalysts that speed up the reaction without being consumed or permanently changed. They reduce the activation energy needed to convert the reactants into products. Enzymes are proteins, that usually work by binding to a substrate—a reactant molecule that they act upon.
Enzymes exhibit substrate specificity, meaning that they can only bind to certain substrates. This is mainly determined by the shape and chemical characteristics of...
Enzymes exhibit substrate specificity, meaning that they can only bind to certain substrates. This is mainly determined by the shape and chemical characteristics of...
E1 Reaction: Stereochemistry and Regiochemistry
One of the critical aspects of the E1 reaction mechanism, as also observed in E2, is the regiochemistry, with multiple regioisomers obtained as products. In the example discussed, the presence of water as a weak base favors elimination over substitution to generate two alkenes. Given that alkenes’ stability increases with the number of alkyl groups across the double bond, typically, E1 reactions lead to the Zaitsev product, for this is more substituted and stable than the Hofmann product.
Catalytically Perfect Enzymes
The theory of catalytically perfect enzymes was first proposed by W.J. Albery and J. R. Knowles in 1976. These enzymes catalyze biochemical reactions at high-speed. Their catalytic efficiency values range from 108-109 M-1s-1. These enzymes are also called 'diffusion-controlled' as the only rate-limiting step in the catalysis is that of the substrate diffusion into the active site. Examples include triose phosphate isomerase, fumarase, and superoxide dismutase.
¹³C NMR: Distortionless Enhancement by Polarization Transfer (DEPT)
When proton-coupled carbon-13 spectra are simplified by a broadband proton decoupling technique, structural information about the coupled protons is lost. Distortionless enhancement by polarization transfer (DEPT) is a technique that provides information on the number of hydrogens attached to each carbon in a molecule. While the DEPT experiment utilizes complex pulse sequences, the pulse delay and flip angle are specifically manipulated. The resulting signals have different phases depending on...
Polymer Classification: Stereospecificity
Polymerization generates chiral centers along the entire backbone of a polymer chain. Accordingly, the stereochemistry of the substituent group has a significant effect on polymer properties. Polymers formed from monosubstituted alkene monomers feature chiral carbons at every alternate position in the polymer backbone. Relative to the predominant orientation of substituents at the adjacent chiral carbons, the polymer can exist in three different configurations: isotactic, syndiotactic, and...
Cationic Chain-Growth Polymerization: Mechanism
The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the generated carbocation,...


