催化由米oglobin 和色素溶解的C(sp3) -H键的氧化
Koji Oohora1, Yushi Kihira, Eiichi Mizohata
1Department of Applied Chemistry, Graduate School of Engineering, Osaka University , Suita, 565-0871, Japan.
Journal of the American Chemical Society
|November 7, 2013
概括
在这项研究中,他们设计了一种色基胺基蛋白生物催化剂,该生物催化剂有效地氧化乙基. 这种新型酶模仿了P450细胞染色体.
科学领域:
- 生物化学 生物化学
- 生物有机化学 生物有机化学
- 酵素工程是什么? 酶工程是什么
背景情况:
- 肌球蛋白是一种参与氧气运输的血红蛋白.
- 原生肌球蛋白和改性变体通常不会催化基C-H氧化.
- 开发用于选择性催化剂的人造金属酶是一个关键的研究领域.
研究的目的:
- 创建一个新型的生物催化剂,通过使肌球蛋白与色素复合.
- 为了研究复制的肌球蛋白的催化活性和机制.
- 探索人工辅助因子在修改酶功能的潜力.
主要方法:
- 复制蛋白质的光谱表征.
- 进行X射线晶体学以确定辅因子的结合部位.
- 酶分析测量催化活性 (周转率,产品形成).
- 同位素效应研究和动态分析以阐明反应机制.
主要成果:
- 色素辅因子成功地被重组到肌球蛋白的血结合部位.
- 复制的肌球蛋白催化H2O2依赖乙烯氧化为1-乙醇的氧化,其周转率为13.
- 动态同位素效应和线性自由能量关系表明原子抽象机制.
- 催化活性与原生肌球蛋白不同,类似于细胞染色体P450.
结论:
- 甲基基菌蛋白作为一种有效的人工酶,用于C-H氧化.
- 反应机制涉及通过一种Mn(IV) = O物种抽取原子,类似于细胞染色体P450.
- 这项工作表明了蛋白质工程和辅因子修饰的潜力,以创造新的生物催化剂.
相关概念视频
Radical Oxidation of Allylic and Benzylic Alcohols
2.3K
Activated manganese(IV) oxide can selectively oxidize allylic and benzylic alcohols via a radical intermediate mechanism. Primary allylic alcohols are oxidized to aldehydes, while secondary allylic alcohols yield ketones. The redox reaction of potassium permanganate with an Mn(II) salt such as manganese sulfate (under either alkaline or acidic conditions), followed by thorough drying, yields the oxidizing agent: activated MnO2. While MnO2 is insoluble in the solvents used for the reaction, the...
2.3K
Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate
15.7K
Alkenes can be dihydroxylated using potassium permanganate. The method encompasses the reaction of an alkene with a cold, dilute solution of potassium permanganate under basic conditions to form a cis-diol along with a brown precipitate of manganese dioxide.
15.7K
Properties of Organometallic Compounds
2.1K
Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
2.1K
Gene Families
8.0K
Gene families consist of groups of genes proposed to have originated from a common ancestor. Typically these arise through events in which a gene or genes are mistakenly duplicated during cell division. Unlike their parent genes (which are subject to selection pressure to maintain function), these gene copies do not need to preserve their sequences and may evolve at a relatively faster rate.
Occasionally these regions can be adapted to take on new roles within the organism, becoming novel genes...
Occasionally these regions can be adapted to take on new roles within the organism, becoming novel genes...
8.0K
Protein and Protein Structure
72.3K
Proteins are one of the most abundant organic molecules in living systems and have the most diverse range of functions of all macromolecules. Proteins may be structural, regulatory, contractile, or protective. They may serve in transport, storage, or membranes; or they may be toxins or enzymes. Their structures, like their functions, vary greatly. They are all, however, amino acid polymers arranged in a linear sequence.
A protein's shape is critical to its function. For example, an enzyme...
A protein's shape is critical to its function. For example, an enzyme...
72.3K
Oxidation of Phenols to Quinones
4.6K
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...
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...
4.6K


