在Flavoenzyme TrmFO中识别TyrOH•+基离子
Lipsa Nag1, Pierre Sournia1, Hannu Myllykallio1
1LOB, Ecole Polytechnique, CNRS, INSERM, Université Paris-Saclay , Palaiseau 91128 Cedex, France.
Journal of the American Chemical Society
|July 27, 2017
概括
研究人员确定了质子化基 (TyrOH•+),这是生物化学反应中的关键中间体. 这一发现有助于理解电荷转移过程和黄蛋白光化学.
科学领域:
- 生物化学
- 生物物理
- 光谱学
背景情况:
- 氨酸 (TyrOH) 和氨酸基是生物电荷转移反应中的关键中间体.
- 虽然基存在于质子和中性形式,但仅在中性,无质子状态下观察到基.
- 了解这些激素的不同形式是阐明复杂的生化途径的关键.
研究的目的:
- 通过一种酶模型系统来描述质子化基 (TyrOH•+).
- 研究TyrOH•+的光谱和时间性质.
- 为了澄清TyrOH氧化和脱质的关系.
主要方法:
- 使用一种基因改造的酶TrmFO作为模型.
- 使用超快光和吸收光谱.
- 分析了原基的形成和衰变动力学.
主要成果:
- 描述了质子化基 (TyrOH•+),观察到一个明显的可见吸收带.
- 确定TyrOH•+的过渡时刻在对称轴附近.
- 通过电子转移显示TyrOH•+形成在~1 ps内,并通过电荷重组在~3 ps内衰变.
结论:
- 质子基 (TyrOH•+) 有不同的光谱和时间性质.
- 氧化TyrOH并不总是导致即时脱质.
- 这些发现有助于区分flavoproteins中的光产物状态,并了解涉及tyrosyl中间体的氧化还原链.
相关概念视频
Aromatic Hydrocarbon Cations: Structural Overview
4.0K
Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
Removing one hydrogen from the intervening CH2 group...
Removing one hydrogen from the intervening CH2 group...
4.0K
Keto–Enol Tautomerism: Mechanism
8.0K
The keto and enol forms are known as tautomers and they constantly interconvert (or tautomerize) between the two forms under acid or base catalyzed conditions. Both the reactions involve the same steps—protonation and deprotonation— although in the reverse order.
8.0K
Radicals: Electronic Structure and Geometry
5.3K
This lesson delves into the geometry of a radical, which is influenced by the electronic structure of the molecule. The principle is similar to that of a lone pair, where the unpaired electron influences the geometry at the radical center.
Accordingly, the structure of a trivalent radical lies between the geometries of carbocations and carbanions. An sp2-hybridized carbocation is trigonal planar, while an sp3-hybridized carbanion is trigonal pyramidal. Here, the difference in geometry is...
Accordingly, the structure of a trivalent radical lies between the geometries of carbocations and carbanions. An sp2-hybridized carbocation is trigonal planar, while an sp3-hybridized carbanion is trigonal pyramidal. Here, the difference in geometry is...
5.3K
Thermal and Photochemical Electrocyclic Reactions: Overview
3.1K
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
3.1K
Radical Autoxidation
3.3K
The oxidation of an organic compound in the presence of air or oxygen is called autoxidation. For example, cumene reacts with oxygen to form hydroperoxide. Autoxidation involves initiation, propagation, and termination steps. Many organic compounds are susceptible to autoxidation—especially ethers in the presence of oxygen, which form hydroperoxides. Even though this reaction is slow, old ether bottles contain small amounts of peroxide, which leads to laboratory explosions during ether...
3.3K
Radical Reactivity: Overview
2.8K
Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
2.8K


