通过硫氧化状态控制进行强力触发热力学上升降解硫
Marc Mora1,2, Georgia Cohen1,2, William Cranton1,2
1Department of Physics, Randall Centre for Cell and Molecular Biophysics, Centre for the Physical Science of Life and London Centre for Nanotechnology, King's College London, Strand, London WC2R 2LS, U.K.
Journal of the American Chemical Society
|October 1, 2025
概括
机械力量可以激活化学反应,包括通过无机氧离子减少蛋白质二硫化键. 这种强力解锁反应影响蛋白质弹性,揭示了新的机械化学路径.
科学领域:
- 机械化学
- 生物物理
- 蛋白质科学
背景情况:
- 机械力,热能,电流和光线可以激活化学反应并改变反应路径.
- 单分子机械化学表明,力加快了聚合物中的结合裂变和环开放.
- SN2二醇二硫化反应是研究依赖力核替代的模型,但对无机硫氧离子的反应性不太了解.
研究的目的:
- 调查机械力量是否可以激活无机硫酸离子破坏蛋白质二硫化键.
- 探索涉及蛋白质二硫化键的热力学非受益反应的依赖力反应性.
主要方法:
- 单分子力光谱测量依赖力反应速率.
- 密度函数理论 (DFT) 计算以建模反应机制.
- 颜值测试测量以量化反应结果.
主要成果:
- 证明机械力可以激活无机氧离子对二硫化键的热力学不有利的减少.
- 显示这种强力激活的反应发生在蛋白质核中,影响具有生理机械作用的蛋白质.
- 量化了强力解锁二硫化物键破裂对蛋白质弹性的直接影响.
结论:
- 机械力可以克服热力学障碍,通过不太反应的无机氧离子激活二硫化键的减少.
- 这种机械化学激活对了解蛋白质机制和作用具有重要意义.
- 这些发现揭示了通过强力诱导的化学转换调节蛋白质弹性的新途径.
相关概念视频
Preparation and Reactions of Thiols
7.5K
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.
7.5K
Preparation and Reactions of Sulfides
5.7K
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
5.7K
Sulfur Assimilation
321
Sulfur is an essential element in biological systems, contributing to synthesizing key biomolecules, including amino acids such as cysteine and methionine, and cofactors such as coenzyme A and biotin. Microorganisms primarily assimilate sulfur as sulfate (SO₄²⁻) from the environment, which must undergo a series of biochemical transformations before it can be incorporated into cellular components. As sulfate is highly oxidized, it must undergo assimilatory sulfate reduction to...
321
Structure and Nomenclature of Thiols and Sulfides
5.6K
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,...
5.6K
Electrophilic Aromatic Substitution: Sulfonation of Benzene
7.8K
Sulfonation of benzene is a reaction wherein benzene is treated with fuming sulfuric acid at room temperature to produce benzenesulfonic acid. Fuming sulfuric acid is a mixture of sulfur trioxide and concentrated sulfuric acid.
7.8K
Oxidation and Reduction of Organic Molecules
9.1K
Energy production within a cell involves many coordinated chemical pathways. Most of these pathways are combinations of oxidation and reduction reactions, which occur at the same time. An oxidation reaction strips an electron from an atom in a compound, and the addition of this electron to another compound is a reduction reaction. Because oxidation and reduction usually occur together, these pairs of reactions are called redox reactions.
The removal of an electron from a molecule, results in a...
The removal of an electron from a molecule, results in a...
9.1K


