在hofmeister效果的机制上
Marc C Gurau1, Soon-Mi Lim, Edward T Castellana
1Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77843, USA.
Journal of the American Chemical Society
|August 26, 2004
概括
脂肪胺单层显示电解质溶液的离子特异性排序变化,遵循霍夫迈斯特系列. 表面水结构的变化偏离,这表明分散力驱动霍夫迈斯特效应,而不是水结构本身.
科学领域:
- 表面化学 表面化学
- 物理化学 物理化学
- 频谱学是一种光谱学.
背景情况:
- 霍夫迈斯特系列描述了离子对蛋白质溶解度和其他现象的特异性影响.
- 在分子水平上了解离子-表面相互作用对于各种应用至关重要.
- 脂肪胺单层作为接口研究的模型系统.
研究的目的:
- 研究各种电解质离子对脂肪胺单层的影响.
- 为了将单层结构的变化与水界结构的变化相关联.
- 在接口上阐明霍夫迈斯特效应背后的主要驱动力.
主要方法:
- 振动总频谱学 (VSFS) 用于探测分子结构.
- 表面潜力的测量是作为离子组成的函数进行的.
- 脂肪氨基单层分散在各种电解质溶液上.
主要成果:
- 观察到单层排序的离子特异性变化,与霍夫迈斯特系列保持一致.
- 表面电位变化与基链排序有很好的相关性,但与水结构的相关性较小.
- 界面水结构显示出与霍夫迈斯特系列趋势的偏差.
结论:
- 离子透到单层的疏水区域是破坏顺序的关键.
- 界面水结构变化不是霍夫迈斯特效应的主要来源.
- 在霍夫迈斯特系列中,分散力可能起着重要作用.
相关概念视频
Allosteric Regulation
Allosteric regulation of enzymes occurs when the binding of an effector molecule to a site that is different from the active site causes a change in the enzymatic activity. This alternate site is called an allosteric site, and an enzyme can contain more than one of these sites. Allosteric regulation can either be positive or negative, resulting in an increase or decrease in enzyme activity. Most enzymes that display allosteric regulation are metabolic enzymes involved in the degradation or...
Mechanisms of Membrane-bending
The living membranes are flexible due to their fluid mosaic nature; however, their bending into different shapes is an active process regulated by specific lipids and proteins. The membrane bending can be transient as seen in vesicles or stable for a long time as in microvilli. Cells regulate the size, location, and duration of the membrane curvature.
Membrane bending can happen due to intrinsic changes in lipid composition or extrinsic association with different proteins. The proteins involved...
Membrane bending can happen due to intrinsic changes in lipid composition or extrinsic association with different proteins. The proteins involved...
Regioselectivity and Stereochemistry of Hydroboration
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Amines to Alkenes: Hofmann Elimination
Alkenes can be obtained from amines via an E2 elimination. The amine is first converted into a good leaving group, such as a quaternary ammonium salt. This is accomplished by treating the amine with an excess of alkyl halide, which results in a halide salt. Next, the halide salt is transformed into a hydroxide salt that functions as a base to enable elimination.
Under thermal conditions, the hydroxide can abstract a proton from the β carbon; this generates an alkene with the simultaneous...
Under thermal conditions, the hydroxide can abstract a proton from the β carbon; this generates an alkene with the simultaneous...
Preparation of 1° Amines: Hofmann and Curtius Rearrangement Mechanism
The Hofmann and Curtius rearrangement reactions can be applied to synthesize primary amines from carboxylic acid derivatives such as amides and acyl azides. In the Hofmann rearrangement, a primary amide undergoes deprotonation in the presence of a base, followed by halogenation to generate an N-haloamide. A second proton abstraction produces a stabilized anionic species, which rearranges to an isocyanate intermediate via an alkyl group migration from the carbonyl carbon to the neighboring...
Indirect-Acting Cholinergic Agonists: Mechanism of Action
Indirect-acting cholinergic agonists work by interacting with an enzyme called acetylcholinesterase (AChE) in the synaptic cleft. They can be reversible or irreversible inhibitors and have different effects on the enzyme.
Reversible inhibitors like edrophonium bind to a specific part of the enzyme called the anionic catalytic site. They form noncovalent bonds, which means they are not strongly attached to the enzyme. This creates a temporary and less stable enzyme–inhibitor complex, leading to...
Reversible inhibitors like edrophonium bind to a specific part of the enzyme called the anionic catalytic site. They form noncovalent bonds, which means they are not strongly attached to the enzyme. This creates a temporary and less stable enzyme–inhibitor complex, leading to...


