对亚氨基酸中亚氨基酶作用的对比作用的晶体学分析
Michele Cianci1, Bartlomiej Tomaszewski, John R Helliwell
1European Molecular Biology Laboratory, Hamburg Outstation, c/o DESY, Building 25a, Notkestrasse 85, 22603 Hamburg, Germany. m.cianci@embl-hamburg.de
Journal of the American Chemical Society
|January 27, 2010
概括
非水性介质中的酶在与等特定离子结合时表现出增加的活性. 这些离子,特别是在活性部位附近,可以通过静电变化或改变的水分来增强蛋白质功能.
科学领域:
- 生物化学 生物化学
- 结构生物学 结构生物学
- 酶学 是一种酶学.
背景情况:
- 低电介质非水性介质中的酶预计与对照子的关联性会增加.
- 在有机溶剂中发表的蛋白质晶体结构缺乏增加对联的明确证据.
- 在晶体结构中区分特定离子与水分子可能是具有挑战性的.
研究的目的:
- 为了呈现 (Cs+) 和 (Cl-) 离子在血清蛋白酶子的晶体中的放置.卡尔斯伯格.
- 为了研究这些离子对非水性介质中的酶活性的影响.
- 探索离子诱导酶激活的潜在机制.
主要方法:
- 结晶学使用异常衍射和软X射线来确定离子位置.
- 用CsCl.Cl.确定卡尔斯伯格亚微素的晶体结构.
- 在乙尼中对酶晶体的酶活性测定.
主要成果:
- 鉴定了11个Cs+和8个Cl-离子结合点在亚素分子周围,许多部分占用.
- 观察到被结合的离子所造成的活跃点裂的最小硬质扰动.
- 与含有Na+的晶体相比,CsCl处理的细素晶体在氨中显示出几倍更高的催化活性.
结论:
- 像Cs+这样的特定对象可以显著增强非水性环境中的血清蛋白酶活性.
- 在活性部位附近的离子结合可以通过静电再分配或改变的水化球来影响催化.
- 对有机溶剂中离子-蛋白相互作用的进一步研究是有必要的,以了解酶调节.
相关概念视频
Solvating Effects
An understanding of the solvating effect helps rationalize the relation between solvation and acidity of the compound. In addition, this also explains the relative stability of conjugate bases for compounds with different pKa values. This lesson details, in-depth, the principle of solvating effects. The strength of an acid and the stability of its corresponding conjugate base are determined using pKa values. This observed relationship is a consequence of solvation, which is the interaction...
Substituent Effects on Acidity of Carboxylic Acids
The acidity of carboxylic acids is influenced by the nature of the substituents bounded to the functional group. The acid strength is determined by the stability of the carboxylate anion—the conjugate base formed by dissociating the corresponding carboxylic acid.
Leveling Effect and Non-Aqueous Acid-Base Solutions
This lesson defines the leveling effect in acidic and basic solutions and its role in aqueous and non-aqueous solutions. It is essential to understand the competing nature of various species in a chemical system.
The Leveling Effect of a Solvent
A generic acid (HA) reacts with the generic base (B-) to yield the corresponding conjugate base (A-) and conjugate acid (HB):
The Leveling Effect of a Solvent
A generic acid (HA) reacts with the generic base (B-) to yield the corresponding conjugate base (A-) and conjugate acid (HB):
Amides to Carboxylic Acids: Hydrolysis
Amides can undergo either acid-catalyzed hydrolysis or base-promoted hydrolysis through a typical nucleophilic acyl substitution. Each hydrolysis requires severe conditions.
Acid-catalyzed hydrolysis:
Hydrolysis of amides under acidic conditions yields carboxylic acids. Since the reaction occurs slowly, hydrolysis requires the conditions of heat.
The mechanism begins with the protonation of the carbonyl oxygen by the acid catalyst. The protonation makes the amide carbonyl carbon more...
Acid-catalyzed hydrolysis:
Hydrolysis of amides under acidic conditions yields carboxylic acids. Since the reaction occurs slowly, hydrolysis requires the conditions of heat.
The mechanism begins with the protonation of the carbonyl oxygen by the acid catalyst. The protonation makes the amide carbonyl carbon more...
Leveling Effect
In acid-base chemistry, the leveling effect refers to the limitation imposed by the solvent on the strength of acids and bases in solution. When a base stronger than the solvent's conjugate base is used, it deprotonates the solvent until the base is entirely consumed, making it ineffective against weaker acids. Conversely, an acid stronger than the solvent's conjugate acid protonates the solvent until the acid is depleted, rendering it ineffective against weaker bases. Essentially, the solvent...
Acidity of 1-Alkynes
The acidic strength of hydrocarbons follows the order: Alkynes > Alkenes > Alkanes. The strength of an acid is commonly expressed in units of pKa — the lower the pKa, the stronger the acid. Among the hydrocarbons, terminal alkynes have lower pKa values and are, therefore, more acidic. For example, the pKa values for ethane, ethene, and acetylene are 51, 44, and 25, respectively, as shown here.


