相关实验视频
Updated: Jul 10, 2026

11:37
Sigma's Non-specific Protease Activity Assay - Casein as a Substrate
Published on: September 17, 2008
同位素对胆酸盐的酶和非酶反应的影响
S Kirk Wright1, Michael S DeClue, Ajay Mandal
1Institute for Enzyme Research and Department of Biochemistry, University of Wisconsin, 1710 University Avenue, Madison, Wisconsin 53726, USA.
Journal of the American Chemical Society
|September 15, 2005
概括
霍里斯马特通过两个途径进行热再排列,即消除和克莱森再排列,这两种过程都是协同的西格马特热过程. 同位素效应揭示了过渡状态不对称性和酶类相似性,活性位可能有利于极化过渡状态.
科学领域:
- 生物化学 生物化学
- 有机化学 有机化学
- 酶学 是一种酶学.
背景情况:
- 霍里斯马酸是一种关键的生物合成中间体.
- 它通过消除或克莱森重组进行热反应.
- 了解这些途径对于代谢研究至关重要.
研究的目的:
- 为了研究 chorismate 的热反应的机制.
- 为了比较 chorismate 的溶液和酶反应.
- 阐明酶活性位点在反应过渡状态中的作用.
主要方法:
- 同位素标记的可里斯马酸盐衍生物的热反应.
- 运动同位素效应测量 (2H,18O,13C).
- 溶液反应与由大肠杆菌和B. subtilis. chorismate突变酶催化的酶反应的比较.
主要成果:
- 清除和克莱森重排合物都是协同的西格马特罗普过程.
- 同位素效应表明溶液中的不对称过渡状态.
- 酶反应表现出类似的协同机制,但可能具有更极化的过渡状态.
- 在溶液和酶反应之间以及不同细菌物种之间观察到相似之处.
结论:
- 霍里斯马酸盐的热反应通过协同的[3,3]-sigmatropic路径进行.
- 化突变酶的酶催化反应反映了溶液机制,但可能涉及更极化的过渡状态.
- 酶活性位点可以影响过渡状态的极性.
相关概念视频
Common Ion Effect
Compared with pure water, the solubility of an ionic compound is less in aqueous solutions containing a common ion (one also produced by dissolution of the ionic compound). This is an example of a phenomenon known as the common ion effect, which is a consequence of the law of mass action that may be explained using Le Châtelier’s principle. Consider the dissolution of silver iodide:
Brønsted-Lowry Acids and Bases
In 1923, the Brønsted–Lowry definition of acids and bases was proposed by Johannes Brønsted and Thomas Lowry. According to this theory, a Brønsted acid is defined as a species that donates a proton in a chemical reaction and gets converted to its conjugate base. A Brønsted base is defined as a species that accepts a proton in a chemical reaction and gets converted into its conjugate acid. These transfers of protons are caused by the displacement of electrons in these reactions, which is...
Basicity of Aliphatic Amines
Amines can behave as Brønsted–Lowry bases by accepting a proton from the acid to form corresponding conjugate acids. Due to a lone pair of nonbonding electrons, aliphatic amines can also act as Lewis bases by forming a covalent bond with an electrophile.
To measure the basicity of amines, two conventions are generally used. The first defines Kb as the basicity constant for the deprotonation reaction of water by the amine, as presented in Figure 1. Conventionally, lower Kb indicates higher...
To measure the basicity of amines, two conventions are generally used. The first defines Kb as the basicity constant for the deprotonation reaction of water by the amine, as presented in Figure 1. Conventionally, lower Kb indicates higher...
Acids, Bases and Neutralization Reactions
Acids and bases play several important roles in biology. The pH of a biological system can significantly impact the function of biological molecules, including enzymes, proteins, and nucleic acids. For example, enzymes have optimal pH ranges for their activity, and changes in pH can denature or alter their structure, affecting their function. Acids and bases also play a crucial role in cellular signaling and communication. The pH of the extracellular fluid around cells can influence the...
Titration of a Weak Base with a Strong Acid
The titration curve of a weak base like ammonia with a strong acid like hydrochloric acid is the mirror image of the titration curve of a weak acid with a strong base.
Using the ICE table and substituting the Kb value, we calculate the initial pH of 50 mL of 0.1 M ammonia to be 11.11. Addition of 25 mL of 0.1 M hydrochloric acid to this solution of ammonia results in a buffer with an equal concentration of ammonia and ammonium ions. The pH of this buffer can be calculated by substituting these...
Using the ICE table and substituting the Kb value, we calculate the initial pH of 50 mL of 0.1 M ammonia to be 11.11. Addition of 25 mL of 0.1 M hydrochloric acid to this solution of ammonia results in a buffer with an equal concentration of ammonia and ammonium ions. The pH of this buffer can be calculated by substituting these...
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...

