在没有一般的酸催化过程的情况下,O-GlcNAcase催化了类甘油酸的裂变
Matthew S Macauley1, Keith A Stubbs, David J Vocadlo
1Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, BC, Canada V5A 1S6.
Journal of the American Chemical Society
|December 8, 2005
概括
O-GlcNAcase有效地解硫糖化物,挑战了关于糖化酶耐药性的先前假设. 这种酶起到双功能催化剂的作用,稳定了O-和S-葡萄糖体分裂的过渡状态.
科学领域:
- 生物化学 生物化学
- 酶学 是一种酶学.
背景情况:
- O-GlcNAcase通过基质辅助和一般酸催化从蛋白质中去除N-乙糖胺.
- 硫糖化物一般耐受于糖化酶的水解.
研究的目的:
- 为了研究O-GlcNAcase在thio.glycosides上的催化机制.
- 为了通过O-GlcNAcase比较O-糖酸和S-糖酸的水解.
主要方法:
- 布伦斯特德分析和pH活性研究.
- 阿尔法-的动态同位素效应和塔夫特式分析.
主要成果:
- 在没有一般的酸催化过程的情况下,O-GlcNAcase有效地化S-糖化物.
- 硫糖化物的水解涉及到晚期过渡状态的稳定,其中2 - 乙胺基组的核友性参与较大.
- O-GlcNAcase对O-和S-糖化物表现出类似的催化能力.
结论:
- O-GlcNAcase是一种双功能催化剂,能够裂解硫糖化物.
- 这种酶分裂硫糖化物的能力可能会对生物产生重大影响.
相关概念视频
Oligosaccharide Assembly
Protein glycosylation starts in the ER lumen and continues in the Golgi apparatus. Glycosyltransferases catalyze the addition of sugar molecules or glycosylation of proteins. Usually, these enzymes add sugars to the hydroxyl groups of selected serine or threonine residues to form O-linked glycans or the amino groups of asparagine residues to form N-linked glycans. Different positions on the same polypeptide chain can contain differently linked glycans.
Multiple sugar molecules that may or may...
Multiple sugar molecules that may or may...
Loss of Carboxy Group as CO2: Decarboxylation of β-Ketoacids
Carboxylic acids, upon heating, undergo a decarboxylation reaction by releasing carbon dioxide gas. Monocarboxylic acids do not undergo decarboxylation easily. However, a silver salt of carboxylic acid reacts with bromine or iodine under high temperature to release carbon dioxide gas and forms halide with one less carbon. This reaction is called the Hunsdiecker reaction.
Esters to Carboxylic Acids: Saponification
Esters can be hydrolyzed to carboxylic acids under acidic or basic conditions. Base-promoted hydrolysis of esters is a nucleophilic acyl substitution reaction in which esters react with an aqueous base, followed by an acid to give carboxylic acids. This reaction is also known as saponification because it forms the basis for making soaps from fats.
The reaction requires a base in stoichiometric amounts, which participates in the reaction and is not regenerated later. So, the base acts as a...
The reaction requires a base in stoichiometric amounts, which participates in the reaction and is not regenerated later. So, the base acts as a...
Esters to Carboxylic Acids: Acid-Catalyzed Hydrolysis
Hydrolysis of esters under acidic conditions proceeds through a nucleophilic acyl substitution. In the presence of excess water, the reaction proceeds in a reversible manner, forming carboxylic acids and alcohols.
During hydrolysis, the ester is first activated towards nucleophilic attack through the protonation of the carboxyl oxygen atom by the acid catalyst. The protonation makes the ester carbonyl carbon more electrophilic. In the next step, water acts as a nucleophile and adds to the...
During hydrolysis, the ester is first activated towards nucleophilic attack through the protonation of the carboxyl oxygen atom by the acid catalyst. The protonation makes the ester carbonyl carbon more electrophilic. In the next step, water acts as a nucleophile and adds to the...
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...
GPCRs Regulate Adenylyl Cylase Activity
Some GPCRs transmit signals through adenylyl cyclase (AC), a transmembrane enzyme. AC helps synthesize second messenger cyclic adenosine monophosphate (cAMP). AC catalyzes cyclization reaction and converts ATP to cAMP by releasing a pyrophosphate. The pyrophosphate is further hydrolyzed to phosphate by the enzyme pyrophosphatase, which drives cAMP synthesis to completion. However, cAMP is rapidly degraded to 5′ AMP by the enzymes phosphodiesterase (PDE), preventing overstimulation of cells.
Two...
Two...


