苯甲酸盐在endo-5-[4'（5'）咪唑基]-双环[2.2.1]庚-endo-2-基反式肉桂酸酯水解中的催化作用：对丝氨酸蛋白酶催化的电荷转移机制的影响。
Benzoate catalysis in the hydrolysis of endo-5-[4'(5')imidazolyl]-bicyclo[2.2.1]hept-endo- 2-yl trans-cinnamate: Implications for the charge-transfer mechanism of catalysis by serine proteases.
机构信息
Gates and Crellin Laboratories of Chemistry, California Institute of Technology, Pasadena, California 91125.
出版信息
Proc Natl Acad Sci U S A. 1980 Jun;77(6):3095-7. doi: 10.1073/pnas.77.6.3095.
Abstract
The acceleration, by a factor of 2500, of the hydrolysis of endo-5-[4'(5')imidazolyl]bicyclo[2.2.1]hept-endo- 2-yl trans-cinnamate by 0.5 M sodium benzoate in 42 mol% dioxane in water can be explained without resort to operation of a "charge-relay" mechanism similar to that often postulated to account for the enzymatic activity of serine proteases. The degree of ionization of 4-methylimidazole and of sodium benzoate in 42 mol% dioxane in water at 60 degrees C have been measured by NMR spectroscopy.
摘要
在 60°C 时，通过 NMR 光谱法测量了 42mol%二氧六环中的水、4-甲基咪唑和苯甲酸钠的离解度。0.5M 苯甲酸钠在 42mol%二氧六环中的水，可以将 5-[4'（5'）咪唑基]双环[2.2.1]庚-2-endo-2-基反肉桂酸酯的水解加速 2500 倍，这一过程无需采用类似于通常用来解释丝氨酸蛋白酶酶活性的“电荷传递”机制。
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Benzoate catalysis in the hydrolysis of endo-5-[4'(5')imidazolyl]-bicyclo[2.2.1]hept-endo- 2-yl trans-cinnamate: Implications for the charge-transfer mechanism of catalysis by serine proteases.苯甲酸盐在endo-5-[4'（5'）咪唑基]-双环[2.2.1]庚-endo-2-基反式肉桂酸酯水解中的催化作用：对丝氨酸蛋白酶催化的电荷转移机制的影响。
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本文引用的文献
1
Role of a buried acid group in the mechanism of action of chymotrypsin.一个埋藏的酸性基团在胰凝乳蛋白酶作用机制中的作用。
Nature. 1969 Jan 25;221(5178):337-40. doi: 10.1038/221337a0.
2
Carbon nuclear magnetic resonance studies of the histidine residue in alpha-lytic protease. Implications for the catalytic mechanism of serine proteases.α-裂解蛋白酶中组氨酸残基的碳核磁共振研究。对丝氨酸蛋白酶催化机制的启示。
Biochemistry. 1973 Nov 6;12(23):4732-43. doi: 10.1021/bi00747a028.
3
Applications of natural-abundance nitrogen-15 nuclear magnetic resonance to large biochemically important molecules.天然丰度氮-15核磁共振在大型生物化学重要分子中的应用。
Proc Natl Acad Sci U S A. 1975 Dec;72(12):4696-700. doi: 10.1073/pnas.72.12.4696.
4
Mechanism of action of serine proteases: tetrahedral intermediate and concerted proton transfer.丝氨酸蛋白酶的作用机制：四面体中间体与协同质子转移
Biochemistry. 1976 Dec 14;15(25):5581-8. doi: 10.1021/bi00670a024.
5
Energetics of enzyme catalysis.酶催化的能量学
Proc Natl Acad Sci U S A. 1978 Nov;75(11):5250-4. doi: 10.1073/pnas.75.11.5250.
6
Model for "charge-relay": acceleration by carboxylate anion in intramolecular general base-catalyzed ester hydrolysis by the imidazolyl group.“电荷中继”模型：咪唑基在分子内广义碱催化的酯水解中被羧酸根阴离子加速。
Proc Natl Acad Sci U S A. 1977 Jul;74(7):2634-8. doi: 10.1073/pnas.74.7.2634.
7
Intramolecular general base-catalyzed ester hydrolyses by the imidazolyl group.由咪唑基进行的分子内广义碱催化的酯水解反应。
Proc Natl Acad Sci U S A. 1977 Jan;74(1):23-5. doi: 10.1073/pnas.74.1.23.
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