稀土配合物及稀土胶束模拟磷酸酯水解酶的分析-analysis of rare earth complexes and rare earth micelles simulating phosphate hydrolase.docxVIP

稀土配合物及稀土胶束模拟磷酸酯水解酶性能研究 稀土配合物及稀土胶束模拟磷酸酯水解酶性能研究 IV IV the most effective Ce(Ⅲ)-BS complexes was improved by 1.52× 108 times (kobsd = 1.67× 10-3s-1) to Spontaneous hydrolysis. The mole ratio of Ce(Ⅲ) to BS in catalytic activity species obtained from the Job curve of the hydrolysis of BNPP catalyzed by the Ce(Ⅲ) -BS system is 1:2. The changes of the apparent rate constant kobsd with the pH value are bell-shaped curves. And the constants also increase with the increasing temperature, the apparent activation energy of the hydrolysis reaction was figured out by Arrhenius formula. At last the catalytic mechanism of hydrolysis reaction was discussed. 3. The effects of the two novel cation gemini surfactants [C16H33N+(CH3)2- (CH2)2-N+(CH3)2C14H29].2Br- (C16-2-C16), [C14H29N+(CH3)2-CH2-O-CO2-CH2-N+ (CH3)2C14H29].2Br- (C14-1-C14) on the hydrolysis of BNPP catalyzed by the Ce(Ⅲ)– TEA and Ce(Ⅲ)–BS system were studied, and were compared with the two traditional surfactants cetyltrimethylammonium bromide(CTAB) and triton X-100. The results show that, the apparent rate constants of BNPP hydrolysis kobsd catalyzed by the two rare earth complexes in CTAB micelle were about an order of magnitude lower. The kobsd were increased by 1.87 times and 2.44 times to Spontaneous hydrolysis in triton X-100 micelle, and in C16-2- C16 micelle they were increased by 5.16 times and 1.85 times to Spontaneous hydrolysis. Hydrolysis of BNPP catalyzed by two kinds of rare earth complexes showed different results in C14-1-C14 micelle. We suppose that this is closely related to special structure of C14-1-C14. Key words: metal complex, metallomicelle, BNPP, hydrolysis, gemini surfactant 第一章 第一章 绪论 PAGE PAGE 10 第一章 绪论 生物体内进行的化学反应都是在温和的生理条件下 ,经酶催化快速地实现 的，这种反应最显著的特点就是高度的专一性和催化效率。而这种高选择性和 高效性正是因为所有生物体内都存在一类特殊蛋白质——酶。对酶的结构与功 能的研究，是理解生物进化过程的基础，而且酶催化反应是消耗小、效率高、 无污染的理想反应，是化学工业生产中最渴望达到的反应状态。由于酶是一种 敏感易变、结构复杂、来源有限的生物蛋白质，这都限制了对酶结构与功能的 探索与研究。所以开展对天然酶的模拟研究，从结构和功能上对天然酶进行模 拟，有助于研发有效的人工酶和进一步探索酶反应的机理。 天然酶的重要成员