RUI: Mechanistic Studies of Encapsulated Metalloenzymes

无机，生物无机和有机化学计划的这一奖项支持汉密尔顿学院的Timothy Elgren教授使用溶胶-凝胶包封酶作为分离和表征酶催化循环中中间体的方法。 酶的包封1）抑制分子间缩合，2）减慢反应动力学，和3）允许反应在非质子溶剂中进行，从而产生水限制性环境。本研究利用溶胶-凝胶材料的这些特点，对以下几个方面进行了机理研究：1）含铜胺氧化酶的氧活化; 2）过氧化物酶催化的卤化反应; 3）过氧化物酶催化的氧化脱卤反应。 溶胶-凝胶可以常规地浇铸成各种取样配置，当与溶胶-凝胶材料的透明性质结合时，其允许光谱表征，包括UV-Vis吸收、共振拉曼和EPR。该提案概述了一种独特的方法来捕获和表征酶周转周期中的催化中间体。 这项工作将完全与本科生合作完成。每年将邀请两名参加奥奈达国家/汉密尔顿学院联合暑期科学项目的美国原住民高中学生参加为期两周的暑期项目。鼓励学生在美国化学学会的全国会议上介绍他们的工作。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Timothy Elgren at Hamilton College to use sol-gel encapsulation of enzymes as a method for isolating and characterizing intermediates in the enzyme catalytic cycle. Encapsulation of the enzymes 1) inhibits intermolecular disproportionation, 2) slows reaction kinetics, and 3) allows reactions to be run in aprotic solvents creating a water-limiting environment. The proposed studies take advantage of these aspects of the sol-gel materials and will provide mechanistic insight into: 1) Oxygen activation in copper-containing amine oxidase, 2) Halogenations catalyzed by peroxidases, 3) Oxidative dehalogenations catalyzed by peroxidases. Sol-gels can be routinely cast in a variety of sampling configurations which, when combined with the transparent nature of the sol-gel materials, allows for spectroscopic characterization, including UV-Vis absorption, resonance Raman, and EPR. This proposal outlines a unique approach to trapping and characterizing catalytic intermediates in the turnover cycles of enzymes. The work will be done entirely in collaboration with undergraduate students. Two Native American high school students participating in the Oneida Nation/Hamilton College Joint Summer Science Program will be invited each year to participate in the project during the two-week summer program. Students will be encouraged to present the work at the national meeting of the American Chemical Society.