RUI: Mechanistic Studies of Encapsulated Metalloenzymes

这个无机、生物无机和有机金属化学项目的奖项支持汉密尔顿学院蒂莫西·埃尔格伦教授的研究，他使用酶的溶胶-凝胶包封作为分离和表征酶催化循环中间体的方法。酶的封装1)抑制分子间歧化，2)减缓反应动力学，3)允许反应在非质子溶剂中进行，创造一个限水环境。所提出的研究利用了溶胶-凝胶材料的这些方面，并将提供机制见解：1)含铜胺氧化酶的氧活化，2)过氧化物酶催化的卤化，3)过氧化物酶催化的氧化脱卤。溶胶-凝胶可以常规浇铸成各种采样配置，当结合溶胶-凝胶材料的透明性质时，可以进行光谱表征，包括紫外-可见吸收，共振拉曼和EPR。本提案概述了一种独特的方法来捕获和表征酶周转循环中的催化中间体。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生参加为期两周的暑期项目。学生将被鼓励在美国化学会的全国会议上展示他们的工作。

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.