RUI: Mechanistic Studies of Encapsulated Metalloenzymes

无机化学、生物无机化学和金属有机化学项目的这一奖项支持了汉密尔顿学院的蒂莫西·埃尔格伦教授的研究，该研究使用溶胶凝胶法对酶进行封装，作为分离和表征酶催化循环中中间体的方法。酶的包裹1)抑制了分子间歧化，2)减缓了反应动力学，3)允许反应在非质子溶剂中进行，从而创造了限制水的环境。这些研究利用了溶胶-凝胶材料的这些方面，并将从机理上深入了解：1)含铜胺氧化酶中的氧活化，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化反应。Sol-Gel可以常规地以各种采样配置浇注，当与Sol-Gel材料的透明性质相结合时，允许进行光谱表征，包括UV-Vis吸收、共振拉曼和EPR。这项提案概述了一种在酶的周转周期中捕获和表征催化中间体的独特方法。这项工作将完全与本科生合作完成。参加奥奈达民族/汉密尔顿学院联合暑期科学计划的两名美洲原住民高中生将在为期两周的暑期计划期间每年被邀请参加该项目。学生将被鼓励在美国化学学会的全国会议上展示这项工作。

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.