CAREER: Biomimetic Chemistry Relevant to Nonheme Iron Dioxygenases Involved in Bioremediation Processes

马奎特大学的Adam Fiedler教授得到化学系化学催化（CAT）项目的支持，设计和合成模拟金属酶功能的过渡金属络合物。更具体地说，PI主要靶向具有聚咪唑配体的Fe（II）络合物，以模拟在几种铁加氧酶中发现的3 His基序，所述铁加氧酶使用O2切割污染物的C-C键。将使用灵活的合成方法制备具有一系列电子和空间特性的复合物，并在各种条件下探索其催化双氧化反应的能力。一系列的光谱和计算工具将被用来获得详细的几何和电子结构的描述所产生的复合物。此外，PI将采用一系列生物相关的配体与能够形成分子内氢键的非配位基团，从而提供对已知在酶功能中重要的第二球相互作用的深入了解。含金属的双加氧酶能够将氧原子掺入烃中，从而启动其降解过程。拟议的研究将产生重大的环境补救影响，因为它可能导致能够促进单环和多环碳氢化合物的好氧降解的复合物，这是一种主要的环境污染物。研究机会将提供给来自代表性不足和低收入群体的学生，通过已经在马奎特大学管理的外展计划，并将为大学预科和本科科学实验室计划准备环境修复和氧化催化实验室。

Professor Adam Fiedler of Marquette University is supported by the Chemical Catalysis (CAT) Program in the Division of Chemistry to design and synthesize transition metal complexes that mimic the function of metalloenzymes. More specifically, the PI is mainly targeting Fe(II) complexes with polyimidazole ligands to mimic the 3His motif found in several iron oxygenases which use O2 to cleave the C-C bonds of pollutants. Complexes with a range of electronic and steric properties will be prepared using a flexible synthetic approach, and their ability to catalyze dioxygenation reactions will be explored under various conditions. An array of spectroscopic and computational tools will be used to obtain detailed geometric- and electronic-structure descriptions of the resulting complexes. In addition, the PI will employ a series of biologically-relevant ligands with non-coordinating groups capable of forming intramolecular hydrogen-bonds, thereby providing insight into second-sphere interactions that are known to be significant in enzymatic function.Metal-containing dioxygenases are capable of incorporating oxygen atoms into hydrocarbons, thus initiating their degradation process. The proposed research will have a significant environmental remediation impact, in that it could potentially lead to complexes that are capable of facilitating the aerobic degradation of single and multi-ring hydrocarbons which are a major class of environmental pollutants. Research opportunities will be provided to students from underrepresented and low-income groups through outreach programs already administered at Marquette University, and laboratory experiments on environmental remediation and oxidation catalysis will be prepared for pre-college and undergraduate science laboratory programs.