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

马奎特大学的Adam Fiedler教授在化学系化学催化(CAT)计划的支持下，设计和合成了模拟金属酶功能的过渡金属络合物。更具体地说，PI主要针对Fe(II)与聚咪唑配体的络合物，以模拟几种铁加氧酶中发现的3His基序，这些加氧酶利用O2来裂解污染物的C-C键。具有一系列电子和空间性质的配合物将通过灵活的合成方法来制备，并将在不同的条件下探索它们催化双氧反应的能力。将使用一系列光谱和计算工具来获得所得到的络合物的详细的几何结构和电子结构描述。此外，PI将使用一系列具有非配位基团的生物相关配体，能够形成分子内氢键，从而深入了解已知在酶功能中重要的第二球相互作用。含金属的双加氧酶能够将氧原子结合到碳氢化合物中，从而启动其降解过程。拟议的研究将产生重大的环境修复影响，因为它可能导致能够促进作为主要环境污染物类别的单环烃和多环烃的有氧降解的复合体。通过马奎特大学已经管理的推广项目，将为来自代表性不足和低收入群体的学生提供研究机会，并将为大学预科和本科科学实验室项目准备环境修复和氧化催化的实验室实验。

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.