Rational Design of Fluorinated Environments for Aerobic "Green" Catalysis

0967934巴拉特将由教授进行的工作。新泽西理工学院的Barat和Gorun正在设计活性催化剂，这些催化剂本质上是微型反应容器。这一特征使它们类似于酶催化剂位点。PI打算使用全氟酞菁作为疏水容器，围绕亲水金属中心，用于硫醇有氧氧化为二硫化物。这些全氟酞菁应该比其他氧化催化剂更能抵抗催化产生的氧自由基的破坏，这是酶的另一个共同特征。 提出的工作是一个简单的研究配体结构对催化剂活性和稳定性的影响。作者建议研究均相自由基氧化的动力学，以及评估催化剂的多相化版本（钴基酞菁通过咪唑基与SiO2配位）。该项目旨在提供比以前的催化剂更“绿色绿色”的分子氧化催化剂，允许使用空气进行反应，而催化剂不会被氧气破坏。这是通过用催化剂物质中的非反应性C-F键取代反应性C-H键来实现的。通过使用催化剂的有机化学改性，可以进一步微调催化剂。研究人员选择了现在用于从汽油中去除硫的催化氧化作为研究的第一反应。这是一个有用的基准，并且成功将允许将该概念投射到其他催化剂和反应。这些研究将是感兴趣的社区在NJIT招生，和PI将涉及本科生在研究计划。

0967934BaratThe work which will be conducted by Profs. Barat and Gorun at New Jersey Institute of Technology is to design active catalyst species which are in essence miniature reaction vessels. This feature makes them similar to enzyme catalyst sites. The PIs intend to use perfluorinated phthalocyanines as hydrophobic vessels surrounding hydrophilic metal centers for the aerobic oxidation of mercaptans to disulfides. These perfluorinated phthalocyanines should be more resistant to damage by catalytically-produced oxygen radicals than other oxidation catalysts, which is another feature in common with enzymes. The work proposed is a straightforward study of the influence of ligand structure on catalyst activity, and stability. The authors propose to study the kinetics of the homogeneous radical-based oxidation, as well as evaluating heterogenized versions of the catalyst (Cobalt-based phthalocyanines coordinated to SiO2 through imidazolyl groups).The project aims to provide catalysts for oxidation of molecules which are more "green" than previous catalysts by allowing the use of air for the reaction without the catalyst being destroyed by the oxygen. This is done by replacing reactive C-H bonds with unreactive C-F bonds in the catalyst species. Further fine tuning of the catalyst is possible by using organic chemistry modifications of the catalyst. The investigators have chosen mercaptan oxidation, now used to remove sulfur from gasoline, as the first reaction for study. This is a useful benchmark, and success will allow projection of the concept to other catalysts and reactions. These studies will be of interest to the community enrolling at NJIT, and the PIs will involve undergraduates in the research program.