CAREER: Roles of Transition Metals in Dioxygen Activation and Superoxide Scavenging

无机化学、生物无机化学和金属有机化学项目的这一职业奖支持约翰霍普金斯大学的贾斯汀·罗斯教授通过测定氧同位素效应来探索O2与过渡金属的相互作用。对自然丰度中O-16和O-18比值变化的测量将揭示在氧气与过渡金属试剂相互作用中发挥作用的热力学和动力学因素。氧化还原过程中氧键的变化在工业氧化和氧气作为能源的生物利用中是重要的。将研究金属-O2加合物的性质，并收集电化学数据以解决这些物种执行C-H和O-H氧化的能力。我们将探讨电子、质子和氢原子转移反应的驱动力和速率之间的关系。巴尔的摩将在与马里兰科学中心相关的暑期研讨会的基础上，为中学年龄女性提供密集的指导计划。经过两年以演示为中心的研讨会，第三年将专注于为科学中心制作生物技术展示。氧化过程在生物系统和工业环境中非常重要。元素氧与过渡金属络合物的相互作用机理与大尺度化学和生物化学有关。比较氧同位素的动力学分布和平衡分布将有助于深入了解金属络合物和有机底物中氧的活化和结合所伴随的成键变化。

This CAREER award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports work by Professor Justine Roth at Johns Hopkins University to probe the interaction of O2 with transition metals via the determination of oxygen isotope effects. Measurements of the variation in O-16 and O-18 ratios from natural abundance will reveal thermodynamic and kinetic factors that play a role in the interaction of dioxygen with transition metal reagents. Changes in oxygen bonding during redox processes are important in industrial oxidations and in biological utilzation of O2 as an energy source. The properties of metal-O2 adducts will be investigated, and electrochemical data will be gathered to address the ability of these species to carry out C-H and O-H oxidations. Correlations between driving-force and rate will be explored for electron, proton and hydrogen atom transfer reactions. An intensive mentoring program for middle school aged females in Baltimore will build on summer workshops associated with the Maryland Science Center. After two years of centering the workshops on demonstrations, the third year will focus on crafting a biotechnology display for the science center.Oxidation processes are important in biological systems and in industrial settings. The mechanism of elemental dioxygen interacting with transition metal complexes is relevant to large scale chemistry and biochemistry. Comparing kinetic and equilibrium distributions of oxygen isotopes will provide insight into the bonding changes that accompany activation and incorporation of oxygen into metal complexes and organic substrates.