CAREER: Photoactivatable atomic oxygen precursors for the rapid, selective oxidation of biological thiols to sulfenic acids

在化学结构，动力学和机制B和生命过程化学项目的支持下，圣刘易斯大学的Ryan McCulla教授将探索原子氧与生物分子的反应性以及由此产生的瞬态氧化产物。 最初的研究表明，原子氧是一种比其他活性氧更有选择性的氧化剂。 这种选择性与原子氧的光化学释放相结合，允许研究活性中间体，否则将难以表征。 特别是，将通过利用光活化原子氧前体和计算方法研究生理相关条件下的次磺酸化学。 亚磺酸通常是细胞内氧化还原控制过程中的假定中间体。 除非特别稳定，简单的次磺酸不能分离，这使得研究它们的反应性具有挑战性。 一个互补的教育计划，整合计算化学与引导探究方法也将被开发。 计算方法的使用使学生能够快速生成数据，从而使学生在探索化学概念的同时发挥创造力。 该计划的有效性将通过在当地高中实施短期课程来评估，这些高中主要由科学代表性不足的群体组成。 除了提高对化学概念的理解外，该计划还旨在通过让学生接触创造力在科学发现中所起的作用来激励他们从事科学事业。

With support of this CAREER award from the Chemical Structure, Dynamics, and Mechanisms B and Chemistry of Life Processes Programs, Professor Ryan McCulla of Saint Louis University will explore the reactivity of atomic oxygen with biomolecules and the resulting transient oxidation products. Initial studies have indicated that atomic oxygen is a more selective oxidant than other reactive oxygen species. This selectivity combined with the photochemical release of atomic oxygen allows the study of reactive intermediates that would otherwise be difficult to characterize. In particular, the chemistry of sulfenic acids in physiologically relevant conditions will be investigated by utilizing photo-activatable atomic oxygen precursors and computational methods. Sulfenic acids are often putative intermediates in redox-controlled processes within cells. Unless specifically stabilized, simple sulfenic acid cannot be isolated, which makes studying their reactivity challenging. A complementary educational program that integrates computational chemistry with guided inquiry method will also be developed. The use of computational methods allows students to rapidly generate data, which allows students to use their creativity while exploring chemical concepts. The effectiveness of this program will be assessed by implementing a short course in local high schools, which are largely populated by groups underrepresented in science. In addition to improved understanding of chemical concepts, this program seeks to inspire students to pursue careers in science by exposing them to the role creativity plays in scientific discovery.