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

职业：光活化原子氧前体，用于将生物硫醇快速选择性氧化为次磺酸

• 批准号: 1255270
• 负责人: Ryan McCulla
• 金额: $ 57万
• 依托单位: Saint Louis University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-04-01 至 2019-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1255270&HistoricalAwards=false
• 关键词: CAREER; Photoactivatable; atomic; oxygen; precursors

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.

在化学结构、动力学和机制B以及生命过程化学项目的这一职业奖项的支持下，圣路易斯大学的Ryan Mcculla教授将探索原子氧与生物分子的反应以及由此产生的瞬时氧化产物。初步研究表明，与其他活性氧物种相比，原子氧是一种更具选择性的氧化剂。这种选择性与原子氧的光化学释放相结合，使得研究本来难以表征的活性中间体成为可能。特别是，将利用可光激活的原子氧前体和计算方法来研究生理相关条件下的磺酸的化学。在细胞内氧化还原控制的过程中，磺酸通常是假定的中间体。除非特别稳定，否则无法分离简单的磺酸，这使得研究它们的反应性具有挑战性。还将开发一个将计算化学与指导性探究方法相结合的互补教育项目。计算方法的使用使学生能够快速生成数据，这使得学生在探索化学概念的同时可以发挥他们的创造力。这项计划的有效性将通过在当地高中实施短期课程来评估，当地高中的人口主要是在科学领域代表性不足的群体。除了提高对化学概念的理解外，这个项目还试图通过让学生接触到创造力在科学发现中所起的作用来激励他们追求科学事业。