Developing a Conceptual Framework for the Rare Dual-release Photochemistry of Sulfoximines and Sulfondiimines.

为亚磺酰亚胺和磺二亚胺的罕见双释放光化学开发概念框架。

• 批准号: 2247716
• 负责人: Ryan McCulla
• 金额: $ 49.6万
• 依托单位: Saint Louis University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-07-01 至 2026-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2247716&HistoricalAwards=false
• 关键词: Developing; Conceptual; Framework; Rare; Dual

With the support of the Chemical Structure, Dynamics & Mechanisms-B (CSDM-B) Program of the Chemistry Division, Professor Ryan McCulla of the Department of Chemistry at Saint Louis University will investigate the photochemistry of sulfoximines and sulfondiimines which are capable of releasing two different reactive intermediates upon irradiation with light. The goal of this research is to establish general principles that govern the sequence of photorelease of reactive intermediates by sulfoximines and sulfondiimines. Sulfoximines are one of the few classes of compounds that are capable of undergoing dual-release photochemistry, and this project is expected to establish which properties regulate the sequence of release. By providing a basis to control the sequence of photorelease, this project is expected to facilitate the development of dual-release photochemistry for uses in biochemical assays and phototherapies. Summer research opportunities and events promoting scientific career options for high school students from underrepresented groups will also be part of the funded project.The generation of two different reactive intermediates from a single chromophore is a rare occurrence in photochemistry. One of the few examples is the release of nitrenes and atomic oxygen from dibenzothiophene sulfoximines upon irradiation with light. The scarcity of systems capable of undergoing dual-release photochemistry means there is no conceptual framework to predict which properties will control the sequence of release. Thus, the overall objective of this project is to establish the general principles that govern dual-release photochemistry by investigating the photochemistry of thiophene-based sulfoximines. Specifically, the effect of modulating the bond dissociation energies and the excited state properties on the sequence of release will be interrogated with computational and spectroscopic methods. The second important objective of this proposal is to test the generality of the proposed framework by examining if the principles observed for sulfoximines can predict the sequence of release for sulfondiimines. The intriguing potential of dual-release photochemistry arises from the proximity that two reactive intermediates can be produced, which is expected to allow two transient intermediates to combine to form new intermediates that are inaccessible by other means.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

圣路易斯大学化学系的Ryan McCulla教授将在化学系化学结构、动力学和机理- b （CSDM-B）项目的支持下，研究亚砜亚胺和磺基二亚胺的光化学性质，这两种物质在光照射下能够释放两种不同的反应中间体。本研究的目的是建立控制亚砜亚胺和磺胺二亚胺的反应性中间体光释放顺序的一般原则。亚砜亚胺是少数几种能够进行双重释放光化学的化合物之一，该项目有望确定哪些性质调节释放顺序。通过提供控制光释放顺序的基础，该项目有望促进双释放光化学的发展，用于生化分析和光治疗。夏季研究机会和促进来自代表性不足群体的高中生的科学职业选择的活动也将成为资助项目的一部分。在光化学中，由一个发色团生成两种不同的反应中间体是很少见的。为数不多的例子之一是二苯并噻吩亚砜在光照射下释放亚硝基和原子氧。能够进行双释放光化学的系统的稀缺性意味着没有概念框架来预测哪些性质将控制释放顺序。因此，该项目的总体目标是通过研究噻吩基亚砜的光化学，建立控制双释放光化学的一般原则。具体地说，调节键解离能和激发态性质对释放顺序的影响将用计算和光谱方法来研究。本建议的第二个重要目标是通过审查对亚砜亚胺所观察到的原则是否能够预测亚砜二胺的释放顺序，来检验所提议的框架的普遍性。双释放光化学的有趣潜力来自于可以产生两种反应中间体的接近性，这有望使两种瞬态中间体结合形成其他方法无法获得的新中间体。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。