Chemical Dynamics and Green Chemistry Strategies with Organic Nanocrystals

美国国家科学基金会化学部的有机和大分子化学项目支持加州大学洛杉矶分校的Miguel Garcia-Garibay教授，他将利用绝对动力学测量的优势，对结晶固体的化学反应性进行更深入的了解。与此同时，他提出了雄心勃勃的绿色化学合成应用的步骤，包括具有挑战性的吡咯烷喹啉生物碱家族的天然产物。在本提案的第二部分，研究旨在更深入地了解一个非常令人兴奋的量子链脱碳反应最近建立了二苯基环丙烯晶体描述。Garcia-Garibay教授将研究这种反应的范围，包括揭示高发射、线性共轭发色团的结构。在本论文的第三部分，我们将在研究反应范围和空间极限的同时，探索对映选择性合成和经典的分辨策略来制备光纯化合物。对固态化学反应性的详细了解和预测将解决许多持续存在的问题，包括药物的不良分解，结构固体的降解和老化，以及固态器件的疲劳。除了这项工作在当前反应性理论的前沿所带来的挑战外，固体中的反应在过去几年中也引起了人们的极大兴趣，因为它们在发展绿色化学策略以减少有害溶剂的使用方面具有潜力。PI通过保持高度支持和创造性的环境，成功地吸引了女性和少数民族学生加入他的研究小组，培养了许多科学教育方面的职业。这项研究的影响超出了加州大学洛杉矶分校，尽管与邻近机构的同事合作，包括圣玛丽山大学（一所女子学院）、洛约拉玛丽蒙特大学（一所本科院校）和加州州立大学洛杉矶分校（一所拥有化学硕士课程的综合性大学），所有这些大学都有很高的西班牙裔和非裔美国学生入学率。

The Organic and Macromolecular Chemistry Program in the Chemistry Division at the National Science Foundation supports Professor Miguel Garcia-Garibay at the University of California- Los Angeles, who will seek to gain a deeper understanding of chemical reactivity in crystalline solids by taking advantage of absolute kinetic measurements. At the same time, he proposes steps towards ambitious green chemistry synthetic applications involving challenging natural products of the pyrrolidinoindoline alkaloid family. In the second part of this proposal, studies aimed at a deeper understanding of a very exciting quantum chain decarbonylation reaction recently established with crystals of diphenylcyclopropenone are described. Professor Garcia-Garibay will investigate the scope of this reaction to include structures that unveil highly emissive, linearly conjugated chromophores. In the third part of this proposal, while studying the scope and steric limits of the reaction, enantioselective syntheses and classic resolution strategies to prepare optically pure compounds will be explored. Detailed understanding and prediction of chemical reactivity in the solid state will address many on-going problems, which includes the undesirable decomposition of pharmaceuticals, the degradation and aging of structural solids, and the fatigue of solid state devices. In addition to challenges arising from this work being at the frontiers of current reactivity theories, reactions in solids have attracted a great deal of interest during the last few years due to their potential in the development of Green Chemistry strategies to reduce the use of harmful solvents. The PI has been successful in attracting women and minority students to his research group by maintaining a highly supportive and creative environment that has fostered many careers in science education. The impact of this research extends beyond UCLA though collaborations with colleagues from neighboring institutions, including Mount St. Mary University (a women's college), Loyola Marymount University (an undergraduate institution), and Cal State Los Angeles (a comprehensive university with a MS program in Chemistry), all of which have a high enrollments of Hispanic and African American students.