CAREER: Imprinting Molecular Chirality In Solution During Photo-Transformations

在美国国家科学基金会有机和高分子化学计划职业奖的支持下，北达科他州州立大学的西瓦鲁鲁·贾亚拉曼教授将领导一项研究计划，重点是通过使用分子手性发色团来控制光诱导的不对称转化过程中的立体选择。该研究计划是高度跨学科的，并为在光转化过程中控制溶液中的立体选择打开了机会，这是一项传统上困难的任务。该方法使用光作为试剂，在反应物中印迹分子手性，从而在溶液中的光产物中产生手性。PI实验室的初步结果表明，在溶液中，对映体选择性可高达97%。这一方法学提供了巨大的希望，将为在光反应中获得具有高立体选择性的手性分子开辟新的途径。作为该计划的一部分，PI将探索各种立体选择性光诱导过程(电子和能量转移)。这些研究有望提供：(A)通过旋转异构体控制的不对称光转化的新见解；以及(B)大量分子手性的新结构。这项拟议的工作将补充现有的控制光转化过程中的反应性和选择性的方法。这项授予北达科他州州立大学Jayaraman教授的职业奖项将利用光在溶液中利用分子手性发色团在光转化过程中访问具有高立体选择性的手性分子。与用于控制热反应选择性的传统方法相比，这是一个重大的范式转变。拟议活动的一个重要目标是通过在最高科学、智力、专业和实验水平上对学生和研究人员进行探究方法的教学和培训，将教育和研究结合起来。拟议活动的一些更广泛的影响来自于PI承诺利用信息、教学和学习技术的最新发展，特别是计算机和相关技术(便于理解概念的动画)和万维网，在本科生和教师之间建立智力伙伴关系。在北达科他州立大学的第一年，PI成功地招募和监督了代表性不足的团体，其中包括一名少数族裔本科生、一名女本科生和一名州长学校的女学生。预计拟议研究的社会效益将体现在创造基本科学知识、培训具有跨学科和合作研究方面各种经验和专门知识的学生以及建立研究与教育相结合的基础设施方面。在社区影响方面，正在作出特别努力，让父母及其子女(9-12年级)共同了解现代科学技术的影响。为了开始这一进程，国际学生联合会在法戈-穆尔黑德地区当地高中的帮助下，通过野餐(家长参与儿童，培养对科学的好奇心)计划，提出并开发了一系列讲座。

With the support of a CAREER award from the Organic and Macromolecular Chemistry Program at the National Science Foundation, Professor Sivaguru Jayaraman of North Dakota State University will lead a research program that will focus on ways to control stereoselection during light-induced asymmetric transformations by employing molecularly chiral chromophores. The research program is highly interdisciplinary and opens up an opportunity to control stereoselection in solution during phototransformations, a traditionally difficult task. The methodology employs light as a reagent, to imprint molecular chirality in the reactant leading to chirality in the photoproducts in solution. Preliminary results from the PI's lab shows that enantioselectivity as high as 97% can be achieved in solution. Considerable promise offered by this methodology shall open up new approaches to access chiral molecules with high stereoselectivity in photoreactions. As part of the program, the PI will explore various stereoselective light induced processes (electron and energy transfer). These studies are expected to offer, (a) new insights into asymmetric phototransformations through rotamer control; and, (b) a multitude of new structures that will be molecularly chiral. The proposed work will complement the existing methodologies for controlling reactivity and selectivity during phototransformations.This CAREER award to Professor Jayaraman of North Dakota State University will use light to access chiral molecules with high stereoselectivity during phototransformations in solution using molecularly chiral chromophores. This represents a major paradigm shift in comparison to conventional methods that are used to control selectivity in thermal reactions. An important objective of the proposed activity is to integrate education and research through teaching and training of students and researchers in methods of inquiry at the highest scientific, intellectual, professional, and experimental levels. Some of the broader impacts of the proposed activities derive from the PI's commitment to employ the latest developments in information, instruction, and learning technologies, in particular, computers and related technology (animations for easy understanding of concepts) and the World Wide Web, to create intellectual partnerships between the undergraduates and the teacher. The PI, during the first year at North Dakota State University, has successfully recruited and supervised underrepresented groups that include one minority undergraduate, one female undergraduate, and one female Governor School student. Social benefits of the proposed research are expected to be in the areas of creation of basic scientific knowledge, training of students with a range of experience and expertise in interdisciplinary and collaborative research, and creation of an infrastructure for integration of research with education. In terms of community impact, special efforts are being made to inform both parents and their children (grades 9-12) together about the impact of modern science and technology. To begin this process, lecture series are being proposed and developed by the PI with the help of local high schools in the Fargo-Moorhead area through the PICNICS (Parents Involvement in Children, Nurturing Intellectual Curiosity in Science) program.