CAREER: Imprinting Molecular Chirality In Solution During Photo-Transformations

在国家科学基金会有机和大分子化学计划的职业奖的支持下，北达科他州州立大学的Sivaguru Jayaraman教授将领导一项研究计划，该计划将专注于通过采用分子手性发色团在光诱导的不对称转化过程中控制立体选择的方法。该研究计划是高度跨学科的，并开辟了一个机会，以控制在解决方案中的立体选择在光转化，一个传统上困难的任务。该方法采用光作为试剂，在反应物中压印分子手性，从而导致溶液中光产物的手性。PI实验室的初步结果表明，在溶液中可以实现高达97%的对映选择性。这种方法学的巨大潜力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）。这些研究预计将提供，（a）通过旋转异构体控制的不对称光转化的新见解;和（B）将是分子手性的许多新结构。拟议的工作将补充现有的方法来控制反应性和选择性在phototransformation.This职业生涯奖教授Jayaraman的北达科他州州立大学将使用光访问手性分子在溶液中使用分子手性生色团的光转化过程中具有高立体选择性。与用于控制热反应中的选择性的常规方法相比，这代表了一个重大的范式转变。拟议活动的一个重要目标是通过对学生和研究人员进行最高科学、知识、专业和实验水平的探究方法的教学和培训，将教育与研究结合起来。拟议活动的一些更广泛的影响来自PI的承诺，采用信息，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。PI在北达科他州州立大学的第一年，成功地招募和监督了代表性不足的群体，其中包括一名少数民族本科生，一名女本科生和一名女州长学校学生。拟议研究的社会效益预计将在创造基础科学知识，培养学生在跨学科和合作研究方面的一系列经验和专业知识，以及建立研究与教育相结合的基础设施等领域。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，PI在法戈-穆尔黑德地区当地高中的帮助下，通过PICNICS（家长参与儿童，培养科学知识）方案提出并制定了系列讲座。

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.