CAREER: Imprinting Molecular Chirality In Solution During Photo-Transformations

在美国国家科学基金会有机和大分子化学项目CAREER奖的支持下，北达科他州立大学的Sivaguru Jayaraman教授将领导一个研究项目，重点研究如何通过使用分子手性发色团来控制光诱导不对称转化过程中的立体选择。该研究项目是高度跨学科的，为控制光变换过程中溶液中的立体选择提供了机会，这是一项传统上困难的任务。该方法采用光作为试剂，在反应物中刻印分子手性，从而导致溶液中光产物的手性。PI实验室的初步结果表明，溶液中的对映体选择性高达97%。该方法为在光反应中获得具有高立体选择性的手性分子开辟了新的途径。作为项目的一部分，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)通过旋转体控制对不对称光转化的新见解；(b)大量具有分子手性的新结构。所提出的工作将补充现有的方法来控制光转化过程中的反应性和选择性。该职业奖授予北达科他州立大学的Jayaraman教授，他将利用分子手性发色团在溶液的光转化过程中利用光获得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，这代表了一个主要的范式转变。拟议活动的一个重要目标是通过教学和培训学生和研究人员在最高的科学、智力、专业和实验水平上的探究方法，将教育和研究结合起来。所提议的活动的一些更广泛的影响来自PI的承诺，即采用信息、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。在北达科他州立大学的第一年，PI成功地招募并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体现在以下领域：创造基本科学知识，培养具有跨学科和合作研究的一系列经验和专门知识的学生，以及建立将研究与教育相结合的基础设施。在社区影响方面，正在作出特别努力，让父母和他们的孩子（9-12年级）一起了解现代科学技术的影响。为了开始这个过程，PI在Fargo-Moorhead地区当地高中的帮助下，通过PICNICS（父母参与孩子，培养科学中的求知欲）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.