Stereodynamic Coordination Complexes

立体动力学配位络合物

• 批准号: 0848234
• 负责人: James Canary
• 金额: $ 54万
• 依托单位: New York University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2009
• 资助国家: 美国
• 起止时间: 2009-07-01 至 2013-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0848234&HistoricalAwards=false
• 关键词: Stereodynamic; Coordination; Complexes

Over the last several years, the Canary laboratory has discovered bistable molecules that can be electrically switched between two distinct states. These substances are complexes of copper with three-armed organic ligands that exhibit a molecular propeller-like twist, the pitch of which can be modulated or inverted. Mechanistic investigations revealed that oxidation/reduction of the central copper ion led to exchange of the atoms bound to the metal which in turn resulted in dramatic changes in the conformation and shape of the organic portion of the complex. In this grant cycle, electron-induced changes in conformation of the organic ligand will be applied to three problems. First, the reorientation of two of the arms in the three-arm complexes will be used to study take-up and release of neurotransmitter-like guest molecules and electrically controlled catalysis of organic reactions. Such technology could enable electronic control of chemical signaling, catalysis, or open new strategies for redox-mediated drug delivery. Second, ligand reorganization will be used to construct a molecule that can be extended or retracted with an electrical trigger, affording a nanometer-scale electromechanical transducer whose properties will be probed by atomic force microscopy (AFM). Such materials could be of interest for valves and constrictors in nanodevices. Third, the principles used to develop the three-arm copper complexes will be applied to the design of peptides that reversibly convert between alpha-helical and beta-sheet secondary structures upon electronic stimulation. Besides potential materials applications, such peptide transitions may be relevant to processes associated with redox stress in biological systems or neurodegenerative disease. This research project will be undertaken by undergraduate and graduate students and postdoctoral fellows, including individuals from underrepresented groups, who will learn valuable synthetic and physical skills that will enable them to become productive contributors to our nation?s research enterprise. Summers will include participation by faculty from predominantly undergraduate institutions as well as New York City high school students. The members of the research team will participate in annual outreaches at public museums and other K-12 activities. The project leader will serve the scientific community by organizing and facilitating interdisciplinary conferences and discussion groups.

在过去的几年里，金丝雀实验室已经发现了可以在两种不同状态之间进行电转换的电子分子。 这些物质是铜与三臂有机配体的络合物，其表现出分子螺旋桨状扭曲，其螺距可以调节或反转。机理研究表明，中心铜离子的氧化/还原导致与金属结合的原子的交换，这反过来又导致络合物的有机部分的构象和形状的急剧变化。 在这个赠款周期中，电子诱导的有机配体构象的变化将应用于三个问题。首先，在三臂复合物中的两个臂的重新取向将用于研究神经递质样客体分子的吸收和释放以及有机反应的电控催化。这种技术可以实现化学信号、催化的电子控制，或为氧化还原介导的药物递送开辟新的策略。其次，配体重组将用于构建一个分子，可以延长或收回的电触发，提供纳米级的机电换能器，其属性将被探测原子力显微镜（AFM）。这种材料可能对纳米器件中的阀门和收缩器感兴趣。第三，用于开发三臂铜络合物的原理将应用于设计在电子刺激时在α-螺旋和β-折叠二级结构之间可逆转化的肽。 除了潜在的材料应用之外，这种肽转变可能与生物系统或神经退行性疾病中与氧化还原应激相关的过程有关。 这个研究项目将由本科生、研究生和博士后研究员进行，包括来自代表性不足群体的个人，他们将学习有价值的合成和物理技能，使他们能够成为我们国家的富有成效的贡献者。的研究企业。 暑期将包括来自主要本科院校的教师以及纽约市高中学生的参与。研究小组的成员将参加公共博物馆和其他K-12活动的年度外展活动。 项目负责人将通过组织和促进跨学科会议和讨论小组为科学界服务。