New Redox Tags For Bioorganometallic Chemistry and Electrode Modification

用于生物有机金属化学和电极修饰的新型氧化还原标签

• 批准号: 1212339
• 负责人: William Geiger
• 金额: $ 40万
• 依托单位: University of Vermont & State Agricultural College
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2012
• 资助国家: 美国
• 起止时间: 2012-08-15 至 2017-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1212339&HistoricalAwards=false
• 关键词: New; Redox; Tags; Bioorganometallic; Chemistry

With support from the Chemical Measurement and Imaging (CMI) Program the Chemical Structure, Dynamics and Mechanisms (CSDM) Program in the Division of Chemistry, Professor William Geiger and his group at the University of Vermont are seeking to identify new directions in the application of organometallic redox tags to medical imaging and to surface science. It takes advantage of the one-electron oxidation of strongly IR-active "piano-stool" tags bonded to molecular substrates or to conducting surfaces through their cyclopentadienyl (Cp) or cyclobutadiene (Cb) rings. Before or after tagging, one or more carbonyl ligands can be substituted by donor ligands using "redox switching" to manipulate both the chemical and physical effects of the tag, including E1/2 potential, IR frequency, lipophilicity, and topology. A key goal is to provide to the chemical and biological communities a molecularly broadened toolbox of organometallic redox tags having a dramatic IR spectroscopic signature, allowing redox and IR imaging even at the cellular level. Anodic oxidative studies will be carried out for compounds in which MCp(CO)3 (M = Mn, Re) groups are tagged to tamoxifen as a model to allow, for the first time, imaging of both the location and redox state of organometallic tags in biological systems. Covalent attachment of piano-stools to electrodes will also be carried out for the purpose of providing entry to a molecularly diverse set of strongly IR-active organometallic monolayers. Piano-stool compounds anchored via cycloadditon click attachment to carbon will be characterized using advanced surface analysis methods in collaboration with the Energy Materials Center at Cornell University. Unprecedented studies of CO-substitution rates, ion-pairing effects, and monomer/dimer equilibria in organometallic monolayers will be carried out, increasing our understanding of the reactivities of surface-bound organometallics. Success in the proposed research could lead to the basis of a new approach to cell imaging, one in which the redox state of a molecular tag can be followed as a function of time and place. The proposed innovative organometallic electro-grafting methods will broaden the molecular possibilities for chemically-modified conducting surfaces, and the ways in which they may be applied to needs in catalysis, corrosion, composite materials, sensors, and energy. Strong collaborations with ENS Paris and with Prof. Jannie Swarts and other students and faculty at the University of the Free State in South Africa will provide an aspect of international outreach to the program. Expansion of the pool of underrepresented groups will be addressed through Project SEED internships at the University of Vermont (UVM) and by inclusion of African-American or Hispanic summer research interns at UVM recruited from either Chicago State University or the University of New Mexico.

在化学测量和成像计划（CMI）计划的支持下，化学结构，动力学和机制（CSDM）在化学划分中，William Geiger教授及其佛蒙特大学的小组寻求在应用机构层状标签在医学成像和表面科学方面确定新方向。它利用了与分子底物键合的强大IR活性“钢琴凳”标签的单电子氧化，或通过其环戊二烯基（CP）或环丁二烯（CB）环进行表面。在标记之前或之后，可以使用“氧化还原切换”来代替一个或多个羰基配体，以操纵标签的化学和物理效应，包括E1/2电位，IR频率，亲脂性和拓扑。一个关键目标是为化学和生物群落提供具有巨大IR光谱特征的有机金属氧化还原标签的分子宽的工具箱，即使在细胞水平上也可以氧化还原和IR成像。将对MCP（CO）3（M = MN，RE）组的化合物进行阳极氧化研究，将其标记为他莫昔芬，作为一种模型，以首次允许对生物系统中有机金属标签的位置和氧化还原状态进行成像。还将进行钢琴凳子与电极的共价附着，目的是为了提供一组分子多样的强大的IR活性有机金属单层。通过CycloadDiton点击附件固定在碳上的钢琴台化合物将使用高级表面分析方法与康奈尔大学的能量材料中心合作。将对有机金属单层中的共同判例速率，离子配对效应和单体/二聚体平衡进行前所未有的研究，从而增强我们对表面结合有机金属的反应性的理解。 在拟议的研究中的成功可能会导致一种新的细胞成像方法，其中可以跟踪分子标签的氧化还原状态，这是时间和地点的函数。所提出的创新有机金属电解方法将扩大化学修饰的导电表面的分子可能性，以及它们可用于催化，腐蚀，复合材料，传感器和能量的需求的方式。与ENS巴黎以及南非自由州大学的其他学生以及其他学生以及其他学生以及教职员工的牢固合作将为该计划提供国际宣传的方面。将通过佛蒙特州（UVM）的Project Seed Internhips来解决代表性不足的群体的扩建，并通过芝加哥州立大学或新墨西哥大学招募的UVM的非裔美国人或西班牙裔夏季研究实习生包括在内。