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（CMI）计划化学结构，动力学和机制（CSDM）计划的支持下，佛蒙特大学的William盖革教授和他的团队正在寻求确定有机金属氧化还原标记在医学成像和表面科学中应用的新方向。它利用了强IR活性的“钢琴粪便”标签的单电子氧化，这些标签通过其Cp（Cp）或Cb（Cb）环键合到分子基质或导电表面。在标记之前或之后，一个或多个羰基配体可以使用“氧化还原转换”被供体配体取代，以操纵标签的化学和物理效应，包括E1/2电位、IR频率、亲脂性和拓扑结构。一个关键的目标是提供给化学和生物界的有机金属氧化还原标签的分子拓宽的工具箱具有显着的IR光谱特征，允许氧化还原和IR成像，甚至在细胞水平。阳极氧化的研究将进行化合物，其中MCp（CO）3（M = Mn，Re）基团标记到他莫昔芬作为一个模型，允许，第一次，成像的位置和氧化还原状态的有机金属标签在生物系统中。为了提供进入一组分子多样性的强IR活性有机金属单层的目的，也将进行钢琴粪便与电极的共价连接。通过环加成点击附着在碳上的钢琴粪便化合物将与康奈尔大学能源材料中心合作，使用先进的表面分析方法进行表征。前所未有的CO-取代率，离子配对效应，和单体/二聚体的平衡在有机金属单分子膜的研究将进行，增加我们的理解的表面结合的有机金属的反应性。 这项研究的成功可能会为细胞成像的新方法奠定基础，其中分子标签的氧化还原状态可以作为时间和地点的函数进行跟踪。所提出的创新有机金属电接枝方法将拓宽化学改性导电表面的分子可能性，以及它们可以应用于催化，腐蚀，复合材料，传感器和能源需求的方式。与ENS巴黎和詹尼·斯沃茨教授以及南非自由州大学的其他学生和教师的密切合作将为该计划提供国际推广的一个方面。将通过在佛蒙特大学（UVM）的SEED项目实习以及从芝加哥州立大学或新墨西哥州大学招募的非裔美国人或西班牙裔夏季研究实习生来解决代表性不足群体的扩大问题。