Metal-based Electron Transfer Processes under Confinement: A Kinetic and Spectroscopic Study of Modified Reactivity in Oil-water RM Microemulsions

约束下金属基电子转移过程：油水 RM 微乳液中改性反应性的动力学和光谱研究

• 批准号: 1213594
• 负责人: Michael Johnson
• 金额: $ 24万
• 依托单位: New Mexico State University
• 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: 2012-09-01 至 2017-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1213594&HistoricalAwards=false
• 关键词: Metal; based; Electron; Transfer; Processes

The Chemical Structure, Dynamics and Mechanisms Program supports Professor Michael D. Johnson of New Mexico State University to investigate and characterize the location of redox active metal complexes in reverse micelles (RMs) using a combination of NMR, UV-vis and FTIR techniques. The goal is to better understand complex reactivity as a function of compartmentalization via interfacial penetration, and to investigate catalysis via increased ion pairing at the interface. Microelectrode electrochemistry will be used to establish whether modified reactivity in RMs is due to a change in the Marcus driving force. Professor Johnson will also measure the rates of electron transfer for a set of complexes with systematic variation in complex charge (local electrostatics at the interface), location, hydrophobicity and ligand nucleophilicity. The aim is to correlate reactant location with thermodynamic parameters such as redox potentials. The work has potentially broad biological impact in the refining of metallodrug uptake efficiency and assimilation when redox chemistry precedes the onset of physiological activity, e.g., in anti-cancer agents (PtIV/II, RuIII/II) and vanadium agents for diabetes (VV/IV). The results may also help predict the rates of redox reactions in vivo within small molecule siderophores (FeIII/II). Non-biological applications include predictions of aqueous chemical reactivity within the cavities of catalytic microporous solids, and within the water droplets formed during electrospray MS, which have been assumed (but not verified) to be representative of the chemistry in bulk solution.Professor Johnson has extensive experience in student training and outreach and is especially committed to undergraduate research involving underrepresented groups, particularly Hispanic and Native American students. He is directly involved in a Minority Access to Research Careers program at NMSU - one of the largest MARC programs in the country, sending 8-10 graduating senior students per year to graduate programs in the physical and life sciences. Other students have gone on for MD, DDS, DPharm., D.Psy. or other post graduate degrees. Through this program Professor Johnson has impacted over 200 undergraduates during the past 15 years. Professor Johnson also participates in the Bridges programs at NMSU, whose mission is to increase the transfer rate of Native American Students in Arizona and New Mexico from area community colleges to 4-year degree programs. He is also active in the annual Undergraduate Research and Creative Arts Symposium (URCAS) at NMSU.

化学结构、动力学和机制项目支持新墨西哥州立大学的Michael D. Johnson教授使用NMR、UV-vis和FTIR技术的组合来研究和表征反胶束（RMs）中氧化还原活性金属配合物的位置。目标是通过界面渗透更好地理解复杂反应性作为区隔化的功能，并通过界面上离子配对的增加来研究催化作用。微电极电化学将用于确定rm中的修饰反应性是否由于马库斯驱动力的变化。约翰逊教授还将测量一组配合物的电子转移率，这些配合物在配合电荷（界面处的局部静电）、位置、疏水性和配体亲核性等方面有系统的变化。目的是将反应物位置与热力学参数（如氧化还原电位）联系起来。当氧化还原化学先于生理活性开始时，这项工作对金属药物摄取效率和同化的改善具有潜在的广泛生物学影响，例如抗癌药物（PtIV/II, RuIII/II）和糖尿病钒药物（VV/IV）。该结果也可能有助于预测小分子铁载体（FeIII/II）体内氧化还原反应的速率。非生物应用包括预测催化微孔固体腔内的水化学反应性，以及电喷雾质谱过程中形成的水滴内的化学反应性，这些都被认为（但尚未得到验证）可以代表散装溶液中的化学反应。约翰逊教授在学生培训和拓展方面拥有丰富的经验，尤其致力于涉及代表性不足群体的本科生研究，特别是西班牙裔和美洲原住民学生。他直接参与了NMSU的少数族裔研究职业项目，这是全国最大的MARC项目之一，每年送8-10名即将毕业的高年级学生去攻读物理和生命科学的研究生课程。其他学生继续攻读医学博士、法学博士和药学博士。, D.Psy。或者其他研究生学位。通过这个项目，约翰逊教授在过去的15年里影响了200多名本科生。约翰逊教授还参与了新密歇根州立大学的桥梁项目，该项目的任务是提高亚利桑那州和新墨西哥州土著美国学生从地区社区学院转学到四年制学位课程的比率。他还积极参加了每年一度的NMSU本科生研究与创意艺术研讨会（URCAS）。