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

化学结构、动力学和机理计划支持新墨西哥州立大学的Michael D.Johnson教授结合使用核磁共振、UV-Vis和FTIR技术来研究和表征氧化还原活性金属络合物在反胶束(RMS)中的位置。我们的目标是通过界面渗透更好地理解复杂的反应活性作为隔室作用的函数，并通过增加界面上的离子对来研究催化作用。微电极电化学将被用来确定RMS中的修饰反应是否由于马库斯驱动力的变化。约翰逊教授还将测量一组络合物的电子转移速率，这些络合物的复电荷(界面上的局部静电性)、位置、疏水性和配体亲核性都有系统的变化。其目的是将反应物的位置与氧化还原电位等热力学参数相关联。这项工作在精炼金属药物摄取效率和同化方面具有潜在的广泛生物学影响，例如在抗癌药物(PtIV/II，RuIII/II)和糖尿病钒试剂(VV/IV)中，当氧化还原化学发生在生理活性开始之前。研究结果还有助于预测体内小分子铁载体的氧化还原反应速率(FeIII/II)。非生物应用包括预测在催化微孔固体的空腔内和在电喷雾MS过程中形成的水滴内的水的化学反应，这些被认为(但未被证实)代表了大量溶液中的化学。约翰逊教授在学生培训和推广方面有丰富的经验，尤其致力于涉及代表性不足的群体的本科生研究，特别是西班牙裔和美洲原住民学生。他直接参与了NMSU的少数族裔访问研究职业计划-全国最大的MARC计划之一，每年送8-10名毕业的大四学生参加物理和生命科学的研究生课程。其他学生则继续攻读医学博士、医学博士。或其他研究生学位。在过去的15年里，约翰逊教授通过这个项目影响了200多名本科生。约翰逊教授还参与了NMSU的布里奇斯项目，该项目的使命是提高亚利桑那州和新墨西哥州的美国原住民学生从地区社区大学到四年制学位课程的转化率。他还积极参加了国立大学每年一度的本科生研究与创意艺术研讨会(URCAS)。

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.