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

化学结构，动力学和机制计划支持教授迈克尔D。约翰逊的新墨西哥州州立大学的研究和表征氧化还原活性金属络合物在反胶束（RM）中的位置，使用NMR，UV-vis和FTIR技术的组合。 我们的目标是更好地理解复杂的反应性作为通过界面渗透的区室化的函数，并通过增加界面处的离子配对来研究催化作用。 微电极电化学将用于确定RM中的反应性是否因Marcus驱动力的变化而改变。 约翰逊教授还将测量一组复合物的电子转移速率，这些复合物具有复合物电荷（界面处的局部静电）、位置、疏水性和亲核性的系统变化。 其目的是关联反应物的位置与热力学参数，如氧化还原电位。 当氧化还原化学先于生理活性开始时，这项工作在金属药物摄取效率和同化的精炼方面具有潜在的广泛生物学影响，例如，在抗癌剂（PtIV/II、RuIII/II）和用于糖尿病的钒剂（VV/IV）中。 这些结果也可能有助于预测小分子铁载体（Fe III/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的空腔内的水化学反应性，以及在电喷雾MS期间形成的水滴内的水化学反应性，（但未经验证）代表本体溶液中的化学性质。约翰逊教授在学生培训和推广方面拥有丰富的经验，特别致力于涉及代表性不足群体的本科生研究，尤其是西班牙裔和美洲原住民学生。 他直接参与了NMSU的少数民族研究职业计划-全国最大的MARC计划之一，每年派遣8-10名毕业的高年级学生参加物理和生命科学研究生课程。 其他的学生已经去了MD，DDS，DPharm。D.Psy.或其他研究生学位。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。 教授约翰逊还参加了桥梁计划在NMSU，其使命是提高美国本土学生在亚利桑那州和新墨西哥州从地区社区学院到4年制学位课程的转移率。 他还积极参加NMSU的年度本科生研究和创意艺术研讨会（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.