Gas-phase and Solution Reactivity Studies on para-Benzyne Analogs and Related Bi, Tri- and Tetraradicals

通过这一奖项，化学结构、动力学和机制项目支持普渡大学Hilkka Kenttämaa教授的基础研究。Kenttämaa教授和她的学生使用傅立叶变换离子回旋共振和线性四极杆离子陷阱质谱仪，以及在溶液中使用光反应器和高效液相色谱/质谱仪，探索各种高活性自由基物种在气相中与多达四个自由基位点的反应性。为了补充实验研究，进行了高水平的量子化学计算。在这项研究中获得的关于控制有机双自由基和多自由基化学性质的因素的信息提高了对有机化学的基本理解，以及在设计具有定制性质的双自由基和多自由基方面的应用，如有机合成、新有机材料的开发、更好的合成抗肿瘤药物的设计和抗衰老治疗。20多名研究生和5-10名本科生(包括几名女性和来自代表性不足群体的学生)在调查员的监督下开展了所有方面的研究。与工业和学术团体合作的项目拓宽了学生对研究的理解，并促进他们发展成为独立的科学家。在这项研究中，开发了一种方法，用于在气相和溶液中生成和研究各种带电的芳香族、碳中心的双和多自由基。使用精心选择的试剂考察了自由基物种的反应性和反应动力学。高水平的量子化学计算补充了实验研究，以描绘出气相和溶液中最重要的反应性控制参数。最终目标是开发智能框架，允许预测和调整这种类型的有机双和多自由基在气相和溶液中的化学性质。

With this award, the Chemical Structure, Dynamics and Mechanisms Program is supporting fundamental research of Professor Hilkka Kenttämaa at Purdue University. Professor Kenttämaa and her students explore the reactivity of a variety of highly reactive radical species with up to four radical sites in the gas phase by using Fourier-transform ion cyclotron resonance and linear quadrupole ion trap mass spectrometry and in solution by using a photoreactor and HPLC/mass spectrometry. High-level quantum chemical calculations are carried out to complement the experimental studies. The information obtained in this research on the factors that control organic bi- and polyradicals' chemical properties improves the fundamental understanding of organic chemistry as well as in the design of bi- and polyradicals with tailored properties for applications such as organic synthesis, development of new organic materials, design of better synthetic antitumor drugs and treatments for aging. More than 20 graduate and 5-10 undergraduate students (including several females and students from underrepresented groups) carry out all aspects of the research under investigator's supervision. Collaborative projects with industrial and academic groups broaden the students' understanding of research and facilitate their development into independent scientists. In this research, methods are developed for the generation and study of a variety of charged aromatic, carbon-centered bi- and polyradicals in the gas phase and in solution. The reactivity and reaction kinetics of the radical species are examined using carefully selected reagents. Experimental studies are complemented by high-level quantum chemical calculations in order to delineate the most important reactivity-controlling parameters in the gas phase and in solution. The ultimate goal is to develop the intellectual framework that allows prediction and tuning the chemical properties of this type of organic bi- and polyradicals in the gas phase and in solution.