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

通过这个奖项，化学结构、动力学和机制项目正在支持普渡大学Hilkka教授Kenttämaa的基础研究。Kenttämaa教授和她的学生利用傅里叶变换离子回旋共振和线性四极离子阱质谱法，在气相和溶液中利用光反应器和HPLC/质谱法，探索了多种高活性自由基的反应性，最多可达四个自由基位点。进行了高阶量子化学计算，以补充实验研究。本研究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认识，也有助于设计具有定制性质的双自由基和多自由基，用于有机合成、开发新的有机材料、设计更好的合成抗肿瘤药物和治疗衰老等应用。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）在研究者的指导下进行了研究的各个方面。与工业和学术团体的合作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。在本研究中，开发了在气相和溶液中生成和研究各种带电芳香、碳中心双自由基和多自由基的方法。使用精心挑选的试剂检查自由基的反应活性和反应动力学。实验研究辅以高水平的量子化学计算，以描述气相和溶液中最重要的反应性控制参数。最终目标是开发一种智能框架，允许预测和调整这类有机双自由基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.