CAREER: Functional Metal-Ligand Assemblies: Self-Sorting, Supramolecular Catalysis and Molecular Dynamics

化学系的大分子、超分子和纳米化学计划支持加州大学河滨分校的理查德·胡利博士的研究小组，通过基于金属配体的自组装创造新的水溶性功能合成受体，并研究它们在分子识别和超分子催化方面的应用。这项研究旨在解决目前合成受体与酶相比所面临的主要缺陷之一：无法向结合在腔内的客体呈现功能基团。金属配体簇合物的合成路线是模块化的，很容易调节，允许接触到广泛的内向基团。通过将官能团定向到结合客体上，选择性底物识别和超分子催化将得到加强。团簇内部手性物种、氢键供体或亲核剂的存在使许多新的受体性质得以研究。此外，通过将催化活性基团定位在与结合底物紧密接近的位置，仿生反应和催化成为可能。核磁共振波谱将被用来研究客体结合、配体交换和反应动力学，这一研究将扩展合成主体分子在分子识别和催化等领域的能力，并将为仿生有机化学的研究开辟新的途径。这一跨学科项目将为教育和培训学生，包括代表人数不足的群体的成员提供一个富有启发性的研究环境。此外，这项研究与旨在通过在较低级别的有机化学课程序列中使用以问题为基础的协作案例研究来吸引学生参与STEM领域的旨在增加本科生(特别是未被充分代表的少数民族)留住的教育部分相结合。

The Macromolecular, Supramolecular and Nanochemistry Program of the Chemistry Division supports the research group of Dr. Richard Hooley of the University of California-Riverside to create new water-soluble functional synthetic receptors via metal-ligand based self-assembly and investigate their application towards molecular recognition and supramolecular catalysis. This research aims to address one of the main deficiencies faced by current synthetic receptors when compared to enzymes; the inability to present a functional group towards a guest bound on the interior of the cavity. The synthetic route to the metal-ligand clusters is modular and easily tunable, allowing access to a wide scope of introverted groups. By orienting functional groups towards the bound guest, selective substrate recognition and supramolecular catalysis will be enhanced. The presence of chiral species, hydrogen bond donors or nucleophiles on the interior of the clusters allows a number of novel receptor properties to be studied. In addition, by positioning catalytically active groups in close proximity with bound substrates, biomimetic reactions and catalysis are possible. NMR spectroscopy will be used to investigate guest binding, ligand exchange and reaction kinetics.This research will extend the capabilities of synthetic host molecules in a number of fields including molecular recognition and catalysis and will introduce new avenues of research in biomimetic organic chemistry. This interdisciplinary project will offer a stimulating research environment for the education and training of students, including members of underrepresented groups. In addition, this research is integrated with an educational component that aims at increasing retention of undergraduate students (and especially underrepresented minorities) in STEM fields by engaging students through the use of collaborative problem-based case studies in the lower division organic chemistry course sequence.