International Collaboration in Chemistry: Aqueous Host-Guest Chemistry with Self-Assembling Metal-templated Cages

国际化学合作：采用自组装金属模板笼的水性主客体化学

• 批准号: 1124244
• 负责人: Laura Gagliardi
• 金额: $ 48.5万
• 依托单位: University of Minnesota-Twin Cities
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2011
• 资助国家: 美国
• 起止时间: 2011-09-01 至 2015-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1124244&HistoricalAwards=false
• 关键词: International; Collaboration; Chemistry; Aqueous; Host

With an International Collaborations in Chemistry (ICC) award, Professors Laura Gagliardi (PI) and Christopher J. Cramer (co-PI) of the University of Minnesota, supported jointly by the Macromolecular, Supramolecular, and Nanochemistry (MSN) Program and the Chemical Theory, Models and Computational Methods Program (CTMCM) in the Division of Chemistry as well as the NSF Office of International Science and Engineering (OISE), will engage in research with Professor Jonathan Nitschke of the Department of Chemistry, Cambridge University, United Kingdom, to assess the fundamental factors affecting binding and recognition in the aqueous host-guest chemistry of small to moderate-sized organic molecules inside self-assembling, metal-templated cages. By taking advantage of spiral feedback between modeling and experiment, they will identify key steric and electrostatic interactions in the complexes, the control of which will facilitate the rational design of improved host-guest combinations. Theoretical models based on both quantum and molecular mechanics will be employed. Quantum mechanical models will be employed to supplement experiment with benchmark data for the selection of classical mechanical force fields and also be used to compute spectral data (e.g., NMR and UV/Vis) in order to compare to experimental host-guest combinations. Classical mechanical force field modeling will be used to simulate the dynamical behavior of host-guest combinations and for the prediction of potentials of mean force associated with aqueous binding events. With sufficient validating data in hand, in silico design efforts will be undertaken with the goal of focusing synthetic efforts on host-guest combinations showing enhanced selectivity and binding efficiencies.Molecular cages have been shown to stabilize unstable molecules, such as white phosphorus, a spontaneously-flammable and highly toxic form of the element. Cages can also selectively speed up (catalyze) reactions by binding to high-energy reactive intermediates, thus lowering their energies. In order to extend these uses and develop new ones, fundamental understanding must be gained as to the weak interactions between encapsulated molecules and their hosts. This collaborative research project will allow a US-UK team to combine theory and experiment to come to an understanding of the fundamentals of this 'host-guest chemistry' with the goal of being able to design new cages for applications as yet undreamt-of.

通过获得化学国际合作（ICC）奖，明尼苏达大学的劳拉·加利亚尔迪（Laura Gagliardi）（PI）和克里斯托弗·J·克莱默（Christopher J.科学与工程学（OISE）将与英国剑桥大学化学系的乔纳森·尼奇克（Jonathan Nitschke）教授进行研究，以评估影响自我大量大量，金属，金属填充的笼子内部至中度大小的有机分子的水性宿主宿主化学的基本因素。通过利用建模和实验之间的螺旋反馈，它们将确定复合物中的关键空间和静电相互作用，其控制将有助于改进的宿主 - 宿主组合的合理设计。将采用基于量子力学和分子力学的理论模型。量子机械模型将用于补充基准数据，以选择经典的机械力场，并用于计算光谱数据（例如，NMR和UV/VIS），以与实验性的宿主 - 环组合进行比较。经典的机械力场模型将用于模拟宿主 - 阵阵组合的动力学行为，并预测与水结合事件相关的平均力的电势。借助足够的验证数据，将在硅胶设计工作中进行，目的是将合成工作集中在宿主 - 球形组合上，显示出增强的选择性和结合效率。已显示出稳定不稳定的分子，例如稳定不稳定的分子，例如白色磷酸盐，一种自发性易受毒性的元素和元素的形式和元素的元素。笼子还可以通过与高能量反应性中间体结合，从而选择性地加快（催化）反应，从而降低其能量。为了扩展这些用途并开发新的用途，必须对封装分子及其宿主之间的弱相互作用获得基本的理解。该协作研究项目将使一个US-UK团队能够将理论和实验结合在一起，以了解这种“宿主 - 阵线化学”的基本原理，目的是能够为尚未提高的应用程序设计新的笼子。

项目成果

A Porous Crystalline Nitrone‐Linked Covalent Organic Framework**

多孔结晶硝酮 - 连接共价有机框架**

• DOI: 10.1002/anie.202307674
• 发表时间: 2023
• 期刊: Angewandte Chemie International Edition
• 作者: Kurandina, Daria;Huang, Banruo;Xu, Wentao;Hanikel, Nikita;Darù, Andrea;Stroscio, Gautam D.;Wang, Kaiyu;Gagliardi, Laura;Toste, F. Dean;Yaghi, Omar M.
• 通讯作者: Yaghi, Omar M.