SusChEM: Metal Organic Nanoparticles (MONPs) for Supramolecularly Assisted Covalent Assembly

范围广泛的重要有机化合物，包括药物制剂，都是由更简单的、市售的材料制备的。这些有机化合物的合成通常需要几个步骤，其中一些需要金属基催化剂。开发出产率更高且在水中运行的催化剂，既减少了挥发性有机溶剂的使用，也减少了重金属的浪费，从而使这些合成过程更具可持续性。在美国国家科学基金会化学部大分子、超分子和纳米化学项目的支持下，伊利诺伊大学厄巴纳-香槟分校的Steven C. Zimmerman教授正在开发纳米级聚合物金属催化剂，这种催化剂可以在水中进行这种反应，而且由于其毒性低，甚至可以在人体细胞中进行这种反应。因此，这项工作的一个更广泛的影响是创造了一种纳米级机器人，一种“纳米机器人”，它可以选择性地进入某些类型的细胞，并从更小的、可渗透细胞的、但不活跃的小分子中制备生物活性物质。另一个更广泛的影响是培养了一批多样化的本科生和研究生。伊利诺伊大学的研究小组正在开发新的聚合物催化剂，通过开环复分解聚合制备，扩大了反应的类型。设计了优化的金属-有机聚合物纳米颗粒（MONPs），用于催化铜辅助的“咔嗒”反应、钯催化的Suzuki-Miyaura偶联反应和钌介导的合环复分解反应。这些单克隆抗体的疏水内部被设计为利用纳米颗粒的疏水内部，使反应在低浓度催化剂的水中进行。努力的方向是制备含有两个不同催化中心的MONP，以允许顺序的、正交的过程发生，增加MONP方法的复杂性和能力。最后，一种使用疏水结合模块化结合金属催化剂的ONP正在成为一种更通用的即插即用策略。

A wide range of important organic compounds, including pharmaceutical agents, are prepared from simpler, commercially available materials. The synthesis of these organic compounds often takes several steps, some of which involve metal-based catalysts. Developing catalysts that give higher yields and operate in water reduces both the amount of volatile organic solvents used and the heavy metal waste, thus, making these synthetic processes more sustainable. With the support from the Macromolecular, Supramolecular and Nanochemistry Program of the NSF Chemistry Division, Prof. Steven C. Zimmerman at the University of Illinois at Urbana-Champaign is developing nanoscale, polymer-based metal catalysts that can perform such reactions in water and, because of their low toxicity, even in human cells. Thus, a broader impact of the work is the creation of a nanoscale robot, a "nanobot" that selectively enter certain types of cells and prepare bioactive agents from smaller, cell-permeable, but inactive small molecules. Another broader impact is the training of a diverse group of undergraduate and graduate students.The research team at the University of Illinois is developing new polymeric catalysts, prepared by ring-opening metathesis polymerization, that expand the types of reactions performed. Optimized metal-organic polymeric nanoparticles (MONPs) are designed to catalyze the copper-assisted "click" reaction, the palladium-catalyzed Suzuki-Miyaura coupling reaction, and the ruthenium-mediated ring-closing metathesis reaction. The hydrophobic interior of these MONPs is designed to allow the reactions to proceed in water at low concentrations of catalyst by taking advantage of the hydrophobic interior of the nanoparticles. Efforts are directed toward the preparation of MONPs that contain two different catalytic centers to allow sequential, orthogonal processes to occur, increasing the complexity and power of the MONP approach. Finally, an ONP that modularly binds metal catalysts using hydrophobic binding is being pursued as a more universal, plug-and-play strategy.