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

许多重要的有机化合物，包括药剂，都是由更简单的市售材料制备的。这些有机化合物的合成通常需要几个步骤，其中一些涉及金属基催化剂。开发具有更高产率和在水中操作的催化剂可以减少挥发性有机溶剂的使用量和重金属废物，从而使这些合成工艺更具可持续性。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，Steven C。伊利诺伊大学厄巴纳-香槟分校的齐默尔曼正在开发纳米级的聚合物基金属催化剂，这种催化剂可以在水中进行这种反应，由于毒性低，甚至可以在人类细胞中进行。因此，这项工作的更广泛影响是创造了一种纳米级机器人，一种“纳米机器人”，它选择性地进入某些类型的细胞，并从较小的、可渗透细胞但不活跃的小分子中制备生物活性剂。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，通过开环易位聚合制备，扩大了所进行的反应类型。优化的金属-有机聚合物纳米颗粒（MONP）被设计用于催化铜辅助的“点击”反应、钯催化的Suzuki-Miyaura偶联反应和钯介导的闭环复分解反应。这些MONP的疏水内部被设计成通过利用纳米颗粒的疏水内部来允许反应在低浓度的催化剂下在水中进行。努力针对制备含有两个不同催化中心的MONP，以允许顺序的正交过程发生，增加MONP方法的复杂性和能力。最后，使用疏水结合模块化地结合金属催化剂的ONP正被追求为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.