SusChEM: Supramolecular chaperones for organic reactions in water

有了这个奖项，化学系的大分子，超分子和纳米化学项目资助斯克里普斯研究所的朱利叶斯·雷贝克教授研究水中有机反应的超分子“伴侣”。目前，在工业中进行的大多数化学反应在有机溶剂中进行，所述有机溶剂通常从石油化学品获得。该提案旨在研究如何在水中进行这些反应。这项研究涉及使用新的合成化合物作为较小分子的容器。 当分子在容器内时，它们会采用新的形状，增加它们进行已知反应的概率，并使容器外的未知反应成为可能。基础研究的目标是科学培训和发现;应用研究的目标是将化学反应从石化产品的局限性转移到最环保、最便宜的溶剂--水。该提案旨在应用合成的水溶性容器宿主“空腔”来改变容器内小分子的行为。空穴结合它们的目标客人，暂时将它们从水介质中隔离，将它们置于疏水环境中并将它们折叠成反应性形状。空穴在一定的pH范围内工作，并以掩埋客人的疏水部分并使其末端靠近在一起的构象吸收烃链。客体分子的不寻常形状将被利用来引导反应沿着沿着不可能的路径进行，甚至在本体溶液中是未知的。U形排列可以促进许多大环过程和远程官能化反应。将测试在水中使用空腔来强制转换和促进催化的策略。应用程序是偏离现有的方法，涉及模板效应和原子转移反应，通常在有机介质中进行。

With this award, the Macromolecular, Supramolecular and Nanochemistry Program in the Chemistry Division is funding Professor Julius Rebek of the Scripps Research Institute to study supramolecular "chaperones" for organic reactions in water. Currently the majority of chemical reactions performed in industry take place in organic solvents, solvents that are generally obtained from petrochemicals. This proposal intends to research how those reactions could be performed in water. The research involves the use of new synthetic compounds that act as containers for smaller molecules. While molecules are inside the containers, they adopt new shapes that increase their probability for known reactions and make possible reactions that are unknown outside the containers in water. The basic research proposed is targeted at scientific training and discovery; the applied research proposed is aimed at inventions that move chemical reactions from the limitations of petrochemicals into the most ecofriendly and least expensive solvent, water.This proposal intends to apply synthetic, water-soluble container hosts "cavitands" to alter the behavior of small molecules held inside. Cavitands bind their target guests, temporarily isolate them from the aqueous medium, place them a hydrophobic environment and fold them into reactive shapes. The cavitands operate over a range of pH and take up hydrocarbon chains in conformations that bury the hydrophobic parts of the guests and bring their ends close together. The unusual shape of the guest molecules will be harnessed to guide reactions along pathways that are improbable, or even unknown in bulk solution. The U-shaped arrangements can promote a number of macrocyclic processes and remote functionalization reactions. Tactics to force turnover and promote catalysis with the cavitands in water will be tested. The applications are departures from existing methods involving template effects and atom transfer reactions that are typically performed in organic media.