Interplay of water and a supramolecular capsule for catalysis of reductive elimination reaction from gold.,Nature Communications

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Interplay of water and a supramolecular capsule for catalysis of reductive elimination reaction from gold.
Nature Communications ( IF 14.7 ) Pub Date : 2020-01-21 , DOI: 10.1038/s41467-019-14251-6
Valerie Vaissier Welborn _{1,

2,

3,

4} , Wan-Lu Li _{1,

2,

3} , Teresa Head-Gordon _{1,

2,

3,

5,

6}

Affiliation

Supramolecular assemblies have gained tremendous attention due to their ability to catalyze reactions with the efficiencies of natural enzymes. Using ab initio molecular dynamics, we identify the origin of the catalysis by the supramolecular capsule Ga4L612- on the reductive elimination reaction from gold complexes and assess their similarity to natural enzymes. By comparing the free energies of the reactants and transition states for the catalyzed and uncatalyzed reactions, we determine that an encapsulated water molecule generates electric fields that contributes the most to the reduction in the activation free energy. Although this is unlike the biomimetic scenario of catalysis through direct host-guest interactions, the electric fields from the nanocage also supports the transition state to complete the reductive elimination reaction with greater catalytic efficiency. However it is also shown that the nanocage poorly organizes the interfacial water, which in turn creates electric fields that misalign with the breaking bonds of the substrate, thus identifying new opportunities for catalytic design improvements in nanocage assemblies.

中文翻译：

水和超分子胶囊的相互作用，催化金的还原消除反应。

超分子组装由于其以天然酶的效率催化反应的能力而获得了极大的关注。使用从头算的分子动力学，我们确定了超分子胶囊Ga4L612-对金复合物的还原消除反应的催化作用，并评估了其与天然酶的相似性。通过比较反应物的自由能和过渡态的催化反应和未催化反应，我们确定封装的水分子产生的电场对活化自由能的降低贡献最大。尽管这与通过直接宿主-客体相互作用催化的仿生场景不同，纳米笼中的电场也支持过渡态，从而以更高的催化效率完成还原消除反应。然而，还显示出纳米笼状体组织不良的界面水，这反过来产生了与基底的断裂键不对准的电场，从而为纳米笼状体组件的催化设计改进寻找了新的机会。

更新日期：2020-01-22

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