期刊
NATURE CHEMISTRY
卷 8, 期 3, 页码 231-236出版社
NATURE PUBLISHING GROUP
DOI: 10.1038/NCHEM.2452
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资金
- Engineering and Physical Sciences Research Council (EPSRC)
- Engineering and Physical Sciences Research Council [EP/K025627/2] Funding Source: researchfish
- EPSRC [EP/K025627/2] Funding Source: UKRI
The hollow cavities of coordination cages can provide an environment for enzyme-like catalytic reactions of small-molecule guests. Here, we report a new example (catalysis of the Kemp elimination reaction of benzisoxazole with hydroxide to form 2-cyanophenolate) in the cavity of a water-soluble M8L12 coordination cage, with two features of particular interest. First, the rate enhancement is among the largest observed to date: at pD 8.5, the value of k(cat)/k(uncat) is 2 x 10(5), due to the accumulation of a high concentration of partially desolvated hydroxide ions around the bound guest arising from ionpairing with the 16+ cage. Second, the catalysis is based on two orthogonal interactions: (1) hydrophobic binding of benzisoxazole in the cavity and (2) polar binding of hydroxide ions to sites on the cage surface, both of which were established by competition experiments.
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