Inside or outside the box? Effect of substrate location on coordination-cage based catalysis.

ABSTRACT: In this work we compare and contrast the hydrolysis of two different aromatic esters using an octanuclear cubic Co₈ coordination cage host as the catalyst. Diacetyl fluorescein (DAF) is too large to bind inside the cage cavity, but in aqueous solution it interacts with the exterior surface of the cage via a hydrophobic interaction with K = 1.5(2) × 10⁴ M^-1. This is sufficient to bring it into close proximity to the layer of hydroxide ions which also surrounds the 16+ cage surface even at modest pH values, accelerating the hydrolysis of DAF to fluorescein with k_cat/k_uncat (the rate acceleration for that fraction of DAF in contact with the cage surface in the equilibrium) ≈50. This is far smaller than many kno

SUBMITTER: Solea AB 

PROVIDER: S-EPMC9344580 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature