Binding-promoted chemical reaction in the nanospace of a binding site: effects of environmental constriction.

Chemical reactions in a confined nanospace can be very different from those in solution. Imine formation between molecular amines and an aldehyde inside a molecularly imprinted receptor was promoted strongly by the binding. Although how well the amine fit in the binding pocket and its electronic nature both influenced the reaction, the freedom of movement for the amine was the most important factor determining the binding-normalized reactivity.