Molecularly imprinted nanozymes with faster catalytic activity and better specificity.

Nanozymes are nanomaterials mimicking the activity of natural enzymes, while most nanozymes lack substrate specificity. Molecular imprinting on nanozymes provides a simple solution to this problem, and the catalytic activity is also enhanced. To understand enhanced activity, a surface science approach is taken by dissecting the nanozyme reaction into adsorption of substrates, reaction, and product release. Each step is individually studied using reaction kinetics measurement, dynamic light scattering, UV-vis spectrometry. Enrichment of local substrate concentration due to imprinting is around 8-fold, and increased substrate concentration could contribute to increased activity. Diffusion of the substrate across the imprinted gel layer is studied by a pre-incubation experiment, also highlighting the difference between imprinted and non-imprinted gel layers. The activation energy is measured and a substrate-imprinted sample had the lowest activation energy of 13.8 kJ mol-1. Product release is also improved after imprinting as indicated by isothermal titration calorimetry using samples respectively imprinted with the substrate and the product. This study has rationalized improved activity and specificity of molecularly imprinted nanozymes and may guide further rational design of such materials.