Enzyme Mimics Based on Guanidinocalix[4]arene/ Nanodiamond Hybrid Systems with Phosphodiesterase Activity

Abstract

Diamond nanoparticles are an extremely promising class of carbon-based nanomaterials. Because of their versatility, they have an interest in a large variety of applications, however, their use in the fabrication of enzyme mimics was not previously investigated. In this study, we realized hybrid systems based on guanidinium derivatives and diamond nanoparticles by simple adsorption of the organic material on their surface. The guanidinium derivatives chosen for this study are calix[4]arenes, blocked in the cone conformation via functionalization at the lower rim with alkyl chains, and decorated with guanidinium or arginine units at the upper rim. The corresponding monofunctional counterparts were also investigated as model compounds. These materials were characterized with different experimental techniques, i. e. thermogravimetric analysis, dynamic light scattering, ζ-potential measurements and IR/Raman spectroscopy. Their catalytic properties in the cleavage of phosphodiesters were investigated by an in-depth kinetic analysis. The whole experimental picture points to conclude that these compounds are stably adsorbed onto the nanodiamonds surface and are active in the transesterification reaction of the RNA model compound 2-hydroxypropyl p-nitrophenyl phosphate in water, with a notable advantage over their catalytic performances at the same concentration in solution.