Conceptual similarities between zeolites and artificial enzymes.

Abstract

By using a Diels-Alder (DA) reaction as a base case, we show that a pure silica zeolite acting as an entropy-trapping scaffold can be synthesized with an organic structure directing agent (OSDA) analogue of the transition state (TS) of the DA reaction. A cavity stabilization of the TS is observed with the corresponding decrease in the activation energy of the reaction. A lower enthalpy of activation and a larger decrease in entropy are obtained with the zeolite synthesized with the analogue of the DA TS when compared with other zeolitic structures. Those differences are maintained, while catalytic activity is increased, when active sites are introduced in the zeolite. The catalytic zeolitic system synthesized with the OSDA analogue of the TS shows conceptual similarities with "de novo design" of an artificial enzyme to perform DA reactions, in where a suitable scaffold of existing proteins is chosen, and computationally designed active sites able to catalyze the cycloaddition reaction are introduced.