Synthetic Catalysts Inspired by Hydrolytic Enzymes

Abstract

Enzymes, as nature’s catalysts, speed up the very reactions that make life possible. Hydrolytic enzymes are a particularly important enzyme class responsible for the catalytic breakdown of lipids, starches, and proteins in nature, and they are displaying increasing industrial relevance. While the unrivalled catalytic effect of enzymes continues to be unmatched by synthetic systems, recent progress has been made in the design of hydrolase-inspired catalysts by imitating and incorporating specific features observed in native enzyme protein structures. The development of such enzyme-inspired materials holds promise for more robust and industrially relevant alternatives to enzymatic catalysis, as well as deeper insights into the function of native enzymes. This Review will explore recent research in the development of synthetic catalysts based on the chemistry of hydrolytic enzymes. A focus on the key aspects of hydrolytic enzyme structure and catalytic mechanism will be exploredincluding active-site chemistry, tuning transition-state interactions, and establishing reactive nanoenvironments conducive to attracting, binding, and releasing target molecules. A key focus is to highlight the progress toward an effective, versatile hydrolase-inspired catalyst by incorporating the molecular design principles laid down by nature.

On the Catalytic Activity of the Engineered Coiled-Coil Heptamer Mimicking the Hydrolase Enzymes: Insights from a Computational Study

“…In any case, we underline that the used substrate pNPA present different properties with respect to the usual substrates of natural proteases, since its leaving group is more reactive. Furthermore, we note as the topology of the CC-Hept-Cys-His-Glu does not allow the formation of the oxyanion hole, noted in other esterases [ 28 , 29 ], due to the engagement of the backbone N-H in the formation of α-helical barrels.…”

Progress and Perspectives Beyond Traditional RAFT Polymerization

“…Inspired by the precision of natural biopolymers, the synthesis of polymers with uniform molecular weight and precisely defined monomer sequence has long been regarded as a holy grail of polymer chemistry. [137][138][139][140] The technique of SUMI has emerged as a highly promising strategy for the preparation of sequencedefined polymers. [120] Notably, SUMI via PET-RAFT exploits the orthogonality of photocatalyst activation under different wavelengths of light to selectively cleave the C-S bonds of target TCT compounds.…”

Hydrolytic Nanozymes

“…Enzymes operating with only two of these functions are known. The mimicry of these systems has attracted scientists since the very early days of biomimetic chemistry , . One of the most studied nanosystems is constituted by micellar aggregates of functionalized surfactants.…”