The function of peptide-mimetic anionic groups and salt bridges in the antimicrobial activity and conformation of cationic amphiphilic copolymers

Amino acid-mimetic anionic groups and salt bridges in cationic amphiphilic copolymers control the polymer conformation and dynamics in solution.

Embedded Enzyme Nanoclusters Depolymerize Polyesters via Chain-End Mediated Processive Degradation

Many bioactive elements, long perceived as non-viable for material development, are now emerging as viable building blocks to encode material lifecycle and to ensure our harmonious existence with nature. Yet, there is a significant knowledge gap on how bio-elements interface with synthetic counterparts and function outside of their native environments. Here, we show that when enzymes are dispersed as nanoclusters confined within macromolecular matrices, their reaction kinetics, pathway, and substrate selectivity can be modulated to achieve programmable polymer degradation down to repolymerizable small molecules. Specifically, when enzyme nanoclusters are dispersed in trace amount (~0.02 wt%) in polyesters, i.e. poly(caprolactone) (PCL) and poly(lactic acid) (PLA), chain-end mediated processive depolymerization can be realized, leading to scalable bioactive plastics for efficient sorting, such as recovery of precious metal filler from flexible electronics. Present studies demonstrate that when the enzyme is confined at dimensions similar to that of polymer chains, their behaviors are governed by the polymer conformation, segmental dynamic and thermal history, highlighting the importance to consider bioactive plastics differently from solution enzymology.

Organocatalytic Control over a Fuel-Driven Transient Esterification Network

<p>Signal transduction in living systems is the conversion of information into a chemical change and the principal process by which cells communicate. This process enables phenomena such as time-keeping and signal amplification. In nature, these functions are encoded in non-equilibrium (bio)chemical reaction networks (CRNs) controlled by enzymes. While these catalytically controlled processes are an integral part of biocatalytic pathways, man-made analogs are rare. Here, we incorporate catalysis in an artificial fuel driven out-of-equilibrium CRN. The study entails the design of an organocatalytically controlled fuel driven esterification CRN, where the forward (ester formation) and backward reaction (ester hydrolysis) are controlled by varying the ratio of two different organocatalysts: pyridine and imidazole. This catalytic regulation enables full control over ester yield and lifetime. The fuel-driven strategy is subsequently used in the design of a responsive polymer system, where transient polymer conformation and aggregation can be controlled through variation of fuel and catalysts levels. Altogether, we show how organocatalysis is an important tool to exert control over a man-made fuel driven system and induce a change in a macromolecular superstructure, as ubiquitously found in natural non-equilibrium systems. </p>

Organocatalytic Control over a Fuel-Driven Transient Esterification Network

<p>Signal transduction in living systems is the conversion of information into a chemical change and the principal process by which cells communicate. This process enables phenomena such as time-keeping and signal amplification. In nature, these functions are encoded in non-equilibrium (bio)chemical reaction networks (CRNs) controlled by enzymes. While these catalytically controlled processes are an integral part of biocatalytic pathways, man-made analogs are rare. Here, we incorporate catalysis in an artificial fuel driven out-of-equilibrium CRN. The study entails the design of an organocatalytically controlled fuel driven esterification CRN, where the forward (ester formation) and backward reaction (ester hydrolysis) are controlled by varying the ratio of two different organocatalysts: pyridine and imidazole. This catalytic regulation enables full control over ester yield and lifetime. The fuel-driven strategy is subsequently used in the design of a responsive polymer system, where transient polymer conformation and aggregation can be controlled through variation of fuel and catalysts levels. Altogether, we show how organocatalysis is an important tool to exert control over a man-made fuel driven system and induce a change in a macromolecular superstructure, as ubiquitously found in natural non-equilibrium systems. </p>