Thermomagneto-Responsive Smart Biocatalysts for Malonyl-Coenzyme A Synthesis.

Smart biocatalysts, in which enzymes are conjugated to stimuli-responsive polymers, have gained considerable attention because of their catalytic switchability and recyclability. Although many systems have been developed, they require separate laboratory techniques for their recovery, making them unsuitable for many practical applications. To address these issues, we designed a thermomagneto-responsive biocatalyst by immobilizing an enzyme on the terminal of thermo-responsive polymer brushes tethered on magnetic nanoparticle (NP) clusters. The concept is demonstrated by a system consisting of iron oxide NPs, poly(N-isopropyl-acrylamide), and a malonyl-Coenzyme A synthetase (MatB). By using free malonate and coenzyme A (CoA), the designed catalyst exhibits adequate activity for the production of malonyl-CoA. Thanks to the use of a magnetic NP cluster, whose magnetic moment is high, this system is fully recoverable under the magnetic field at above 32 °C because of the collapse of the thermo-responsive polymer shell in the clusters. In addition, the recycled catalyst maintains moderate activity even after three cycles, and it also shows excellent catalytic switchability, that is, negligible catalytic activity at 25 °C because of the blockage of the active sites of the enzyme by the extended hydrophilic polymer chains but great catalytic activity at a temperatures above the lower critical solution temperature at which the enzymes are exposed to the reaction medium because of the thermo-responsive contraction of polymer chains. Because the azide functionality in our system can be easily functionalized depending upon our need, such catalytically switchable, fully recoverable, and recyclable multiresponsive catalytic systems can be of high relevance for other cell-free biosynthetic approaches.

Controlling the Localization of Liquid Droplets in Polymer Matrices by Evaporative Lithography.

Localized inclusions of liquids provide solid materials with many functions, such as self-healing, secretion, and tunable mechanical properties, in a spatially controlled mode. However, a strategy to control the distribution of liquid droplets in solid matrices directly obtained from a homogeneous solution has not been reported thus far. Herein, we describe an approach to selectively localize liquid droplets in a supramolecular gel directly obtained from its solution by using evaporative lithography. In this process, the formation of droplet-embedded domains occurs in regions of free evaporation where the non-volatile liquid is concentrated and undergoes a phase separation to create liquid droplets prior to gelation, while a homogeneous gel matrix is formed in the regions of hindered evaporation. The different regions of a coating with droplet embedment patterns display different secretion abilities, enabling the control of the directional movement of water droplets.