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We report the hydrophobicity-enhanced reactivity of Cu²⁺ions as an ester hydrolase.

 

Chirality plays a significant role in the manufacture of pharmaceuticals and fine chemicals. The use of chemical catalysts to control stereoselectivity relies on the use of chiral catalysts with labor–intensive synthesis and purification. Natural enzymes offer inherent stereoselectivity, making them attractive catalysts for this purpose. We report here chiral biocatalytic oxidations in microemulsions driven by horseradish peroxidase coupled with a synthetic Cu²⁺‐polymer catalyst. This hybrid system features crosslinked layer–by–layer (LBL) films composed of polyions with Cu²⁺‐containing pyrene–labelled poly(2‐hydroxy‐3‐dipicolylamino) propyl methacrylate (Py−PGMADPA) to drive oxygen reduction to form hydrogen peroxide. Peroxide in turn activates horseradish peroxidase (HRP) crosslinked in LbL films on magnetic particle beads to biocatalytically oxidize styrene, ethylbenzene, and methyl phenylacetate to chiral products. R‐stereoisomers of these reactants were selectively formed with a high enantiomeric excess of ≥80 % at 90 °C. The enzyme films show high thermal stability at 90 °C in cetyltrimethylammonium bromide microemulsion. Reactions at 90 °C were essentially complete in 2 hr. This hybrid approach opens a door to new designs of biocatalytic syntheses using a separate electrocatalyst for enzyme activation.

 

Abstract We report the synthesis of ordered mesoporous ceria ( m CeO 2 ) with highly crystallinity and thermal stability using hybrid polymer templates consisting of organosilanes. Those organosilane-containing polymers can convert into silica-like nanostructures that further serve as thermally stable and mechanically strong templates to prevent the collapse of mesoporous frameworks during thermal-induced crystallization. Using a simple evaporation-induced self-assembly process, control of the interaction between templates and metal precursors allows the co-self-assembly of polymer micelles and Ce 3+ ions to form uniform porous structures. The porosity is well-retained after calcination up to 900 °C. After the thermal engineering at 700 °C for 12 h ( m CeO 2 -700-12 h), m CeO 2 still has a specific surface area of 96 m 2 g −1 with a pore size of 14 nm. m CeO 2 is demonstrated to be active for electrochemical oxidation of sulfite. m CeO 2 -700-12 h with a perfect balance of crystallinity and porosity shows the fastest intrinsic activity that is about 84 times more active than bulk CeO 2 and 5 times more active than m CeO 2 that has a lower crystallinity. 

Adding metals into synthetic polymers is of broad interest to design multifunctional materials, particularly harnessing unique properties and functionalities not found in pure organic polymers. Other than simple emergence of the two, such hybridization often enables synergies to amplify the existing properties and/or create new properties not existing in either component. In this review, we highlight recent examples of metal/polymer hybrids based on either well-defined or ill-defined metal–ligand (M–L) coordination to design multifunctional materials. This review describes how in the hybridization of metal ions and polymers they complement each other synergistically in terms of their optical, mechanical and catalytic functionalities. Synthetic polymers once bound to metals enable stimuli-responsive properties of the metals and control over the luminescence of the metals in response to a change in the environment. As the second coordination sphere, synthetic polymers also enhance the reactivity of metal sites as a means to design bioinspired artificial enzymes. Additionally, the impact of the M–L coordination on the dynamic properties of polymers is summarized in the context of self-healable and tough materials built on the reversible network of interchangeable M–L coordination. 

Metal nanoparticles (NPs) tethered by synthetic polymers are of broad interest for self-assembly, nanomedicine and catalysis. The binding motifs in polymer ligands usually as the end functional groups of polymers are mostly limited to thiolates. Since the binding motif only represents a tiny fraction of many repeating units in polymers, its importance is often ignored. We herein report the uniqueness of polymeric N-heterocyclic carbene (NHC) ligands in providing oxidative stability and promoting the catalytic activity of noble metal NPs. Two “grafting to” methods were developed for polymer NHCs for pre-synthesized metal NPs in various solvents and with different sizes. Remarkably, imidazolium-terminated polystyrene can modify gold NPs (AuNPs) within 2 min while reaching a similar grafting density to polystyrene-thiol (SH) requiring 6 h modification. We demonstrate that polymer NHCs are extremely stable at high temperature in air. Interestingly, the binding motifs of polymer ligands dominate the catalytic activity of metal NPs. Polymer NHC modified metal NPs showed improved activity regardless of the surface crowdedness. In the case of AuNPs, AuNPs modified with polystyrene NHCs are approximately 5.2 times more active than citrate-capped ones and 22 times more active than those modified with polystyrene thiolates. In view of ligand-controlled catalytic properties of metal NPs, our results illustrate the importance of binding motifs that has been overlooked in the past. 

Self-healing polymers often have a trade-off between healing efficiency and mechanical stiffness. Stiff polymers that sacrifice their chain mobility are slow to repair upon mechanical failure. We herein report adaptable polymer films with dynamically moisture-controlled mechanical and optical properties, therefore having tunable self-healing efficiency. The design of the polymer film is based on the coordination of europium (Eu) with dipicolylamine (DPA)-containing random copolymers of poly( n -butyl acrylate- co -2-hydroxy-3-dipicolylamino methacrylate) (P( n BA- co -GMADPA)). The Eu–DPA complexation results in the formation of mechanically robust polymer films. The coordination of Eu–DPA has proven to be moisture-switchable given the preferential coordination of lanthanide metals to O over N, using nuclear magnetic resonance and fluorescence spectroscopy. Water competing with DPA to bind Eu 3+ ions can weaken the cross-linking networks formed by Eu–DPA coordination, leading to the increase of chain mobility. The in situ dynamic mechanical analysis and ex situ rheological studies confirm that the viscofluid and the elastic solid states of Eu-polymers are switchable by moisture. Water speeds up the self-healing of the polymer film by roughly 100 times; while it can be removed after healing to recover the original mechanical stiffness of polymers.