Mechanism of NCNTs Growth on Foamed Nickel and Thus-Prepared PS Hydrogenation High-Performance Carrier NCNTs@FN.

Traditional heterogeneous catalysts are affected in the catalytic hydrogenation of PS by the scale effect, viscosity effect, adhesion effect, and conformational effect, resulting in poor activity and stability. Monolithic Pd-CNTs@FN catalysts could eliminate or weaken the impact of these negative effects. We grew nitrogen-doped carbon nanotubes (NCNTs) on monolithic-foamed nickel (FN) and investigate their growth mechanism. Meanwhile, the feasibility of using the NCNTs@FN carrier for PS hydrogenation reaction was also verified. The growth of NCNTs on FN can be divided into 3 stages: initial growth stage, stable growth stage, and supersaturation stage. Finally, a three-layer structure of NCNT layer, dense carbon layer, and FN skeleton is formed. Two types of structures, nickel-doped carbon nanotubes (NiCNTs) and C-Ni alloy, are formed by combining C and Ni, while four nitrogen-doped structures, NPD, NPR, NG, and NO, are formed by C and N. The prepared carrier exhibited an extremely outstanding specific surface area (2.829 × 106 cm2/g) and strength (no NCNTs falling off after 24 h 500 rpm agitation), as well as high catalytic activity for PS hydrogenation after loaded with Pd (2.13 ± 0.95 nm), with a TOF of up to 27.6 gPS/(gPd•h). After 8 repetitions of the catalyst, there was no significant decrease in activity. This proves the excellent performance of Pd-NCNTs@FN in polymer hydrogenation reactions, laying a solid foundation for further research on the mechanism of NCNTs promoting PS hydrogenation and regulating the growth of NCNTs.

A self-powered delivery substrate boosts active enzyme delivery in response to human movements.

Stimulated drug releases in response to human movements are highly appealing in medical therapy and various daily uses. However, the design of a mechanically responsive substrate that presents high delivery capacities and can also preserve the activities of sensitive molecules such as enzymes is still challenging. Taking advantage of the recent development in effective piezoelectric flexible films and in molecular delivery devices, we propose a composite delivery substrate that preserves enzyme activities and enhances molecular delivery in response to human movements such as finger presses or massages. The substrate is achieved by combining two parts, which are the energy converting unit and the molecular loading and releasing unit. The energy converting unit is a piezoelectric-dielectric flexible composite film that produces enhanced electricity and preserves the electricity longer compared to a pure piezoelectric polymer. The molecular delivery unit is a layer-by-layer multilayer containing mesoporous silica particles that are assembled at pH 9 but used in neutral solutions. The releases of molecules including small molecules, peptides, and proteins are all accelerated in response to finger presses irrespective of the signs or densities of their charges. More importantly, the enzyme CAT preserves its activity after release from the composite substrates, meaning that the CAT-loaded (PAH/MS)n(PAH/DAS)n@rGO-TFB/PVDF-HFP composite substrate holds promise as a self-powered soothing pad that effectively removes residue H2O2.

Molecularly Selective Regulation of Delivery Fluxes by Employing Supramolecular Interactions in Layer-by-Layer Films.

The molecularly selective regulation of molecular fluxes in a biomaterial that delivers multiple chemical species simultaneously is still beyond the reach of materials scientists. A delivery material was developed by means of the layer-by-layer (LbL) technique. This material discriminatively regulates the delivery flux of bioactive small molecules, as represented by a peptide containing the RGD fragment and the chemotherapy drug doxorubicin (DOX). Molecularly selective flux regulations in LbL films are realized through fast, reversible supramolecular interactions between cyclodextrin and its guests. The mechanism underlining the delivery strategy is that supramolecular interactions promote molecular loading and slow down diffusion-dependent release. In a preliminary survey of materials parameters, a maximum difference in cell viability between healthy human bronchial epithelial cells and cancer cells (A549) was realized.

Multiple-Enzyme Graphene Microparticle Presenting Adaptive Chemical Network Capabilities.

Interrelated reaction networks steered by multiple types of enzymes are among the most intriguing enzyme-based cellular features. These reaction networks display advanced features such as adaptation, stimuli-responsiveness, and decision-making in accordance with environmental cues. However, artificial enzyme particles are still deficient in network-level capabilities, mostly because delicate enzymes are difficult to immobilize and assemble. In this study, we propose a general strategy to prepare enzyme-based particles that demonstrate network reaction capability. We assembled multiple types of proteins with a nanoscopic binder prepared from polyelectrolyte and graphene. After assembly, the enzymes all preserved their catalytic capabilities. By incorporating multiple types of enzymes, the particles additionally displayed network-reaction capabilities. We were able to use NIR irradiations to quasi-reversibly adjust the catalytic abilities of these enzyme-based particles. In addition, after a biomimetic mineralization process was used to wrap the protein complexes in a MOF shell, the particles were more robust and catalytically active even after being immersed in acidic (pH 4) or basic (pH 10) solutions for 3 days. This study provides an insight into the study of network properties of functional enzyme particles experimentally and enriches scientific understanding of multifunctional or stimuli-responsive behaviors at the reaction network level. The building of artificial reaction networks possesses high potential in realizing intelligent microparticles that can perform complicated tasks.