Facile and Universal Defect Engineering Toward Highly Stable Carbon-Based Polymer Brushes with High Grafting Density.

Carbon-based polymer brushes (CBPBs) are an important class of functional polymer materials, which synergistically combine the advantageous properties of both carbons and polymers. However, the conventional fabrication procedures of CBPBs involve tedious multistep modification, including preoxidation of carbon substrates, introduction of initiating groups, and subsequent graft polymerization. In this study, a simple yet versatile defect-engineering strategy is proposed for the efficient synthesis of high-grafting-density CBPBs with highly stable CC linkages via free radical polymerization. This strategy involves the introduction and removal of nitrogen heteroatoms in the carbon skeletons via a simple temperature-Fmed heat treatment, leading to the formation of numerous carbon defects (e.g., pentagons, heptagons, and octagons) with reactive C=C bonds in the carbon substrates. The as-proposed methodology enables the facile fabrication of CBPBs with various carbon substrates and polymers. More importantly, the highly grafted polymer chains in the resulting CBPBs are tethered with the carbon skeletons by robust CC bonds, which can endure strong acid and alkali environments. These interesting findings will shed new light on the well-orchestrated design of CBPBs and broaden their applications in various areas with fascinating performances.

N-Halaminated spermidine-containing polymeric coating enables titanium to achieve dual functions of antibacterial and osseointegration.

Titanium (Ti) and its alloys have been widely employed in the treatment of orthopedics and other hard tissue diseases. However, Ti-based implants are bioinert and suffer from bacterial infections and poor osseointegration in clinical applications. Herein, we successfully modified Ti with a porous N-halaminated spermidine-containing polymeric coating (Ti-SPD-Cl) through alkali-heat treatment, surface grafting and chlorination, and it has both excellent antibacterial and osteogenic abilities to significantly enhance osseointegration. The as-obtained Ti-SPD-Cl contains abundant N-Cl groups and demonstrates effective antibacterial ability against S. aureus and E. coli. Meanwhile, due to the presence of the spermidine component and construction of a porous hydrophilic surface, Ti-SPD-Cl is also beneficial for maintaining cell membrane homeostasis and promoting cell adhesion, exhibiting good biocompatibility and osteogenic ability. The rat osteomyelitis model demonstrates that Ti-SPD-Cl can effectively suppress bacterial infection and enhance bone-implant integration. Thus, Ti-SPD-Cl shows promising clinical applicability in the prevention of orthopedic implant infections and poor osseointegration.

One-Pot Construction of Articular Cartilage-Like Hydrogel Coating for Durable Aqueous Lubrication.

Articular cartilage has an appropriate multilayer structure and superior tribological properties and provides a structural paradigm for design of lubricating materials. However, mimicking articular cartilage traits on prosthetic materials with durable lubrication remains a huge challenge. Herein, an ingenious three-in-one strategy is developed for constructing an articular cartilage-like bilayer hydrogel coating on the surface of ultra-high molecular weight polyethylene (BH-UPE), which makes full use of conceptions of interfacial interlinking, high-entanglement crosslinking, and interface-modulated polymerization. The hydrogel coating is tightly interlinked with UPE substrate through hydrogel-UPE interchain entanglement and bonding. The hydrogel chains are highly entangled with each other to form a dense tough layer with negligible hysteresis for load-bearing by reducing the amounts of crosslinker and hydrophilic initiator to p.p.m. levels. Meanwhile, the polymerization of monomers in the top surface region is suppressed via interface-modulated polymerization, thus introducing a porous surface for effective aqueous lubrication. As a result, BH-UPE exhibits an ultralow friction coefficient of 0.0048 during 10 000 cycles under a load of 0.9 MPa, demonstrating great potential as an advanced bearing material for disc prosthesis. This work may provide a new way to build stable bilayer coatings and have important implications for development of biological lubricating materials.

A Versatile Sulfur-Assisted Pyrolysis Strategy for High-Atom-Economy Upcycling of Waste Plastics into High-Value Carbon Materials.

With the overconsumption of disposable plastics, there is a considerable emphasis on the recycling of waste plastics to relieve the environmental, economic, and health-related consequences. Here, a sulfur-assisted pyrolysis strategy is demonstrated for versatile upcycling of plastics into high-value carbons with an ultrahigh carbon-atom recovery (up to 85%). During the pyrolysis process, the inexpensive elemental sulfur molecules are covalently bonded with polymer chains, and then thermally stable intermediates are produced via dehydrogenation and crosslinking, thereby inhibiting the decomposition of plastics into volatile small hydrocarbons. In this manner, the carbon products obtained from real-world waste plastics exhibit sulfur-rich skeletons with an enlarged interlayer distance, and demonstrate superior sodium storage performance. It is believed that the present results offer a new solution to alleviate plastic pollution and reduce the carbon footprint of plastic industry.

Molecular Engineering toward High-Crystallinity Yet High-Surface-Area Porous Carbon Nanosheets for Enhanced Electrocatalytic Oxygen Reduction.

Carbon-based nanomaterials have been regarded as promising non-noble metal catalysts for renewable energy conversion system (e.g., fuel cells and metal-air batteries). In general, graphitic skeleton and porous structure are both critical for the performances of carbon-based catalysts. However, the pursuit of high surface area while maintaining high graphitization degree remains an arduous challenge because of the trade-off relationship between these two key characteristics. Herein, a simple yet efficient approach is demonstrated to fabricate a class of 2D N-doped graphitized porous carbon nanosheets (GPCNSs) featuring both high crystallinity and high specific surface area by utilizing amine aromatic organoalkoxysilane as an all-in-one precursor and FeCl3 ·6H2 O as an active salt template. The highly porous structure of the as-obtained GPCNSs is mainly attributed to the alkoxysilane-derived SiOx nanodomains that function as micro/mesopore templates; meanwhile, the highly crystalline graphitic skeleton is synergistically contributed by the aromatic nucleus of the precursor and FeCl3 ·6H2 O. The unusual integration of graphitic skeleton with porous structure endows GPCNSs with superior catalytic activity and long-term stability when used as electrocatalysts for oxygen reduction reaction and Zn-air batteries. These findings will shed new light on the facile fabrication of highly porous carbon materials with desired graphitic structure for numerous applications.

Peritoneum-Inspired Janus Porous Hydrogel with Anti-Deformation, Anti-Adhesion, and Pro-Healing Characteristics for Abdominal Wall Defect Treatment.

Implantable meshes used in tension-free repair operations facilitate treatment of internal soft-tissue defects. However, clinical meshes fail to achieve anti-deformation, anti-adhesion, and pro-healing properties simultaneously, leading to undesirable surgery outcomes. Herein, inspired by the peritoneum, a novel biocompatible Janus porous poly(vinyl alcohol) hydrogel (JPVA hydrogel) is developed to achieve efficient repair of internal soft-tissue defects by a facile yet efficient strategy based on top-down solvent exchange. The densely porous and smooth bottom-surface of JPVA hydrogel minimizes adhesion of fibroblasts and does not trigger any visceral adhesion, and its loose extracellular-matrix-like porous and rough top-surface can significantly improve fibroblast adhesion and tissue growth, leading to superior abdominal wall defect treatment to commercially available PP and PCO meshes. With unique anti-swelling property (maximum swelling ratio: 6.4%), JPVA hydrogel has long-lasting anti-deformation performance and maintains high mechanical strength after immersion in phosphate-buffered saline (PBS) for 14 days, enabling tolerance to the maximum abdominal pressure in an internal wet environment. By integrating visceral anti-adhesion and defect pro-healing with anti-deformation, the JPVA hydrogel patch shows great prospects for efficient internal soft-tissue defect repair.

CoS2 Nanoparticles Embedded in Covalent Organic Polymers as Efficient Electrocatalyst for Oxygen Evolution Reaction with Ultralow Overpotential.

Cobalt disulfide (CoS2 ) has been explored as attractive electrocatalyst for oxygen evolution reaction (OER). However, bulk CoS2 sheets have limited catalytic activity due to low exposure of active sites. Herein, through an in-situ vulcanization approach, CoS2 nanoparticles are embedded into bipyridine-containing covalent organic polymer (BP-COP). The as-prepared nanocomposite CoS2 @BP-COP exhibits high catalytic activity toward OER with an ultra-low overpotential of 270 mV (vs. RHE) at a current density of 10 mA cm-2 , a small Tafel slope of 36 mV dec-1 , and an excellent durability for 24 h without decay. The surface of CoS2 is partially converted into CoOOH to form CoS2 /CoOOH as active sites under OER conditions. CoS2 @BP-COP displays superior OER catalytic activity to CoS2 nanosheets and commercially available RuO2 under the same conditions. The outstanding OER performance activity of CoS2 @BP-COP could be attributed to the uniform and small particle sizes of CoS2 /CoOOH distributed in BP-COP.

Activation-free fabrication of high-surface-area porous carbon nanosheets from conjugated copolymers.

High-surface-area porous carbon nanosheets have been successfully prepared by direct carbonization of graphene oxide sandwiched poly(aniline-co-pyrrole). Benefiting from the distinct structure features of the poly(aniline-co-pyrrole) and its homogeneous deposition on the graphene oxide surface, the surface area of the porous carbon nanosheets is as high as 1606 m2 g-1.