Rapid Defect Engineering in FeCoNi/FeAl2O4 Hybrid for Enhanced Oxygen Evolution Catalysis: A Pathway to High-Performance Electrocatalysts.

Rational modulation of surface reconstruction in the oxygen evolution reaction (OER) utilizing defect engineering to form efficient catalytic activity centers is a topical interest in the field of catalysis. The introduction of point defects has been demonstrated to be an effective strategy to regulate the electronic configuration of electrocatalysts, but the influence of more complex planar defects (e.g., twins and stacking faults), on their intrinsic activity is still not fully understood. This study harnesses ultrasonic cavitation for rapid and controlled introduction of different types of defects in the FeCoNi/FeAl2O4 hybrid coating, optimizing OER catalytic activity. Theoretical calculations and experiments demonstrate that the different defects optimize the coordination environment and facilitate the activation of surface reconstruction into true catalytic activity centers at lower potentials. Moreover, it demonstrates exceptional durability, maintaining stable oxygen production at a high current density of 300 mA cm-2 for over 120 hours. This work not only presents a novel pathway for designing advanced electrocatalysts but also deepens our understanding of defect-engineered catalytic mechanisms, showcasing the potential for rapid and efficient enhancement of electrocatalytic performance.

Au-TiO2/Ti Hybrid Coating as a Liquid and Gas Diffusion Layer with Improved Performance and Stability in Proton Exchange Membrane Water Electrolyzer.

The liquid and gas diffusion layer is a key component of proton exchange membrane water electrolyzer (PEMWE), and its interfacial contact resistance (ICR) and corrosion resistance have a great impact on the performance and durability of PEMWE. In this work, a novel hybrid coating with Au contacts discontinuously embedded in a titanium oxidized layer was constructed on a Ti felt via facile electrochemical metallizing and followed by a pre-oxidization process. The physicochemical characterizations, such as scanning electron microscopy, energy dispersive spectrometer, and X-ray diffraction results confirmed that the distribution and morphology of the Au contacts could be regulated with the electrical pulse time, and a hybrid coating (Au-TiO2/Ti) was eventually achieved after the long-term stability test under anode environment. At the compaction force of 140 N cm-2, the ICR was reduced from 19.7 mΩ cm2 of the P-Ti to 4.2 mΩ cm2 of the Au-TiO2/Ti. The corrosion current density at 1.8 V (RHE) is 0.689 µA cm-2. Both the ICR and corrosion resistance results showed that the prepared protective coating could provide comparable ICR and corrosion resistance to a dense Au coating.

Tailoring the selectivity of titania nanowire arrays grown on titanium fibers by self-assembled modification of trichlorophenylsilane for solid-phase microextraction of polycyclic aromatic hydrocarbons.

The authors describe TiO2 nanowires (TiO2NWs) for solid-phase microextraction of polycyclic aromatic hydrocarbons (PAHs). Well-oriented TiO2NWs were in-situ grown on a titanium wire by a hydrothermal process. The TiO2NWs arrays are radially aligned on the curved titanium fiber substrate. They possess a large surface area and are readily accessible for subsequent self-assembly of trichlorophenylsilane via formation of Ti-O-Si bonds. The TiO2NWs coated fibers show good extraction selectivity for PAHs as shown for phenathrene, fluoranthene, pyrene and benzo[a]pyrene. Following desoption by mobile phases for HPLC analysis, the PAHs were quantified by HPLC with UV detection. The improved extraction capabilities and good selectivity are explained by synergistic hydrophobic and π stacking interactions between the phenyl moieties and the PAHs. Key parameters that affect the extraction performance of the fibers were optimized. The method has a linear response in the 0.1 to 200 µg·L-1 PAH concentration range. Limits of detection (at S/N = 3) range from 20 to 50 ng·L-1. Relative standard deviations (RSDs) for the single fiber repeatability are less than 7.3% (n = 5) and RSDs for the fiber-to-fiber reproducibility are below 8.1% (n = 5). The method was successfully applied to the selective preconcentration and determination of trace PAHs in spiked water samples. Graphical abstract Schematic presentation of fabrication and characterization of the Ti@TiO2NWs@Phenyl fiber. PAHs: polycyclic aromatic hydrocarbons; UVFs: ultraviolet filters; PAEs: phthalate acid esters; CPs: chlorophenols.

Trimethyl Chitosan/Siloxane-Hybrid Coated Fe3O4 Nanoparticles for the Uptake of Sulfamethoxazole from Water.

The presence of several organic contaminants in the environment and aquatic compartments has been a matter of great concern in the recent years. To tackle this problem, new sustainable and cost-effective technologies are needed. Herein we describe magnetic biosorbents prepared from trimethyl chitosan (TMC), which is a quaternary chitosan scarcely studied for environmental applications. Core@shell particles comprising a core of magnetite (Fe3O4) coated with TMC/siloxane hybrid shells (Fe3O4@SiO2/SiTMC) were successfully prepared using a simple one-step coating procedure. Adsorption tests were conducted to investigate the potential of the coated particles for the magnetically assisted removal of the antibiotic sulfamethoxazole (SMX) from aqueous solutions. It was found that TMC-based particles provide higher SMX adsorption capacity than the counterparts prepared using pristine chitosan. Therefore, the type of chemical modification introduced in the chitosan type precursors used in the surface coatings has a dominant effect on the sorption efficiency of the respective final magnetic nanosorbents.

Innovative Formulation Combining Al, Zr and Si Precursors to Obtain Anticorrosion Hybrid Sol-Gel Coating.

The aim of our study is to improve the aluminium alloy corrosion resistance with Organic-Inorganic Hybrid (OIH) sol-gel coating. Coatings are obtained from unusual formulation with precursors mixing: glycidoxypropyltrimethoxysilane (GPTMS), zirconium (IV) propoxide (TPOZ) and aluminium tri-sec-butoxide (ASB). This formulation was characterized and compared with sol formulations GPTMS/TPOZ and GPTMS/ASB. In each formulation, a corrosion inhibitor, cerium (III) nitrate hexahydrate, is employed to improve the corrosion performance. Coatings obtained from sol based on GPTMS/TPOZ/ASB have good anti-corrosion performances with Natural Salt Spray (NSS) resistance of 500 h for a thickness lower than 4 µm. Contact angle measurement showed a coating hydrophobic behaviour. To understand these performances, nuclear magnetic resonance (NMR) analyses were performed, results make sol-gel coating condensation evident and are in very good agreement with previous results.

Protective hybrid coating containing silver, copper and zinc cations effective against human immunodeficiency virus and other enveloped viruses.

BACKGROUND: Healthcare-acquired infections by pathogenic microorganisms including viruses represent significant health concern worldwide. Next to direct transmission from person-to-person also indirect transmission from contaminated surfaces is well documented and important route of infections. Here, we tested antiviral properties of hybrid coating containing silver, copper and zinc cations that was previously shown to be effective against pathogenic bacteria including methicillin-resistant Staphylococcus aureus. Hybrid coatings containing silver, copper and zinc cations were prepared through radical polymerization via sol-gel method and applied on glass slides or into the wells of polymethylmethacrylate plates. A 10 µl droplet of several viruses such as human immunodeficiency virus type 1 (HIV-1), influenza, dengue virus, herpes simplex virus, and coxsackievirus was added to coated and uncoated slides or plates, incubated usually from 5 to 240 min and followed by titer determination of recovered virus. RESULTS: Scanning electron microscopy analysis showed better adhesion of coatings on glass surfaces, which resulted in 99.5-100 % HIV-1 titer reduction (3.1 ± 0.8 log10TCID50, n = 3) already after 20 min of exposure to coatings, than on coated polymethylmethacrylate plates with 75-100 % (1.7 ± 1.1 log10TCID50, n = 3) and 98-100 % (2.3 ± 0.5 log10TCID50, n = 3) HIV-1 titer reduction after 20 and 120 min of exposure, respectively. Slower virucidal kinetics was observed with other enveloped viruses, where 240 min exposure to coated slides lead to 97 % (dengue), 100 % (herpes simplex) and 77 % (influenza) reduction in virus titers. Interestingly, only marginal reduction in viral titer after 240 min of exposure was noticed for non-enveloped coxsackie B3 virus. CONCLUSIONS: Our hybrid coatings showed virucidal activity against HIV and other enveloped viruses thus providing further findings towards development of broad-spectrum antimicrobial coating suitable for surfaces in healthcare settings.

Modified Titanium Surface with Nano Amorphous Calcium Phosphate@Chitosan Oligolactate as Ion Loading Platform with Multifunctional Properties for Potential Biomedical Application.

Titanium (Ti) is widely used in medical and dental implants. Calcium phosphate (CPs) coatings enhance Ti implants' osteoinductive properties, and additives further improve these coatings. Recently, a nano amorphous calcium phosphate (nACP) coating decorated with chitosan oligolactate (ChOL) and selenium (Se) showed immunomodulatory effects. This study investigates the surface morphology, composition, bioactivity, mechanical properties, and Se-release mechanism of the nACP@ChOL-Se hybrid coating on Ti substrates. Amorphous calcium phosphate (ACP) was synthesized, and the nACP@ChOL-Se hybrid coating was deposited on Ti substrates using in situ anaphoretic deposition. Physico-chemical characterization was used to analyze the surface of the coating (scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier Transform Infrared Spectroscopy). The distribution of Se within the coating was examined with energy-dispersive X-ray spectroscopy (EDS). Bioactivity was evaluated in simulated body fluid (SBF), and adhesion was tested using a scratch test method. In vitro testing determined the release mechanism of Se. SEM images illustrated the surface morphology, while AFM provided a detailed analysis of surface roughness. XRD analysis revealed structural and phase composition, and EDS confirmed Se distribution within the coating. The coating exhibited bioactivity in SBF and showed good adhesion according to the scratch test. In vitro testing uncovered the release mechanism of Se from the coating. This study successfully characterized the surface morphology, composition, bioactivity, and Se-release mechanism of the nACP@ChOL-Se hybrid coating on Ti substrates, offering insights for developing immunomodulatory coatings for medical and dental applications.

New approach for processing chitosan as low cost protective hybrid coating for C-steel in acid media.

The novelty of this study is that it the first time blending and formulation of chitosan as a new hybrid (organometallic) protective coatings for achieving synergistic protection for carbon steel alloy during acid pickling. The role of coated silica (by 0.1 wt % stearic acid lubricant) in the improvement of coating performance was highlighted. Variable weight percentage of chitosan and silica in addition to a fixed weight percentage (35 %) of guar gum natural plant resin, 5 × 10-6 mmol (2-Hydrazinyl-6-methyl (or phenyl) -4, 5-di-H pyrimidinone) as organic corrosion inhibitors were compounding as hot melt in the presence of a low cost surfactant as an emulsifying agent improved compatibility between coating constituents. Guar gum increased coating flow during application and grafted chitosan into high molecular copolymer resin insoluble in acid media. Phosphorous acid improved coating flexibility during application by hot dipping. Hybrid coating decreased corrosion potential of carbon steel and retarded both redox reactions of corrosion acting as adsorbed mixed-type inhibitor. Percentages protection (%P) approached hundred percentage as confirmed from the agreement between impedance and polarization parameters. Guar gum plant resin and slice powder increased gloss of coating. The coated silica filled the pores and increased stiffness of coating. Super hydrophobicity of coating was confirmed by the measured contact angle above 150oC indicating good spreading of coating sample as insulating adherent surface film.

Chitosan coatings on titanium-based implants - From development to characterization and behavior: A systematic review.

Chitosan is a promising natural polymer for coatings, it combines intrinsic antibacterial and pro-osteoblastic properties, but the literature still has a gap from the development to behavior of these coatings, so this systematic review aimed to answer, "What is the relationship between the physical and chemical properties of polymeric chitosan coatings on titanium implants on antibacterial activity and osteoblast viability?". PRISMA guidelines was followed, the search was applied into 4 databases and grey literature, without the restriction of time and language. The selection process occurred in 2 blinded steps by the authors. The criteria of eligibility were in vitro studies that evaluated the physical, chemical, microbiological, and biological properties of chitosan coatings on titanium surfaces. The risk of bias was analyzed by the specific tool. Of 734 potential articles 10 were included; all had low risk of bias. The coating was assessed according to the technique of fabrication, FT-IR, thickness, adhesion, roughness, wettability, antibacterial activity, and osteoblast viability. The analyzed coatings showed efficacy on antibacterial activity and cytocompatibility dependent on the class of material incorporated. Thus, this review motivates the development of time-dependent studies to optimize manufacturing and allow for an increase in patents and availability on the market.

Hybrid organic-inorganic coating with enhanced oxygen- and UV-barrier performance: Polyelectrolyte complex based on sodium alginate, poly (vinyl alcohol), and reconstructed layered double hydroxide.

Organic-inorganic hybrid materials with high oxygen- and UV-barrier properties were developed using a polyelectrolyte complex comprising sodium alginate (SA), poly (vinyl alcohol) (PVA), and reconstructed layered double hydroxide (RLDH). These materials were applied to poly (ethylene terephthalate) (PET) as a barrier coating layer at a harsh drying temperature of 120 °C, similar to environments for the industrial coating process. The RLDH nanoplatelets within the coating matrix restricted the polymer chain mobility, elevating the glass transition temperature to 105.222-159.114 °C. Below RLDH 0.2 %, the apparent coating density significantly increased to 0.93-0.94 g/cm3. The embedded RLDH gave a tortuosity within the matrix, as evidenced by an intensified (003) diffraction peak in the XRD analysis. These structural alterations contributed to high oxygen- and UV-barrier performance. Notably, the PET/SA1.0PVA0.5RLDH0.2 film exhibited an extremely low oxygen transmission rate of <0.005 cm3/m2·day, with effectively blocking UV-A (62.41 %), -B (92.45 %), and -C light (100 %). Moreover, the susceptibility of the coated film to water vapor was mitigated by laminating cast polypropylene, achieving a water vapor transmission rate of 1.17 g/m2·day. Overall, the packaging materials with advanced oxygen-, water vapor-, and UV-barrier properties show great potential for practical applications in various sectors, including food packaging and medical/electrical devices.

Engineering Interfacial Fast Ion Channels toward Highly Stable Zn Metal Batteries.

The development of aqueous zinc-ion batteries (AZIBs) is hindered by dendrites and side reactions, such as interfacial byproducts, corrosion, and hydrogen evolution. The construction of an artificial interface protective layer on the surface of the zinc anode has been extensively researched due to its strong operability and potential for large-scale application. In this study, we have designed an organic hydrophobic hybrid inorganic intercalation composite coating to achieve stable Zn2+ plating/stripping. The hydrophobic poly(vinylidene fluoride) (PVDF) effectively prevents direct contact between free water and the zinc anode, thereby mitigating the risk of dendrite formation. Simultaneously, the inorganic layer of vanadium phosphate (VOPO4·2H2O) after the insertion of polyaniline (PA) establishes a robust ion channel for facilitating rapid transport of Zn2+, thus promoting uniform electric field distribution and reducing concentration polarization. As a result, the performance of the modified composite PVDF/PA-VOP@Zn anode exhibited significant enhancement compared with that of the bare zinc anode. The assembled symmetric cell exhibits an exceptionally prolonged lifespan of 3070 h at a current density of 1 mA cm-2, while the full battery employing KVO as the cathode demonstrates a remarkable capability to undergo 2000 cycles at 5 A g-1 with a capacity retention rate of 78.2%. This study offers valuable insights into the anodic modification strategy for AZIBs.

Hybrid Surface Modification and Bulk Doping Enable Spent LiCoO2 Cathodes for High-Voltage Operation.

The emerging market demand for high-energy-density of energy storage devices is pushing the disposal of end-of-life LiCoO2 (LCO) to shift toward sustainable upgrading into structurally stable high-voltage cathode materials. Herein, an integrated bulk and surface commodification strategy is proposed to render spent LCO (S-LCO) to operate at high voltages, involving bulk Mn doping, near surface P gradient doping, and Li3PO4/CoP (LPO/CP) coating on the LCO surface to yield upcycled LCO (defined as MP-LCO@LPO/CP). Benefiting from hybrid surface coating with Li+-conductive Li3PO4 (LPO) and electron conductive CoP (CP) coupled with Mn and P co-doping, the optimized MP-LCO@LPO/CP cathode exhibits enhanced high-voltage performance, delivering an initial discharge capacity of 218.8 mAh g-1 at 0.2 C with excellent capacity retention of 80.9% (0.5 C) after 200 cycles at a cut-off voltage of 4.6 V, along with 96.3% of capacity retention over 100 cycles at 4.5 V. These findings may afford meaningful construction for the upcycling of commercial S-LCO into next-generation upmarket cathode materials through the elaborate surface and bulk modification design.

Hemocompatibility and biocompatibility of antibacterial biomimetic hybrid films.

In previous work, we developed novel antibacterial hybrid coatings based on dextran containing dispersed Ag NPs (~5 nm, DEX-Ag) aimed to offer dual protection against two of the most common complications associated with implant surgery, infections and rejection of the implant. However, their blood-material interactions are unknown. In this study, we assess the hemocompatibility and biocompatibility of DEX-Ag using fresh blood and two cell lines of the immune system, monocytes (THP-1 cells) and macrophages (PMA-stimulated THP-1 cells). Glass, polyurethane (PU) and bare dextran (DEX) were used as reference surfaces. PU, DEX and DEX-Ag exhibited non-hemolytic properties. Relative to glass (100%), platelet attachment on PU, DEX and DEX-Ag was 15%, 10% and 34%, respectively. Further, we assessed cell morphology and viability, pro-inflammatory cytokines expression (TNF-α and IL-1ß), pro-inflammatory eicosanoid expression (Prostaglandin E2, PGE2) and release of reactive oxygen species (ROS, superoxide and H2O2) following incubation of the cells with the surfaces. The morphology and cell viability of THP-1 cells were not affected by DEX-Ag whereas DEX-Ag minimized spreading of PMA-stimulated THP-1 cells and caused a reduction in cell viability (16% relative to other surfaces). Although DEX-Ag slightly enhanced release of ROS, the expression of pro-inflammatory cytokines remained minimal with similar levels of PGE2, as compared to the other surfaces studied. These results highlight low toxicity of DEX-Ag and hold promise for future applications in vivo.

Immunomodulatory Effects Mediated by Nano Amorphous Calcium Phosphate/Chitosan Oligosaccharide Lactate Coatings Decorated with Selenium on Titanium Implants.

The aim of this work is in situ anodization/anaphoretic deposition of a nano amorphous calcium phosphate (ACP)/chitosan oligosaccharide lactate (ChOL) multifunctional hybrid coating decorated with selenium (Se) on a titanium substrate and in vivo investigation of its immunomodulatory and anti-inflammatory effect. Investigating phenomena at the implant-tissue interface of interest for controlled inflammation and immunomodulation was also the aim of the research. In our earlier research, we designed coatings based on ACP and ChOL on titanium with anticorrosive, antibacterial and biocompatible properties, while in the presented results we show that selenium addition makes this coating an immunomodulator. The immunomodulatory effect of the novel hybrid coating is characterized by the examination of the functional aspects in the tissue around the implant (in vivo): proinflammatory cytokines' gene expression, M1 (iNOS) and M2 (Arg1) macrophages, fibrous capsule formation (TGF-ß) and vascularization (VEGF). The EDS, FTIR and XRD analyses prove the formation of a ACP/ChOL/Se multifunctional hybrid coating on Ti and the presence of Se. A higher M2/M1 macrophage ratio in the ACP/ChOL/Se-coated implants compared to pure titanium implants (a higher level of Arg1 expression) is noted at all time points examined (after 7, 14 and 28 days). Lower inflammation measured by gene expression of proinflammatory cytokines IL-1ß and TNF, lower expression of TGF-ß in the surrounding tissue and higher IL-6 expression (solely at day 7 post-implantation) is noted in presence of the ACP/ChOL/Se-coated implants.

Highly Transparent and Zirconia-Enhanced Sol-Gel Hybrid Coating on Polycarbonate Substrates for Self-Cleaning Applications.

To improve the efficacy of polymer-based substrate hybrid coatings, it is essential to simultaneously optimize mechanical strength and preserve the optical properties. In this study, a mixture of zirconium oxide (ZrO2) sol and methyltriethoxysilane modified silica (SiO2) sol-gel was dip-coated onto polycarbonate (PC) substrates to form zirconia-enhanced SiO2 hybrid coatings. Additionally, a solution containing 1H, 1H, 2H, and 2H-perfluorooctyl trichlorosilane (PFTS) was employed for surface modification. The results show that the ZrO2-SiO2 hybrid coating enhanced the mechanical strength and transmittance. The average transmittance of the coated PC reached up to 93.9% (400-800 nm), while the peak transmittance reached up to 95.1% at 700 nm. SEM images and AFM morphologies demonstrate that the ZrO2 and SiO2 nanoparticles were evenly distributed, and a flat coating was observed on the PC substrate. The PFTS-modified ZrO2-SiO2 hybrid coating also exhibited good hydrophobicity (WCA, 113°). As an antireflective coating on PC, with self-cleaning capability, the proposed coating has application prospects in optical lenses and automotive windows.

Halogen-Free Waterborne Polymeric Hybrid Coatings for Improved Fire Retardancy of Textiles.

Wildfires are becoming more intense and more frequent, ravaging the habitations and ecosystems in their path. One solution to reducing the risk of damage to buildings and other structures during a fire event is the use of fire-retardant coatings that can stop or slow down the spread of flames, especially for textile materials. The present study focuses on the preparation and application of halogen-free boron/bentonite-based polymeric fire-retardant (FR) hybrid coating formulations for fabrics such as cotton (CO) and polyester (PE) fibers. For the preparation of FR composites, two types of boron derivatives, disodium octaborate and zinc borate, were used in combination with sodium bentonite. A styrene-acrylic copolymer was specifically synthesized and used as a coating binder for FR components to apply on fabrics. The properties of the synthesized copolymer and FR composites were characterized with a particle size analysis, FTIR spectroscopy, a dynamic mechanical thermal analysis (DMTA), and rheological measurements. The obtained hybrid composites based on styrene-acrylic copolymers and two different inorganic fillers were applied on cotton (CO) and polyester (PE) fabrics with a screen-printing technique, and the flame retardancy performance of the finished textile samples was investigated by means of flame spread and limit oxygen index (LOI) tests. The findings showed that the FR-composite-coated fabrics had higher LOI values and much decreased flame spread rates in comparison with uncoated ones. Among the boron derivatives, the composites prepared with disodium octaborate (FR-A) had much more pronounced LOI values and decreased flame spread behavior in comparison with the composite with zinc borate (FR-B). When compared to a commercial product, the FR-A composite, in conjunction with the specially synthesized polymer, demonstrated commendable fire retardancy performance and emerged as a promising candidate for a halogen-free waterborne fire-retardant coating for fabrics.

Progress in bioactive surface coatings on biodegradable Mg alloys: A critical review towards clinical translation.

Mg and its alloys evince strong candidature for biodegradable bone implants, cardiovascular stents, and wound closing devices. However, their rapid degradation rate causes premature implant failure, constraining clinical applications. Bio-functional surface coatings have emerged as the most competent strategy to fulfill the diverse clinical requirements, besides yielding effective corrosion resistance. This article reviews the progress of biodegradable and advanced surface coatings on Mg alloys investigated in recent years, aiming to build up a comprehensive knowledge framework of coating techniques, processing parameters, performance measures in terms of corrosion resistance, adhesion strength, and biocompatibility. Recently developed conversion and deposition type surface coatings are thoroughly discussed by reporting their essential therapeutic responses like osteogenesis, angiogenesis, cytocompatibility, hemocompatibility, anti-bacterial, and controlled drug release towards in-vitro and in-vivo study models. The challenges associated with metallic, ceramic and polymeric coatings along with merits and demerits of various coatings have been illustrated. The use of multilayered hybrid coating comprising a unique combination of organic and inorganic components has been emphasized with future perspectives to obtain diverse bio-functionalities in a facile single coating system for orthopedic implant applications.

Metal-organic Zn-zoledronic acid and 1-hydroxyethylidene-1,1-diphosphonic acid nanostick-mediated zinc phosphate hybrid coating on biodegradable Zn for osteoporotic fracture healing implants.

Zn and its alloys are increasingly under consideration for biodegradable bone fracture fixation implants owing to their attractive biodegradability and mechanical properties. However, their clinical application is a challenge for osteoporotic bone fracture healing, due to their uneven degradation mode, burst release of zinc ions, and insufficient osteo-promotion and osteo-resorption regulating properties. In this study, a type of Zn2+ coordinated zoledronic acid (ZA) and 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) metal-organic hybrid nanostick was synthesized, which was further mixed into zinc phosphate (ZnP) solution to mediate the deposition and growth of ZnP to form a well-integrated micro-patterned metal-organic/inorganic hybrid coating on Zn. The coating protected noticeably the Zn substrate from corrosion, in particular reducing its localized occurrence as well as suppressing its Zn2+ release. Moreover, the modified Zn was osteo-compatible and osteo-promotive and, more important, performed osteogenesis in vitro and in vivo of well-balanced pro-osteoblast and anti-osteoclast responses. Such favorable functionalities are related to the nature of its bioactive components, especially the bio-functional ZA and the Zn ions it contains, as well as its unique micro- and nano-scale structure. This strategy provides not only a new avenue for surface modification of biodegradable metals but also sheds light on advanced biomaterials for osteoporotic fracture and other applications. STATEMENT OF SIGNIFICANCE: Developing appropriate biodegradable metallic materials is of clinical relevance for osteoporosis fracture healing, whereas current strategies are short of good balance between the bone formation and resorption. Here, we designed a micropatterned metal-organic nanostick mediated zinc phosphate hybrid coating modified Zn biodegradable metal to fulfill such a balanced osteogenicity. The in vitro assays verified the coated Zn demonstrated outstanding pro-osteoblasts and anti-osteoclasts properties and the coated intramedullary nail promoted fracture healing well in an osteoporotic femur fracture rat model. Our strategy may offer not only a new avenue for surface modification of biodegradable metals but also shed light on better understanding of new advanced biomaterials for orthopedic application among others.

Graphene Nanoribbon/Carbon Nanotube Hybrid Hydrogel: Rheology and Membrane for Ultrafast Molecular Diafiltration.

Hybrids based on carbon nanotubes (CNTs) and graphene nanoribbons (GNRs) are expected to have synergistic effects for various applications. Herein, we demonstrate a simple one-pot synthesis of a CNT/GNR hybrid material by adjusting the oxidation and unzipping conditions of multi-walled CNTs (MWNTs). The MWNT/graphene oxide nanoribbon (GONR) hybrid was dispersed in various solvents, particularly showing the hybrid hydrogel phase in water at a concentration of 40 mg mL-1. The MWNT/GONR hydrogel exhibited shear-thinning behavior, which can be beneficial for coating a large-area MWNT/GONR layer onto a polymeric porous support by using a scalable slot-die coater. The MWNT/GONR membrane exhibited an outstanding nanofiltration performance, with a molecular weight cutoff of 300 Da and a dye/salt diafiltration performance with a separation factor of 1000 and a water flux of 367.8 LMH, far surpassing the upper bound of diafiltration performance of the existing membranes.

Importance of Halide Ions in the Stabilization of Hybrid Sn-Based Coatings for Lithium Electrodes.

The properties of hybrid Sn-based artificial solid electrolyte interphase (SEI) layers in protecting Li-metal electrodes toward surface instabilities were investigated via a combined experimental and theoretical approach. The performance of coating layers can be coherently explained based on the nature of the coating species. Notably, when starting from a chloride precursor, the hybrid coating layer is formed by an intimate mixture of Li7Sn2 and LiCl: the first ensures a high bulk ionic conductivity, while the second forms an external layer allowing a fast surface diffusion of Li+ to avoid dendrite growth, a low surface tension to guarantee the thermodynamic stability of the protective layer, and a negative underneath plating energy (UPE) to promote lithium plating at the interface between the Li metal and the coating layer. The synergy between the two components and, in particular, the crucial role of LiCl in the promotion of such an underneath plating mechanism are shown to be the key properties to improve the performance of artificial SEI layers.