Dual Therapy Coating on Micro/Nanoscale Porous Polyetheretherketone to Eradicate Biofilms and Accelerate Bone Tissue Repair

Defective osteogenesis and latent infections continue to be two major issues in the therapy of bone tissue regeneration. In this study, a unique hierarchically micro/nanoscale‐architecture is first proposed and produced on polyetheretherketone (PEEK). Besides, a “simvastatin‐PLLA film‐tobramycin microspheres” delivery system is subsequently fabricated to endow the PEEK implant with osteogenic and antibacterial capabilities. In vitro antibacterial evaluations confirm that the decorated PEEK scaffolds possess excellent resistance against planktonic/adherent bacteria. In vitro cell attachment/proliferation, lactate dehydrogenase (LDH) content, alkaline phosphatase (ALP) activity, calcium mineral deposition experiments, and real‐time PCR analysis all exhibit that the superior proliferation rate and osteo‐differentiation potential of MC3T3‐E1 pre‐osteoblasts are presented on the PEEK samples with dual functional decoration. In the mouse calvarial defect model, the micro‐CT and histological results demonstrate that our scaffolds display a remarkable bone forming capability. Generally, the PEEK scaffolds co‐endowed with simvastatin and tobramycin microspheres possess great potential in clinics.     

Graphene‐Oxide‐Decorated Microporous Polyetheretherketone with Superior Antibacterial Capability and In Vitro Osteogenesis for Orthopedic Implant

Due to its similar elastic modulus of human bones, polyetheretherketone (PEEK) has been considered as an excellent cytocompatible material. However, the bioinertness, poor osteoconduction, and weak antibacterial activity of PEEK limit its wide applications in clinics. In this study, a facile strategy is developed to prepare graphene oxide (GO) modified sulfonated polyetheretherketone (SPEEK) (GO‐SPEEK) through a simple dip‐coating method. After detailed characterization, it is found that the GO closely deposits on the surface of PEEK, which is attributed to the π–π stacking interaction between PEEK and GO. Antibacterial tests reveal that the GO‐SPEEK exhibits excellent suppression toward Escherichia coli. In vitro cell attachment, growth, differentiation, alkaline phosphatase activity, quantitative real‐time polymerase chain reaction analyses, and calcium mineral deposition all illustrate that the GO‐SPEEK substrate can significantly accelerate the proliferation and osteogenic differentiation of osteoblast‐like MG‐63 cells compared with those on PEEK and SPEEK groups. These results suggest that the GO‐SPEEK has an improved antibacterial activity and cytocompatibility in vitro, showing that the developed GO‐SPEEK has a great potential as the bioactive implant material in bone tissue engineering.     

Hydrothermal Growth of Ag‐Doped ZnO Nanoparticles on Electrospun Cellulose Nanofibrous Mats for Catechol Detection

We fabricated a novel hierarchical composite mat composed of electrospun cellulose nanofibers decorated with Ag‐doped ZnO (Ag‐ZnO) nanoparticles and further demonstrated its potential application as the efficient laccase (Lac) biosensor substrate material. The cyclic voltammograms revealed that the Ag‐ZnO/cellulose nanofibrous mat provided an excellent microenvironment for Lac immobilization and benefited direct electron transfer of Lac. The fabricated Lac/Ag‐ZnO/cellulose/GCE exhibited a highly sensitive detection of catechol with a wide linear range from 0.995 to 811 µM and a low detection limit of 0.205 µM. The results indicated that Ag‐ZnO/cellulose nanofibers were the promising nanostructured materials for the construction of different biosensors.     

One‐Step Synthesis of Silver Nanoparticle‐Decorated Hydroxyapatite Nanowires for the Construction of Highly Flexible Free‐Standing Paper with High Antibacterial Activity

A highly flexible and free‐standing paper with high antibacterial activity made from silver nanoparticle (AgNP)‐decorated ultralong hydroxyapatite nanowires (HAPNWs) is reported. The HAPNWs@AgNPs nanocomposites were obtained from a facile one‐step solvothermal process and utilized for the construction of highly flexible and free‐standing inorganic paper through a simple vacuum‐filtration procedure. The structure and properties of the HAPNWs@AgNPs paper were characterized in detail. Scanning electron microscope (SEM) and transmission electron microscope (TEM) micrographs show that AgNPs are highly dispersed and stabilized in the nanocomposite and exhibit a narrow particle size distribution. The effects of the concentration of silver nitrate, solvothermal temperature and time on the product were systematically investigated. This method is simple, convenient and reproducible. The as‐prepared HAPNWs@AgNPs paper shows long‐time sustained silver‐ion release, high antibacterial activity against both Gram‐negative and Gram‐positive bacteria, and good biocompatibility. Overall, this work provides a novel pathway for the preparation of a new type of highly flexible, free‐standing and antibacterial inorganic paper made from silver nanoparticle‐decorated hydroxyapatite nanowires for various applications, as a promising functional biomaterial.     

Silver nanoparticle‐decorated multiwalled carbon nanotube/pramipexole nanocomposite: Synthesis,characterization and application as an antibacterial agent

This work reports the preparation of multiwalled carbon nanotube/pramipexole/Ag (CNT/pra/Ag) as a novel antibacterial agent, in which pramipexole groups are utilized as linkers to secure Ag nanoparticles to carbon nanotube surfaces without agglomeration. The resulting CNT/pra/Ag sample was characterized by performing transmission and scanning electron microscopy, wavelength‐ and energy‐dispersive X‐ray, X‐ray diffraction, Fourier transform infrared, inductively coupled plasma and Raman measurements. Using this approach, monodisperse spherical Ag nanoparticles in CNT/pra/Ag have narrow size distributions with average diameters of ca 3–8 nm. The antibacterial activity of CNT/pra/Ag was investigated against bacterial species Staphylococcus aureus , methicillin‐resistant S. aureus , Pseudomonas aeruginosa and Escherichia coli using the paper‐disc diffusion method and by determining the minimal inhibitory concentration. CNT/pra/Ag showed better inhibitory activity towards Gram‐positive bacteria than Gram‐negative bacteria in this study, which indicates its potential as an antibacterial material for laboratory and medical purposes.     

One Modification,Two Functions: Single Ni‐modified Light‐Driven ZnO Microrockets with Both Efficient Propulsion and Steerable Motion

Efficient propulsion and effective direction control are essential for self‐propelled micro/nanomotors. Here, a new “two‐in‐one” strategy for making attractive light‐driven micro/nanomotors is demonstrated. We make use of the metallic and magnetic properties of low‐cost Ni and incorporate just a single Ni layer into ZnO‐based microrockets, so that the resulting ZnO‐Ni microrockets can be both efficiently propelled by low energy (low light intensities and fuel concentrations) and effectively steered by a magnetic field. This successful demonstration of ZnO‐Ni microrockets is significant for the development of highly efficient synthetic micro/nanomotors, which have strong delivery ability and efficient direction control for future applications across the micro/nanoscale field.     

Multifunctional polyacrylonitrile‐ZnO/Ag electrospun nanofiber membranes with various ZnO morphologies for photocatalytic,UV‐shielding,and antibacterial applications

New multifunctional polyacrylonitrile (PAN)‐ZnO/Ag composite electrospun nanofiber membranes consisting of pineal‐type, flower‐type, and sea‐urchin‐type ZnO morphologies were prepared using a single‐capillary electrospinning technique, hydrothermal ZnO synthesis, and Ag reduction. The various ZnO architectures exhibited differences in photocatalytic activity and UV‐shielding efficiency, and were ranked as follows: sea‐urchin type > flower type > pineal type. Sea‐urchin‐type ZnO features a higher surface‐to‐volume ratio than other ZnO architectures do because of its distinctive structure, thus yielding higher performance. The present study demonstrated that self‐standing PAN‐ZnO/Ag composite fiber membranes, especially those with the sea‐urchin‐type ZnO structure, can be applied in multifunctional textiles such as water purification filters and antibacterial and UV‐shielding clothes. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 262–269     

Synthesis and antibacterial activity of surface‐coated catechol‐conjugated polymer with silver nanoparticles on versatile substrate

In the present study, 2‐chloro‐3′,4′‐dihydroxyacetophenone (CCDP), a catechol derivative, was quaternized with poly(propylene oxide)‐g‐poly(dimethylaminoethyl methacrylate) (PPO‐g‐PDMA, PgP) to prepare surface coatings for various substrates. The surfaces of noble metals, oxides, and synthetic polymers were coated by immersion in an aqueous solution of CCDP quaternized with PgP (C‐PgP). The catechol functional groups that remained on the surface were used for deposition of Ag nanoparticles (AgNPs) on the coated surface, to provide a water‐resistant antibacterial polymer with long‐term antimicrobial activity. X‐ray photoelectron spectroscopy confirmed deposition of C‐PgP and AgNPs on the surface coated with the antibacterial polymer. Surface‐immobilized C‐PgP/AgNPs showed outstanding antibacterial activities against Staphylococcus aureus, a Gram‐positive bacterium, and Escherichia coli, a Gram‐negative bacterium. C‐PgP/AgNPs can be applied to a variety of substrates and can therefore be used as antibacterial materials in various fields. Copyright © 2016 John Wiley & Sons, Ltd.     

Active Salt/Silica‐Templated 2D Mesoporous FeCo‐Nx‐Carbon as Bifunctional Oxygen Electrodes for Zinc–Air Batteries

Two types of templates, an active metal salt and silica nanoparticles, are used concurrently to achieve the facile synthesis of hierarchical meso/microporous FeCo‐N_x‐carbon nanosheets (meso/micro‐FeCo‐N_x‐CN) with highly dispersed metal sites. The resulting meso/micro‐FeCo‐N_x‐CN shows high and reversible oxygen electrocatalytic performances for both ORR and OER, thus having potential for applications in rechargeable Zn–air battery. Our approach creates a new pathway to fabricate 2D meso/microporous structured carbon architectures for bifunctional oxygen electrodes in rechargeable Zn–air battery as well as opens avenues to the scale‐up production of rationally designed heteroatom‐doped catalytic materials for a broad range of applications.     

Galvanic Replacement Reactions of Active‐Metal Nanoparticles

We present a systemic investigation of a galvanic replacement technique in which active‐metal nanoparticles are used as sacrificial seeds. We found that different nanostructures can be controllably synthesized by varying the type of more noble‐metal ions and liquid medium. Specifically, nano‐heterostructures of noble metal (Ag, Au) or Cu nanocrystals on active‐metal (Mg, Zn) cores were obtained by the reaction of active‐metal nanoparticles with more noble‐metal ions in ethanol; Ag nanocrystal arrays were produced by the reaction of active‐metal nanoparticles with Ag⁺ ions in water; spongy Au nanospheres were generated by the reaction of active‐metal nanoparticles with AuCl₄^? ions in water; and SnO₂ nanoparticles were prepared when Sn²⁺ were used as the oxidant ions. The key factors determining the product morphology are shown to be the reactivity of the liquid medium and the nature of the oxidant–reductant couple, whereas Mg and Zn nanoparticles played similar roles in achieving various nanostructures. When microsized Mg and Zn particles were used as seeds in similar reactions, the products were mainly noble‐metal dendrites. The new approach proposed in this study expands the capability of the conventional nanoscale galvanic replacement method and provides new avenues to various structures, which are expected to have many potential applications in catalysis, optoelectronics, and biomedicine.     

Sulfonated N‐heterocyclic carbine‐silver (I) complexes: Synthesis,characterisation and biological evaluation

The synthesis, characterisation and biological activity of water‐soluble Ag(I)‐NHC complexes, general formula Na[(NHC)AgCl] where NHC is a sulfonated and sterically hindered N‐heterocyclic carbene, is reported. The Ag‐NHC complexes (2a–e) were synthesised by reacting the corresponding sulfonated NHC ligands with Ag₂O in the presence of NaCl or NaBr in methanol/water (1:1) solution. Synthesised silver (I)‐N‐heterocyclic carbene complexes have been characterised by NMR, micro‐analysis and HRMS spectroscopic methods. The IC₅₀ values of these complexes were determined by a proliferation BrdU enzyme‐linked immunosorbent assay (ELISA) against HeLa (human cervix carcinoma), HT29 (human adenocarcinoma) and L929 (mouse fibroblast) cell lines. These complexes have been highlighted as promising and original platforms for building new types of metalodrug. All new water‐soluble Ag(I) complexes demonstrated remarkable cytotoxic activity against HeLa, HT29 and L929 cell lines.     

Hierarchical‐Structured Anatase‐Titania/Cellulose Composite Sheet with High Photocatalytic Performance and Antibacterial Activity

Bulk hierarchical anatase‐titania/cellulose composite sheets were fabricated by subjecting an ultrathin titania gel film pre‐deposited filter paper to a solvo‐co‐hydrothermal treatment by using titanium butoxide as the precursor to grow anatase‐titania nanocrystallites on the cellulose nanofiber surfaces. The titanium butoxide specie is firstly absorbed onto the nanofibers of the cellulose substance through a solvothermal process, which was thereafter hydrolyzed and crystallized upon the subsequent hydrothermal treatment, leading to the formation of fine anatase‐titania nanoparticles with sizes of 2–5 nm uniformly anchored on the cellulose nanofibers. The resulting anatase‐titania/cellulose composite sheet shows a significant photocatalytic performance towards degradation of a methylene blue dye, and introduction of silver nanoparticles into the composite sheet yields an Ag‐NP/anatase‐titania/cellulose composite material possessing excellent antibacterial activity against both Gram‐positive and Gram‐negative bacteria.     

Ostwald‐Ripening‐Induced Growth of Parallel Face‐Exposed Ag Nanoplates on Micro‐Hemispheres for High SERS Activity

Ag nanoplates, as two‐dimensional plasmonic nanostructures, have attracted intensive attention due to their strong shape‐dependent optical properties and related applications. Here parallel face‐exposed Ag nanoplates vertically grown on micro‐hemisphere surfaces have been achieved by firstly electrodepositing the micro‐hemispheres assembled by Ag nanoplates, whose planar surfaces are stuck together, on indium tin oxide substrates, and then Ostwald ripening the as‐electrodeposited micro‐hemispheres in water. The sizes of the nanoplates and the gaps between the neighboring nanoplates have been tailored by tuning the Ostwald‐ripening duration, so that the SERS activity of the micro‐hemispheres has been remarkably improved. The improved SERS activity can be well explained by our systematic finite‐element simulation. Therefore, Ostwald ripening offers a route to the synthesis of Ag nanoplates, and the optimization of plasmon coupling and SERS activity of nanostructure‐assembled systems.     

2‐Aminobenzenethiol‐Functionalized Silver‐Decorated Nanoporous Silicon Photoelectrodes for Selective CO2 Reduction

A molecularly thin layer of 2‐aminobenzenethiol (2‐ABT) was adsorbed onto nanoporous p‐type silicon (b‐Si) photocathodes decorated with Ag nanoparticles (Ag NPs). The addition of 2‐ABT alters the balance of the CO₂ reduction and hydrogen evolution reactions, resulting in more selective and efficient reduction of CO₂ to CO. The 2‐ABT adsorbate layer was characterized by Fourier transform infrared (FTIR) spectroscopy and modeled by density functional theory calculations. Ex situ X‐ray photoelectron spectroscopy (XPS) of the 2‐ABT modified electrodes suggests that surface Ag atoms are in the +1 oxidation state and coordinated to 2‐ABT via Ag?S bonds. Under visible light illumination, the onset potential for CO₂ reduction was ?50 mV vs. RHE, an anodic shift of about 150 mV relative to a sample without 2‐ABT. The adsorption of 2‐ABT lowers the overpotentials for both CO₂ reduction and hydrogen evolution. A comparison of electrodes functionalized with different aromatic thiols and amines suggests that the primary role of the thiol group in 2‐ABT is to anchor the NH₂ group near the Ag surface, where it serves to bind CO₂ and also to assist in proton transfer.     

In Situ Photocatalytically Heterostructured ZnOAg Nanoparticle Composites as Effective Cathode‐Modifying Layers for Air‐Processed Polymer Solar Cells

A heterostructured semiconductor–metal ZnO?Ag nanoparticle (NP) composite was constructed through a straightforward photocatalytic strategy by using UV irradiation of ZnO NPs and an aqueous solution of Ag precursor. The ZnO?Ag NP composites serve as an effective cathode‐modifying layer in polymer solar cells (PSCs) with increased short‐circuit current density owing to the light‐trapping effect, and improved optical and electrical conductivity properties compared with pure ZnO NPs. The Ag NPs, which are photodeposited in situ on ZnO NPs, can act as effective antennas for incident light to maximize light harvesting and minimize radiative decay or nonradiative losses, consequently resulting in the enhanced photogeneration of excitons in PSCs. Systematic photoelectron and ‐physical investigations confirm that heterostructured ZnO?Ag NPs can significantly improve charge separation, transport, and collection, as well as lower charge recombination at the cathode interface, leading to a 14.0 % improvement in air‐processed device power conversion efficiency. In addition, this processable, cost‐effective, and scalable approach is compatible with roll‐to‐roll manufacturing of large‐scale PSCs.     

A Supramolecular‐Based Dual‐Wavelength Phototherapeutic Agent with Broad‐Spectrum Antimicrobial Activity Against Drug‐Resistant Bacteria

With the ever‐increasing threat posed by the multi‐drug resistance of bacteria, the development of non‐antibiotic agents for the broad‐spectrum eradication of clinically prevalent superbugs remains a global challenge. Here, we demonstrate the simple supramolecular self‐assembly of structurally defined graphene nanoribbons (GNRs) with a cationic porphyrin (Pp4N) to afford unique one‐dimensional wire‐like GNR superstructures coated with Pp4N nanoparticles. This Pp4N/GNR nanocomposite displays excellent dual‐modal properties with significant reactive‐oxygen‐species (ROS) production (in photodynamic therapy) and temperature elevation (in photothermal therapy) upon light irradiation at 660 and 808 nm, respectively. This combined approach proved synergistic, providing an impressive antimicrobial effect that led to the complete annihilation of a wide spectrum of Gram‐positive, Gram‐negative, and drug‐resistant bacteria both in vitro and in vivo. The study also unveils the promise of GNRs as a new platform to develop dual‐modal antimicrobial agents that are able to overcome antibiotic resistance.     

Controlled Orientation in a Bio‐Inspired Assembly of Ag/AgCl/ZnO Nanostructures Enables Enhancement in Visible‐Light‐Induced Photocatalytic Performance

In a bio‐inspired approach, polyamine‐mediated mineralization of ZnO was explored to develop an environmentally benign methodology for synthesizing Ag/AgCl/ZnO nanostructures. The assembling properties displayed by the polyamines to create composite structures was utilized to have the nanocomponents effectively interact with each other in a way that is desirable for the application envisaged. The polyamines, which act as a mineralizing agent for ZnO nanoparticles, also facilitate the formation of Ag/AgCl within ZnO under ambient conditions. Thus synthesized Ag/AgCl/ZnO nanostructures represent a multi‐heterojunction system in which the nanocomponents lead in a synergistic way to enhancement in the photocatalytic activity under visible‐light irradiation.     

Disposable Injection‐Moulded Cell‐on‐a‐Chip Microfluidic Devices with Integrated Conducting Polymer Electrodes for On‐Line Voltammetric and Electrochemiluminescence Detection

This work reports the construction and characterization of plastic electrochemical micro‐flow‐cells with integrated injection‐moulded polymer electrodes. The three electrodes (working, auxiliary, and reference) were fabricated by injection‐moulding from a conducting grade of polystyrene loaded with carbon fibers. On‐chip reference electrodes were prepared by coating one of the conducting polymer electrodes with a Ag/AgCl layer (implemented either by e‐beam evaporation of Ag followed by electrochemical formation of AgCl or by applying a Ag/AgCl paste). Working electrodes were either polymer electrodes coated with Au by e‐beam evaporation or bare conducting polymer electrodes. The electrodes were integrated into the micro‐flow‐cells by an over‐moulding process followed by ultrasonic welding. The devices were characterized by optical and electrochemical techniques. Studies by cyclic voltammetry (CV), anodic stripping voltammetry (ASV) and electrochemiluminescence (ECL) demonstrate ‘proof–of‐principle’ of the micro‐flow‐cells as electrochemical sensors.     

Ag/ZnO Catalysts with Different ZnO Nanostructures for Non‐enzymatic Detection of Urea

Silver coated ZnO nanorods and nanoflakes with different crystallographic orientations were synthesized by a combination of sputter deposition and solution growth process. Catalytic properties of morphology‐dependent Ag/ZnO nanostructures were then investigated for urea sensors without enzyme. Ag/ZnO nanorods on carbon electrodes exhibit a higher catalytic activity and an improved efficiency than Ag/ZnO nanoflakes on carbon electrodes. Ag/ZnO nanorod catalysts with more electrochemically surface area (169 cm² mg^?1) on carbon electrode facilitate urea electrooxidation due to easier electron transfer, which further promotes the urea electrolysis. The Ag/ZnO nanorod catalysts also show a significant reduction in the onset voltage (0.410 V vs. Ag/AgCl) and an increase in the current density (12.0 mA cm^?2 mg^?1) at 0.55 V vs Ag/AgCl. The results on urea electrooxidation show that Ag/ZnO nanostructures can be a potential catalyst for non‐enzymatic biosensors and fuel cells.     

Multi‐Stimuli‐Responsive Polymer Materials: Particles,Films, and Bulk Gels

Stimuli‐responsive polymers have received tremendous attention from scientists and engineers for several decades due to the wide applications of these smart materials in biotechnology and nanotechnology. Driven by the complex functions of living systems, multi‐stimuli‐responsive polymer materials have been designed and developed in recent years. Compared with conventional single‐ or dual‐stimuli‐based polymer materials, multi‐stimuli‐responsive polymer materials would be more intriguing since more functions and finer modulations can be achieved through more parameters. This critical review highlights the recent advances in this area and focuses on three types of multi‐stimuli‐responsive polymer materials, namely, multi‐stimuli‐responsive particles (micelles, micro/nanogels, vesicles, and hybrid particles), multi‐stimuli‐responsive films (polymer brushes, layer‐by‐layer polymer films, and porous membranes), and multi‐stimuli‐responsive bulk gels (hydrogels, organogels, and metallogels) from recent publications. Various stimuli, such as light, temperature, pH, reduction/oxidation, enzymes, ions, glucose, ultrasound, magnetic fields, mechanical stress, solvent, voltage, and electrochemistry, have been combined to switch the functions of polymers. The polymer design, preparation, and function of multi‐stimuli‐responsive particles, films, and bulk gels are comprehensively discussed here.