In-Situ Intermolecular Interaction in Composite Polymer Electrolyte for Ultralong Life Quasi-Solid-State Lithium Metal Batteries.

Solid-state lithium metal batteries built with composite polymer electrolytes using cubic garnets as active fillers are particularly attractive owing to their high energy density, easy manufacturing and inherent safety. However, the uncontrollable formation of intractable contaminant on garnet surface usually aggravates poor interfacial contact with polymer matrix and deteriorates Li+ pathways. Here we report a rational designed intermolecular interaction in composite electrolytes that utilizing contaminants as reaction initiator to generate Li+ conducting ether oligomers, which further emerge as molecular cross-linkers between inorganic fillers and polymer matrix, creating dense and homogeneous interfacial Li+ immigration channels in the composite electrolytes. The delicate design results in a remarkable ionic conductivity of 1.43×10-3  S cm-1 and an unprecedented 1000 cycles with 90 % capacity retention at room temperature is achieved for the assembled solid-state batteries.

Recent Advances in Zinc Oxide Nanostructures with Antimicrobial Activities.

This article reviews the recent developments in the synthesis, antibacterial activity, and visible-light photocatalytic bacterial inactivation of nano-zinc oxide. Polycrystalline wurtzite ZnO nanostructures with a hexagonal lattice having different shapes can be synthesized by means of vapor-, liquid-, and solid-phase processing techniques. Among these, ZnO hierarchical nanostructures prepared from the liquid phase route are commonly used for antimicrobial activity. In particular, plant extract-mediated biosynthesis is a single step process for preparing nano-ZnO without using surfactants and toxic chemicals. The phytochemical molecules of natural plant extracts are attractive agents for reducing and stabilizing zinc ions of zinc salt precursors to form green ZnO nanostructures. The peel extracts of certain citrus fruits like grapefruits, lemons and oranges, acting as excellent chelating agents for zinc ions. Furthermore, phytochemicals of the plant extracts capped on ZnO nanomaterials are very effective for killing various bacterial strains, leading to low minimum inhibitory concentration (MIC) values. Bioactive phytocompounds from green ZnO also inhibit hemolysis of Staphylococcus aureus infected red blood cells and inflammatory activity of mammalian immune system. In general, three mechanisms have been adopted to explain bactericidal activity of ZnO nanomaterials, including direct contact killing, reactive oxygen species (ROS) production, and released zinc ion inactivation. These toxic effects lead to the destruction of bacterial membrane, denaturation of enzyme, inhibition of cellular respiration and deoxyribonucleic acid replication, causing leakage of the cytoplasmic content and eventual cell death. Meanwhile, antimicrobial activity of doped and modified ZnO nanomaterials under visible light can be attributed to photogeneration of ROS on their surfaces. Thus particular attention is paid to the design and synthesis of visible light-activated ZnO photocatalysts with antibacterial properties.

Polyetheretherketone and Its Composites for Bone Replacement and Regeneration.

In this article, recent advances in the development, preparation, biocompatibility and mechanical properties of polyetheretherketone (PEEK) and its composites for hard and soft tissue engineering are reviewed. PEEK has been widely employed for fabricating spinal fusions due to its radiolucency, chemical stability and superior sterilization resistance at high temperatures. PEEK can also be tailored into patient-specific implants for treating orbital and craniofacial defects in combination with additive manufacturing process. However, PEEK is bioinert, lacking osseointegration after implantation. Accordingly, several approaches including surface roughening, thin film coating technology, and addition of bioactive hydroxyapatite (HA) micro-/nanofillers have been adopted to improve osseointegration performance. The elastic modulus of PEEK is 3.7-4.0 GPa, being considerably lower than that of human cortical bone ranging from 7-30 GPa. Thus, PEEK is not stiff enough to sustain applied stress in load-bearing orthopedic implants. Therefore, HA micro-/nanofillers, continuous and discontinuous carbon fibers are incorporated into PEEK for enhancing its stiffness for load-bearing applications. Among these, carbon fibers are more effective than HA micro-/nanofillers in providing additional stiffness and load-bearing capabilities. In particular, the tensile properties of PEEK composite with 30wt% short carbon fibers resemble those of cortical bone. Hydrophobic PEEK shows no degradation behavior, thus hampering its use for making porous bone scaffolds. PEEK can be blended with hydrophilic polymers such as polyglycolic acid and polyvinyl alcohol to produce biodegradable scaffolds for bone tissue engineering applications.

Interactions of Zinc Oxide Nanostructures with Mammalian Cells: Cytotoxicity and Photocatalytic Toxicity.

This article presents a state-of-the-art review and analysis of literature studies on the morphological structure, fabrication, cytotoxicity, and photocatalytic toxicity of zinc oxide nanostructures (nZnO) of mammalian cells. nZnO with different morphologies, e.g., quantum dots, nanoparticles, nanorods, and nanotetrapods are toxic to a wide variety of mammalian cell lines due to in vitro cell-material interactions. Several mechanisms responsible for in vitro cytotoxicity have been proposed. These include the penetration of nZnO into the cytoplasm, generating reactive oxygen species (ROS) that degrade mitochondrial function, induce endoplasmic reticulum stress, and damage deoxyribonucleic acid (DNA), lipid, and protein molecules. Otherwise, nZnO dissolve extracellularly into zinc ions and the subsequent diffusion of ions into the cytoplasm can create ROS. Furthermore, internalization of nZnO and localization in acidic lysosomes result in their dissolution into zinc ions, producing ROS too in cytoplasm. These ROS-mediated responses induce caspase-dependent apoptosis via the activation of B-cell lymphoma 2 (Bcl2), Bcl2-associated X protein (Bax), CCAAT/enhancer-binding protein homologous protein (chop), and phosphoprotein p53 gene expressions. In vivo studies on a mouse model reveal the adverse impacts of nZnO on internal organs through different administration routes. The administration of ZnO nanoparticles into mice via intraperitoneal instillation and intravenous injection facilitates their accumulation in target organs, such as the liver, spleen, and lung. ZnO is a semiconductor with a large bandgap showing photocatalytic behavior under ultraviolet (UV) light irradiation. As such, photogenerated electron-hole pairs react with adsorbed oxygen and water molecules to produce ROS. So, the ROS-mediated selective killing for human tumor cells is beneficial for cancer treatment in photodynamic therapy. The photoinduced effects of noble metal doped nZnO for creating ROS under UV and visible light for killing cancer cells are also addressed.

Versatile Strategy for Realizing Flexible Room-Temperature All-Solid-State Battery through a Synergistic Combination of Salt Affluent PEO and Li6.75La3Zr1.75Ta0.25O12 Nanofibers.

All-solid-state lithium metal batteries are highly attractive because of their high energy density and inherent safety. However, it is still a great challenge to design the solid electrolytes with high ionic conductivity at room temperature and good electrode/electrolyte interfacial compatibility simultaneously in a facile and scalable way. In this work, for the first time, the combination of salt affluent Poly(ethylene oxide) with Li6.75La3Zr1.75Ta0.25O12 nanofibers was designed and intensively evaluated. The synergistic effect of each component in the electrolyte enhances the ionic conductivity to 2.13 × 10-4 S cm-1 at 25 °C and exhibits a high transference number of 0.57. The composite electrolyte possesses superior interfacial stability against Li metal for over 680 h in Li symmetric cells even at a relatively high current density of 2 mA cm-2. The all-solid-state batteries employing the solid electrolytes exhibit excellent cycling stability at room temperature and superior safety performance. This work proposes a brand-new strategy to design and fabricate solid electrolytes in a versatile way for room-temperature all-solid-state batteries.

Visible-Light Active Titanium Dioxide Nanomaterials with Bactericidal Properties.

This article provides an overview of current research into the development, synthesis, photocatalytic bacterial activity, biocompatibility and cytotoxic properties of various visible-light active titanium dioxide (TiO2) nanoparticles (NPs) and their nanocomposites. To achieve antibacterial inactivation under visible light, TiO2 NPs are doped with metal and non-metal elements, modified with carbonaceous nanomaterials, and coupled with other metal oxide semiconductors. Transition metals introduce a localized d-electron state just below the conduction band of TiO2 NPs, thereby narrowing the bandgap and causing a red shift of the optical absorption edge into the visible region. Silver nanoparticles of doped TiO2 NPs experience surface plasmon resonance under visible light excitation, leading to the injection of hot electrons into the conduction band of TiO2 NPs to generate reactive oxygen species (ROS) for bacterial killing. The modification of TiO2 NPs with carbon nanotubes and graphene sheets also achieve the efficient creation of ROS under visible light irradiation. Furthermore, titanium-based alloy implants in orthopedics with enhanced antibacterial activity and biocompatibility can be achieved by forming a surface layer of Ag-doped titania nanotubes. By incorporating TiO2 NPs and Cu-doped TiO2 NPs into chitosan or the textile matrix, the resulting polymer nanocomposites exhibit excellent antimicrobial properties that can have applications as fruit/food wrapping films, self-cleaning fabrics, medical scaffolds and wound dressings. Considering the possible use of visible-light active TiO2 nanomaterials for various applications, their toxicity impact on the environment and public health is also addressed.

Antibacterial Activities of Aliphatic Polyester Nanocomposites with Silver Nanoparticles and/or Graphene Oxide Sheets.

Aliphatic polyesters such as poly(lactic acid) (PLA), polycaprolactone (PCL) and poly(lactic-co-glycolic) acid (PLGA) copolymers have been widely used as biomaterials for tissue engineering applications including: bone fixation devices, bone scaffolds, and wound dressings in orthopedics. However, biodegradable aliphatic polyesters are prone to bacterial infections due to the lack of antibacterial moieties in their macromolecular chains. In this respect, silver nanoparticles (AgNPs), graphene oxide (GO) sheets and AgNPs-GO hybrids can be used as reinforcing nanofillers for aliphatic polyesters in forming antimicrobial nanocomposites. However, polymeric matrix materials immobilize nanofillers to a large extent so that they cannot penetrate bacterial membrane into cytoplasm as in the case of colloidal nanoparticles or nanosheets. Accordingly, loaded GO sheets of aliphatic polyester nanocomposites have lost their antibacterial functions such as nanoknife cutting, blanket wrapping and membrane phospholipid extraction. In contrast, AgNPs fillers of polyester nanocomposites can release silver ions for destroying bacterial cells. Thus, AgNPs fillers are more effective than loaded GO sheets of polyester nanocomposiites in inhibiting bacterial infections. Aliphatic polyester nanocomposites with AgNPs and AgNPs-GO fillers are effective to kill multi-drug resistant bacteria that cause medical device-related infections.

Bi-directional regulatable mechanical properties of 3D braided polyetheretherketone (PEEK).

Fabricating adjustable mechanical properties of biomaterials at different level remains an important challenge in obtaining suitable bone substitutes with stiffness at micro scale and toughness at macro level. In this study, the changes in structure and properties of three dimension braided polyetheretherketone (3D-braided PEEK) after hot-pressed at 345 °C, 355 °C and 365 °C were investigated. The hyperfield 3D microscopy images and DSC revealed more compact macrostructure and lower crystallinity of 3D braided PEEK at higher hot-pressing temperature. The depth-sensing indentation data exhibited a reduction in elastic modulus of 3D braided PEEK with increasing the hot-press temperature, but its strength and toughness measured via universal material experiment machine increased. These results suggested that the micro-mechanics properties of braided PEEK matrix can be adjusted by altering its intrinsic crystal structure that governed by the hot-pressing temperature, whereas its macro-mechanics characteristics by changing its macrostructure that depended on textile structure. Present findings made a breakthrough in simultaneously regulating the micro- and macro-mechanics properties of PEEK in an opposite manner, which should have promising application in the development of customized orthopedic implants.

Electrospun Polyvinylidene Fluoride-Based Fibrous Scaffolds with Piezoelectric Characteristics for Bone and Neural Tissue Engineering.

Polyvinylidene fluoride (PVDF) and polyvinylidene fluoride-trifluoroethylene (P(VDF-TrFE) with excellent piezoelectricity and good biocompatibility are attractive materials for making functional scaffolds for bone and neural tissue engineering applications. Electrospun PVDF and P(VDF-TrFE) scaffolds can produce electrical charges during mechanical deformation, which can provide necessary stimulation for repairing bone defects and damaged nerve cells. As such, these fibrous mats promote the adhesion, proliferation and differentiation of bone and neural cells on their surfaces. Furthermore, aligned PVDF and P(VDF-TrFE) fibrous mats can enhance neurite growth along the fiber orientation direction. These beneficial effects derive from the formation of electroactive, polar ß-phase having piezoelectric properties. Polar ß-phase can be induced in the PVDF fibers as a result of the polymer jet stretching and electrical poling during electrospinning. Moreover, the incorporation of TrFE monomer into PVDF can stabilize the ß-phase without mechanical stretching or electrical poling. The main drawbacks of electrospinning process for making piezoelectric PVDF-based scaffolds are their small pore sizes and the use of highly toxic organic solvents. The small pore sizes prevent the infiltration of bone and neuronal cells into the scaffolds, leading to the formation of a single cell layer on the scaffold surfaces. Accordingly, modified electrospinning methods such as melt-electrospinning and near-field electrospinning have been explored by the researchers to tackle this issue. This article reviews recent development strategies, achievements and major challenges of electrospun PVDF and P(VDF-TrFE) scaffolds for tissue engineering applications.

Synthetic Biodegradable Aliphatic Polyester Nanocomposites Reinforced with Nanohydroxyapatite and/or Graphene Oxide for Bone Tissue Engineering Applications.

This paper provides review updates on the current development of bionanocomposites with polymeric matrices consisting of synthetic biodegradable aliphatic polyesters reinforced with nanohydroxyaptite (nHA) and/or graphene oxide (GO) nanofillers for bone tissue engineering applications. Biodegradable aliphatic polyesters include poly(lactic acid) (PLA), polycaprolactone (PCL) and copolymers of PLA-PGA (PLGA). Those bionanocomposites have been explored for making 3D porous scaffolds for the repair of bone defects since nHA and GO enhance their bioactivity and biocompatibility by promoting biomineralization, bone cell adhesion, proliferation and differentiation, thus facilitating new bone tissue formation upon implantation. The incorporation of nHA or GO into aliphatic polyester scaffolds also improves their mechanical strength greatly, especially hybrid GO/nHA nanofilllers. Those mechanically strong nanocomposite scaffolds can support and promote cell attachment for tissue growth. Porous scaffolds fabricated from conventional porogen leaching, and thermally induced phase separation have many drawbacks inducing the use of organic solvents, poor control of pore shape and pore interconnectivity, while electrospinning mats exhibit small pores that limit cell infiltration and tissue ingrowth. Recent advancement of 3D additive manufacturing allows the production of aliphatic polyester nanocomposite scaffolds with precisely controlled pore geometries and large pores for the cell attachment, growth, and differentiation in vitro, and the new bone formation in vivo.

Bactericidal and Cytotoxic Properties of Silver Nanoparticles.

Silver nanoparticles (AgNPs) can be synthesized from a variety of techniques including physical, chemical and biological routes. They have been widely used as nanomaterials for manufacturing cosmetic and healthcare products, antimicrobial textiles, wound dressings, antitumor drug carriers, etc. due to their excellent antimicrobial properties. Accordingly, AgNPs have gained access into our daily life, and the inevitable human exposure to these nanoparticles has raised concerns about their potential hazards to the environment, health, and safety in recent years. From in vitro cell cultivation tests, AgNPs have been reported to be toxic to several human cell lines including human bronchial epithelial cells, human umbilical vein endothelial cells, red blood cells, human peripheral blood mononuclear cells, immortal human keratinocytes, liver cells, etc. AgNPs induce a dose-, size- and time-dependent cytotoxicity, particularly for those with sizes ≤10 nm. Furthermore, AgNPs can cross the brain blood barrier of mice through the circulation system on the basis of in vivo animal tests. AgNPs tend to accumulate in mice organs such as liver, spleen, kidney and brain following intravenous, intraperitoneal, and intratracheal routes of administration. In this respect, AgNPs are considered a double-edged sword that can eliminate microorganisms but induce cytotoxicity in mammalian cells. This article provides a state-of-the-art review on the synthesis of AgNPs, and their applications in antimicrobial textile fabrics, food packaging films, and wound dressings. Particular attention is paid to the bactericidal activity and cytotoxic effect in mammalian cells.

Graphene Nanomaterials: Synthesis, Biocompatibility, and Cytotoxicity.

Graphene, graphene oxide, and reduced graphene oxide have been widely considered as promising candidates for industrial and biomedical applications due to their exceptionally high mechanical stiffness and strength, excellent electrical conductivity, high optical transparency, and good biocompatibility. In this article, we reviewed several techniques that are available for the synthesis of graphene-based nanomaterials, and discussed the biocompatibility and toxicity of such nanomaterials upon exposure to mammalian cells under in vitro and in vivo conditions. Various synthesis strategies have been developed for their fabrication, generating graphene nanomaterials with different chemical and physical properties. As such, their interactions with cells and organs are altered accordingly. Conflicting results relating biocompatibility and cytotoxicity induced by graphene nanomaterials have been reported in the literature. In particular, graphene nanomaterials that are used for in vitro cell culture and in vivo animal models may contain toxic chemical residuals, thereby interfering graphene-cell interactions and complicating interpretation of experimental results. Synthesized techniques, such as liquid phase exfoliation and wet chemical oxidation, often required toxic organic solvents, surfactants, strong acids, and oxidants for exfoliating graphite flakes. Those organic molecules and inorganic impurities that are retained in final graphene products can interact with biological cells and tissues, inducing toxicity or causing cell death eventually. The residual contaminants can cause a higher risk of graphene-induced toxicity in biological cells. This adverse effect may be partly responsible for the discrepancies between various studies in the literature.

Preparation and application of ratiometric polystyrene-based microspheres as oxygen sensors.

Mono-dispersed polystyrene-based microspheres with diameters about 1 µm encapsulating rhodamine moieties as oxygen insensitive internal reference probes and platinum octaethylporphyrin units as oxygen sensitive probes were synthesized as new ratiometric oxygen sensors (Rhod-PtOEP-PS). The dual luminophors of rhodamines and platinum porphyrin moieties exhibited emissions maxima at 585 nm and 644 nm, respectively. The microspheres showed good oxygen sensing properties in different oxygen partial pressures (pO2) and dissolved oxygen (DO) concentrations. It was found the oxygen probes and reference probes in microspheres showed higher photo-stability than their corresponding free fluorophores in solution. The microspheres also showed good sensitivity for air-pressure and cellular oxygen in cell culture medium. These microspheres were used to detect DOs in a few kinds of liquids including some daily drinks and it was found the measured errors were within positive/negative 11% as compared with the measured results using traditional oxygen electrodes.

Scalable Fabrication of High-Performance Transparent Conductors Using Graphene Oxide-Stabilized Single-Walled Carbon Nanotube Inks.

Recent development in liquid-phase processing of single-walled carbon nanotubes (SWNTs) has revealed rod-coating as a promising approach for large-scale production of SWNT-based transparent conductors. Of great importance in the ink formulation is the stabilizer having excellent dispersion stability, environmental friendly and tunable rheology in the liquid state, and also can be readily removed to enhance electrical conductivity and mechanical stability. Herein we demonstrate the promise of graphene oxide (GO) as a synergistic stabilizer for SWNTs in water. SWNTs dispersed in GO is formulated into inks with homogeneous nanotube distribution, good wetting and rheological properties, and compatible with industrial rod coating practice. Microwave treatment of rod-coated films can reduce GOs and enhance electro-optical performance. The resultant films offer a sheet resistance of ~80 Ω/sq at 86% transparency, along with good mechanical flexibility. Doping the films with nitric acid can further decrease the sheet resistance to ~25 Ω/sq. Comparing with the films fabricated from typical surfactant-based SWNT inks, our films offer superior adhesion as assessed by the Scotch tape test. This study provides new insight into the selection of suitable stabilizers for functional SWNT inks with strong potential for printed electronics.

Variation in the coordination mode of arenedisulfonates: syntheses and structural characterization of mononuclear and dinuclear cadmium(II) arenedisulfonate complexes with two- to zero-dimensional architectures.

Seven cadmium(II) arenedisulfonate compounds, namely [Cd(2,2'-bpy)(2)(H(2)O)(peds)].4H(2)O (1), [Cd(2)(2,2'-bpy)(4)(H(2)O)(2)(1,5nds)](1,5nds).4H(2)O (2), [Cd(cyclam)(1,5nds)](2) (3), ([Cd(inia)(2)(H(2)O)(2)(2,6nds)].4H(2)O)(n)(4), ([Cd(inia)(2)(H(2)O)(2)(bpds)].4H(2)O)(n)(5), ([Cd(2)(inia)(4)(H(2)O)(3)(peds)(2)].2H(2)O)(n)(6), and [Cd(1,5nds)(H(2)O)(2)](n) (7), where 2,2'-bpy = 2,2'-bipyridyl, cyclam = 1,4,8,11-tetraazacyclotetradecane, inia = isonicotinamide, nds = naphthalenedisulfonate, bpds = 4,4'-biphenyldisulfonate, and peds = 4,4'-phenyletherdisulfonate, have been obtained from aqueous solution by using similar procedures and structurally characterized by X-ray single-crystal diffraction, IR spectroscopy, and thermal gravimetric analysis. In 1, the peds anion coordinates as a monodentate ligand, leading to a mononuclear unit. In 2 and 3, the 1,5nds anions coordinate as mu(2)-bridging ligands in different modes, producing charged or neutral dinuclear clusters. In 4 and 5, 2,6nds and bpds behave as mu(2)-spacers, resulting in 1-dimensional polymers. While in 6, the peds acts both as terminal and bridging ligands with the SO(3)(-) groups being either monodentate or mu(2)-bridging, creating a knotted 1-dimensional polymer with dinuclear clusters as the repeating units. In 7, 1,5nds acts as a bridging ligand with each SO(3)(-) coordinated as a mu(2)-bridging group to adjacent Cd(II) centers, leading to a 2-dimensional polymer. Together with the reported ([Cu(en)(2)(1,5nds)].2H(2)O)(n) (8), all of the six possible coordination modes adopted by organodisulfonate anions, on the assumption that each SO(3)(-) group could be monodentate or mu(2)-bridging, are realized by introducing nitrogen-containing organic ligands as auxiliaries.