Electronic structure modelling of the edge-functionalisation of graphene by MnxOy particles.

The use of graphenic carbon is attractive as a basal or intermediate support for catalytic particles in advanced catalytic electrodes. This popularity is motivated by its excellent electrical properties and ability to form foliated conformal coatings of exceptional surface area and flexibility. Surface- and edge-functionalisation of graphene sheets affords diverse routes to the covalent attachment of candidate catalytic species. Of particular interest to advanced water oxidation is the possibility of covalent attachment of MnxOy species partially recapitulating the chemistry of the Mn4O5Ca active site of Photosystem II (PSII), which achieves the four-electron oxidation of water under physiological conditions. Here, we report aperiodic density functional theory (DFT) investigations of candidate attachment geometries for a variety of manganese oxide particles to graphene sheets. We find that the flexibility of graphene sheets as well as the conformational degrees of freedom of candidate edge functionalisation permits a large variety of realistic attachment geometries that can act as attachment sites for molecular manganese-oxide species or nuclei for the growth of periodic manganese oxides. We find that substantially simplified models of graphene attachment afford an excellent compromise between computational efficiency, tractability, and accuracy, and characterise the accuracy of these models in detail.

Non-Periodic Epsilon-Near-Zero Metamaterials at Visible Wavelengths for Efficient Non-Resonant Optical Sensing.

Epsilon-near-zero (ENZ) materials offer unique properties for applications including optical clocking, nonlinear optics, and telecommunication. To date, the fabrication of ENZ materials at visible wavelengths relies mostly on the use of periodic structures, providing some manufacturing and material challenges. Here, we present the engineering of nonperiodic sodium tungsten bronzes (NaxWO3) metamaterials featuring ENZ properties in the visible spectrum. We showcase their use as efficient optical sensors, demonstrating a nonresonant sensing mechanism based on refractive index matching. Our optimized ENZ metamaterials display an unconventional blue-shift of the transmittance maximum to increasing refractive index of the surrounding environment, achieving sensitivity as high as 150 nm/RIU. Our theoretical and experimental investigations provide first insights on this sensing mechanism, establishing guidelines for the future engineering and implementation of efficient ENZ sensors. The unique optoelectronic properties demonstrated by this class of tunable NaxWO3 materials bear potential for various applications ranging from light-harvesting to optical photodetectors.

Mixed oxide nanotubes in nanomedicine: A dead-end or a bridge to the future?

Nanomedicine has seen a significant rise in the development of new research tools and clinically functional devices. In this regard, significant advances and new commercial applications are expected in the pharmaceutical and orthopedic industries. For advanced orthopedic implant technologies, appropriate nanoscale surface modifications are highly effective strategies and are widely studied in the literature for improving implant performance. It is well-established that implants with nanotubular surfaces show a drastic improvement in new bone creation and gene expression compared to implants without nanotopography. Nevertheless, the scientific and clinical understanding of mixed oxide nanotubes (MONs) and their potential applications, especially in biomedical applications are still in the early stages of development. This review aims to establish a credible platform for the current and future roles of MONs in nanomedicine, particularly in advanced orthopedic implants. We first introduce the concept of MONs and then discuss the preparation strategies. This is followed by a review of the recent advancement of MONs in biomedical applications, including mineralization abilities, biocompatibility, antibacterial activity, cell culture, and animal testing, as well as clinical possibilities. To conclude, we propose that the combination of nanotubular surface modification with incorporating sensor allows clinicians to precisely record patient data as a critical contributor to evidence-based medicine.

Metal-Organic Frameworks/Conducting Polymer Hydrogel Integrated Three-Dimensional Free-Standing Monoliths as Ultrahigh Loading Li-S Battery Electrodes.

The lithium-sulfur (Li-S) system is a promising material for the next-generation of high energy density batteries with application extending from electrical vehicles to portable devices and aeronautics. Despite progress, the energy density of current Li-S technologies is still below that of conventional intercalation-type cathode materials due to limited stability and utilization efficiency at high sulfur loading. Here, we present a conducting polymer hydrogel integrated highly performing free-standing three-dimensional (3D) monolithic electrode architecture for Li-S batteries with superior electrochemical stability and energy density. The electrode layout consists of a highly conductive three-dimensional network of N,P codoped carbon with well-dispersed metal-organic framework nanodomains of ZIF-67 and HKUST-1. The hierarchical monolithic 3D carbon networks provide an excellent environment for charge and electrolyte transport as well as mechanical and chemical stability. The electrically integrated MOF nanodomains significantly enhance the sulfur loading and retention capabilities by inhibiting the release of lithium polysulfide specificities as well as improving the charge transfer efficiency at the electrolyte interface. Our optimal 3D carbon-HKUST-1 electrode architecture achieves a very high areal capacity of >16 mAh cm-2 and volumetric capacity (CV) of 1230.8 mAh cm-3 with capacity retention of 82% at 0.2C for over 300 cycles, providing an attractive candidate material for future high-energy density Li-S batteries.

Strong, Self-Healable, and Recyclable Visible-Light-Responsive Hydrogel Actuators.

The most pressing challenges for light-driven hydrogel actuators include reliance on UV light, slow response, poor mechanical properties, and limited functionalities. Now, a supramolecular design strategy is used to address these issues. Key is the use of a benzylimine-functionalized anthracene group, which red-shifts the absorption into the visible region and also stabilizes the supramolecular network through π-π interactions. Acid-ether hydrogen bonds are incorporated for energy dissipation under mechanical deformation and maintaining hydrophilicity of the network. This double-crosslinked supramolecular hydrogel developed via a simple synthesis exhibits a unique combination of high strength, rapid self-healing, and fast visible-light-driven shape morphing both in the wet and dry state. As all of the interactions are dynamic, the design enables the structures to be recycled and reprogrammed into different 3D objects.

Screening of cannabinoids in industrial-grade hemp using two-dimensional liquid chromatography coupled with acidic potassium permanganate chemiluminescence detection.

Widely known for its recreational use, the cannabis plant also has the potential to act as an antibacterial agent in the medicinal field. The analysis of cannabis plants/products in both pharmacological and forensic studies often requires the separation of compounds of interest and/or accurate identification of the whole cannabinoid profile. In order to provide a complete separation and detection of cannabinoids, a new two-dimensional liquid chromatography method has been developed using acidic potassium permanganate chemiluminescence detection, which has been shown to be selective for cannabinoids. This was carried out using a Luna 100 Å CN column and a Poroshell 120 EC-C18 column in the first and second dimensions, respectively. The method has utilized a large amount of the available separation space with a spreading angle of 48.4° and a correlation of 0.66 allowing the determination of more than 120 constituents and mass spectral identification of ten cannabinoids in a single analytical run. The method has the potential to improve research involved in the characterization of sensitive, complex matrices.

Facts and myths of antibacterial properties of silk.

Silk cocoons provide protection to silkworm from biotic and abiotic hazards during the immobile pupal phase of the lifecycle of silkworms. Protection is particularly important for the wild silk cocoons reared in an open and harsh environment. To understand whether some of the cocoon components resist growth of microorganisms, in vitro studies were performed using gram negative bacteria Escherichia coli (E. coli) to investigate antibacterial properties of silk fiber, silk gum, and calcium oxalate crystals embedded inside some cocoons. The results show that the previously reported antibacterial properties of silk cocoons are actually due to residues of chemicals used to isolate/purify cocoon elements, and properly isolated silk fiber, gum, and embedded crystals free from such residues do not have inherent resistance to E. coli. This study removes the uncertainty created by previous studies over the presence of antibacterial properties of silk cocoons, particularly the silk gum and sericin.

Photoprotection by silk cocoons.

A silk cocoon protects a silkworm during its pupal stage from various threats. We systematically investigated the role of fiber, sericin, and embedded crystals in the UV protection of a silk cocoon. Diffuse reflectance and UV absorbance were measured and free radicals generated during exposure to UV radiation were quantified using photoinduced chemiluminescence (PICL). We identified the response to both UV-A and UV-B radiations by silk materials and found that sericin was primarily responsible for UV-A absorption. When sericin was removed, the photoinduced chemiluminescence intensity increased significantly, indicating higher UV-A-induced reactions of cocoons in the absence of sericin. There is progressively higher sericin content toward the outer part of the cocoon shell that allows an effective shield to pupae from UV radiation and resists photodegradation of silk fibers. The study will inspire development of advanced organic photoprotective materials and designing silk-based, free-radical-scavenging antioxidants.

Structure and biodegradation mechanism of milled Bombyx mori silk particles.

The aim of this study was to understand the structure and biodegradation relationships of silk particles intended for targeted biomedical applications. Such a study is also useful in understanding structural remodelling of silk debris that may be generated from silk-based implants. Ultrafine silk particles were prepared using a combination of efficient wet-milling and spray-drying processes with no addition of chemicals other than those used in degumming. Milling reduced the intermolecular stacking forces within the ß-sheet crystallites without changing the intramolecular binding energy. Because of the rough morphology and the ultrafine size of the particles, degradation of silk particles by protease XIV was increased by about 3-fold compared to silk fibers. Upon biodegradation, the thermal degradation temperature of silk increased, which was attributed to the formation of tight aggregates by the hydrolyzed residual macromolecules. A model of the biodegradation mechanism of silk particles was developed based on the experimental data. The model explains the process of disintegration of ß-sheets, supported by quantitative secondary structural analysis and microscopic images.

Facile one pot preparation of magnetic chitosan-palygorskite nanocomposite for efficient removal of lead from water.

Development of polymeric magnetic adsorbents is a promising approach to obtain efficient treatment of contaminated water. However, the synthesis of magnetic composites involving multiple components frequently involves tedious preparation steps. In the present study, a magnetic chitosan-palygorskite (MCP) nanocomposite was prepared through a straight-forward one pot synthesis approach to evaluate its lead (Pb2+) removal capacity from aqueous solution. The nano-architectural and physicochemical properties of the newly-developed MCP composite were described via micro- and nano-morphological analyses, and crystallinity, surface porosity and magnetic susceptibility measurements. The MCP nanocomposite was capable to remove up to 58.5 mg Pb2+ g-1 of MCP from water with a good agreement of experimental data to the Langmuir isotherm model (R2 = 0.98). The Pb2+ adsorption process on MCP was a multistep diffusion-controlled phenomenon evidenced by the well-fitting of kinetic adsorption data to the intra-particle diffusion model (R2 = 0.96). Thermodynamic analysis suggested that the adsorption process at low Pb2+ concentration was controlled by chemisorption, whereas that at high Pb2+ concentration was dominated by physical adsorption. X-ray photoelectron and Fourier transform infrared spectroscopy results suggested that the Pb adsorption on MCP was governed by surface complexation and chemical reduction mechanisms. During regeneration, the MCP retained 82% Pb2+ adsorption capacity following four adsorption-desorption cycles with ease to recover the adsorbent using its strong magnetic property. These findings highlight the enhanced structural properties of the easily-prepared nanocomposite which holds outstanding potential to be used as an inexpensive and green adsorbent for remediating Pb2+ contaminated water.

Superior Hemostatic and Wound-Healing Properties of Gel and Sponge Forms of Nonoxidized Cellulose Nanofibers: In Vitro and In Vivo Studies.

Many materials have been engineered and commercialized as hemostatic agents. However, there is still a gap in the availability of hemostats that offer biocompatibility and biodegradability in combination with effective hemostatic properties. Cellulose nanofibers are investigated as hemostatic materials with most studies focusing on oxidized cellulose-derived hemostats. The recent studies demonstrate that by optimizing the morphological properties of nonoxidized cellulose nanofibers (CNFs) enhanced hemostasis is achieved. Herein, the hemostatic and wound-healing properties of CNFs with optimized morphology using two forms, gel, and sponge is investigated. In vitro thromboelastometry studies demonstrate that CNFs reduce clotting time by 68% (±SE 2%) and 88% (±SE 5%) in gel and sponge forms, respectively. In an in vivo murine liver injury model, CNFs significantly reduce blood loss by 38% (±SE 10%). The pH-neutral CNFs do not damage red blood cells, nor do they impede the proliferation of fibroblast or endothelial cells. Subcutaneously-implanted CNFs show a foreign body reaction resolving with the degradation of CNFs on histological examination and there is no scarring in the skin after 8 weeks. Demonstrating superior hemostatic performance in a variety of forms, as well as biocompatibility and biodegradability, CNFs hold significant potential for use in surgical and first-aid environments.

Shielding Surfaces from Viruses and Bacteria with a Multiscale Coating.

The spread of viral and bacterial pathogens mediated by contact with surfaces is a leading cause of infection worldwide. COVID-19 and the continuous rise of deaths associated with antibiotic-resistant bacteria highlight the need to impede surface-mediated transmission. A sprayable coating with an intrinsic ability to resist the uptake of bacteria and viruses from surfaces and droplets, such as those generated by sneezing or coughing, is reported. The coating also provides an effective microbicidal functionality against bacteria, providing a dual barrier against pathogen uptake and transmission. This antimicrobial functionality is fully preserved following scratching and other induced damage to its surface or 9 days of submersion in a highly concentrated suspension of bacteria. The coatings also register an 11-fold decrease in viral contamination compared to the noncoated surfaces.

Mechanochemical synthesis of metal oxide nanoparticles.

In the last decades, mechanochemical processing has emerged as a sustainable method for the large-scale production of a variety of nanomaterials. In particular, mechanochemical synthesis can afford well-dispersed metal-oxide nanoparticles, which are used in wide-ranging applications including energy storage and conversion, environmental monitoring, or biomedical uses. This article reviews recent progress in the mechanochemical synthesis of metal-oxide nanoparticles, explores reaction mechanisms, and contrasts the influence of chosen process parameters on the properties of end products. The role of choice of reaction pathway, as well as advantages and limitations compared to other synthesis methods are discussed. A prospect for future development of this synthetic method is proposed.

Non-oxidized cellulose nanofibers as a topical hemostat: In vitro thromboelastometry studies of structure vs function.

Hemorrhage remains a significant cause of morbidity and mortality following trauma and during complex surgeries. A variety of nanomaterials, including oxidized cellulose nanofibers (OCNFs), have been studied to overcome the disadvantages of current commercial topical hemostats. However, the relationship between nano-structural characteristics and hemostatic efficacy of non-oxidized cellulose nanofibers (CNFs) has not been elucidated. Herein, we present the first report of the correlation between structure and hemostatic performance of CNFs. In vitro thromboelastometry studies on CNFs, synthesized by ball-milling, showed that there is an optimum balance point between the aspect ratio (AR) and specific surface area (SSA) of nanofibers in terms of their maximum contribution to platelet function and plasma coagulation. The optimized CNFs with high SSA (17 m2/g) and a high AR (166) shortened normal whole blood clotting time by 68 %, outperforming cellulose-based hemostats. Additionally, CNFs reduced clotting time in platelet-deficient blood (by 80 %) and heparinized blood (by 54 %).

Chitin nanofibers trigger membrane bound defense signaling and induce elicitor activity in plants.

The present study demonstrated that chitin-based nanofibers (CNFs) trigger the chitinase genes (PGIP1 and CaChi2), while elevating salicylic acid that can protect plants against pathogens. Cross-talk between this genetic induction and salicylic-acid-mediated immune response was also observed, which may arm a plant against multiple pathovars. Crab and mushroom based CNFs were synthesized by electrospinning and ball milling techniques. Plants (mung bean, Vigna radiata) (pepper, Capsicum annuum) were pre-inoculated with CNFs and treated with the pathogens Scrolotium rolfsii for pepper and Macrophomina phaseolina for mung bean and shrimp-based CNFs were used as a control. Treated plants had elevated levels of chitinase genes in response to CNFs at inoculation concentrations <10 mg/mL both in soil and media, to protect them against the pathogenic fungal disease. After 24 h of exposure to the pathogens, qRT-PCR showed genes class II chitinase gene (CaChi2) and polygalacturonase inhibitor protein 1 (PGIP1) to be up-regulated in both root and shoot at 0.1 and 1 mg/mL of inoculation, respectively. The ball milled mushroom CNFs were sufficient to trigger the membrane based enzymes with less diameter (≥15 nm) to be most efficient versus others. In vitro analysis showed IC50 of ball milled mushroom CNFs to be most efficient in limiting the growth of fungal biomass. Further trigger-like effects were prominent in reducing pathogenic fungal spread in both species.

Concentration-Dependent Solar Thermochemical CO2/H2O Splitting Performance by Vanadia-Ceria Multiphase Metal Oxide Systems.

The effects of V and Ce concentrations (each varying in the 0-100% range) in vanadia-ceria multiphase systems are investigated for synthesis gas production via thermochemical redox cycles of CO2 and H2O splitting coupled to methane partial oxidation reactions. The oxidation of prepared oxygen carriers is performed by separate and sequential CO2 and H2O splitting reactions. Structural and chemical analyses of the mixed-metal oxides revealed important information about the Ce and V interactions affecting their crystal phases and redox characteristics. Pure CeO2 and pure V2O5 are found to offer the lowest and highest oxygen exchange capacities and syngas production performance, respectively. The mixed-oxide systems provide a balanced performance: their oxygen exchange capacity is up to 5 times higher than that of pure CeO2 while decreasing the extent of methane cracking. The addition of 25% V to CeO2 results in an optimum mixture of CeO2 and CeVO4 for enhanced CO2 and H2O splitting. At higher V concentrations, cyclic carbide formation and oxidation result in a syngas yield higher than that for pure CeO2.

Janus Conductive/Insulating Microporous Ion-Sieving Membranes for Stable Li-S Batteries.

Lithium-sulfur batteries are one of the most promising next-generation high-density energy storage systems. Despite progress, the poor electrical conductivity and cycling stability of sulfur cathodes still hinder their practical implementation. Here, we developed a facile approach for the engineering of Janus double-sided conductive/insulating microporous ion-sieving membranes that significantly enhance recharge efficiency and long-term stability of Li-S batteries. Our membrane consists of an insulating Li-anode side and an electrically conductive S-cathode side. The insulating side consists of a standard polypropylene separator, while the conductive side is made of closely packed multilayers of high-aspect-ratio MOF/graphene nanosheets having a thickness of few nanometers and a specific surface area of 996 m2 g-1 (MOF, metal-organic framework). Our models and experiments reveal that this electrically conductive microporous nanosheet architecture enables the reuse of polysulfide trapped in the membrane and decreases the polysulfide flux and concentration on the anode side by a factor of 250× over recent microporous membranes made of granular MOFs and standard battery separators. Notably, Li-S batteries using our Janus microporous membranes achieve an outstanding rate capability and long-term stability with 75.3% capacity retention over 1700 cycles. We demonstrate the broad applicability of our high-aspect-ratio MOF/graphene nanosheet preparation strategy by the synthesis of a diverse range of MOFs, including ZIF-67, ZIF-8, HKUST-1, NiFe-BTC, and Ni-NDC, providing a flexible approach for the design of Janus microporous membranes and electrically conductive microporous building blocks for energy storage and various other electrochemical applications.

Hierarchical Metal-Organic Framework Films with Controllable Meso/Macroporosity.

The structuring of the metal-organic framework material ZIF-8 as films and membranes through the vapor-phase conversion of ZnO fractal nanoparticle networks is reported. The extrinsic porosity of the resulting materials can be tuned from 4% to 66%, and the film thickness can be controlled from 80 nm to 0.23 mm, for areas >100 cm2. Freestanding and pure metal-organic frameworks (MOF) membranes prepared this way are showcased as separators that minimize capacity fading in model Li-S batteries.

Challenges in Determining the Location of Dopants, to Study the Influence of Metal Doping on the Photocatalytic Activities of ZnO Nanopowders.

Impurity doping is one of the common approaches to enhance the photoactivity of semiconductor nanomaterials by increasing photon-capture efficiency in the visible light range. However, many studies on the doping effects have produced inconclusive and conflicting results. There are some misleading assumptions and errors that are frequently made in the data interpretation, which can lead to inconsistent results about the doping effects on photocatalysis. One of them is the determination of the location of dopants. Even using advanced analytical techniques, it is still challenging to distinguish between bulk modification and surface modification. The paper provides a case study of transition-metal-doped ZnO nanoparticles, whereby demonstrating common pitfalls in the interpretation of the results of widely-used analytical methods in detail, and discussing the importance of using a combination of many characterization techniques to correctly determine the location of added impurities, for elucidating the influence of metal doping on the photocatalytic activities of semiconductor nanoparticles.

Green synthesis of sulfur nanoparticles and evaluation of their catalytic detoxification of hexavalent chromium in water.

Chromium contamination in the aquatic environment is an urgent and serious issue due to its mutagenic and carcinogenic effects against living organisms. The present study demonstrates the capability of biogenic sulfur nanoparticles (SNPs) for the reduction of hexavalent chromium into a less toxic state. A green approach was adapted for the synthesis of SNPs using F. benghalensis leaf extract which acts as a reducing and capping agent. The biosynthesized SNPs were characterized by UV-Vis spectroscopy, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM) and energy dispersive X-ray spectroscopy (EDX). TEM micrographs revealed that the zero-valent sulfur nanoparticles were in the range of 2-15 nm and the average size of 5.1 nm. The conversion rate of Cr(vi) into Cr(iii) in the presence of SNPs was 88.7% in 80 min. The optimum concentration ratio between SNPs and formic acid was 10 ppm : 480 mM.