Stoichiometrically optimized eg orbital occupancy of Ni-Co oxide catalysts for Li-air batteries.

Li-air battery (LAB) technology is making continuous progress toward its theoretical capacity, which is comparable to gasoline. However, the sluggish reaction at the cathode is still a challenge. We propose a simple strategy to optimize the surface eg occupancy by adjusting the stoichiometric ratios of transition metal-based spinel structures through a controlled hydrothermal synthesis. Three distinct stoichiometries of Ni-Co oxides were used to demonstrate the direct correlation between stoichiometry and catalytic performance. The groundsel flower-like structure having a 1 : 1.4 Ni : Co atomic ratio with high surface area, high defect density, and an abundance of Ni3+ at the surface with semi-filled eg orbitals was found to benefit the structure promoting high catalytic activities in aqueous and aprotic media. The assembled LAB cells employing this cathode demonstrate an exceptional lifespan, operating for 3460 hours and completing 173 cycles while achieving the highest discharge capacity of 13 759 mA h g-1 and low charging overpotentials. The key to this prolonged performance lies in the full reversibility of the cell, attributed to its excellent OER performance. A well-surface adsorbed, amorphous LiO2/Li2O2 discharge product is found to possess high diffusivity and ease of decomposition, contributing significantly to the enhanced longevity of the cell.

Enhancement of Release and Solubility of Curcumin from Electrospun PEO-EC-PVP Tripolymer-Based Nanofibers: A Study on the Effect of Hydrogenated Castor Oil.

This study reveals the state-of-the-art fabrication of a tripolymer-based electrospun nanofiber (NF) system to enhance the release, solubility, and transdermal penetration of curcumin (Cur) with the aid of in situ release of infused castor oil (Co). In this regard, Cur-loaded Co-infused polyethylene oxide (PEO), ethyl cellulose (EC), and polyvinyl pyrrolidone (PVP) tripolymer-based NF systems were developed to produce a hybridized transdermal skin patch. Weight percentages of 1-4% Cur and 3-10% of Co were blended with PEO-EC-PEO and PEO-EC-PVP polymer systems. The prepared NFs were characterized by SEM, TEM, FT-IR analysis, PXRD, differential scanning calorimetry (DSC), and XPS. Dialysis membranes and vertical Franz diffusion cells were used to study the in vitro drug release and transdermal penetration, respectively. The results indicated that maintaining a Cur concentration of 1-3 wt % with 3 wt % Co in both PEO-EC-Co-Cur@PEO and PEO-EC-Co-Cur@PVP gave rise to nanofibers with lowered diameters (144.83 ± 48.05-209.26 ± 41.80 nm and 190.20 ± 59.42-404.59 ± 45.31 nm). Lowered crystallinity observed from the PXRD patterns and the disappearance of exothermic peaks corresponding to the melting point of Cur suggested the formation of an amorphous NF structure. Furthermore, the XPS data revealed that the Cur loading will possibly take place at the inner interface of PEO-EC-Co-PEO and PEO-EC-Co-PVP NFs rather than on the surface. The beneficiary role of Co on the release and dermal penetration of Cur was further confirmed from the respective release data which indicated that PEO-EC-Co-Cur@PEO would lead to a rapid release (4-5 h), while PEO-EC-Co-Cur@PVP would lead to a sustained release over a period of 24 h in the presence of Co. Transdermal penetration of the released Cur was further evidenced with the development of color in the receiver compartment of the diffusion cell. DPPH results further corroborated that a sustained antioxidant activity is observed in the released Cur where the free-radical scavenging activity is intact even after subjecting to an electrospinning process and under extreme freeze-thaw conditions.

Mechanochemical Synthesis of Polymorphic Urea ⋠Adipic Acid Cocrystal as a Sustained-Release Nitrogen Source.

A 2 : 1 urea ⋅ adipic acid cocrystal was obtained in two polymorphic forms (Form I reported earlier, and Form II synthesized in this study) using mechanochemistry as well as solution crystallization. Lower solubility and leaching study showed the newly synthesized urea ⋅ adipic acid 2 : 1 cocrystal to be an efficient sustained-release nitrogen fertilizer compared to commercially available urea.

Nanomagnetite- and Nanotitania-Incorporated Polyacrylonitrile Nanofibers for Simultaneous Cd(II)- and As(V)-Ion Removal Applications.

This work reports the fabrication of nanomagnetite- and nanotitania-incorporated polyacrylonitrile nanofibers (MTPANs) by an electrospinning process, which has the potential to be used as a membrane material for the selective removal of Cd(II) and As(V) in water. The fiber morphology was characterized by scanning electron microscopy (SEM). The incorporation of nanomagnetite and nanotitania in the composite fiber matrix was confirmed by energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and Fourier transform infrared (FT-IR) spectroscopy. The fibers doped with nanomagnetite and nanotitania (MPAN and TPAN fibers, respectively), as well as MTPAN and neat polycrylonitrile (PAN) fibers, after thermally stabilizing at 275 °C in air, were assessed for their comparative As(V)- and Cd(II)-ion removal capacities. The isotherm studies indicated that the highest adsorption of Cd(II) was shown by MTPAN, following the Langmuir model with a q m of 51.5 mg/m2. On the other hand, MPAN showed the highest As(V)adsorption capacity, following the Freundlich model with a K F of 0.49. The mechanism of adsorption of both Cd(II) and As(V) by fibers was found to be electrostatically driven, which was confirmed by correlating the point of zero charges (PZC) exhibited by fibers with the pH of maximum ion adsorptions. The As(V) adsorption on MPAN occurs by an inner-sphere mechanism, whereas Cd(II) adsorption on MTPAN is via both surface complexation and an As(V)-assisted inner-sphere mechanism. Even though the presence of coexistent cations, Ca(II) and Mg(II), has been shown to affect the Cd(II) removal by MTPAN, the MTPAN structure shows >50% removal efficiency even for minute concentrations (0.5 ppm) of Cd(II) in the presence of high common ion concentrations (10 ppm). Therefore, the novel polyacrylonitrile-based nanofiber material has the potential to be used in polymeric filter materials used in water purification to remove As(V) and Cd(II) simultaneously.

A Novel Green Approach to Synthesize Curcuminoid-Layered Double Hydroxide Nanohybrids: Adroit Biomaterials for Future Antimicrobial Applications.

Thermal instability, photodegradation, and poor bioavailability of natural active ingredients are major drawbacks in developing effective natural product-based antimicrobial formulations. These inherited issues could be fruitfully mitigated by the introduction of natural active ingredients into various nanostructures. This study focuses on the development of a novel green mechanochemical synthetic route to incorporate curcuminoids into Mg-Al-layered double hydroxides. The developed one-pot and scalable synthetic approach makes lengthy synthesis procedures using toxic solvents redundant, leading to improved energy efficiency. The hydrotalcite-shaped nanohybrids consist of surface and interlayer curcuminoids that have formed weak bonds with layered double hydroxides as corroborated by X-ray diffractograms, X-ray photoelectron spectra, and Fourier transmission infrared spectra. The structural and morphological properties resulted in increased thermal stability of curcuminoids. Slow and sustained release of the curcuminoids was observed at pH 5.5 for a prolonged time up to 7 h. The developed nanohybrids exhibited zeroth-order kinetics, favoring transdermal application. Furthermore, the efficacy of curcuminoid incorporated LDHs (CC-LDH) as an anticolonization agent was investigated against four wound biofilm-forming pathogens, Pseudomonas aeruginosa, Staphylococcus aureus, methicillin-resistant Staphyloccocus aureus, and Candida albicans, using a broth dilution method and an in vitro biofilm model system. Microbiological studies revealed a 54-58% reduction in biofilm formation ability of bacterial pathogens in developed nanohybrids compared to pure curcuminoids. Therefore, the suitability of these green-chemically synthesized CC-LDH nanohybrids for next-generation antimicrobial applications with advanced dermatological/medical properties is well established.

Nano-manganese oxide and reduced graphene oxide-incorporated polyacrylonitrile fiber mats as an electrode material for capacitive deionization (CDI) technology.

Capacitive deionization (CDI) is a trending water desalination method during which the impurity ions in water can be removed by electrosorption. In this study, nano-manganese dioxide (MnO2) and reduced graphene oxide (rGO)-doped polyacrylonitrile (PAN) composite fibers are fabricated using an electrospinning technique. The incorporation of both MnO2 and rGO nanomaterials in the synthesized fibers was confirmed by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDX). The electrochemical characteristics of electrode materials were examined using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and constant current charge-discharge cycles (CCCDs). The specific capacitance of the PAN electrode increased with increasing MnO2 and rGO contents as well as when thermally treated at 280 °C. Thermally treated composite fibers with 17% (w/w) MnO2 and 1% (w/w) rGO (C-rGOMnPAN) were observed to have the best electrochemical performance, with a specific capacitance of 244 F g-1 at a 10 mV s-1 scan rate. The electrode system was used to study the removal of sodium chloride (NaCl), cadmium (Cd2+) and lead (Pb2+) ions. Results indicated that NaCl showed the highest electrosorption (20 472 C g-1) compared to two heavy metal salts (14 260 C g-1 for Pb2+ and 6265 C g-1 for Cd2+), which is most likely to be due to the ease of mass transfer of lighter Na+ and Cl- ions; When compared, Pb2+ ions tend to show more electrosorption on these fibers than Cd2+ ions. Also, the C-rGOMnPAN electrode system is shown to work with 95% regeneration efficiency when 100 ppm NaCl is used as the electrolyte. Hence, it is clear that the novel binder-free, electrospun C-rGOMnPAN electrodes have the potential to be used in salt removal and also for the heavy metal removal applications of water purification.

Polyaniline/palladium nanohybrids for moisture and hydrogen detection.

Palladium nanoparticles display fascinating electronic, optical and catalytic properties, thus they can be used for various applications such as sensor fabrication. Conducting polymers such as polyaniline have also been widely used in sensor technology due to its cost effectiveness, versatility, and ease of synthesis. In this research, attention was given to unify the exceptional properties of these two materials and construct palladium nanoparticle coated polyaniline films to detect hydrogen and moisture. Electrochemical polymerization of aniline was carried out on gold sputtered epoxy resin boards. Polyaniline film was generated across a gap of 0.2 mm created by a scratch made on the gold coating prior to electrochemical polymerization. A palladium nanoparticle dispersion was prepared using sonochemical reduction method and coated on to polyaniline film using drop-drying technique. Polyaniline only films were also fabricated for comparative analysis. Sensitivity of films towards humidity and hydrogen was evaluated using impedance spectroscopy in the presence of the respective species. According to the results, polyaniline films exhibited an impedance drop in the presence of humidity and the response was significantly improved once palladium nanoparticles were incorporated. Interestingly, polyaniline only films did not respond to hydrogen. Nevertheless, palladium nanoparticle coated polyaniline films exhibited remarkable response towards hydrogen.

Rice bran nanofiber composites for stabilization of phytase.

This study explores the potential application of rice bran (agro waste) to nano-encapsulate phytase, which is a thermally unstable biologically active enzyme. Rice bran was converted to nanofibers (20-50 nm in diameter) using electrospinning. After optimizing the pH, viscosity, voltage and the distance between electrodes for electrospinning, phytase enzyme was encapsulated and the fibers were cross-linked using sodium tripolyphosphate. Thermal stability of phytase enzyme was improved by 90 °C when they are encapsulated and cross-linked with sodium tripolyphosphate. The activity of the phytase enzyme was monitored at different temperatures. The activity of the pure enzyme was lost at 80 °C while the enzyme encapsulated into nanofibers demonstrated the activity up to 170 °C. This study opens up many opportunities for nanotechnology value addition to many waste materials and also to improve the properties of a range of biomaterials through a sustainable approach.

Effect of Citric Acid Surface Modification on Solubility of Hydroxyapatite Nanoparticles.

Worldwide, there is an amplified interest in nanotechnology-based approaches to develop efficient nitrogen, phosphorus, and potassium fertilizers to address major challenges pertaining to food security. However, there are significant challenges associated with fertilizer manufacture and supply as well as cost in both economic and environmental terms. The main issues relating to nitrogen fertilizer surround the use of fossil fuels in its production and the emission of greenhouse gases resulting from its use in agriculture; phosphorus being a mineral source makes it nonrenewable and casts a shadow on its sustainable use in agriculture. This study focuses on development of an efficient P nutrient system that could overcome the inherent problems arising from current P fertilizers. Attempts are made to synthesize citric acid surface-modified hydroxyapatite nanoparticles using wet chemical precipitation. The resulting nanohybrids were characterized using powder X-ray diffraction to extract the crystallographic data, while functional group analysis was done by Fourier transform infrared spectroscopy. Morphology and particle size were studied using scanning electron microscopy along with elemental analysis using energy-dispersive X-ray diffraction spectroscopy. Its effectiveness as a source of P was investigated using water release studies and bioavailability studies using Zea mays as the model crop. Both tests demonstrated the increased availability of P from nanohybrids in the presence of an organic acid compared with pure hydroxyapatite nanoparticles and rock phosphate.

Urea-Hydroxyapatite Nanohybrids for Slow Release of Nitrogen.

While slow release of chemicals has been widely applied for drug delivery, little work has been done on using this general nanotechnology-based principle for delivering nutrients to crops. In developing countries, the cost of fertilizers can be significant and is often the limiting factor for food supply. Thus, it is important to develop technologies that minimize the cost of fertilizers through efficient and targeted delivery. Urea is a rich source of nitrogen and therefore a commonly used fertilizer. We focus our work on the synthesis of environmentally benign nanoparticles carrying urea as the crop nutrient that can be released in a programmed manner for use as a nanofertilizer. In this study, the high solubility of urea molecules has been reduced by incorporating it into a matrix of hydroxyapatite nanoparticles. Hydroxyapatite nanoparticles have been selected due to their excellent biocompatibility while acting as a rich phosphorus source. In addition, the high surface area offered by nanoparticles allows binding of a large amount of urea molecules. The method reported here is simple and scalable, allowing the synthesis of a urea-modified hydroxyapatite nanohybrid as fertilizer having a ratio of urea to hydroxyapatite of 6:1 by weight. Specifically, a nanohybrid suspension was synthesized by in situ coating of hydroxyapatite with urea at the nanoscale. In addition to the stabilization imparted due to the high surface area to volume ratio of the nanoparticles, supplementary stabilization leading to high loading of urea was provided by flash drying the suspension to obtain a solid nanohybrid. This nanohybrid with a nitrogen weight of 40% provides a platform for its slow release. Its potential application in agriculture to maintain yield and reduce the amount of urea used is demonstrated.