Crossover of positive and negative magnetoconductance in composites of nanosilica glass containing dual transition metal oxides.

A facile sol-gel approach to prepare composites of nanosilica glass containing dual transition metal oxides with compositions xCoO·(20 - x)NiO·80SiO2 comprising x values 5 (NC-1), 10 (NC-2) and 15 (NC-3) within hexagonal pores of SBA-15 template has been demonstrated. The synergistic effect of dual transition metal oxide ions on MD properties and crossover of positive and negative magnetoconductance phenomena were observed in these nanocomposite systems. The physical origin of magnetoconductance switching is explained based on the factors: nanoconfinement effect, wave-function shrinkage and spin polarized electron hopping. DFT calculations were performed to understand the structural correlation of the nanoconfined system. The static (dc) and dynamic (ac) responses of magnetization revealed the spin-glass behaviour of the investigated samples. Both scaling law and Vogel-Fulcher law provide a satisfactory fit to our experimental results which are considered as a salient feature of the spin-glass system. Our studies indicate the possibilities of fabricating magnetically controlled multifunctional devices.

Giant Dielectric Constant of Copper Nanowires/Amorphous SiO2 Composite Thin Films for Supercapacitor Application.

Transparent thin films comprising ultralong (within the range 52-387 µm) copper nanowires with diameter ∼7-9 nm encapsulated in amorphous silica have been successfully fabricated using an electrodeposition technique. The length and number density were controlled by electrodeposition time and concentration of precursor materials, respectively. Giant dielectric constant values (∼1010) obtained from these systems were quantitatively explained as a function of the length of the nanowires on the basis of quantum mechanical theory derived by Rice and Bernasconi. These transparent thin films offer a specific capacitance value of 550 F/g with more than 73% cyclic stability over a period of 900 cycles. Our findings demonstrate a facile pathway to control and improve the properties of metal nanowire-based transparent materials for use in supercapacitor applications.

Large magnetodielectric effect and negative magnetoresistance in NiO nanoparticles at room temperature.

Nickel oxide nanoparticles having a mean particle size of 19.5 nm were synthesized by a simple chemical method. Those nanoparticles exhibited a spin glass like behaviour at a temperature around 9 K. The samples showed electronic conduction arising out of small polaron hopping between the Ni2+ and Ni3+ species present in the material. A large magnetodielectric parameter with a maximum value of 52.2% was observed in the sample at room temperature which resulted from the Maxwell-Wagner polarization effect. This was explained as arising due to a large negative magnetoresistance caused by spin polarized electron hopping between Ni2+ and Ni3+ sites with the consequential formation of space charge polarization at the interfaces of the NiO nanoparticles. This was substantiated by direct measurement of magnetoresistance of the samples which gave identical results. It is believed that negative magnetoresistance after direct measurement occurred due to the interaction between ferromagnetic and antiferromagnetic phases and the value was 37%, the highest reported in the literature so far. As a result of the presence of Ni3+ ions, antiferromagnetic phase and ferromagnetic like behaviour of NiO nanoparticles gave higher magnetization than other reported nanoparticles. Such large values of magnetoresistance of the samples will make the material useful as an ideal magnetic sensor.

Synthesis of multilayered structure of nano-dimensional silica glass/reduced graphene oxide for advanced electrochemical applications.

During the past few years, intensive research has been carried out to design new functional materials for superior electrochemical applications. Due to low storage capacity and low charge transport, silica based glasses have not yet been investigated for their supercapacitive behavior. Therefore, in the present study, a multilayered structure of silica-based nanoglass and reduced graphene oxide has been designed to remarkably enhance the specific capacitance by exploiting the porosity, large surface area, sufficient dangling bonds in the nanoglass and high electrical conductivity of rGO. The charge transport in the composite structure is also investigated to understand the electrochemical properties. It is found that Simmons tunneling or direct tunneling is the dominant mechanism of charge conduction between the graphene layers via the potential barrier of silica nanoglass phase. We believe that this study will open up a new area in the design of glass-based two-dimensional nanocomposites for superior supercapacitor applications.

Magnetic response of chlorophyll self-assembly within hydrogel: a mechanistic approach towards enhanced photoharvesting.

Self-assembly of chlorophyll-a (Chl-a) molecules within a protein environment serves as the key factor behind controlled and efficient light energy harvesting in natural photosystems. Long-range ordering among supramolecular structures in terms of spin-orbit coupling and edge effect helps in untrapping of excitons in the disordered energy landscape. Mimicking the photosynthetic machinery would give a new paradigm for organic photovoltaic material design where a large amount of disorder exists. In this paper, we report the experimental evidence of room temperature magnetic domain wall formation and edge effect along with spin flop canting in self-assembled Chl-a within hydrogel matrix via SQUID magnetometry. This was further correlated with intermolecular coupling and exciton delocalization through specific arrangements of self-assembly as evident from NMR spectral and photophysical characteristics. The data cumulatively suggest electronic backscattering protection which is also substantiated by the ferroelectric behavior coming from coexisting symmetry lowering. Here the polarization evolves through primary distribution of π electronic density along with a photoresponsive IV loop, similar to the photoprotection of photosynthesis. This work thus proposes a promising design principle for room temperature Chl-a based biomimetic systems efficient in photoharnessing.

NiO Nanoparticle Synthesis Using a Triblock Copolymer: Enhanced Magnetization and High Specific Capacitance of Electrodes Prepared from the Powder.

Nickel oxide nanoparticles of diameter ∼21 nm were prepared by a sol-gel method using the triblock copolymer poly(ethylene glycol)-b-(propylene glycol)-b-(ethylene glycol). X-ray photoelectron spectroscopy analysis showed the presence of Ni2+ and Ni3+ ions in the material. The electrical conductivity of this material was due to small polaron hopping between Ni2+ and Ni3+ sites. The magnetization shown by these nanoparticles was much higher than that reported in the literature. This is ascribed to the presence of Ni3+ ions with uncompensated spin moments. Spin-glass behavior was exhibited by the material at 10.7 K. The electrochemical characterization of electrodes comprising of these NiO nanoparticles using cyclic voltammetric measurements showed a specific capacitance value of 810 F/g, the highest reported for this material. These materials will thus form one of the useful multifunctional systems.

1-Aza-15-Crown-5 Functionalized Graphene Oxide for 2D Graphene-Based Li⁺-ion Conductor.

Attachment of Li(+) ion on graphene surface to realize Li(+)-ion conductor is a real challenge because of the weak interaction between the ions and the functional groups of graphene oxide; although, a large number of theoretical results are already available in the literature. To overcome this problem, graphene oxide is functionalized by 1-aza-15-crown-5, the cage-like structure containing four oxygens that can bind Li(+) ion through electrostatic interaction. Li(+) migration on graphene surface has been investigated using ac relaxation mechanism. Perfect Debye-type relaxation behavior with ß (relaxation exponent) value ≈1 resulting from single ion is observed. The activation energy of Li(+) migration arising due to cation-π interaction is found to be 0.37 eV, which agrees well with recently reported theoretical value. It is believed that this study will help to design isolated ion conductors for Li(+)-ion battery.

Investigation of antimicrobial physiology of orthorhombic and monoclinic nanoallotropes of sulfur at the interface of transcriptome and metabolome.

Nanosized elemental sulfur (ES) is already reported to exert superior antimicrobial efficacy than micron-sized ES, which encourages their use in drugs and therapeutics. The aim of the present study is to explore the possible route and mode of antimicrobial action of orthorhombic (α-SNPs) and monoclinic (ß-SNPs) allotropes of sulfur, respectively, at their nano-dimensions. The antimicrobial efficacy of α- and ß-SNPs was determined against both the conventionally ES-resistant and ES-susceptible fungi and bacteria. Both the SNPs inhibited the microbial growth, irrespective of their resistance profile to ES and caused significant deformities on the microbial cell surfaces. However, the extent of antimicrobial efficacy was found to be optimum for α-SNPs, which can be attributed to their size, shape, and surface modification. Subsequent transcript profiling, metabolite profiling, and enzymatic analyses revealed that α- and ß-SNPs impaired a cluster of mitochondrial enzymes involved in cellular respiration and oxidative phosphorylation. ES and SNPs stress were found to elicit the NADPH-dependent glutathione reductase mediated ES-detoxification response in fungi and caused them to undertake the glyoxylate shunt in favor of energy conservation. A simultaneous study was also undertaken to assess the biocompatible or bio-adverse properties of SNPs in terms of their cytotoxic and genotoxic effects against the human derived lung fibroblast cell line (MRC-5). The present study hence explores the antimicrobial physiology of two novel functional materials and demonstrates their compatibility as a future putative antimicrobial drug.

Surface-modified sulfur nanoparticles: an effective antifungal agent against Aspergillus niger and Fusarium oxysporum.

Surface-modified sulfur nanoparticles (SNPs) of two different sizes were prepared via a modified liquid-phase precipitation method, using sodium polysulfide and ammonium polysulfide as starting material and polyethylene glycol-400 (PEG-400) as the surface stabilizing agent. Surface topology, size distribution, surface modification of SNPs with PEG-400, quantitative analysis for the presence of sulfur in nanoformulations, and thermal stability of SNPs were determined by atomic force microscopy (AFM), dynamic light scattering (DLS) plus high-resolution transmission electron microscopy (HR-TEM), fourier transform infrared (FT-IR) spectroscopy, energy dispersive X-ray (EDX) spectroscopy, and thermogravimetric analysis (TGA), respectively. A simultaneous study with micron-sized sulfur (S(0)) and SNPs was carried out to evaluate their fungicidal efficacy against Aspergillus niger and Fusarium oxysporum in terms of radial growth, sporulation, ultrastructural modifications, and phospholipid content of the fungal strains using a modified poisoned food technique, spore-germination slide bioassay, environmental scanning electron microscopy (ESEM), and spectrometry. SNPs expressed promising inhibitory effect on fungal growth and sporulation and also significantly reduced phospholipid content.

Sol-gel synthesized SnO2 nanoparticles and their properties.

Sol-gel synthesized SnO2 nanoparticles with an average size of 2.0 nm obtained at 373 K were gradually annealed to 673 K in air for 25 minutes. Sequentially taken transmission electron microscopy (TEM) images showed that particle agglomeration of these non-matrix SnO2 nanocrystals was a very slow process. The blue shifts of the band gap (approximately 2.3 eV) obtained from the optical absorbance spectra were matched with the theoretical results of the size related excitonic binding energies. These calculations also supported the observed slow grain growth. The depth sensitive hardness measurements of the thin films indicated hardness in the range of 5.03 GPa to 6.79 GPa. These undoped and non-matrix SnO2 nanoparticles were also investigated with the X-ray photoelectrons spectroscopy (XPS), atomic force microscope (AFM), X-ray diffraction spectroscopy (XRD), and ac impedance analyzer.

Dendron-like growth of silver nanoparticles using a water-soluble oligopeptide.

A dendron-like nanostructure of silver was grown in solution using a water-soluble tetrapeptide Tyr-Aib-Tyr-Val (Aib, alpha-amino isobutyric acid), silver nitrate, and methanol. These structures are composed of silver nanoparticles having a bimodal size distribution with the median diameters around 2.0 and 19.5 nm, respectively. The dendron-like growth is ascribed to the effect of the local electric field generated by the dipoles associated with the peptide molecules. The optical absorption spectra have been analyzed by Mie scattering theory, which shows that there is a metal-nonmetal transition in silver particles having diameters less than approximately 2.0 nm.

One-dimensional ZnO nanostructure arrays: synthesis and characterization.

One-dimensional ZnO nanostructure arrays such as nanowires, nanonails, and nanotrees, have been synthesized by oxygen assisted thermal evaporation of metallic zinc on a quartz substrate over a large area. Morphological evolution of ZnO nanostructures at different time scales and different positions of the substrates have been studied by electron microscopy. A self-catalyzed vapor-liquid-solid (VLS) process is believed to be responsible for the nucleation and subsequently a vapor-solid process is operative for further longitudinal growth. The photoluminescence spectrum showed a weak UV and a broad green emission peak at 3.25 and 2.49 eV, respectively. The latter was attributed to the presence of zinc interstitial defects. Electrical resistivity as a function of temperature showed activated mechanisms to be present. The electrical response of the ZnO nanonail arrays to different gases (CO, NO2, and H2S) indicated that there could be possible application as gas sensors for this material.