Probing size-dependent defects in zinc oxide using synchrotron techniques: impact on photocatalytic efficiency.

In the present study, synchrotron-based X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS) and X-ray excited optical luminescence (XEOL) have been used to investigate the induced defect states in metal oxide nanomaterials. Specifically, two synthesis approaches have been followed to develop unique nano-sized peanut-shaped (N-ZnO) nanostructures and micron-sized hexagonal rods (M-ZnO). XANES analysis at the Zn K-edge revealed the presence of defect states with a divalent oxidation state of zinc (Zn2+) in a tetrahedral structure. Furthermore, XAS measurements performed at the Zn L3,2-edge and O K-edge confirm higher oxygen-related defects in M-ZnO, while N-ZnO appeared to have a higher concentration of surface defects due to size confinement. Moreover, the in-line XEOL and time dependent-XEOL measurements exposed the radiative excitonic recombination phenomena occurring in the band-tailing region as a function of absorption length, X-ray energy excitation, and time. Based on the chronology developed in the defect state improvement, a possible energy band diagram is proposed to accurately locate the defect states in the two systems. Furthermore, the increased absorption intensity at the Zn L3,2-edge and the O K-edge under the UV lamp suggests delayed recombination of electrons and holes, highlighting their potential use as photo catalysts. The photocatalytic activity degrading the rhodamine B dye established M-ZnO as a superior catalyst with a rapid degradation rate and significant mineralization. Overall, this work provides valuable insights into ZnO defect states and provides a foundation for efficient advanced materials for environmental or other optoelectronic applications.

Temperature dependent characteristics of flexible p-PANI/n-ZnO based hybrid heterojunction diode.

This study aims to develop and characterize a flexible p-PANI/n-ZnO heterojunction diode developed from a combination of electrochemical and sputtering technique. Investigation of structural properties and morphology of the thin films has been done from XRD and SEM analysis. To study the temperature effect on the electrical properties of the diode, current-voltage-temperature (I-V-T) measurements were done for the temperature range 25-300 K. Applying the ideal thermionic emission theory, various diode parameters like reverse saturation current, quality factor, series resistance and barrier height were computed utilizing the semilogarithmic plot ofI-Vcurve and Cheungs' method. Barrier height, reverse saturation current and quality factor calculated from ln(I)versusVcurve were observed to vary from 0.0627-0.725 eV, 0.236-98.8 nA and 54.43-3.29 respectively over the temperature range 25-300 K. It has been found that the series resistance falls with a rise in temperature. The barrier height, series resistance and ideality factor were observed to vary from 0.0628-0.692 eV, 15 900-46.8 Kohm and 41.88-2.27 respectively for the temperature range 25-300 K. The activation energy estimated from Arrhenius plot was observed to be 14.51 meV. Additionally, the fabricated PANI/ZnO diode was mechanically robust that can be bent without affecting its performance.

Domain state modulation by interfacial diffusion in FePt/FeCo thin films: experimental approach with micromagnetic modelling.

We report the complex implications of inter-diffusion between polycrystalline FePt/FeCo layers as an impact of the FeCo underlayer on the structural and magnetic properties of the system. The crystalline growth of FePt strongly reduces in an entirely diffused system compared to the one with lesser diffusion, while the crystalline structure of FeCo is apparently less affected. Charge redistribution occurs between Fe, Co and Pt ensuring increased Co-Pt and Fe-Pt interactions with higher diffusion. Thereafter, we combine hysteresis and magnetic force microscopy measurements to show that the interfacial deformations result in the distinct out-plane magnetic behaviour of the system. FeCo@FePt nano-composite like structure, originating due to interfacial diffusion, shows interactions between two magnetic phases with in-plane low anisotropy exhibiting wasp-shaped out-plane hysteresis loop. Whereas the layered structure of FePt/FeCo films shows random anisotropy with a significant out-plane contribution even in the polycrystalline films. Micromagnetic modelling demonstrates coercivity deterioration and reduction of switching field due to the formation of a slightly diffused interface. Contrarily, the experimental observations for complete diffusion between the two layers are explained by simulating the inhomogeneous distribution of anisotropies along the film plane. These studies provide deep perceptions of the magnetic properties of FePt/FeCo system governed by diffusion kinetics which are valuable to achieve desired magnetic characteristics using this system.

FeCo nanoparticles as antibacterial agents with improved response in magnetic field: An insight into the associated toxicity mechanism.

The emergence of multi-drug resistant bacterial infections has resulted in increased interest in the development of alternative systems which can sensitize bacteria to overcome resistance. In an attempt to contribute to the existing literature of potential antibacterial agents, we present here, a first report of the antibacterial potential of FeCo nanoparticles, both as stand-alone devices and in presence of magnetic field, against the bacterial strains of S. aureus and E. coli. A relatively simple polyol process was employed for nanoparticle synthesis. Formation of FeCo alloy in the desired BCC phase was confirmed by X-Ray Diffraction with a high saturation magnetization (Ms~180 Am2kg-1). Uniformly sized spherical structures with sharp edges were obtained. Solution stability was confirmed by the zeta potential value of -27.8 mV. Dose dependent bacterial growth inhibition was observed, the corresponding linear correlation coefficients being, R2 = 0.74 for S. aureus and R2 = 0.76 for E. coli. Minimum inhibitory concentration was accordingly ascertained to be >1024 µg/ml for both. Bacterial growth curves have been examined upon concomitant application of external magnetic field of varying intensities and revealed considerable enhancement in the antibacterial response upto 63% in a field of 100 mT. An effort has been made to understand the bacterial inhibitory mechanism by relating with the chemical and physical properties of the nanoparticles. The ease of field assisted targeting and retrieval of these highly magnetic, antibacterial nano-devices, with considerably improved response with magnetic fields, make them promising for several medical and environment remediation technologies.

Photo generated charge transport studies of defects-induced shuttlecock-shaped ZnO/Ag hybrid nanostructures.

We report the stimulating effects of interfacial charge transfer process between spherical Ag nanoparticles and shuttlecock-shaped ZnO nanostructures observed by UV-visible spectroscopy and x-ray absorption spectroscopy. In specific, ZnO nanorods and shuttlecock-shaped ZnO/Ag nanostructures were developed using a simple chemical colloidal method and characterized for structural variations using XRD. The observed red shift in plasmonic peak and the increase in Urbach energy signify interfacial interactions and increased randomness in the hybrid ZnO/Ag nanostructures. Simultaneously, the enhanced intensity of deep-level emission in the ZnO/Ag hybrid suggests the increased recombination rate of electron-hole pairs. The red and blue emissions evolving with temperature subsequently suggests the presence of oxygen vacancies or zinc interstitials in the system. The decrease in intensities and emerging features in O K-edge and Zn L-edge indicates the charge transfer from Ag to ZnO at the interface of ZnO/Ag hybrids. Moreover, the differences in absorption edges with alternating light on/off conditions were analyzed for the exploitation of this ZnO-based system in various applications.

Synthesis of ZnO@Ag dumbbells for highly efficient visible-light photocatalysts.

The photocatalytic activity (PCA) of ZnO@Ag nanocomposites for different concentrations of Ag is reported. Dumbbells shaped zinc oxide (ZnO) nanostructures with silver (Ag) nanoparticles were synthesized by a simple chemical colloidal method. The as synthesized nanocomposites (without any heat treatment) were used for optical and photocatalytic studies. The FESEM analysis shows that the composite catalysts are composed of ZnO dumbbells coated with spherical Ag nanoparticles. UV-visible spectrum of ZnO@Ag photocatalysts shows a strong absorption band of ZnO at 380 nm with a plasmonic peak of Ag at 440 nm. The PL emission intensity of the composites varies with Ag concentration and has a minimum for the catalyst containing 13.7% of Ag. A possible growth mechanism of ZnO nanostructures with hexagonal cross-section has been proposed. Photocatalytic property of the as synthesized ZnO and ZnO@Ag catalysts was studied by investigating the degradation of methylene blue (MB) dye on exposure to UV-visible radiation. A relatively faster degradation of the dye was observed for ZnO@Ag composites as compared to pure ZnO, showing an improved photocatalytic behavior in the visible region. We proposed a possible mechanism for the enhancement in photocatalytic activity of Ag coated ZnO photocatalysts.

Structural, morphological, and optical characterisation of ZnO nanostructures fabricated by electrochemical deposition.

The controlled growth of oriented ZnO nanostructures is desirable for their varied applications. In this study, an electrochemical technique is used for deposition of ZnO. The large area morphology shows sheet-like structures oriented perpendicular to the substrate. X-ray diffraction studies show that the crystallinity and purity of electrodeposited ZnO improved by using a moderate thermal annealing. TEM shows randomly oriented rod-like structures. The Raman spectra further confirm the crystallinity of the films. The photoluminescence spectra show emission peaks in the blue-green visible region. Furthermore, we also investigate the potential of the electrochemically-formed ZnO nanostructures as a suitable template for electrochemical deposition of polypyrrole (Ppy).

Magnetic properties of iron nanoparticles prepared by exploding wire technique.

Nanoparticles of iron were prepared in distilled water using very thin iron wires and sheets, by the electro-exploding wire technique. Transmission electron microscopy reveals the size of the nanoparticles to be in the range 10 to 50 nm. However, particles of different sizes can be segregated by using ultrahigh centrifuge. X-ray diffraction studies confirm the presence of the cubic phase of iron. These iron nanoparticles were found to exhibit fluorescence in the visible region in contrast to the normal bulk material. The room temperature hysteresis measurements upto a field of 1.0 tesla were performed on a suspension of iron particles in the solution as well as in the powders obtained by filtration. The hysteresis loops indicate that the particles are superparamagnetic in nature. The saturation magnetizations was approximately 60 emu/gm. As these iron particles are very sensitive to oxygen a coating of non-magnetic iron oxide tends to form around the particles giving it a core-shell structure. The core particle size is estimated theoretically from the magnetization measurements. Suspensions of iron nanoparticles in water have been proposed to be used as an effective decontaminant for ground water.

Psychrophilic Pseudomonas syringae requires trans-monounsaturated fatty acid for growth at higher temperature.

A psychrophilic bacterium, Pseudomonas syringae (Lz4W) from Antarctica, was used as a model system to establish a correlation, if any, between thermal adaptation, trans-fatty acid content and membrane fluidity. In addition, attempts were made to clone and sequence the cti gene of P. syringae (Lz4W) so as to establish its characteristics with respect to the cti of other Pseudomonas spp. and also to in vitro mutagenize the cti gene so as to generate a cti null mutant. The bacterium showed increased proportion of saturated and trans-monounsaturated fatty acids when grown at 28 degrees C compared to cells grown at 5 degrees C, and the membrane fluidity decreased with growth temperature. In the mutant, the trans-fatty acid was not synthesized, and the membrane fluidity also decreased with growth temperature, but the decrease was not to the extent that was observed in the wild-type cells. Thus, it would appear that synthesis of trans-fatty acid and modulation of membrane fluidity to levels comparable to the wild-type cells is essential for growth at higher temperatures since the mutant exhibits growth arrest at 28 degrees C. In fact, the cti null mutant-complemented strain of P. syringae (Lz4W-C30b) that was capable of synthesizing the trans-fatty acid was indeed capable of growth at 28 degrees C, thus confirming the above contention. The cti gene of P. syringae (Lz4W) that was cloned and sequenced exhibited high sequence identity with the cti of other Pseudomonas spp. and exhibited all the conserved features.

Immobilization of urease on poly(N-vinyl carbazole)/stearic acid Langmuir-Blodgett films for application to urea biosensor.

Urease was immobilized in mixed monolayers of poly(N-vinyl carbazole) (PNVK) and stearic acid (SA) formed at an air-water interface. The monolayers were transferred onto indium-tin-oxide (ITO) coated glass plates using Langmuir-Blodgett (LB) film deposition technique. Urease immobilized on PNVK/SA LB films, characterized using FTIR and UV-visible spectroscopy, was found to exhibit increased stability over a wide pH (6.5-8.5) and temperature (25-50 degrees C) range. Potentiometric measurements on these urease electrodes were carried out using an ammonium ion analyzer. Two values for K(m)(app) were obtained at lower and higher concentrations of substrate urea.

Synthesis and characterization of fluoro-substituted polyaniline.

Poly(2-fluoroaniline) was prepared by both chemical and electrochemical polymerization in acidic medium. Characterization of poly(2-fluoroaniline) was accomplished experimentally using ultraviolet-visible, Fourier transform infrared, differential scanning calorimetry, thermal gravimetric analysis, and X-ray diffraction techniques, respectively. Scanning electron microscopy studies revealed globular morphology of chemically synthesized poly(2-fluoroaniline). The cyclic voltammetric studies revealed diffusion-controlled phenomenon in electrochemically synthesized poly(2-fluoroaniline).

Preparation and characterization of poly-N-vinyl carbazole Langmuir-Blodgett films.

Langmuir monolayers of poly-N-vinyl carbazole (PNVK) were obtained by dispensing PNVK dissolved in tetrahydrofuran onto an air-water interface. Surface pressure-area isotherms of mixed monolayer of the PNVK were studied under different subphase conditions such as temperature and pH of the subphase. It was demonstrated that the monolayer of PNVK remained stable over a temperature range of 10-40 degrees C. The area per molecule of the solid phase was found to be 31 A2. These monolayers were transferred onto indium-tin-oxide-coated glass plates and characterized by spectroscopic and electrochemical techniques.