Synthesis and structural characterization of two-dimensional hierarchical covellite nano-structures

We report a simple, template free and low-temperature hydrothermal reaction pathway using Cu(II) - thiourea complex (prepared in situ from copper (II) chloride and thiourea as precursors) and citric acid as complexing agent to synthesize two-dimensional hierarchical nano-structures of covellite (CuS). The product was characterized with the help of X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy dispersive analysis of X-ray spectroscopy (EDAX) and X-ray photoelectron spectroscopy (XPS). The concentration of citric acid in the hydrothermal precursor solution was seen to have a profound effect on the nanostructure of the product generated. Based on the outcoming product nano-architecture at different concentration of the ionic surfactant in the hydrothermal precursor solution a possible mechanism suited for reaction and further nucleation is also discussed. (C) 2012 Elsevier B.V. All rights reserved.

Synthesis, morphology, optical and photocatalytic performance of nanostructured beta-Ga2O3

Fine powders of beta-Ga2O3 nanostructures were prepared via low temperature reflux condensation method by varying the pH value without using any surfactant. The pH value of reaction mixture had great influence on the morphology of final products. High crystalline single phase beta-Ga2O3 nanostructures were obtained by thermal treatment at 900 degrees C which was confirmed by X-ray diffraction and Raman spectroscopy. The morphological analysis revealed rod like nanostructures at lower and higher pH values of 6 and 10, while spindle like structures were obtained at pH = 8. The phase purity and presence of vibrational bands were identified using Fourier transform infrared spectroscopy. The optical absorbance spectrum showed intense absorption features in the UV spectral region. A broad blue emission peak centered at 441 nm due to donor-acceptor gallium-oxygen vacancy pair recombination appeared. The photocatalytic activity toward Rhodamine B under visible light irradiation was higher for nanorods at pH 10.

Liquefied Petroleum Gas Sensing of Polyaniline-Titanium Dioxide Nanocomposites

Polyaniline/titaniurn dioxide nanocomposites were prepared using alpha-dextrose as surfactant and ammonium persulphate as an oxidant. The PANI/TiO2 nanocomposite is characterized by FTIR, XRD and TEM. The FTIR spectra revel that the presence of characteristic peaks of benzenoid, qunoide rings and metal-oxygen stretching. The XRD studies show the monoclinic structure of the nanocomposites. The TEM study shows that the size of TiO2 is in the order of 9 nm where as the composite size is of the order of 13 nm and further it was observed that the TiO2 particles are intercalated to form a core shell of PANI. The maximum sensing response for LPG is found to be 90% for 30 wt.% of PANI/TiO2 nanocomposites at 400 ppm whereas for Benzene and Toluene it is negligibly small (<= 20%) and for the cyclohexane sensing response it is around 30% for different wt.%.

Facile synthesis of Cu2CoSnS4 nanoparticles exhibiting red-edge-effect: Application in hybrid photonic devices

Cu2CoSnS4 (CCTS) quaternary semiconducting nanoparticles with size distribution from 20 nm to 60 nm were synthesized by one-pot low temperature time and surfactant dependent hydrothermal route. Nanoparticles were characterized structurally and optically. Excitation dependent fluorescence exhibited a dynamic stoke shift referring to the Red-Edge-Effect with peak shifting by a greater magnitude (>100 nm) towards red side, in all the samples. Hybrid devices, fabricated from CCTS nanoparticle inorganic counterparts benefitting from the conjugation of organic P3HT polymer matrix, were demonstrated for photodetection under infra-red and A. M 1.5 solar light illuminations. Faster rise and decay constants of 37 ms and 166 ms, with one order photocurrent amplification from 1.6 x 10(-6) A in the dark to 6.55 x 10(-5) A, upon the 18.50 mW cm(-2) IR lamp illumination, make CCTS a potential candidate for photodetector and photovoltaic applications. (C) 2013 AIP Publishing LLC.

Contrast in luminescence characteristics (intense UV to bright visible light) of ZnO nanostructures with the variation in microstructure

We report the controlled variation of luminescence of ZnO nanostructures from intense ultraviolet to bright visible light. Deliberate addition of surfactants in the reaction medium not only leads to growth anisotropy of ZnO, but also alters the luminescence property. ZnO nanoclusters comprising of very fine particles with crystallite sizes approximate to 15-22nm were prepared in a non-aqueous medium, either from a single alcohol or from their mixtures. Introduction of the aqueous solution of the surfactant helps in altering the microstructure of ZnO nanostructure to nanorods, nanodumb-bells as well as the luminescence property. The as-prepared powder material is found to be well crystallized. Defects introduced by the surfactant in aqueous medium play an important role in substantial transition in the optical luminescence. Chromaticity coordinates were found to lie in the yellow region of color space. This gives an impression of white light emission from ZnO nanocrystals, when excited by a blue laser. Oxygen vacancy is described as the major defect responsible for visible light emission as quantified by X-ray photoelectron spectroscopy and Raman analysis.

Physical understanding of pore formation on supported lipid bilayer by bacterial toxins

Pore forming toxins are being classified in the protein community based on their ability of forming pores in living cell membranes. Some initial study has apparently pointed out the crystallographic pathway rather can be viewed as a structural as well as morphological changes of proteins in terms of self assembly before and during the pore formation process in surfactant medium. Being a water soluble compound, it changes its conformation and originates some pre-pore complex, which later partially goes inside the cell membrane causing a pore. The physical mechanism for this whole process is still unknown. In this study we have tried to understand these types of biological processes from physical point of view by using supported lipid bilayer as a model system.

In vitro exposure of tobacco specific nitrosamines decreases the rat lung phospholipids by enhanced phospholipase A(2) activity

Tobacco-specific nitrosamines (TSNA) have implications in the pathogenesis of various lung diseases and conditions are prevalent even in non-smokers. N-nitrosonornicotine (NNN) and 4-(methyl nitrosamino)-1-(3-pyridyl)-1-butanone (NNK) are potent pulmonary carcinogens present in tobacco product and are mainly responsible for lung cancer. TSNA reacts with pulmonary surfactants, and alters the surfactant phospholipid. The present study was undertaken to investigate the in vitro exposure of rat lung tissue slices to NNK or NNN and to monitor the phospholipid alteration by P-32]orthophosphate labeling. Phospholipid content decreased significantly in the presence of either NNK or NNN with concentration and time dependent manner. Phosphatidylcholine (PC) is the main phospholipid of lung and significant reduction was observed in PC similar to 61%, followed by phosphatidylglycerol (PG) with 100 mu M of NNK, whereas NNN treated tissues showed a reduction in phosphatidylserine (PS) similar to 60% and PC at 250 mu M concentration. The phospholipase A(2) assays and expression studies reveal that both compounds enhanced phospholipid hydrolysis, thereby reducing the phospholipid content. Collectively, our data demonstrated that both NNK and NNN significantly influenced the surfactant phospholipid level by enhanced phospholipase A(2) activity. (C) 2014 Elsevier Ltd. All rights reserved.

Laterally structured ripple and square phases with one and two dimensional thickness modulations in a model bilayer system

Molecular dynamics simulations of bilayers in a surfactant/co-surfactant/water system with explicit solvent molecules show formation of topologically distinct gel phases depending upon the bilayer composition. At low temperatures, the bilayers transform from the tilted gel phase, L beta', to the one dimensional (1D) rippled, P beta' phase as the surfactant concentration is increased. More interestingly, we observe a two dimensional (2D) square phase at higher surfactant concentration which, upon heating, transforms to the gel L beta' phase. The thickness modulations in the 1D rippled and square phases are asymmetric in two surfactant leaflets and the bilayer thickness varies by a factor of similar to 2 between maximum and minimum. The 1D ripple consists of a thinner interdigitated region of smaller extent alternating with a thicker non-interdigitated region. The 2D ripple phase is made up of two superimposed square lattices of maximum and minimum thicknesses with molecules of high tilt forming a square lattice translated from the lattice formed with the thickness minima. Using Voronoi diagrams we analyze the intricate interplay between the area-per-head-group, height modulations and chain tilt for the different ripple symmetries. Our simulations indicate that composition plays an important role in controlling the formation of low temperature gel phase symmetries and rippling accommodates the increased area-per-head-group of the surfactant molecules.

Effect of surfactants on the instability of a two-layer film flow down an inclined plane

The effect of insoluble surfactants on the instability of a two-layer film flow down an inclined plane is investigated based on the Orr-Sommerfeld boundary value problem. The study, focusing on Stokes flow P. Gao and X.-Y. Lu, ``Effect of surfactants on the inertialess instability of a two-layer film flow,'' J. Fluid Mech. 591, 495-507 (2007)], is further extended by including the inertial effect. The surface mode is recognized along with the interface mode. The initial growth rate corresponding to the interface mode accelerates at sufficiently long-wave regime in the presence of surface surfactant. However, the maximum growth rate corresponding to both interface and surface modes decelerates in the presence of surface surfactant when the upper layer is more viscous than the lower layer. On the other hand, when the upper layer is less viscous than the lower layer, a new interfacial instability develops due to the inertial effect and becomes weaker in the presence of interfacial surfactant. In the limit of negligible surface and interfacial tensions, respectively, two successive peaks of temporal growth rate appear in the long-wave and short-wave regimes when the interface mode is analyzed. However, in the case of the surface mode, only the long-wave peak appears. (C) 2014 AIP Publishing LLC.

Synergetic effect of size and morphology of cobalt ferrite nanoparticles on proton relaxivity

Cobalt ferrite nanoparticles with average sizes of 14, 9 and 6 nm were synthesised by the chemical co-precipitation technique. Average particle sizes were varied by changing the chitosan surfactant to precursor molar ratio in the reaction mixture. Transmission electron microscopy images revealed a faceted and irregular morphology for the as-synthesised nanoparticles. Magnetic measurements revealed a ferromagnetic nature for the 14 and 9 nm particles and a superparamagnetic nature for the 6 nm particles. An increase in saturation magnetisation with increasing particle size was noted. Relaxivity measurements were carried out to determine T-2 value as a function of particle size using nuclear magnetic resonance measurements. The relaxivity coefficient increased with decrease in particle size and decrease in the saturation magnetisation value. The observed trend in the change of relaxivity value with particle size was attributed to the faceted nature of as-synthesised nanoparticles. Faceted morphology results in the creation of high gradient of magnetic field in the regions adjacent to the facet edges increasing the relaxivity value. The effect of edges in increasing the relaxivity value increases with decrease in the particle size because of an increase in the total number of edges per particle dispersion.

Tunability of monodispersed intermetallic AuCu nanoparticles through understanding of reaction pathways

Synthesis of size selective monodispersed nanoparticles particularly intermetallic with well-defined compositions represents a challenge. This paper presents a way for the synthesis of intermetallic AuCu nanoparticles as a model system. We show that reduction of Au and Cu precursors is sensitive to the ratio of total molar concentrations of surfactant to metal precursors. A careful design of experiments to understand the kinetics of the reduction process reveals initial formation of seed nanoparticles of pure Au. Reduction of Cu occurs on the surface of the seed followed by diffusion to yield AuCu. This understanding allows us to develop a two step synthesis where the precise size controlled seed of Au nanoparticles produced in the first step is used in the second step reaction mixture as an Au precursor to allow deposition and interdiffusion of Cu that yields size selected AuCu intermetallics of sub 10 nm sizes.

How does spacer length of imidazolium gemini surfactants control the fabrication of 2D-Langmuir films of silver-nanoparticles at the air-water interface?

A series of gemini surfactants based on cationic imidazolium ring as polar headgroup, abbreviated as lm-n-lm], 2Br(-) (n = 2, 5, 6 and 12), was synthesized. Their ability to stabilize silver nanoparticles in aqueous media was investigated. The resulting suspensions were characterized by UV-Vis spectroscopy and transmission electron microscopy (TEM). They exhibit specific morphologies by adopting different supramolecular assemblies in aqueous media depending on the internal packing arrangements and on the number of spacer methylene units -(CH2)(n)-]. Individual colloids were extracted from the aqueous to chloroform layer and spread at the air/water interface to allow the formation of well-defined Langmuir films. By analysis of the surface pressure-area isotherms, the details about the packing behavior and orientation of the imidazolium gemini surfactant capped silver nanoparticles were obtained. Morphological features of the dynamic process of monolayer compression at the air-water interface were elucidated using Brewster angle microscopy (BAM). These monolayers were further transferred on mica sheets by the Langmuir-Blodgett technique at their associated collapse pressure and the morphology of these monolayers was investigated by atomic force microscopy (AFM). The number of spacer methylene units -(CH2)(n)-] of the gemini surfactants exerted critical influence in modulating the characteristics of the resulting Langmuir films. (C) 2014 Elsevier Inc. All rights reserved.

How does spacer length of imidazolium gemini surfactants control the fabrication of 2D-Langmuir films of silver-nanoparticles at the air-water interface?

A series of gemini surfactants based on cationic imidazolium ring as polar headgroup, abbreviated as Im-n-Im], 2Br(-) (n = 2, 5,6 and 12), was synthesized. Their ability to stabilize silver nanoparticles in aqueous media was investigated. The resulting suspensions were characterized by UV-Vis spectroscopy and transmission electron microscopy (TEM). They exhibit specific morphologies by adopting different supramolecular assemblies in aqueous media depending on the internal packing arrangements and on the number of spacer methylene units -(CH2)(n)-]. Individual colloids were extracted from the aqueous to chloroform layer and spread at the air/water interface to allow the formation of well-defined Langmuir films. By analysis of the surface pressure-area isotherms, the details about the packing behavior and orientation of the imidazolium gemini surfactant capped silver nanoparticles were obtained. Morphological features of the dynamic process of monolayer compression at the air-water interface were elucidated using Brewster angle microscopy (BAM). These monolayers were further transferred on mica sheets by the Langmuir-Blodgett technique at their associated collapse pressure and the morphology of these monolayers was investigated by atomic force microscopy (AFM). The number of spacer methylene units (CH2)(n)-] of the gemini surfactants exerted critical influence in modulating the characteristics of the resulting Langmuir films. (C) 2014 Elsevier Inc. All rights reserved.

Enhanced photocatalytic efficiency of AuPd nanoalloy decorated ZnO-reduced graphene oxide nanocomposites

Inhibition of electron-hole pair recombination is the most desirable solution for stimulating photocatalytic activity in semiconductor nanostructures. To implement this, herein we study the photocatalytic efficiency of elemental Au, Pd and bimetallic AuPd nanoalloy decorated pristine and reduced graphene oxide (RGO) hybridized ZnO nanorods for degrading rhodamine 6G (R6G) dye. Fabrication of Au, Pd and AuPd nanoalloy on pristine and RGO modified ZnO nanorods is simple and more importantly surfactant or polymer free. AuPd nanoalloyed ZnO-RGO nanocomposites exhibit higher photocatalytic activity for degrading dye than both Au and Pd hybridized ones, indicating the promising potential of bimetallic nanoalloys over elemental components. A non-monotonic dependence on the composite composition was found by analyzing photodegradation efficiency of a series of ZnO-RGO-AuPd hybrid nanostructures with different weight percentages of RGO. The hybrid nanostructure ZnO-RGO (5 wt%)-AuPd (1 wt%) exhibits highest photodegradation efficiency (similar to 100% degradation in 20 min) with an improvement in rate constant (k) by a factor of 10 compared to that of the ZnO-RGO nanocomposite. The enhancement of the photocatalytic activity is attributed to the better separation of photogenerated charge carriers in photocatalysts thereby suggesting possible usefulness in a broad range of applications, such as sensing, photocatalysis and solar energy conversion.

Synthesis, luminescence properties and EPR investigation of hydrothermally derived uniform ZnO hexagonal rods

One-dimensional (1D) zinc oxide (ZnO) hexagonal rods have been successfully synthesized by surfactant free hydrothermal process at different temperatures. It can be found that the reaction temperature play a crucial role in the formation of ZnO uniform hexagonal rods. The possible formation processes of 1-D ZnO hexagonal rods were investigated. The zinc hydroxide acts as the morphology-formative intermediate for the formation of ZnO nanorods. Upon excitation at 325 nm, the sample prepared at 180 degrees C show several emission bands at 400 nm (similar to 3.10 eV), 420 nm (similar to 2.95 eV), 482 nm (similar to 2.57 eV) and 524 nm (similar to 2.36 eV) corresponding to different kind of defects. TL studies were carried out by pre-irradiating samples with gamma-rays ranging from 1 to 7 kGy at room temperature. A well resolved glow peak at similar to 354 degrees C was recorded which can be ascribed to deep traps. Furthermore, the defects associated with surface states in ZnO nano-structures are characterized by electron paramagnetic resonance. (C) 2014 Elsevier B.V. All rights reserved.