Synergistic effect of reactor chemistry and compressive stress on dislocation bending during GaN growth

The synergistic effect of compressive growth stresses and reactor chemistry, silane presence, on dislocation bending at the very early stages of GaN growth has been studied using in-situ stress measurements and cross-sectional transmission electron microscopy. A single 100 nm Si-doped GaN layer is found to be more effective than a 1 mu m linearly graded AlGaN buffer layer in reducing dislocation density and preventing the subsequent layer from transitioning to a tensile stress. 1 mu m crack-free GaN layers with a dislocation density of 7 x 10(8)/cm(2), with 0.13 nm surface roughness and no enhancement in n-type background are demonstrated over 2 inch substrates using this simple transition scheme. (C) 2013 AIP Publishing LLC.

Investigating thermal stability of structural defects and its effect on d(0) ferromagnetism in undoped SnO2

The effect of annealing on structural defects and d(0) ferromagnetism in SnO2 nanoparticles prepared by solution combustion method is investigated. The as-synthesized SnO2 nanoparticles were annealed at 400-800 degrees C for 2 h, in ambient conditions. The crystallinity, size, and morphology of the samples were studied using x-ray diffraction and transmission electron microscopy studies. The annealing results in grain growth due to coarsening as well as reduction in oxygen vacancies as confirmed by Raman spectroscopy, photoluminescence spectroscopy, and x-ray photoelectron spectroscopy. All the as synthesized and annealed samples exhibit room temperature ferromagnetism (RTFM) with distinct hysteresis loops and the saturation magnetization as high as similar to 0.02 emu/g in as-synthesized samples. However, the saturation magnetization is drastically reduced with increasing annealing temperature. Further the presence of singly charged oxygen vacancies (V-o(-) signal at g-value 1.99) is confirmed by electron paramagnetic resonance studies, which also diminish with increasing annealing temperature. The observed diminishing RTFM and simultaneous evidences of diminishing O vacancies clearly indicate that RTFM is driven by defects in oxide lattice and confirms primary role of oxygen vacancies in inducing ferromagnetic ordering in metal oxide semiconductors. The study also provides improved fundamental understanding regarding the ambiguity in the origin of intrinsic RTFM in semiconducting metal oxides and projects their technological application in the field of spintronics. (C) 2013 AIP Publishing LLC.

Induction of Supramolecular Chirality in the Self-Assemblies of Lipophilic Pyrimidine Derivatives by Choice of the Amino Acid-Based Chiral Spacer

A new family of supramolecular organogelators, based on chiral amino acid derivatives of 2,4,6-trichloro-pyrimidine-5-carbaldehyde, has been synthesized. L-alanine was incorporated as a spacer between the pyrimidine core and long hydrocarbon tails to compare the effect of chirality and hydrogen bonding to that of the achiral analogue. The role of aromatic moiety on the chiral spacer was also investigated by introducing L-phenyl alanine moieties. The presence of intermolecular hydrogen-bonding leading to the chiral self-assembly was probed by concentration-dependent FTIR and UV/Vis spectroscopies, in addition to circular dichroism (CD) studies. Temperature and concentration-dependent CD spectroscopy ascribed to the formation of -sheet-type H-bonded networks. The morphology and the arrangements of the molecules in the freeze-dried gels were examined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), and X-ray diffraction (XRD) techniques. Calculation of the length of each molecular system by energy minimization in its extended conformation and comparison with the small-angle XRD pattern reveals that this class of gelator molecules adopts a lamellar organization. Polarized optical microscopy (POM) and differential scanning calorimetry (DSC) indicate that the solid state phase behavior of these molecules is totally dependent on the choice of their amino acid spacers. Structure-induced aggregation properties based on the H-bonding motifs and the packing of the molecule in three dimensions leading to gelation was elucidated by rheological studies. However, viscoelasticity was shown to depend only marginally on the H-bonding interactions; rather it depends on the packing of the gelators to a greater extent.

Deformation-induced grain growth and twinning in nanocrystalline palladium thin films

The microstructure and mechanical properties of nanocrystalline Pd films prepared by magnetron sputtering have been investigated as a function of strain. The films were deposited onto polyimide substrates and tested in tensile mode. In order to follow the deformation processes in the material, several samples were strained to defined straining states, up to a maximum engineering strain of 10%, and prepared for post-mortem analysis. The nanocrystalline structure was investigated by quantitative automated crystal orientation mapping (ACOM) in a transmission electron microscope (TEM), identifying grain growth and twinning/detwinning resulting from dislocation activity as two of the mechanisms contributing to the macroscopic deformation. Depending on the initial twin density, the samples behaved differently. For low initial twin densities, an increasing twin density was found during straining. On the other hand, starting from a higher twin density, the twins were depleted with increasing strain. The findings from ACOM-TEM were confirmed by results from molecular dynamics (MD) simulations and from conventional and in-situ synchrotron X-ray diffraction (CXRD, SXRD) experiments.

Gene Transfection in High Serum Levels: Case Studies with New Cholesterol Based Cationic Gemini Lipids

Background: Six new cationic gemini lipids based on cholesterol possessing different positional combinations of hydroxyethyl (-CH2CH2OH) and oligo-oxyethylene -(CH2CH2O)(n)- moieties were synthesized. For comparison the corresponding monomeric lipid was also prepared. Each new cationic lipid was found to form stable, clear suspensions in aqueous media. Methodology/Principal Findings: To understand the nature of the individual lipid aggregates, we have studied the aggregation properties using transmission electron microscopy (TEM), dynamic light scattering (DLS), zeta potential measurements and X-ray diffraction (XRD). We studied the lipid/DNA complex (lipoplex) formation and the release of the DNA from such lipoplexes using ethidium bromide. These gemini lipids in presence of a helper lipid, 1, 2-dioleoyl phophatidyl ethanol amine (DOPE) showed significant enhancements in the gene transfection compared to several commercially available transfection agents. Cholesterol based gemini having -CH2-CH2-OH groups at the head and one oxyethylene spacer was found to be the most effective lipid, which showed transfection activity even in presence of high serum levels (50%) greater than Effectene, one of the potent commercially available transfecting agents. Most of these geminis protected plasmid DNA remarkably against DNase I in serum, although the degree of stability was found to vary with their structural features. Conclusions/Significance: -OH groups present on the cationic headgroups in combination with oxyethylene linkers on cholesterol based geminis, gave an optimized combination of new genera of gemini lipids possessing high transfection efficiency even in presence of very high percentage of serum. This property makes them preferential transfection reagents for possible in vivo studies.

Multifunctional Properties of Multistage Spark Plasma Sintered HA-BaTiO3-Based Piezobiocomposites for Bone Replacement Applications

This work reports the processing-microstructure-property correlation of novel HA-BaTiO3-based piezobiocomposites, which demonstrated the bone-mimicking functional properties. A series of composites of hydroxyapatite (HA) with varying amounts of piezoelectric BaTiO3 (BT) were optimally processed using uniquely designed multistage spark plasma sintering (SPS) route. Transmission electron microscopy imaging during in situ heating provides complementary information on the real-time observation of sintering behavior. Ultrafine grains (0.50m) of HA and BT phases were predominantly retained in the SPSed samples. The experimental results revealed that dielectric constant, AC conductivity, piezoelectric strain coefficient, compressive strength, and modulus values of HA-40wt% BT closely resembles with that of the natural bone. The addition of 40wt% BT enhances the long-crack fracture toughness, compressive strength, and modulus by 132%, 200%, and 165%, respectively, with respect to HA. The above-mentioned exceptional combination of functional properties potentially establishes HA-40wt% BT piezocomposite as a new-generation composite for orthopedic implant applications.

In vitro Evidence that an Aqueous Extract of Centella asiatica Modulates alpha-Synuclein Aggregation Dynamics

alpha-Synuclein aggregation is one of the major etiological factors implicated in Parkinson's disease (PD). The prevention of aggregation of alpha-synuclein is a potential therapeutic intervention for preventing PD. The discovery of natural products as alternative drugs to treat PD and related disorders is a current trend. The aqueous extract of Centella asiatica (CA) is traditionally used as a brain tonic and CA is known to improve cognition and memory. There are limited data on the role of CA in modulating amyloid-beta (A beta) levels in the brain and in A beta aggregation. Our study focuses on CA as a modulator of the alpha-synuclein aggregation pattern in vitro. Our investigation is focused on: (i) whether the CA leaf aqueous extract prevents the formation of aggregates from monomers (Phase I: alpha-synuclein + extract co-incubation); (ii) whether the CA aqueous extract prevents the formation of fibrils from oligomers (Phase II: extract added after oligomers formation); and (iii) whether the CA aqueous extract disintegrates the pre-formed fibrils (Phase III: extract added to mature fibrils and incubated for 9 days). The aggregation kinetics are studied using a thioflavin-T assay, circular dichroism, and transmission electron microscopy. The results showed that the CA aqueous extract completely inhibited the alpha-synuclein aggregation from monomers. Further, CA extract significantly inhibited the formation of oligomer to aggregates and favored the disintegration of the preformed fibrils. The study provides an insight in finding new natural products for future PD therapeutics.

Structural Evolution and Phase Stability of Hume-Rothery Phase in a Mechanically Driven Nanostructured Ag-15 at. pct Sn Alloy

The paper reports phase evolution in mechanically driven Ag-15 at. pct Sn alloy powder starting with elemental powders in order to establish the feasibility of designing nanocomposites of a Ag-Sn solid solution. This alloy lies in the phase field of the hexagonal zeta-phase which is a well-known Hume-Rothery electron compound with an electron-to-atom ratio of about 1.45 and hexagonal crystal structure (a = 0.2966 nm, c = 0.4782 nm). Through a systematic use of X-ray diffraction and transmission electron microscopy, the results establish the formation of the zeta-phase which co-exists with the Ag solid solution during the initial phase of milling. Mechanical milling for long duration (55 hours) destabilizes the zeta-phase. A complete solid solution of Ag with a grain size of similar to 8 nm could be achieved after 60 hours of milling. Additional milling can induce decomposition of the solid solution that results in a reappearance of zeta-phase. We present a detailed thermodynamic calculation which indicates that complete Ag solid solution of the present alloy composition would be possible if the crystallites size can be reduced below a certain critical size. In particular, we show that both Ag and zeta-phase grain sizes need to be taken into account for determining the metastable equilibrium and the phase change that has been experimentally observed. Finally, we argue that recrystallization processes set a limit to the achievable size of the nanoparticles with metastable Ag solid solution.

Evolution of Nanocrystalline Ba2NaNb5O15 in 2BaO-0.5Na(2)O-2.5Nb(2)O(5)-4.5B(2)O(3) Glass System and Its Refractive Index and Band Gap Tunability

Monophasic Ba2NaNb5O15 was crystallized at nanometer scale (12-36 nm) in 2BaO-0.5Na(2)O-2.5Nb(2)O(5)- 4.5B(2)O(3) glass system. To begin with, optically transparent glasses, in this system, were fabricated via the conventional melt. quenching technique. The amorphous and glassy characteristics of the as-quenched samples were respectively confirmed by X-ray powder diffraction and differential thermal analyses. Nearly homogeneous distribution of Ba2NaNb5O15 (BNN) nanocrystals associated with tungsten bronze structure akin to their bulk parent structure was accomplished by subjecting the as-fabricated glasses to appropriate heat-treatment temperatures. Indeed transmission electron microscopy (TEM) carried out on these samples corroborated the presence of Ba2NaNb5O15 nanocrystals dispersed in a continuous glass matrix. The as-quenched glasses were similar to 75% transparent in the visible range of the electromagnetic spectrum. The optical band gap and refractive index were found to have crystallite size (at nanoscale) dependence. The optical band gap increased with the decrease in crystallite size. The refractive indices of the glass nanocrystal composites as determined by Brewster angle method were rationalized using different empirical models. The refractive index dispersion with wavelength of light was analyzed on the basis of the Sellmeier relations. At room temperature under UV excitation (355 nm) these glass nanocrystal composites displayed violet-blue emission which was ascribed to the defects states.

Structural Investigations on the Compositional Anomalies in Lanthanum Zirconate System Synthesized by Coprecipitation Method

The study set out to investigate the compositional inconsistency in lanthanum zirconate system revealed the presence of nonstoichiometry in lanthanum zirconate powders when synthesized by coprecipitation route. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) investigations confirmed the depletion of La3+ ions in the system. Analysis using Vegard's law showed the La/Zr mole ratio in the sample to be around 0.45. An extra step of ultrasonication, introduced during the washing stage followed by the coprecipitation reaction, ensured the formation of stoichiometric La2Zr2O7. Noteworthy is also the difference between crystal sizes in the samples prepared by with and without ultrasonication step. This difference has been explained in light of the formation of individual nuclei and their scope of growth within the precipitate core. The differential scanning calorimetry (DSC) analyses revealed that optimum pH for the synthesis of La2Zr2O7 is about 11. The ultrasonication step was pivotal in assuring consistency in mixing and composition for the lanthanum zirconate powders.

Formation and Thermal Stability of Gold-Silica Nanohybrids: Insight into the Mechanism and Morphology by Electron Tomography

Gold-silica hybrids are appealing in different fields of applications like catalysis, sensorics, drug delivery, and biotechnology. In most cases, the morphology and distribution of the heterounits play significant roles in their functional behavior. Methods of synthesizing these hybrids, with variable ordering of the heterounits, are replete; however, a complete characterization in three dimensions could not be achieved yet. A simple route to the synthesis of Au-decorated SiO2 spheres is demonstrated and a study on the 3D ordering of the heterounits by scanning transmission electron microscopy (STEM) tomography is presentedat the final stage, intermediate stages of formation, and after heating the hybrid. The final hybrid evolves from a soft self-assembled structure of Au nanoparticles. The hybrid shows good thermal stability up to 400 degrees C, beyond which the Au particles start migrating inside the SiO2 matrix. This study provides an insight in the formation mechanism and thermal stability of the structures which are crucial factors for designing and applying such hybrids in fields of catalysis and biotechnology. As the method is general, it can be applied to make similar hybrids based on SiO2 by tuning the reaction chemistry as needed.

Synthesis and luminescence properties of Sm3+ doped CaTiO3 nanophosphor for application in white LED under NUV excitation

CaTiO3:Sm3+ (1-11 mol%) nanophosphors were successfully synthesized by a low temperature solution combustion method LCS]. The structural and morphological properties of the phosphors were studied by using Powder X-ray diffractometer (PXRD), Fourier transform infrared (FTIR), X-ray photo electron spectroscopy (XPS), scanning electron microscope (SEM) and transmission electron microscopy (TEM). TEM studies indicate that the size of the phosphor is similar to 20-35 nm. Photoluminescence (PL) properties of Sm3+ (1-11 mol%) doped CaTiO3 for NUV excitation (407 nm) was studied in order to investigate the possibility of its use in White light emitting diode (WLED) applications. The emission spectra consists of intra 4f transitions of Sm3+, such as (4)G(5/2) -> H-6(5/2) (561 nm), (4)G(5/2) -> H-6(7/2) (601-611 nm), (4)G(5/2) -> H-6(9/2) (648 nm) and (4)G(5/2) -> H-6(11/2) (703 nm) respectively. Further, the emission at 601-611 nm show strong orange-red emission and can be applied to the orange-red emission of phosphor for the application for near ultra violet (NUV) excitation. Thermoluminescence (TL) of the samples irradiated with gamma source in the dose range 100-500 Gy was recorded at a heating rate of 5 degrees C s(-1). Two well resolved glow peaks at 164 degrees C and 214 degrees C along with shouldered peak at 186 degrees C were recorded. TL intensity increases up to 300 Gy and thereafter, it decreases with further increase of dose. The kinetic parameters namely activation energy (E), frequency factor (s) and order of kinetics were estimated and results were discussed in detail. (C) 2014 Elsevier B.V. All rights reserved.

In-situ Stabilization of Tin Nanoparticles in Porous Carbon Matrix derived from Metal Organic Framework: High Capacity and High Rate Capability Anodes for Lithium-ion Batteries

It is a formidable challenge to arrange tin nanoparticles in a porous matrix for the achievement of high specific capacity and current rate capability anode for lithium-ion batteries. This article discusses a simple and novel synthesis of arranging tin nanoparticles with carbon in a porous configuration for application as anode in lithium-ion batteries. Direct carbonization of synthesized three-dimensional Sn-based MOF: K2Sn2(1,4-bdc)(3)](H2O) (1) (bdc = benzenedicarboxylate) resulted in stabilization of tin nanoparticles in a porous carbon matrix (abbreviated as Sn@C). Sn@C exhibited remarkably high electrochemical lithium stability (tested over 100 charge and discharge cycles) and high specific capacities over a wide range of operating currents (0.2-5 Ag-1). The novel synthesis strategy to obtain Sn@C from a single precursor as discussed herein provides an optimal combination of particle size and dispersion for buffering severe volume changes due to Li-Sn alloying reaction and provides fast pathways for lithium and electron transport.

Synthesis of benzimidazole-grafted graphene oxide/multi-walled carbon nanotubes composite for supercapacitance application

We are reporting the fabrication, characterizations and supercapacitance performance of benzimidazole-grafted graphene oxide/multi-walled carbon nanotubes (BI-GO/MWCNTs) composite. The synthesis of BI-GO materials involves cyclization reaction of carboxylic groups on GO among the hydroxyl and amino groups on o-phenylenediamine. The BI-GO/MWCNTs composite has been fabricated via in situ reduction of BI-GO using hydrazine in presence of MWCNTs. Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Raman spectroscopy, X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) have been used to characterize its surface and elemental composition. The uniform dispersion of MWCNTs with BI-GO helps to improve the charge transfer reaction during electrochemical process. The specific capacitance of BI-GO/MWCNTs composite is 275 and 460 F/g at 200 and 5 mV/s scan rate in 1 mol/L aqueous solution of H2SO4. This BI-GO/MWCNTs composite has shown 224 F/g capacitance after 1300 cycles at 200 mV/s scan rate, which represents its good electrochemical stability. (C) 2014 Elsevier B.V. All rights reserved.