Synthesis and Mechanism of Composition and Size Dependent Morphology Selection in Nanoparticles of Ag-Cu Alloys Processed by Laser Ablation Under Liquid Medium

We have synthesized Ag-Cu alloy nanoparticles of four different compositions by using the laser ablation technique with the target under aqueous medium. Following this, we report a morphological transition in the nanoparticles from a normal two-phase microstructure to a structure with random segregation and finally a core shell structure at small sizes as a function of Cu concentration. To illustrate the composition dependence of morphology, we report observations carried out on nanoparticles of two different sizes: similar to 5 and similar to 20 nm. The results could be rationalized through the thermodynamic modeling of free energy of phase mixing and wettability of the alloying phases.

The morphology dependent electrocatalytic activity of Ir nanostructures towards oxygen reduction

Iridium nanostructures with different morphologies are synthesized by a simple, environmentally friendly approach in aqueous media under mild conditions. The morphology dependent electrocatalytic activity of Ir nanochains and nanoparticles towards oxygen reduction reaction (ORR) has been demonstrated in both acidic and alkaline media. Comparative electrochemical studies reveal that nanochains exhibit significantly enhanced ORR activities in both acidic and alkaline media as compared with nanoparticles, as a result of the continuous structure of interconnected particles. The mechanism of oxygen reduction on Ir nanostructures predominantly follows a four-electron pathway in alkaline and acidic solutions. Excellent stability and good selectivity towards methanol tolerance are reported.

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.

Directing peptide conformation with centrally positioned pre-organized dipeptide segments: studies of a 12-residue helix and beta-hairpin

Secondary structure formation in oligopeptides can be induced by short nucleating segments with a high propensity to form hydrogen bonded turn conformations. Type I/III turns facilitate helical folding while type II'/I' turns favour hairpin formation. This principle is experimentally verified by studies of two designed dodecapeptides, Boc-Val-Phe-Leu-Phe-Val-Aib-Aib-Val-Phe-Leu-Phe-Val-OMe 1 and Boc-Val-Phe-Leu-Phe-Val- (D) Pro- (L) Pro-Val-Phe-Leu-Phe-Val-OMe 2. The N- and C-terminal flanking pentapeptide sequences in both cases are identical. Peptide 1 adopts a largely alpha-helical conformation in crystals, with a small 3(10) helical segment at the N-terminus. The overall helical fold is maintained in methanol solution as evidenced by NMR studies. Peptide 2 adopts an antiparallel beta-hairpin conformation stabilized by 6 interstrand hydrogen bonds. Key nuclear Overhauser effects (NOEs) provide evidence for the antiparallel beta-hairpin structure. Aromatic proton chemical shifts provide a clear distinction between the conformation of peptides 1 (helical) and 2 (beta-hairpin). The proximity of facing aromatic residues positioned at non-hydrogen bonding positions in the hairpin results in extensively ring current shifted proton resonances in peptide 2.

Molecules support morphology: species status of South Indian populations of the widely distributed Hanuman langur

The taxonomy of the Hanuman langur (Semnopithecus spp.), a widely distributed Asian colobine monkey, has been in a flux for a long time due to much disagreement between various classification schemes. However, results from a recent field-based morphological study were consistent with Hill's (Ceylon J Sci 21:277-305, 1939) species level classification scheme. Here we tested the validity of S. hypoleucos and S. priam, the two South Indian species recognized by Hill. To this end, one mitochondrial and four nuclear markers were sequenced from over 72 non-invasive samples of Hanuman langurs and S. johnii collected from across India. The molecular data were subjected to various tree building methods. The nuclear data was also used in a Bayesian structure analysis and to determine the genealogical sorting index of each hypothesized species. Results from nuclear data suggest that the South Indian population of Hanuman langur consists of two units that correspond to the species recognized by Hill. However in the mitochondrial tree S. johnii and S. priam were polyphyletic probably due to retention of ancestral polymorphism and/or low levels of hybridization. Implications of these results on conservation of Hanuman langurs are also discussed.

Morphology controlled synthesis of Al doped ZnO nanosheets on Al alloy substrate by low-temperature solution growth method

We report the morphology-controlled synthesis of aluminium (Al) doped zinc oxide (ZnO) nanosheets on Al alloy (AA-6061) substrate by a low-temperature solution growth method without using any external seed layer and doping process. Doped ZnO nanosheets were obtained at low temperatures of 60-90 degrees C for the growth time of 4 hours. In addition to the synthesis, the effect of growth temperature on the morphological changes of ZnO nanosheets is also reported. As-synthesized nanosheets are characterized by FE-SEM, XRD TEM and XPS for their morphology, crystallinity, microstructure and compositional analysis respectively. The doping of Al in ZnO nanosheets is confirmed with EDXS and XPS. Furthermore, the effect of growth temperature on the morphological changes was studied in the range of 50 to 95 degrees C. It was found that the thickness and height of the nanosheets varied with respect to the growth temperature. The study has given an important insight into the structural morphology with respect to the growth temperature, which in turn enabled us to determine the growth temperature window for the ZnO nanosheets. These Al doped ZnO nanosheets have potential application possibilities in gas sensors, solar cells and energy harvesting devices like nanogenerators.

Effect of electrical parameters on morphology and in-vitro corrosion resistance of plasma electrolytic oxidized films formed on zirconium

The objective of the present work is to study the effect of electrical process Parameters (duty cycle and frequency) on morphological, structural, and in-vitro corrosion characteristics of oxide films formed on zirconium by plasma electrolytic oxidation in an electrolyte system consisting of 5 g/L of trisodium orthophosphate. The oxide films fabricated on zirconium by systematically varying the duty cycle and frequency are characterized for its phase composition, surface morphology, chemical composition, roughness, wettability, surface energy, scratch resistance, corrosion resistance, apatite forming ability and osteoblast cell adhesion. X-ray diffraction pattern of all the oxide films showed the predominance of m-ZrO2 phase. Dense and uniform films with thickness varying from 9 to 15 mu m and roughness in the range of 0.62 to 1.03 mu m are formed. Porosity of oxide films is found to be increased with an increase infrequency. The water contact angle results demonstrated that the oxide films exhibited similar hydrophilicity to zirconium substrate. All oxide films showed improved corrosion resistance, as indicated by far lower corrosion current density and passive corrosion potential compared to the zirconium substrate in simulated body fluid environment, and among the four different combinations of duty cycle and frequency employed in the present study, the oxide film formed at 95% duty cycle and 50 Hz frequency (HDLF film) showed superior pitting corrosion resistance, which can be attributed to its pore free morpholOgy. Scratch test results showed that the HDLF oxide film adhered firmly to the substrate by developing a notable scratch resistance at 19.5 +/- 1.2.N. Besides the best corrosion resistance and scratch retistance, the HDLF film also showed good apatite forming ability and osteo sarcoma cell adhesion on its surface. The HDLF oxide film on zirconium with superior surface characteristics is believed to be useful for various types of implants in the dental and orthopedic fields. (C) 2015 Elsevier B.V. All rights reserved.

A spectral element for wave propagation in honeycomb sandwich construction considering core flexibility

Spectral elements are found to be extremely resourceful to study the wave propagation characteristics of structures at high frequencies. Most of the aerospace structures use honeycomb sandwich constructions. The existing spectral elements use single layer theories for a sandwich construction wherein the two face sheets vibrate together and this model is sufficient for low frequency excitations. At high frequencies, the two face sheets vibrate independently. The Extended Higher order SAndwich Plate theory (EHSaPT) is suitable for representing the independent motion of the face sheets. A 1D spectral element based on EHSaPT is developed in this work. The wave number and the wave speed characteristics are obtained using the developed spectral element. It is shown that the developed spectral element is capable of representing independent wave motions of the face sheets. The propagation speeds of a high frequency modulated pulse in the face sheets and the core of a honeycomb sandwich are demonstrated. Responses of a typical honeycomb sandwich beam to high frequency shock loads are obtained using the developed spectral element and the response match very well with the finite element results. It is shown that the developed spectral element is able to represent the flexibility of the core resulting into independent wave motions in the face sheets, for which a finite element method needs huge degrees of freedom. (C) 2015 Elsevier Ltd. All rights reserved.

Morphology control synthesis of Au-Cu2S metal-semiconductor hybrid nanostructures by modulating reaction constituents

A facile methodology for synthesizing Au-Cu2S hybrid nanoparticles is presented. Au-Cu2S nanoparticles have application in visible light driven photocatalytic degradation of dyes. Detailed microstructural and compositional characterization illustrated that the hybrid nanoparticles are composed of cube shaped Au-Cu solid solution and hemispherical shaped Cu2S phases. Investigation of nanoparticles extracted at different stages of the synthesis process revealed that the mechanism of formation of hybrid nanoparticles involved initial formation of isolated cube shaped pure Au nanoparticles and Cu-thiolate complex. In the subsequent stages, the Au nanoparticles get adsorbed onto the Cu-thiolate complex which is followed by the decomposition of the Cu-thiolate complex to form Au-Cu2S hybrid nanoparticles. This study also illustrates that an optimum concentration of dodecanethiol is required both for achieving size and morphological uniformity of the participating phases and for their attachment to form a hybrid nanoparticle.

Design and morphology control of a thiophene derivative through electrospraying using various solvents

In the present work, electrospraying of an organic molecule is carried out using various solvents, obtaining fibril structures along with a range of distinct morphologies. Solvent characteristics play a major role in determining the morphology of the organic material. A thiophene derivative (7,9-di(thiophen-2-yl)-8H-cyclopentaa]acenaphthylen-8-one) (DTCPA) of donor-acceptor-donor (DAD) architecture is used to study this solvent effect. Seven solvents with decreasing vapour pressure are selected for experiments. Electrospraying is conducted at a solution concentration of 1.5 wt% and a constant applied voltage of 15 kV. Gradual transformation in morphology of the electrospun product from spiked-spheres to only spikes is observed. A mechanism describing this transformation is proposed based on electron micrograph analysis and XRD analysis. These data indicate that the morphological change is due to the synergistic effect of both vapour pressure and dielectric constant of the solvents. Through a reasonable control of the crystallite size and morphology along with the proposal of the transformation mechanism, this study elucidates electrospraying as a prospective method for designing architectures in organic electronics.

Dissecting Ubiquitin Folding Using the Self-Organized Polymer Model

Folding of Ubiquitin (Ub), a functionally important protein found in eukaryotic organisms, is investigated at low and neutral pH at different temperatures using simulations of the coarse-grained self-organized-polymer model with side chains (SOP-SC). The melting temperatures (T-m's), identified with the peaks in the heat capacity curves, decrease as pH decreases, in qualitative agreement with experiments. The calculated radius of gyration, showing dramatic variations with pH, is in excellent agreement with scattering experiments. At T-m Ub folds in a two-state manner at low and neutral pH. Clustering analysis of the conformations sampled in equilibrium folding trajectories at T-m with multiple transitions between the folded and unfolded states, shows a network of metastable states connecting the native and unfolded states. At low and neutral pH, Ub folds with high probability through a preferred set of conformations resulting in a pH-dependent dominant folding pathway. Folding kinetics reveal that Ub assembly at low pH occurs by multiple pathways involving a combination of nucleation-collapse and diffusion collision mechanism. The mechanism by which Ub folds is dictated by the stability of the key secondary structural elements responsible for establishing long-range contacts and collapse of Ub. Nucleation collapse mechanism holds if the stability of these elements are marginal, as would be the case at elevated temperatures. If the lifetimes associated with these structured microdomains are on the order of hundreds of microseconds, then Ub folding follows the diffusion collision mechanism with intermediates, many of which coincide with those found in equilibrium. Folding at neutral pH is a sequential process with a populated intermediate resembling that sampled at equilibrium. The transition state structures, obtained using a P-fold analysis, are homogeneous and globular with most of the secondary and tertiary structures being native-like. Many of our findings for both the thermodynamics and kinetics of folding are not only in agreement with experiments but also provide missing details not resolvable in standard experiments. The key prediction that folding mechanism varies dramatically with pH is amenable to experimental tests.

In-plane effective shear modulus of generalized circular honeycomb structures and bundled tubes in a diamond array structure

Use of circular hexagonal honeycomb structures and tube assemblies in energy absorption systems has attracted a large number of literature on their characterization under crushing and impact loads. Notwithstanding these, effective shear moduli (G*) required for complete transverse elastic characterization and in analyses of hierarchical structures have received scant attention. In an attempt to fill this void, the present study undertakes to evaluate G* of a generalized circular honeycomb structures and tube assemblies in a diamond array structure (DAS) with no restriction on their thickness. These structures present a potential to realize a spectrum of moduli with minimal modifications, a point of relevance for manufactures and designers. To evaluate G* in this paper, models based on technical theories - thin ring theory and curved beam theory - and rigorous theory of elasticity are investigated and corroborated with FEA employing contact elements. Technical theories which give a good match for thin HCS offer compact expressions for moduli which can be harvested to study sensitivity of moduli on topology. On the other hand, elasticity model offers a very good match over a large range of thickness along with exact analysis of stresses by employing computationally efficient expressions. (C) 2015 Elsevier Ltd. All rights reserved.

Localized Excitations and the Morphology of Cooperatively Rearranging Regions in a Colloidal Glass-Forming Liquid

We develop a scheme based on a real space microscopic analysis of particle dynamics to ascertain the relevance of dynamical facilitation as a mechanism of structural relaxation in glass-forming liquids. By analyzing the spatial organization of localized excitations within clusters of mobile particles in a colloidal glass former and examining their partitioning into shell-like and corelike regions, we establish the existence of a crossover from a facilitation-dominated regime at low area fractions to a collective activated hopping-dominated one close to the glass transition. This crossover occurs in the vicinity of the area fraction at which the peak of the mobility transfer function exhibits a maximum and the morphology of cooperatively rearranging regions changes from stringlike to a compact form. Collectively, our findings suggest that dynamical facilitation is dominated by collective hopping close to the glass transition, thereby constituting a crucial step towards identifying the correct theoretical scenario for glass formation.

Effect of morphology on the magnetic properties of Gd2O3 nanotubes

Gadolinium oxide (Gd2O3) nanotubes of micron length and average diameter 100 nm have been synthesized by a controlled template-assisted electrochemical deposition technique. Structure and morphology of the synthesized nanotubes have been well characterized by using microscopy and spectroscopy analyses. HRTEM and XRD analysis revealed the crystalline planes of Gd2O3 nanotubes. Magnetic measurements of the aligned Gd2O3 nanotubes have been performed for both parallel and perpendicular orientations of the magnetic field with respect to the axis of the Gd2O3 nanotube array. Large bifurcation in ZFC-FC over the regime of 2-320 K without any signature of long range magnetic ordering confirms the presence of SPM clusters in Gd2O3 nanotubes. Also, large magnetocaloric effect is observed in the cryogenic temperature regime. No anisotropy is seen at the low temperature region but is found to evolve with temperature and becomes significant 300 K. These nanotubes can be considered as promising candidates for magnetic refrigeration at cryogenic temperature. (C) 2016 Elsevier B.V. All rights reserved.

The influence of current density on the morphology and corrosion properties of MAO coatings on AZ31B magnesium alloy

Micro-arc oxidation (MAO) coatings were prepared on AZ31B magnesium alloy using alkaline silicate electrolyte at different current densities (0.026, 0.046 and 0.067 A/cm(2)). Field Emission Scanning Electron Microscopy (FESEM) analysis of the coating revealed an irregular porous structure with cracked morphology. Compositional analysis carried out for MAO coating showed the presence of almost an equal amount of Mg and 0 (34 wt.%) apart from other elements such as F, Si and AI. The cross-sectional FESEM images clearly portrayed that the MAO coating was dense along with the presence of very few fine pores. The surface roughness (R-a) of the coatings increased with an increase in the current density. Potentiodynamic polarization and electrochemical impedance spectroscopic (EIS) studies were carried out for both the bare and MAO coated AZ31B Mg alloy in 3.5% NaCl solution. The corrosion potential (E-corr) and corrosion current density (i(corr)) values obtained for the bare substrate were -1.49 V and 46 mu A/cm(2), respectively. The coating prepared at 0.046 A/cm(2) exhibited the lowest i(corr) value of 7.79 x 10(-10) A/cm(2) and highest polarization resistance (41.6 M Omega cm(2)) attesting to the better corrosion resistance of the coating compared to other samples. EIS results also indicated almost similar corrosion behavior for the MAO coatings. Mott-Schottky analysis showed n-type and p-type semiconductor behavior for the oxide layer present on the bare magnesium alloy and MAO coatings respectively. (C) 2016 Published by Elsevier B.V.