Mechanistic Insights into a Non-Classical Diffusion Pathway for the Formation of Hollow Intermetallics: A Route to Multicomponent Hollow Structures

Hollow nanostructures are used for various applications including catalysis, sensing, and drug delivery. Methods based on the Kirkendall effect have been the most successful for obtaining hollow nanostructures of various multicomponent systems. The classical Kirkendall effect relies on the presence of a faster diffusing species in the core; the resultant imbalance in flux results in the formation of hollow structures. Here, an alternate non-Kirkendall mechanism that is operative for the formation of hollow single crystalline particles of intermetallic PtBi is demonstrated. The synthesis method involves sequential reduction of Pt and Bi salts in ethylene glycol under microwave irradiation. Detailed analysis of the reaction at various stages indicates that the formation of the intermetallic PtBi hollow nanoparticles occurs in steps. The mechanistic details are elucidated using control experiments. The use of microwave results in a very rapid synthesis of intermetallics PtBi that exhibits excellent electrocatalytic activity for formic acid oxidation reaction. The method presented can be extended to various multicomponent systems and is independent of the intrinsic diffusivities of the species involved.

Remarkable Regioisomer Control in the Hydrogel Formation from a Two-Component Mixture of Pyridine-End Oligo(p-phenylenevinylene)s and N-Decanoyl-L-alanine

N-Decanoyl-L-alanine (DA) was mixed with either colorless 4,4-bipyridine (BP) or various derivatives such as chromogenic oligo(p-phenylenevinylene) (OPV) functionalized with isomeric pyridine termini in specific molar ratios. This mixtures form salt-type gels in a water/ethanol (2:1, v/v) mixture. The gelation properties of these two-component mixtures could be modulated by variation of the position of the N atom of the end pyridyl groups in OPVs. The presence of acid-base interactions in the self-assembly of these two-component systems leading to gelation was probed in detail by using stoichiometry-dependent UV/Vis and FTIR spectroscopy. Furthermore, temperature-dependent UV/Vis and fluorescence spectroscopy clearly demonstrated a J-type aggregation mode of these gelator molecules during the sol-to-gel transition process. Morphological features and the arrangement of the molecules in the gels were examined by using scanning electron microscopy (SEM), 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 XRD patterns revealed that this class of gelator molecules adopts lamellar organizations. Rheological properties of these two-component systems provided clear evidence that the flow behavior could be modulated by varying the acid/amine ratio. Polarized optical microscopy (POM), differential scanning calorimetry (DSC), and XRD results revealed that the solid-phase behavior of such two-component mixtures (acid/base=2:1) varied significantly upon changing the proton-acceptor part from BP to OPV. Interestingly, the XRD pattern of these acid/base mixtures after annealing at their associated isotropic temperature was significantly different from that of their xerogels.

New luminescent 2-methoxy-6-(4-methoxy-phenyl)-4-p-tolyl-nicotinonitrile: Synthesis, crystal structure, DFT and photophysical studies

In the current communication, we report the synthesis, spectroscopic, crystal structure, DFT and photophysical studies of a new nicotinonitrile derivative, viz. 2-methoxy-6-(4-methoxy-phenyl)-4-p-tolyl-nicotinonitrile (2) as a potential blue light emitting material. The compound 2 was synthesized in good yield via a simple route. The acquired spectral and elemental analysis data were in consistent with the chemical structure of 2. The single crystal study further confirms its three dimensional structure, molecular shape, and nature of short contacts. Its DFT calculations reveal that compound 2 possesses a non-planar structure and its theoretical IR spectral data are found to be in accordance with experimental values. In addition, its UV visible and fluorescence spectral measurements prove that the compound exhibits good absorption and fluorescence properties. Also, it shows positive solvatochromic effect when the solvent polarity was varied from non-polar to polar. (c) 2014 Elsevier B.V. All rights reserved.

L-p-Integrability, Dimensions of Supports of Fourier Transforms and Applications

It is proved that there does not exist any non zero function in with if its Fourier transform is supported by a set of finite packing -measure where . It is shown that the assertion fails for . The result is applied to prove L-p Wiener Tauberian theorems for R-n and M(2).

Fermions in Synthetic Non-Abelian Gauge Fields

Quantum emulation property of the cold atoms has generated a lot of interest in studying systems with synthetic gauge fields. In this article, we describe the physics of two component Fermi gas in the presence of synthetic non-Abelian SU(2) gauge fields. Even for the non-interacting system with the gauge fields, there is an interesting change in the topology of the Fermi surface by tuning only the gauge field strength. When a trapping potential is used in conjunction with the gauge fields, the non-interacting system has the ability to produce novel Hamiltonians and show characteristic change in the density profile of the cloud. Without trap, the gauge fields act as an attractive interaction amplifier and for special kinds of gauge field configurations, there are two-body bound states for any attraction even in three dimensions. For a many body system, the gauge fields can induce a crossover from a weak superfluid to a strong superfluid with transition temperature as high as the Fermi temperature. The superfluid state obtained for a very large gauge field strength is a superfluid of new kind of bosons, called ``rashbons'', the properties of which are independent of its constituent two component fermions and are solely determined by the gauge field strength. We also discuss the collective excitations over the superfluid ground states and the experimental relevance of the physics.

Non-polio enterovirus association with persistent diarrhea in children as revealed by a follow-up study of an Indian cohort during the first two years of life

Background: We recently reported significant association of non-polio enteroviruses (NPEVs) with acute diarrhea in children. Persistent diarrhea (PD) remains a major cause of morbidity and mortality in infants below two years of age in developing countries. Understanding age-dependent frequency and duration of NPEV infections is important to determine their association with persistent diarrhea and disease burden. Objectives: A cohort of 140 infants was followed for 6 months to 2 years of age to determine the frequency, duration, and association with PD of NPEV infections in comparison with rotavirus and other agents. Study design: Stool samples were collected every 14 days, and diarrheal episodes and their duration were recorded. Enteroviruses were characterized by RT-PCR and VP1 gene sequence analysis, rotavirus by electropherotyping, and other agents by PCR. Results: Of 4545 samples, negative for oral polio vaccine strains, 3907 (85.96%) and 638 (14.04%) were NPEV-negative and NPEV-positive, respectively, representing 403 (8.87%) infection episodes. About 68% of NPEV infections occurred during the first year with every child having at least one episode lasting between four days and four months. Approximately 38% and 22% of total diarrheal episodes were positive for NPEV and RV, respectively. While about 18% of NPEV infection episodes were associated with diarrhea, 6% being persistent, 13% of total diarrheal episodes were persistent involving infections by monotype NPEV strains or sequential infections by multiple strains and other agents. Conclusions: This is the first report revealing NPEVs as the single most frequently and persistently detected viral pathogen in every PD episode. (C) 2014 Elsevier B.V. All rights reserved.

Application of lateral photovoltage towards contactless light beam induced current measurements and its dependence on the finite beam size

The nature of the signal due to light beam induced current (LBIC) at the remote contacts is verified as a lateral photovoltage for non-uniformly illuminated planar p-n junction devices; simulation and experimental results are presented. The limitations imposed by the ohmic contacts are successfully overcome by the introduction of capacitively coupled remote contacts, which yield similar results without any significant loss in the estimated material and device parameters. It is observed that the LBIC measurements introduce artefacts such as shift in peak position with increasing laser power. Simulation of LBIC signal as a function of characteristic length L-c of photo-generated carriers and for different beam diameters has resulted in the observed peak shifts, thus attributed to the finite size of the beam. Further, the idea of capacitively coupled contacts has been extended to contactless measurements using pressure contacts with an oxidized aluminium electrodes. This technique avoids the contagious sample processing steps, which may introduce unintentional defects and contaminants into the material and devices under observation. Thus, we present here, the remote contact LBIC as a practically non-destructive tool in the evaluation of device parameters and welcome its use during fabrication steps. (C) 2014 AIP Publishing LLC.

Modelling of Effect of Non-Uniform Current Density on the Performance of Soluble Lead Redox Flow Batteries

Soluble lead acid redox flow battery (SLRFB) offers a number of advantages. These advantages can be harnessed after problems associated with buildup of active material on. electrodes (residue) are resolved. A mathematical model is developed to understand residue formation in SLRFB. The model incorporates fluid flow, ion transport, electrode reactions, and non-uniform current distribution on electrode surfaces. A number of limiting cases are studied to conclude that ion transport and electrode reaction on anode simultaneously control battery performance. The model fits the reported cell voltage vs. time profiles very well. During the discharge cycle, the model predicts complete dissolution of deposited material from trailing edge side of the electrodes. With time, the active surface area of electrodes decreases rapidly. The corresponding increase in current density leads to precipitous decrease in cell potential before all the deposited material is dissolved. The successive charge-discharge cycles add to the residue. The model correctly captures the marginal effect of flow rate on cell voltage profiles, and identifies flow rate and flow direction as new variables for controlling residue buildup. Simulations carried out with alternating flow direction and a SLRFB with cylindrical electrodes show improved performance with respect to energy efficiency and residue buildup. (C) 2014 The Electrochemical Society. All rights reserved.

On the stability of the L-p-norm of the Riemannian curvature tensor

We consider the Riemannian functional defined on the space of Riemannian metrics with unit volume on a closed smooth manifold M where R(g) and dv (g) denote the corresponding Riemannian curvature tensor and volume form and p a (0, a). First we prove that the Riemannian metrics with non-zero constant sectional curvature are strictly stable for for certain values of p. Then we conclude that they are strict local minimizers for for those values of p. Finally generalizing this result we prove that product of space forms of same type and dimension are strict local minimizer for for certain values of p.

An extended Shine-Dalgarno sequence in mRNA functionally bypasses a vital defect in initiator tRNA

Initiator tRNAs are special in their direct binding to the ribosomal P-site due to the hallmark occurrence of the three consecutive G-C base pairs (3GC pairs) in their anticodon stems. How the 3GC pairs function in this role, has remained unsolved. We show that mutations in either the mRNA or 16S rRNA leading to extended interaction between the Shine-Dalgarno (SD) and anti-SD sequences compensate for the vital need of the 3GC pairs in tRNA(fMet) for its function in Escherichia coli. In vivo, the 3GC mutant tRNA(fMet) occurred less abundantly in 70S ribosomes but normally on 30S subunits. However, the extended SD:anti-SD interaction increased its occurrence in 70S ribosomes. We propose that the 3GC pairs play a critical role in tRNA(fMet) retention in ribosome during the conformational changes that mark the transition of 30S preinitiation complex into elongation competent 70S complex. Furthermore, treating cells with kasugamycin, decreasing ribosome recycling factor (RRF) activity or increasing initiation factor 2 (IF2) levels enhanced initiation with the 3GC mutant tRNA(fMet), suggesting that the 70S mode of initiation is less dependent on the 3GC pairs in tRNA(fMet).

Plasmodium berghei glycine cleavage system T-protein is non-essential for parasite survival in vertebrate and invertebrate hosts

T-protein, an aminomethyltransferase, represents one of the four components of glycine cleavage system (GCS) and catalyzes the transfer of methylene group from H-protein intermediate to tetrahydrofolate (THF) forming N-5, N-10-methylene THF (CH2-THF) with the release of ammonia. The malaria parasite genome encodes T-, H- and L-proteins, but not P-protein which is a glycine decarboxylase generating the aminomethylene group. A putative GCS has been considered to be functional in the parasite mitochondrion despite the absence of a detectable P-protein homologue. In the present study, the mitochondrial localization of T-protein in the malaria parasite was confirmed by immunofluorescence and its essentiality in the entire parasite life cycle was studied by targeting the T-protein locus in Plasmodium berghei (Pb). PbT knock out parasites did not show any growth defect in asexual, sexual and liver stages indicating that the T-protein is dispensable for parasite survival in vertebrate and invertebrate hosts. The absence of P-protein homologue and the non-essentiality of T protein suggest the possible redundancy of GCS activity in the malaria parasite. Nevertheless, the H- and L-proteins of GCS could be essential for malaria parasite because of their involvement in alpha-lcetoacid dehydrogenase reactions. (C) 2014 Elsevier B.V. All rights reserved.

Long-term effects of Macroternies termites, herbivores and annual early fire on woody undergrowth community in Sudanian woodland, Burkina Faso

Termites, herbivores and fire are recognized as major guilds that structure woody plant communities in African savanna and woodland ecosystems. An understanding of their interaction is crucial to design appropriate management regimes. The aim of this study was to evaluate the long-term impacts of herbivore, fire and termite activities on regeneration of trees. Permanent experimental quadrats were established in 1992 in the Sudanian woodland of Burkina Faso subjected to grazing by livestock and annual early fire and the control. Within the treatment quadrats, an inventory of the woody undergrowth community was conducted on termitaria occupied by Macrotermes subhyalinus, extended termitosphere (within 5 m radius from the mound base) and adjacent area (beyond 5 m from the mound base). Hierarchical analysis was performed to determine significant differences in species richness, abundance and diversity indices among vegetation patches within fire and herbivory treatments. Grazed quadrats had significantly (P < 0.001) more species and stem density of woody undergrowth than non-grazed quadrats but maintained similar level of species richness and stem density of woody undergrowth on termitaria. There were not significant differences (P>0.05) in species richness and stem density between burnt and unburnt quadrats. Termitaria supported a highly diverse woody undergrowth with higher stem density than either the extended termitosphere or rest of quadrats. The density of woody undergrowth was significantly related with mature trees of selected species on termitaria (R-2 = 0.593; P<0.001) than that on the extended termitosphere (R-2 = 0.333; P<0.001) and adjacent area (R-2 = 0.197; P<0.001). It can be concluded that termites facilitate the regeneration of woody species while grazing and annual early fire play a minor role in the regeneration of woody species. The current policy that prohibits grazing should be revised to accommodate the interests of livestock herders. (C) 2014 Elsevier GmbH. All rights reserved.

Direct measurements of growing amorphous order and non-monotonic dynamic correlations in a colloidal glass-former

The transformation of flowing liquids into rigid glasses is thought to involve increasingly cooperative relaxation dynamics as the temperature approaches that of the glass transition. However, the precise nature of this motion is unclear, and a complete understanding of vitrification thus remains elusive. Of the numerous theoretical perspectives(1-4) devised to explain the process, random first-order theory (RFOT; refs 2,5) is a well-developed thermodynamic approach, which predicts a change in the shape of relaxing regions as the temperature is lowered. However, the existence of an underlying `ideal' glass transition predicted by RFOT remains debatable, largely because the key microscopic predictions concerning the growth of amorphous order and the nature of dynamic correlations lack experimental verification. Here, using holographic optical tweezers, we freeze a wall of particles in a two-dimensional colloidal glass-forming liquid and provide direct evidence for growing amorphous order in the form of a static point-to-set length. We uncover the non-monotonic dependence of dynamic correlations on area fraction and show that this non-monotonicity follows directly from the change in morphology and internal structure of cooperatively rearranging regions(6,7). Our findings support RFOT and thereby constitute a crucial step in distinguishing between competing theories of glass formation.