An unusual temperature induced isostructural phase transition in a scheelite, Li0.5Ce0.5MoO4

High resolution synchrotron X-ray diffraction, dielectric and Raman scattering study of a scheelite compound Li0.5Ce0.5MoO4 (LCM) revealed that it transforms to a self similar structure above 400 degrees C. The thermally induced isostructural phase transition (IPT), a phenomenon which has rarely been reported in the literature, is preceded by partial softening of the zone centre phonons followed by their hardening above the IPT transition temperature. The high temperature isostructural phase, which exhibits expanded lattice parameters and cell volume, nucleates and grows in the low temperature matrix over a very wide temperature range. Both the phases show nearly identical thermal expansion suggesting similarities in symmetry, unaltered coordination environments around the atoms across the transition.

H/F isosteric substitution to attest different equi-energetic molecular conformations in crystals

The sequential replacement of aromatic H-atoms by F-atoms in 1,6-bis(phenylcarbonate) hexa-2,4-diyne allows access to its possible iso-energetic ``syn'', ``gauche'' and ``anti'' conformations.

Halogen bonding in fluorine: experimental charge density study on intermolecular F center dot center dot center dot F and F center dot center dot center dot S donor-acceptor contacts

The enigmatic type II C-F center dot center dot center dot F-C and C-F center dot center dot center dot S-C interactions in pentafluorophenyl 2,2'-bithiazole are shown to be realistic ``r-hole'' interactions based on high resolution X-ray charge density analysis.

Horizontal pullout capacity of a group of two vertical plate anchors in clay

The horizontal pullout capacity of a group of two vertical strip plate anchors, placed along the same vertical plane, in a fully cohesive soil has been computed by using the lower bound finite element limit analysis. The effect of spacing between the plate anchors on the magnitude of total group failure load (P-uT) has been evaluated. An increase of soil cohesion with depth has also been incorporated in the analysis. For a weightless medium, the total pullout resistance of the group becomes maximum corresponding to a certain optimum spacing between the anchor plates which has been found to vary generally between 0.5B and B; where B is the width of the anchor plate. As compared to a single plate anchor, the increase in the pullout resistance for a group of two anchors becomes greater at a higher embedment ratio. The effect of soil unit weight has also been analyzed. It is noted that the interference effect on the pullout resistance increases further with an increase in the unit weight of soil mass.

Call intensity is a repeatable and dominant acoustic feature determining male call attractiveness in a field cricket

Acoustic signal variation and female preference for different signal components constitute the prerequisite framework to study the mechanisms of sexual selection that shape acoustic communication. Despite several studies of acoustic communication in crickets, information on both male calling song variation in the field and female preference in the same system is lacking for most species. Previous studies on acoustic signal variation either were carried out on populations maintained in the laboratory or did not investigate signal repeatability. We therefore used repeatability analysis to quantify variation in the spectral, temporal and amplitudinal characteristics of the male calling song of the field cricket Plebeiogryllus guttiventris in a wild population, at two temporal scales, within and across nights. Carrier frequency (CF) was the most repeatable character across nights, whereas chirp period (CP) had low repeatability across nights. We investigated whether female preferences were more likely to be based on features with high (CF) or low (CP) repeatability. Females showed no consistent preferences for CF but were significantly more attracted towards signals with short CPs. The attractiveness of lower CP calls disappeared, however, when traded off with sound pressure level (SPL). SPL was the only acoustic feature that was significantly positively correlated with male body size. Since relative SPL affects female phonotaxis strongly and can vary unpredictably based on male spacing, our results suggest that even strong female preferences for acoustic features may not necessarily translate into greater advantage for males possessing these features in the field. (C) 2013 The Association for the Study of Animal Behaviour. Published by Elsevier Ltd. All rights reserved.

In-situ impedance spectroscopy of layer-by-layer self-assembly of polyelectrolytes

In-situ impedance spectroscopy of layer-by-layer self-assembly of weak polyelectrolytes is presented. Interdigitated capacitors with active area of 1×1 mm2 and electrode spacing of 5 μm are fabricated and used for this purpose. Measurement results indicate that the impedance decreases with increase in number of polyelectrolyte layers. About 2.5% of relative change in magnitude of impedance at 104.7 KHz is seen for four bi-layers of Poly(Allylamine Hydrochloride) (PAH)/Poly(Acrylic acid) (PAA). An electrical equivalent for polyelectrolyte binding is obtained.

Better QOS with W/T SPR codes for the transmission of multimedia signals in Optical CDMA networks

In this paper optical code-division multiple-access (O-CDMA) packet network is considered, which offers inherent security in the access networks. The application of O-CDMA to multimedia transmission (voice, data, and video) is investigated. The simultaneous transmission of various services is achieved by assigning to each user unique multiple code signatures. Thus, by applying a parallel mapping technique, we achieve multi-rate services. A random access protocol is proposed, here, where all distinct codes are used, for packet transmission. The codes, Optical Orthogonal Code (OOC), or 1D codes and Wavelength/Time Single-Pulse-per-Row (W/T SPR), or 2D codes, are analyzed. These 1D and 2D codes with varied weight are used to differentiate the Quality of Service (QoS). The theoretical bit error probability corresponding to the quality of each service is established using 1D and 2D codes in the receiver noiseless case and compared. The results show that, using 2D codes QoS in multimedia transmission is better than using 1D codes.

Experimental evidence for `carbon bonding' in the solid state from charge density analysis

The validity of the newly proposed `carbon bonding', an interaction where a carbon atom acts as an electrophilic site towards a variety of nucleophiles, has been investigated in the solid state. X-ray charge density analysis provides experimental evidence for this hitherto unexplored interaction and unravels its nature and strength.

Vertical uplift resistance of two closely spaced horizontal strip anchors embedded in cohesive-frictional weightless medium

The vertical uplift resistance of two closely spaced horizontal strip plate anchors has been investigated by using lower and upper bound theorems of the limit analysis in combination with finite elements and linear optimization. The interference effect on uplift resistance of the two anchors is evaluated in terms of a nondimensional efficiency factor (eta(c)). The variation of eta(c) with changes in the clear spacing (S) between the two anchors has been established for different combinations of embedment ratio (H/B) and angle of internal friction of the soil (phi). An interference of the anchors leads to a continuous reduction in uplift resistance with a decrease in spacing between the anchors. The uplift resistance becomes a minimum when the two anchors are placed next to each other without any gap. The critical spacing (S-cr) between the two anchors required to eliminate the interference effect increases with an increase in the values of both H/B and phi. The value of S-cr was found to lie approximately in the range 0.65B-1.5B with H/B = 1 and 11B-14B with H/B = 7 for phi varying from 0 degrees to 30 degrees.

Structural Insights into Proton Conduction in Gallic Acid-Isoniazid Cocrystals

Hydrated cocrystal of gallic acid-isoniazid displays a single crystal-to-single crystal transformation upon dehydration, resulting in a difference of three orders of magnitude in proton conduction. The conduction pathway is shown to follow the Grotthus mechanism, supported by theoretical (DFT) calculations.

Azide/thiocyanate incorporated cobalt(III)-Schiff base complexes: Characterizations and catalytic activity in aerobic epoxidation of olefins

Reaction of cobalt(II) perchlorate hexahydrate with a potentially tetradentate Schiff base ligand, HL (2-methoxy-6-(2-diethylaminoethylimino)methyl]phenol) in presence of sodium azide and sodium thiocyanate yields two complexes Co( L)( HL)(N-3)]center dot ClO4 ( 1) and Co( L)( HL)(NCS)] center dot ClO4 ( 2); both being characterized by different physicochemical methods. Crystal structure of 1 was determined by single crystal X-ray diffraction while that of 2 was reported earlier. In 1, the central cobalt(III) adopts slightly distorted octahedral geometry with same donor set to that of 2. Catalytic efficacy of the complexes towards epoxidation of different alkenes under aerobic condition were investigated in homogeneous medium which reveals that 1 is better catalyst than 2 with respect to alkene oxidation, reflected from the turn over frequencies (TOF) measured at an optimum temperature of 60 degrees C in acetonitrile. (C) 2014 Published by Elsevier B.V.

Symbiosis in Solid State Interconversion and Synthon Modularity in Hydroxybenzoic Acid-Hexamine Adducts

Systematic cocrystallization of hydroxybenzoic acids with hexamine using liquid-assisted grinding shows facile solid state interconversion among different stoichiometric variants. The reversible interconversion caused by varying both the acid and base components in tandem is shown to be a consequence of hydrogen-bonded synthon modularity present in all representative crystal structures. Among a total of 11 complexes, three are salts and eight are cocrystals. The insulated synthons appear as conserved tetrameric motifs in the structures, and the mechanism of interconversion is closely monitored by the synthon modularity. The interconversion is consistent with the theoretically computed stabilization energies of all the tetramers found in this series of cocrystals based on atoms in molecule calculations.

Pressure-induced semiconducting to metallic transition in multilayered molybdenum disulphide

Molybdenum disulphide is a layered transition metal dichalcogenide that has recently raised considerable interest due to its unique semiconducting and opto-electronic properties. Although several theoretical studies have suggested an electronic phase transition in molybdenum disulphide, there has been a lack of experimental evidence. Here we report comprehensive studies on the pressure-dependent electronic, vibrational, optical and structural properties of multilayered molybdenum disulphide up to 35 GPa. Our experimental results reveal a structural lattice distortion followed by an electronic transition from a semiconducting to metallic state at similar to 19 GPa, which is confirmed by ab initio calculations. The metallization arises from the overlap of the valance and conduction bands owing to sulphur-sulphur interactions as the interlayer spacing reduces. The electronic transition affords modulation of the opto-electronic gain in molybdenum disulphide. This pressure-tuned behaviour can enable the development of novel devices with multiple phenomena involving the strong coupling of the mechanical, electrical and optical properties of layered nanomaterials.

Cationic gemini lipids containing polyoxyethylene spacers as improved transfecting agents of plasmid DNA in cancer cells

Lipoplex nano-aggregates have been analyzed through biophysical characterization (electrostatics, structure, size and morphology), and biological studies (transfection efficiency and cell viability) in five cancer cell lines. Lipoplexes were prepared from pEGFP-C3 plasmid DNA (pDNA) and mixed liposomes, constituted by a zwitterionic lipid (DOPE) and a gemini cationic lipid (GCL) synthesized in this work, bis(hexadecyl dimethyl ammonium) oxyethylene], referred to as (C16Am)(2)(C2O)(n), (where n is the oxyethylene spacer length, n = 1, 2 or 3, between the ammonium heads). Cryo-TEM micrographs show nano-aggregates with two multilamellar structures, a cluster-type (at low-to-medium GCL composition) and a fingerprint-type that coexists with the cluster-type at medium GCL composition and appears alone at high GCL composition. SAXS diffractograms show that these lipoplexes present three lamellar structures, two of them coexisting at low and high GCL composition. The optimized transfection efficiency (TE) of pDNA was higher for lipoplexes containing GCLs with a longer (n = 3) or shorter (n = 1) polyoxyethylene spacer, at high GCL composition (alpha - 0.7) with low charge ratio (rho(eff) 2). In the all cancer cell lines studied, the TE of the optimized formulations was much better than those of both lipofectamine 2000 and lipoplexes with GCLs of the bis(hexadecyl dimethyl ammonium) alkane series recently reported. Probably, (a) the coexistence of two lamellar structures at high GCL composition synergizes the TE of these lipid vectors, (b) the orientation of the polyoxyethylene region in (C16Am)(2)(C2O)(3)/DOPE may occur in such a way that the spacing between two cationic heads becomes smaller than that in (C16Am)(2)(C2O)(2)/DOPE which is poor in terms of TE, and (c) the synergistic interactions between serum proteins and (C16Am)(2)(C2O)(n)/DOPE-pDNA lipoplexes containing a polyoxyethylene spacer improve TE, especially at high GCL content. Lipoplexes studied here show very low levels of toxicity, which confirm them as improved vectors of pDNA in gene therapy.

Tautomeric Preference and Conformation Locking in Fenobam, Thiofenobam, and Their Analogues: The Decisive Role of Hydrogen Bond Hierarchy

The crystal and molecular structures of the potential antidepressant drug fenobam and its derivatives are examined in terms of the preferred form among the two possible tautomeric structures. In this study, chemical derivatization has been utilized as a means to ``experimentally simulate'' the tautomeric preference and conformational variability in fenobam. Eight new derivatives of fenobam have been synthesized, and structural features have been characterized by single-crystal X-ray diffraction and NMR spectroscopy. The specific tautomeric preference found in all of these compounds and their known crystal forms have been construed in terms of the stabilizing intramolecular N-H center dot center dot center dot O and N-H center dot center dot center dot S hydrogen bonding. The hierarchy of intramolecular hydrogen bonds evidenced as the preference of the C-H center dot center dot center dot O hydrogen bond over C-H center dot center dot center dot N and that of the C-H center dot center dot center dot N hydrogen bond over C-H center dot center dot center dot S explains the two distinct conformations adopted by fenobam and thiofenobam derivatives. The relative energy values of different molecular conformations have been calculated and compared.