Thermo-physical and structural studies of sodium zinc borovanadate glasses in the region of high concentration of modifier oxides

This paper reports investigation of Na2O and ZnO modified borovanadate glasses in the highly modified regime of compositions. These glasses have been prepared by microwave route. Ultraviolet (UV) and visible, infrared (IR), Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) and Electron Paramagnetic Resonance (EPR) spectroscopies have been used to characterize the speciation in the glasses. Together with the variation of properties such as molar volume and glass transition temperatures, spectroscopic data indicate that at high levels of modification, ZnO tends to behave like network former. It is proposed that the observed variation of all the properties can be reasonably well understood with a structural model. The model considers that the modification and speciation in glasses are strongly determined by the hierarchy of group electronegativities. Further, it is proposed that the width of the transitions of glasses obtained under same condition reflects the fragility of the glasses. An empirical expression has been suggested to quantify fragility on the basis of width of the transition regions. (C) 2012 Elsevier Ltd. All rights reserved.

Surface Modified CaTiO3 Loaded in Polyaniline by Sodium Dodecyl Benzene Sulphonic Acid for Humidity Sensor

Polyaniline-CaTiO3 nanocomposites with their various weight percentages were prepared by chemical oxidative in situ polymerization technique. The prepared composites were characterized by Fourier transform infrared spectroscopy, scanning electronic microscope, and X-ray diffraction. The temperature-dependent dc conductivity of polyaniline-CaTiO3 nanocomposite was studied within the range of 40-200 degrees C and found that 50 wt% shows high conductivity compared to other composites. Humidity sensor properties of polyaniline-CaTiO3 nanocomposite show better sensing properties and exhibit good linearity in sensing response curve, which discuss the implications of distortions and nonstoichiometry on their physical properties. Among all composites, 50 wt% of polyaniline-CaTiO3 nanocomposites show high sensitivity up to similar to 90% and their response-recovery times are 500 and 453 s, respectively.

Accommodating Unwelcome Guests in Inorganic Layered Hosts: Inclusion of Chloranil in a Layered Double Hydroxide

The host-guest chemistry of most inorganic layered solids is limited to ion-exchange reactions. The guest species are either cations or anions to compensate for the charge deficit, either positive or negative, of the inorganic layers. Here, we outline a strategy to include neutral molecules like ortho- and para-chloranil, that are known to be good acceptors in donor-acceptor or charge-transfer complexes, within the galleries of a layered solid. We have succeeded in including neutral ortho- and para-chloranil molecules within the galleries of an Mg-Al layered double hydroxide (LDH) by using charge-transfer interactions with preintercalated p-aminobenzoate ions as the driving force. The p-aminobenzoate ions are introduced in the Mg-Al LDH via ion exchange. The intercalated LDH can adsorb ortho- and para-chloranil from chloroform solutions by forming charge-transfer complexes with the p-aminobenzoate anions present in the galleries. We use X-ray diffraction, spectroscopy, and molecular dynamics simulations to establish the nature of interactions and arrangement of the charge-transfer complex within the galleries of the layered double hydroxide.

Distinct Disulfide Isomers of mu-Conotoxins KIIIA and KIIIB Block Voltage-Gated Sodium Channels

In the preparation of synthetic conotoxins containing multiple disulfide bonds, oxidative folding can produce numerous permutations of disulfide bond connectivities. Establishing the native disulfide connectivities thus presents a significant challenge when the venom-derived peptide is not available, as is increasingly the case when conotoxins are identified from cDNA sequences. Here, we investigate the disulfide connectivity of mu-conotoxin KIIIA, which was predicted originally to have a C1-C9,C2-C15,C4-C16] disulfide pattern based on homology with closely related mu-conotoxins. The two major isomers of synthetic mu-KIIIA formed during oxidative folding were purified and their disulfide connectivities mapped by direct mass spectrometric collision-induced dissociation fragmentation of the disulfide-bonded polypeptides. Our results show that the major oxidative folding product adopts a C1-C15,C2-C9,C4-C16] disulfide connectivity, while the minor product adopts a C1-C16,C2-C9,C4-C15] connectivity. Both of these peptides were potent blockers of Na(v)1.2 (K-d values of 5 and 230 nM, respectively). The solution structure for mu-KIIIA based on nuclear magnetic resonance data was recalculated with the C1-C15,C2-C9,C4-C16] disulfide pattern; its structure was very similar to the mu-KIIIA structure calculated with the incorrect C1-C9,C2-C15,C4-C16] disulfide pattern, with an alpha-helix spanning residues 7-12. In addition, the major folding isomers of mu-KIIIB, an N-terminally extended isoform of mu-KIIIA, identified from its cDNA sequence, were isolated. These folding products had the same disulfide connectivities as mu-KIIIA, and both blocked Na(v)1.2 (K-d values of 470 and 26 nM, respectively). Our results establish that the preferred disulfide pattern of synthetic mu-KIIIA and mu-KIIIB folded in vitro is 1-5/2-4/3-6 but that other disulfide isomers are also potent sodium channel blockers. These findings raise questions about the disulfide pattern(s) of mu-KIIIA in the venom of Conus kinoshitai; indeed, the presence of multiple disulfide isomers in the venom could provide a means of further expanding the snail's repertoire of active peptides.

Silicon surface texturing with a combination of potassium hydroxide and tetra-methyl ammonium hydroxide etching

A two step silicon surface texturing, consisting of potassium hydroxide (KOH) etching followed by tetra-methyl ammonium hydroxide etching is presented. This combined texturing results in 13.8% reflectivity at 600 nm compared to 16.1% reflectivity for KOH etching due to the modification of microstructure of etched pyramids. This combined etching also results in significantly lower flat-band voltage (V-FB) (-0.19V compared to -1.3 V) and interface trap density (D-it) (2.13 x 10(12) cm(-2) eV(-1) compared to 3.2 x 10(12) cm(-2) eV(-1)). (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4776733]

Fabrication and characterization of micro-arc oxidized fluoride containing titania films on Cp Ti

The present study is focussed at establishing an appropriate electrolyte system for developing electrochemically stable and fluorine (F) containing titania (F-TiO2) films on Cp Ti by micro-arc oxidation (MAO) technique. To fabricate the F-TiO2 films on Cp Ti, different electrolyte solutions of chosen concentrations of tri-sodium orthophosphate (TSOP, Na3PO4 center dot I2H2O), potassium hydroxide (KOH) and various F-containing compounds such as ammonium fluoride (NH4F), potassium fluoride (KF), sodium fluoride (NaF) and potassium fluorotitanate (K2TiF6) are employed. The structural and morphological characteristics, thickness and elemental composition of the developed films have been assessed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) techniques. The in-vitro electrochemical corrosion behavior of the films was studied under Kokubo simulated body fluid (SBF) environment by potentiodynamic polarization, long term potential measurement and electrochemical impedance spectroscopy (EIS) methods. The XRD and SEM-EDS results show that the rutile content in the films vary in the range of 15-37 wt% and the F and P contents in the films is found to be in the range of 2-3 at% and 2.9-4.7 at% respectively, suggesting that the anatase to rutile phase transformation and the incorporation of F and P into the films are significantly controlled by the respective electrolyte solution. The SEM elemental mapping results show that the electrolyte borne F and P elements are incorporated and distributed uniformly in all the films. Among all the films under study, the film developed with 5 g TSOP+2 g KOH+3 g K2TiF6 electrolyte system exhibits considerably improved in-vitro corrosion resistance and therefore best suited for biomedical applications. (C) 2012 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

A Finite Element Method Based Approach for Evaluating the Sensitivity of Faraday-Type Electromagnetic Flow Meter for Liquid Sodium Flow

Faraday-type electromagnetic flow meters are employed for measuring the flow rate of liquid sodium in fast breeder reactors. The calibration of such flow meters, owing to the required elaborative arrangements is rather difficult. On the other hand, theoretical approach requires solution of two coupled electromagnetic partial differential equation with profile of the flow and applied magnetic field as the inputs. This is also quite involved due to the 3D nature of the problem. Alternatively, Galerkin finite element method based numerical solution is suggested in the literature as an attractive option for the required calibration. Based on the same, a computer code in Matlab platform has been developed in this work with both 20 and 27 node brick elements. The boundary conditions are correctly defined and several intermediate validation exercises are carried out. Finally it is shown that the sensitivities predicted by the code for flow meters of four different dimensions agrees well with the results given by analytical expression, thereby providing strong validation. Sensitivity for higher flow rates, for which analytical approach does not exist, is shown to decrease with increase in flow velocity.

Comprehensive investigations on DNa center dot center dot center dot A (D = H/F) complexes show why `sodium bonding' is not commonly observed

A comprehensive study of D-Na center dot center dot center dot A (D = H/F) complexes has been done using advanced ab initio and atoms in molecule (AIM) theoretical analyses. The correlation between electron density at bond critical point and binding energy gives a distinguishing feature for hydrogen bonding, different from the `electrostatic complexes' formed by LiD and NaD. Moreover, the LiD/NaD dimers have both linear and anti-parallel minima, as expected for electrostatic dipole-dipole interactions. The HF dimer has a quasi-linear minimum and the anti-parallel structure is a saddle point. Clearly, characterizing hydrogen bonding as `nothing but electrostatic interaction between two dipoles' is grossly in error.

Charge-transfer-driven inclusion of neutral TCNQ molecules in the galleries of a layered double hydroxide: an experimental and computational study

The layered double hydroxides (LDH) or anionic clays are an important class of ion-exchange materials. They consist of positively charged brucite-like inorganic sheets with charge-compensating exchangeable anions in the interlamellar space. Here we show how neutral TCNQ (7,7,8,8-tetracyanoquinodimethane) molecules can be included within the galleries of an LDH. To do so, we exploit the fact that TCNQ is a good electron acceptor that forms donor acceptor complexes with a variety of donors. The electron donor aniline was intercalated into a Mg-Al LDH as p-aminobenzoate (AB) ions by a conventional ion-exchange reaction. We show here that neutral TCNQ molecules may be driven into the galleries of the layered solid by charge-transfer complex formation with the intercalated p-aminobenzoate anions. We use diffraction and spectroscopic measurements in combination with molecular dynamics simulations and quantum chemical calculations to establish the nature of interactions and arrangement of the charge-transfer complex within the galleries of the layered double hydroxide. Electrostatic interactions between the TCNQ molecules and the anchored AB ions, subsequent to charge transfer, are the driving force for the inclusion of TCNQ molecules in the galleries of the LDH.

Mammalian neuronal sodium channel Blocker mu-conotoxin BuIIIB has a structured N-terminus that influences potency

Among the mu-conotoxins that block vertebrate voltage-gated sodium channels (VGSCs), some have been shown to be potent analgesics following systemic administration in mice. We have determined the solution structure of a new representative of this family, mu-BuIIIB, and established its disulfide connectivities by direct mass spectrometric collision induced dissociation fragmentation of the peptide with disulfides intact The major oxidative folding product adopts a 1-4/2-5/3-6 pattern with the following disulfide bridges: Cys5-Cys17, Cys6-Cys23, and Cys13-Cys24. The solution structure reveals that the unique N-terminal extension in mu-BuIIIB, which is also present in mu-BuIIIA and mu-BuIIIC but absent in other mu-conotoxins, forms part of a short a-helix encompassing Glu3 to Asn8. This helix is packed against the rest of the toxin and stabilized by the Cys5-Cys17 and Cys6-Cys23 disulfide bonds. As such, the side chain of Val1 is located close to the aromatic rings of Trp16 and His20, which are located on the canonical helix that displays several residues found to be essential for VGSC blockade in related mu-conotoxins. Mutations of residues 2 and 3 in the N-terminal extension enhanced the potency of mu-BuIIIB for Na(v)1.3. One analogue, D-Ala2]BuIIIB, showed a 40-fold increase, making it the most potent peptide blocker of this channel characterized to date and thus a useful new tool with which to characterize this channel. On the basis of previous results for related mu-conotoxins, the dramatic effects of mutations at the N-terminus were unanticipated and suggest that further gains in potency might be achieved by additional modifications of this region.

Crystal growth and nonlinear optical properties of sodium D-isoascorbate monohydrate

Optical quality single crystals of sodium D-isoascorbate monohydrate were grown by a slow cooling technique. The crystal possesses a bulky prismatic morphology. Thermal analyses indicate that the crystals are stable up to 125 degrees C. The optical transmission window ranges from 307 nm to 1450 nm. The principal refractive indices have been measured employing Brewster's angle method. The crystallographic and the principal dielectric axes coincide with each other such that a lies along Z, b along X and c along Y. The optic axis is oriented 58 degrees (at 532 nm) to the crystallographic a axis in the XZ plane and the crystal is negative biaxial. Type 1 and type 2 phase matching curves are generated and experimentally verified. No polarization dependence of the light absorption was observed confirming the validity of Kleinman's symmetry conjecture, leading to a single nonvanishing nonlinear tensor component. According to Hobden's classification the crystal belongs to class 3. The crystal also exhibits second order noncollinear conic sections. The single shot and multiple shot surface laser damage thresholds are determined to be 32.7 GW cm(-2) and 6.5 GW cm(-2) respectively for 1064 nm radiation.

A naturally occurring amino acid substitution in the voltage-dependent sodium channel selectivity filter affects channel gating

The pore of sodium channels contains a selectivity filter made of 4 amino acids, D/E/K/A. In voltage sensitive sodium channel (Nav) channels from jellyfish to human the fourth amino acid is Ala. This Ala, when mutated to Asp, promotes slow inactivation. In some Nav channels of pufferfishes, the Ala is replaced with Gly. We studied the biophysical properties of an Ala-to-Gly substitution (A1529G) in rat Nav1.4 channel expressed in Xenopus oocytes alone or with a beta 1 subunit. The Ala-to-Gly substitution does not affect monovalent cation selectivity and positively shifts the voltage-dependent inactivation curve, although co-expression with a beta 1 subunit eliminates the difference between A1529G and WT. There is almost no difference in channel fast inactivation, but the beta 1 subunit accelerates WT current inactivation significantly more than it does the A1529G channels. The Ala-to-Gly substitution mainly influences the rate of recovery from slow inactivation. Again, the beta 1 subunit is less effective on speeding recovery of A1529G than the WT. We searched Nav channels in numerous databases and noted at least four other independent Ala-to-Gly substitutions in Nav channels in teleost fishes. Thus, the Ala-to-Gly substitution occurs more frequently than previously realized, possibly under selection for alterations of channel gating.

Preparation of Self Assembled Sodium Oleate Monolayer on Mild Steel and Its Corrosion Inhibition Behavior in Saline water

A self assembled monolayer (SAM) of sodium oleate was generated on mild steel by the dip coating method. Formation of the SAM on mild steel was examined using Infrared Reflection Absorption Spectroscopy (IRRAS) and contact angle measurements. The chemical and anticorrosive properties of the SAM were analyzed using different techniques. IRRAS and water contact angle data revealed the crystallinity and chemical stability of the SAM modified mild steel. The electrochemical measurements showed that the mild steel with the sodium oleate derived SAM exhibited better corrosion resistance in saline water. The effect of temperature and pH on the SAM formation and its anti corrosion ability was explored.

Biodegradation of sodium isopropyl xanthate by Paenibacillus polymyxa and Pseudomonas putida

Biodegradation of sodium isopropyl xanthate using two types of bacterial strains, Paenibacillus polymyxa and Pseudomonas putida, is demonstrated. At concentrations higher than 50 mg/L, the presence of xanthate in the growth medium resulted in bacterial toxicity, retarding growth kinetics. Adaptation through serial subculturing in the presence of higher xanthate concentrations resulted in the development of xanthate-tolerant bacterial strains. Stress proteins secreted by bacterial cells grown in the presence of xanthate were isolated. Bacterial cells could utilize xanthate as a growth substrate, degrading xanthate species in the process. Acidic metabolic products generated by bacterial metabolism promoted efficient xanthate decomposition. Probable mechanisms for the biodegradation of isopropyl xanthate are illustrated.

Correlations between mechanical and photoluminescence properties in Eu doped sodium bismuth titanate

Nanoindentation technique is utilized to examine mechanical property variation in Eu doped Na0.5Bi0.5 TiO3 (NBT). Doping levels of Eu in NBT is systematically varied. Dilute doping results in a linear reduction in both modulus and hardness. At higher concentrations, a recovery of the mechanical properties (to undoped NBT values) is observed. These experimental trends mirror variations in the optical emission intensities with Eu concentration. Observed trends are rationalized on the basis of a model, which hypothesizes phase segregation beyond a critical Eu doping level. Such segregation leads to the formation of pure NBT, nano-Eu saturated NBT, and nano-mixed Eu oxides in the microstructure. Pure NBT is optically inactive, while saturated Eu:NBT is a much better emitter when compared to europium oxide. Hence beyond the critical concentration, luminescence signal comes primarily from the saturated Eu:NBT phase. The model presented is supported by nanoindentation, and spectroscopic results. (C) 2013 Elsevier Ltd. All rights reserved.