Thermally Controlled Cyclic Insertion/Ejection of Dopant Ions and Reversible Zinc Blende/Wurtzite Phase Changes in ZnS Nanostructures

We report a reversible phase transformation of platelet-shaped ZnS nanostructures between wurtzite (WZ) and zinc blende (ZB) phases by reversible insertion/ ejection of dopant Mn(II) ions induced by a thermocyclic process. In a reaction flask loaded with WZ ZnS platelets and Mn molecular precursors, during heating Mn ions are incorporated and change the phase of the host nanostructures to ZB; during cooling Mn ions are spontaneously ejected, returning the host nanoplatelets to the original WZ phase. These reversible changes are monitored for several cycles with PL, EPR, XRD, and HRTEM. Interestingly, the (0001) WZ platelets transform to (110) ZB following a nucleation and growth process triggered by a local increase/depletion of the Mn2+ concentration in the nanocrystals.

Thermally Controlled Cyclic Insertion/Ejection of Dopant Ions and Reversible Zinc Blende/Wurtzite Phase Changes in ZnS Nanostructures

We report a reversible phase transformation of platelet-shaped ZnS nanostructures between wurtzite (WZ) and zinc blende (ZB) phases by reversible insertion/ ejection of dopant Mn(II) ions induced by a thermocyclic process. In a reaction flask loaded with WZ ZnS platelets and Mn molecular precursors, during heating Mn ions are incorporated and change the phase of the host nanostructures to ZB; during cooling Mn ions are spontaneously ejected, returning the host nanoplatelets to the original WZ phase. These reversible changes are monitored for several cycles with PL, EPR, XRD, and HRTEM. Interestingly, the (0001) WZ platelets transform to (110) ZB following a nucleation and growth process triggered by a local increase/depletion of the Mn2+ concentration in the nanocrystals.

A novel zinc bis(thiosemicarbazone) complex for live cell imaging

Fluorescent zinc complexes have recently attracted a lot of interest owing to their vast applications in cellular imaging. We report the synthesis as well as physical, chemical and biological studies of a novel zinc glyoxalbis(4-methyl-4-phenyl-3-thiosemicarbazone), Zn (GTSC)](3), complex. As compared with the well-studied zinc biacetylbis(4-methyl-3-thiosemicarbazone), Zn(ATSM), complex, which was used as a reference, Zn(GTSC)](3) had 2.5-fold higher fluorescence. When cellular fluorescence was measured using flow cytometry, we observed that Zn(GTSC)](3) had 3.4-fold to 12-fold higher fluorescence than Zn(ATSM) in various cell lines (n = 9) of different tissue origin. Confocal fluorescence microscopy results showed that Zn(GTSC)](3) appeared to have a nuclear localization within 30 mm of addition to MCF7 cells. Moreover, Zn(GTSC)](3) showed minimal cytotoxicity compared with Zn(ATSM), suggesting that Zn(GTSC)](3) may be less deleterious to cells when used as an imaging agent. Our data suggest that the novel Zn(GTSC)](3) complex can potentially serve as a biocompatible fluorescent imaging agent for live cells.

DNA Condensation by the Rat Spermatidal Protein TP2 Shows GC-Rich Sequence Preference and Is Zinc Dependent

Transition protein-2 (TP2), isolated from rat testes, was recently shown to be a zinc metalloprotein. We have now carried out a detailed analysis of the DNA condensing properties of TP2 with various polynucleotides using circular dichroism spectroscopy. The condensation of the alternating copolymers by TP2 (incubated with 10 mu M ZnSO4), namely, poly(dG-dC). poly(dG-dC) and poly(dA-dT). poly(dA-dT), was severalfold higher than condensation of either of the homoduplexes poly(dG). poly-(dC) and poly(dA). poly(dT) or rat oligonucleosomal DNA. Between the two alternating copolymers, poly(dG-dC). poly(dG-dC) was condensed 3.2-fold more effectively than poly(dA-dT). poly(dA-dT). Preincubation of TP2 with 5 mM EDTA significantly reduced its DNA-condensing property. Interestingly, condensation of the alternating copolymer poly(dI-dC). poly(dI-dC) by TP2 was much less as compared to that of poly(dG-dC). poly(dG-dC). The V8 protease-derived N-terminal fragment (88 aa) condensed poly(dA-dT). poly(dA-dT) to a very small extent but did not have any effect on poly(dG-dC). poly-(dG-dC). The C-terminal fragment (28 aa) was able to condense poly(dA-dT) . poly(dA-dT) more effectively than poly(dG-dC). poly(dG-dC). These results suggest that TP2 in its zinc-coordinated form condenses GC-rich polynucleotides much more effectively than other types of polynucleotides. Neither the N-terminal two-thirds of TP2 which is the zinc-binding domain nor the C-terminal basic domain are as effective as intact TP2 in bringing about condensation of DNA.

Preparation and dielectric properties of zinc and cadmium doped barium tantalates, Ba3Zn1?xCdxTa2O9

Members of the Ba2Zn1-xCdxTa2O9 (0 less than or equal to x less than or equal to 1) series have been synthesized by solid state reactions at 1473K. Powder x-ray diffraction studies show a cubic perovskite cell with a similar to 4.1 Angstrom which increases with increase in x. Electron diffraction studies show the presence of hexagonal ordered perovskite structure in addition to the cubic structure seen by x-rays, the x = 0.5 composition showing more ordered crystallites. These samples show high dielectric constants with a maximum (epsilon(r) = 30 at 1 kHz) for the x = 0.5 member. The dielectric loss increases with increase in x at all the frequencies under study.

Metallo-beta-lactamase and phosphotriesterase activities of some zinc(II) complexes

Metallo-beta-lactamases (m beta l) and phosphotriesterase (PTE) are zinc(II) enzymes, which hydrolyze the beta-lactam antibiotics and toxic organophosphotriesters, respectively. In the present work, we have synthesized a few asymmetric phenolate-based ligands by sequential Mannich reaction and their corresponding zinc(II) complexes. These zinc(II) complexes were studied for their m beta l and PTE activities. It is shown that the zinc(II) complexes can hydrolyze oxacillin, the beta-lactam antibiotic, at much higher rates as compared to the hydrolysis of p-nitrophenyl diphenylphosphate (PNPDPP), the phosphotriester. Among the complexes studied, the binuclear asymmetric complex 1 having a water molecule coordinated to one of the zinc(II) ions exhibits much better mbl activity than the mononuclear complexes. However, the mononuclear zinc(II) complexes having labile chloride ions exhibit significant PTE activity, which can be ascribed to the replacement of chloride ions by hydroxide ions during hydrolysis reactions. (C) 2011 Elsevier B.V. All rights reserved.

Bis(acetylacetonato-kappa 2 O,O')(pyridine-kappa N)zinc(II)

In the title compound, Zn(C5H7O2)(2)(C5H5N)], the metal atom has square-pyramidal coordination geometry with the basal plane defined by the four O atoms of the chelating acetylacetonate ligands and with the axial position occupied by the pyridine N atom. The crystal packing is characterized by a C-H...O hydrogen-bonded ribbon structure approximately parallel to 10 ].

The effect of aluminosilicate on the delayed onset of upturn voltages of zinc oxide varistor ceramics

The effect of aluminosilicate (Al2SiO5) on the upturn characteristics of ZnO varistor ceramics has been investigated. Addition of Al2SiO5 shifts the point of upturn above 10(4) A cm(-2). The extended nonlinearity in the high current density region is better correlatable to the presence of higher density of trap stales and changing pattern of trap depths at the grain boundary interface as much as the grain interior conductivity. Microstructure studies show the formation and involvement of a liquid phase during sintering. The secondary phases, predominantly are antimony spinel, Zn7Sb2O12, zinc silicate, Zn2SiO4 and magnesium aluminium silicate. MgAl2Si3O10. Energy dispersive X-ray analyses (EDAX) show that Al and Si are distributed more in the grain boundaries and within the secondary phases than in the grain interiors. Capacitance-voltage analyses and dielectric dispersion studies indicate the presence of negative capacitance and associated resonance, indicative of the oscillatory charge redistribution involving increased trapping at the interface states. The admittance spectroscopy data show that the type of trap slates remains unaltered whereas the addition of Al2SiO5 increases the density of low energy traps. (C) 1997 Published by Elsevier Science S.A.

Structural, dielectric and optical properties of lithium borate-bismuth tungstate glass-ceramicsc

Glasses in the system (1 - x)Li2B4O7-xBi(2)WO(6) (0.1 less than or equal to x less than or equal to 0.35) were prepared by splat quenching technique. Powder X-ray diffraction (XRD) and differential thermal analysis (DTA) were employed to characterize the as-quenched glasses. High-resolution transmission electron microscopy (HR TEM) revealed the presence of fine, nearly spherical crystallites of Bi2WO6 varying from 1.5 to 20 nm in size, depending on x in the as-quenched glasses. The glasses (corresponding to x = 0.3) heat-treated at 723 K for 6 h gave rise to a clear crystalline phase of Bi2WO6 embedded in the Li2B4O7 glass matrix, as observed by X-ray studies. The dielectric constants of the as-quenched glasses as well as the glass-ceramics decreased with increase in frequency (40Hz-100 kHz) at 300 K, and the value obtained for the glass-ceramic (x = 0.2) is in agreement with the values predicted using Maxwell's model and the logarithmic mixture rule. The dielectric constants for both the as-quenched glass and the glass-ceramic increased with increase in temperature (300 - 873 K) and exhibited anomalies close to the onset of the crystallization temperature of the host glass matrix. The optical transmission properties:of these glass-ceramics were found to be compositional dependant. (C) 2000 Elsevier Science Ltd.

Studies on the Effect of Li2SO4 on the Structure of Lithium Borate Glasses

Thermal and spectroscopic investigations have been carried out on a number of glasses with a wide range of compositions in the pseudoternary glass system, Li2SO4-Li2O-B2O3, to understand the role of sulfate ions in modifying the borate glass structure. Both nuclear magnetic resonance (NMR) and infrared (IR) spectroscopic results indicate that four-coordinate boron atoms are retained in the glass structure to a greater extent in sulfate-containing glasses than in pure lithium borate glasses. There seems to be some evidence for the existence of sulfoborate-type units in Raman spectra in the region of 800-960 cm(-1). These conclusions are supported by the observed behavior of glass transition temperatures and molar volumes. The possibility of formation of sulfoborate-type units is discussed from bonding and thermodynamic points of view.

Synthesis of metastable, wurzite-based zinc oxide-cobalt(II) oxide solid solutions by spray pyrolysis

Aqueous solutions of acetates and nitrates of zinc and cobalt have been spray decomposed to study the production of extended solid solutions in the ZnO-CoO system. Examination of the products of a variety of synthesis conditions indicates that up to 70% CoO may be retained in the solid solution in the wurzite phase, even though a comparison of the equilibrium solubility in the phase diagram might be expected to favor the formation of a rock-salt-based solid solution.

Zinc-substituted alpha-nickel hydroxide as an electrode material for alkaline secondary cells

Double hydroxides of the formula, Ni1-xZn2x (OH)(2) (CO3)(x). nH(2)O (x = 0.1 to 0.25) having the same structure as that of alpha-nickel hydroxide have been synthesized by partial substitution of zinc for nickel. The hydroxide having the composition x = 0.25 exhibits prolonged stability in 6 M KOH. Pasted electrodes comprising this material are rechargeable with a stabilized reversible discharge capacity of 410 +/- 15 mAh g(-1) of nickel even under suboptimal conditions of electrode fabrication. This compares favorably with the capacity values achieved for beta-nickel hydroxide (221 mAh g(-1)', This work; 297 mAh g(-1), Delahaye-Vidal and Figlarz;(1) 456 mAh g(-1), theoretical). (C) 1999 The Electrochemical Society. S0013-4651(98)01-071-4. All rights reserved.

Lithium borate-strontium bismuth tantalate glass nanocomposite: a novel material for nonlinear optic and ferroelectric applications

Glass nanocomposites in the system (100 - x)Li2B4O7-xSrBi(2)Ta(2)O(9) (0 less than or equal to x less than or equal to 22.5, in molar ratio) were fabricated via a melt quenching technique followed by controlled heat-treatment. The as-quenched samples were confirmed to be glassy and amorphous by differential thermal analysis (DTA) and X-ray powder diffraction (XRD) techniques, respectively. The phase formation and crystallite size of the heat-treated samples (glass nanocomposites) were monitored by XRD and transmission electron microscopy (TEM). The relative permittivities (epsilon(tau)') of the glass nanocomposites for different compositions were found to lie in between that of the parent host glass (Li2B4O7) and strontium bismuth tantalate (SBT) ceramic in the frequency range 100 Hz-40 MHz at 300 K, whereas the dielectric loss (D) of the glass nanocomposite was less than that of both the parent phases. Among the various dielectric models employed to predict the effective relative permittivity of the glass nanocomposite, the one obtained using the Maxwell's model was in good agreement with the experimentally observed value. Impedance analysis was employed to rationalize the electrical behavior of the glasses and glass nanocomposites. The pyroelectric response of the glasses and glass nanocomposites was monitored as a function of temperature and the pyroelectric coefficient for glass and glass nanocomposite (x = 20) at 300 K were 27 muC m(-2) K-1 and 53 muC m(-2) K-1, respectively. The ferroelectric behavior of these glass nanocomposites was established by P vs. E hysteresis loop studies. The remnant polarization (P-r) of the glass nanocomposite increases with increase in SBT content. The coercive field (E-c) and P-r for the glass nanocomposite (x = 20) were 727 V cm(-1) and 0.527 muC cm(-2), respectively. The optical transmission properties of these glass nanocomposites were found to be composition dependent. The refractive index (n = 1.722), optical polarizability (am = 1.266 6 10 23 cm 3) and third-order nonlinear optical susceptibility (x(3) = 3.046 6 10(-21) cm(3)) of the glass nanocomposite (x = 15) were larger than those of the as-quenched glass. Second harmonic generation (SHG) was observed in transparent glass nanocomposites and the d(eff) for the glass nanocomposite (x = 20) was found to be 0.373 pm V-1.

Pyroelectric, ferroelectric and optical properties of glass nanocomposite: Lithium borate-bismuth tungstate

Glass nanocomposites in the system (1-x)Li2B4O7-xBi(2)WO(6) (0 less than or equal to x less than or equal to 0.35, in molar ratio) were fabricated by splat quenching technique. The as-quenched samples were X-ray amorphous. Differential Thermal Analyses (DTA) confirmed their glassy nature. The composites on heat-treatment at 720 K yielded monophasic crystalline bismuth tungstate in lithium borate glass matrix. The average size and the spherical nature of the dispersed crystallites were assessed via High Resolution Transmission Electron Microscopy (HRTEM). The dielectric constants (epsilon(r)) of both the as-quenched and post heat-treated composites were found to increase with increase in x (bismuth tungstate content) at all the frequencies (100 Hz-40 MHz) in the temperature range 300 K-870 K. While the dielectric loss (D) decreased with increasing x. The pyroelectric coefficients of the as-quenched (consisting 20 nm sized crystallites) and 720 K heat-treated sample (x = 0.3) were determined as a function of temperature (300 K-873 K) and the values obtained at room temperature were 20 and 60 muC/m(2) K respectively. The as-quenched and heat-treated (720 K) glass nanocomposites exhibited ferroelectric (P Vs E) hysteresis loops. The remnant polarization and coercive field of the heat-treated glass nanocomposite at 300 K were respectively 2.597 muC/cm(2) and 543 V/cm. These glass nanocomposites were birefringent in the 300-873 K temperature range.