Synthetic, spectroscopic and structural studies on uranium and thorium complexes of diphosphazane dioxides

Co-ordination complexes of the diphosphazane dioxides Ph(2)P(O)N(Pr-i)P(O)Ph(2) L(1). Ph(2)P(O)N(Pr-i)P(O)Ph(OC(6)H(4)Me-4) L(2) and Ph(2)P(O)N(Pr-i)P(O)(O2C12H8) L(3) with UO22+ or Th4+ ions have been synthesised and characterised by IR and NMR spectroscopy. The structures of [UO2(NO3)(2)L(1)] and [Th(NO3)(2)L(3)(1)][Th(NO3)(6)] are established by X-ray crystallography. In the former, the uranyl ion is bonded to two bidentate nitrate groups and the two phosphoryl groups of the ligand L(1); the co-ordination polyhedron around the metal is a hexagonal bipyramid. The cationic moiety in the thorium complex contains three bidentate diphosphazane dioxide ligands and two bidentate nitrate groups around the ten-co-ordinated metal.

Limiting ionic conductance of symmetrical, rigid ions in aqueous solutions: Temperature dependence and solvent isotope effects

Limiting ionic conductance (Lambda(0)) of rigid symmetrical unipositive ions in aqueous solution shows a strong temperature dependence. For example, Lambda(0) more than doubles when the temperature is increased from 283 to 318 K. A marked variation also occurs when the solvent is changed from ordinary water (H2O) to heavy water (D2O). In addition, Lambda(0) shows a nonmonotonic size dependence with a skewed maximum near Cs+. Although these important results have been known for a long time, no satisfactory theoretical explanation exists for these results. In this article we present a simple molecular theory which provides a nearly quantitative explanation in terms of microscopic structure and dynamics of the solvent. A notable feature of this theory is that it does not invoke any nonquantifiable models involving solvent-berg or clatherates. We find the strong temperature dependence of Lambda(0) to arise from a rather large number of microscopic factors, each providing a small but nontrivial contribution, but all acting surprisingly in the same direction. This work, we believe, provides, for the first time, a satisfactory explanation of both the anomalous size and temperature dependencies of Lambda(0) of unipositive ions in molecular terms. The marked change in Lambda(0) as the solvent is changed from H2O to D2O is found to arise partly from a change in the dielectric relaxation and partly from a change in the effective interaction of the ion with the solvent.

Antiferroelectric lead zirconate thin films by pulsed laser ablation

Lead Zirconate (PbZrO3) thin films were deposited by pulsed laser ablation method. Pseudocubic (110) oriented in-situ films were grown at low pressure. The field enforced anti-ferroelectric (AFE) to ferroelectric (FE) phase transformation behaviour was investigated by means of a modified Sawyer Tower circuit as well as capacitance versus applied voltage measurements. The maximum polarisation obtained was 36 mu C cm(-2) and the critical field to induce ferroelectric state and to reverse the antiferroelectric slates were 65 and 90 kV cm(-1) respectively. The dielectric properties were investigated as a function of frequency and temperature. The dielectric constant of the AFE lead zirconate thin him was 190 at 100 kHz which is more than the bulk ceramic value (120) with a dissipation factor of less than 0.07. The polarisation switching kinetics of the antiferroelectric PbZrO3 thin films showed that the switching time to be around 275 ns between antipolar state to polar states. (C) 1999 Elsevier Science S.A. All rights reserved.

Size effect on the superconducting transition of embedded lead particles in an Al-Cu-V amorphous matrix

We have synthesized specimens of nanometric lead dispersion in a glassy Al-Cu-V matrix by rapid solidification of the corresponding melt. The microstructure has been designed to avoid superconducting percolation due to coupling of the neighboring particles by the proximity effect. Using these specimens, we have determined quantitatively the effect of size of the ultrafine lead particles on the superconducting transition. (C) 1999 American Institute of Physics. [S0003-6951(99)02037-9].

ac transport studies of La-modified antiferroelectric lead zirconate thin films

In recent times antiferroelectric thin-film material compositions have been identified as one of the most significant thin films for development of devices such as high charge storage, charge couplers/decouplers, and high strain microelectromechanical systems. Thus, understanding the dielectric and electrical properties under an ac signal drive in these antiferroelectric thin-film compositions, such as lead zirconate thin films, and the effect of donor doping on them is very necessary. For this purpose, thin films of antiferroelectric lead zirconate and La-modified lead zirconate thin films with mole % concentrations of 0, 3, 5, and 9 have been deposited by pulsed excimer laser ablation. The dielectric and hysteresis properties have confirmed that with a gradual increase of the La content, the room-temperature antiferroelectric lead zirconate thin films can be modified into ferroelectric and paraelectric phases. ac electrical studies revealed that the polaronic related hopping conduction is responsible for the charge transport phenomenon in these films. With a La content of less than or equal to3 mole % in pure lead zirconate, the conductivity of the films has been reduced and followed by an increase of its conductivity for a greater than or equal to3% addition of La to lead zirconate thin films. The polaronic activation energies are also found to follow a similar trend as that of the conductivity.

Reversible and irreversible switching processes in pure and lanthanum modified lead zirconate thin films

The mechanism of field induced phase switching in antiferroelectric lead zirconate and La-modified lead zirconate thin films has been analysed in terms of reversible and irreversible switching process under weak fields as a function of donor concentration. Extension of Rayleigh law of ferromagnetic materials to the present antiferroelectric and modified antiferroelectric compositions have clearly showed that origin of small signal dielectric permittivity is due to reversible domain wall motion. Rayleigh's constant, a measure of irreversible switching process, exhibited a slight increase with lower La3+ concentrations and followed by a gradual fall for higher concentration. This clearly illustrates that donor addition to antiferroelectric thin films controls the domain switching even under weak fields. (C) 2002 Elsevier Science B.V. All rights reserved.

Study of embedded lead-tin nanoparticles in aluminum matrix

Nanoembedded lead-tin alloys in aluminum matrix were synthesized by rapid solidification processing. These melt-spun aluminum alloys were then investigated using XRD, EDX and TEM. The XRD study reveals that the melt-spun samples contain elemental aluminum, lead and tin. The TEM analysis shows that embedded particles in aluminium matrix have a distinct two-phase contrast of lead and tin. The lead and tin in these nanoalloys exhibit an orientation relationship with the matrix aluminum and with each other. DSC studies were conducted to reveal the melting and solidification characteristics of these embedded nanoalloys. DSC thermograms exhibit features of multiple solidification exotherms on thermal cycling, which can be attributed to sequential melting and solidification of lead and tin in the respective alloys.

Effect of neodymium (Nd) doping on the dielectric and ferroelectric characteristics of sol-gel derived lead zirconate titanate (53/47) thin films

The results of the studies on the effect of rare earth Nd doping on the phase formation behavior and electrical properties of sol-gel derived Pb-1.05(Zr0.53Ti0.47)O-3 (PZT) thin films are presented. The perovskite phase is obtained up to 5 at. % doping and beyond that pyrochlore phase was found to coexist with the perovskite phase in all the films. The transition temperature of undoped lead zirconate titanate (PZT) film was found to be reduced with Nd doping. The Nd doped films also exhibited typical relaxor-type behavior and a diffuse phase transition, similar to that observed in relaxor materials. The introduction of Nd into the PZT lattice probably introduces disorder in the B site of ABO(3) lattice, which causes the observed dielectric relaxation. Efforts were made to isolate the irreversible component contributions in low field dielectric and high field polarization switching behavior. (C) 2001 American Institute of Physics.

Superconductivity of embedded lead nano particles in metallic and amorphous matrices

Nanodispersed lead in metallic and amorphous matrices was synthesized by rapid solidification processing. The optimum microstructure was tailored to avoid percolation of the particles. With these embedded particles it is possible to study quantitatively the effect of size on the superconducting transition temperature by carrying out quantitative microstructural characterization and magnetic measurements. Our results suggest the role of the matrices in enhancement or depression of superconducting transition temperature of lead. The origin of this difference in behavior with respect to different matrices and sizes is discussed.

Lead Stereochemistry in Incommensurate Ferroelectric Perovskites and in Incommensurate Lead Monoxide

We have performed Rietveld refinements on neutron and synchrotron diffraction patterns and density functional calculations on various ferroelectric lead perovskites and on α lead monoxide (litharge). These structural data have allowed to shed some light on lead stereochemistry in these compounds. In particular, we discuss the changing in the lead behaviour between the paraelectric cubic phases and the low temperature anti or ferroelectric phases in Pb2CoWO6 and Pb2MgTeO6 (both incommensurate), in Pb2MgWO6 (antiferroelectric) and in PbMg1/3Nb2/3O3 (relaxor). The possible phase transition mechanisms are reviewed and the bonds are compared to those in the aperiodic structure of α-lead monoxide.

Transcription factors that mediate epithelial-mesenchymal transition lead to multidrug resistance by upregulating ABC transporters

Development of multidrug resistance (MDR) is a major deterrent in the effective treatment of metastatic cancers by chemotherapy. Even though MDR and cancer invasiveness have been correlated, the molecular basis of this link remains obscure. We show here that treatment with chemotherapeutic drugs increases the expression of several ATP binding cassette transporters (ABC transporters) associated with MDR, as well as epithelial-mesenchymal transition (EMT) markers, selectively in invasive breast cancer cells, but not in immortalized or non-invasive cells. Interestingly, the mere induction of an EMT in immortalized and non-invasive cell lines increased their expression of ABC transporters, migration, invasion, and drug resistance. Conversely, reversal of EMT in invasive cells by downregulating EMT-inducing transcription factors reduced their expression of ABC transporters, invasion, and rendered them more chemosensitive. Mechanistically, we demonstrate that the promoters of ABC transporters carry several binding sites for EMT-inducing transcription factors, and overexpression of Twist, Snail, and FOXC2 increases the promoter activity of ABC transporters. Furthermore, chromatin immunoprecipitation studies revealed that Twist binds directly to the E-box elements of ABC transporters. Thus, our study identifies EMT inducers as novel regulators of ABC transporters, thereby providing molecular insights into the long-standing association between invasiveness and MDR. Targeting EMT transcription factors could hence serve as novel strategies to curb both metastasis and the associated drug resistance. Cell Death and Disease (2011) 2, e179; doi:10.1038/cddis.2011.61; published online 7 July 2011

Phase transitions in the anchored organic bilayers of long-chain alkylammonium lead iodides (CnH2n+1NH3)(2)PbI4; n=12, 16, 18

The single perovskite slab alkylammonium lead iodides (CnH2n+1NH3)(2)PbI4, n = 12, 16, 18, display two phase transitions, just above room temperature, associated with changes in the alkylammonium chains. We have followed these two phase transitions using scanning calorimetry, X-ray powder diffraction, and IR and Raman spectroscopies. We find the first phase transition to be associated with symmetry changes arising from a dynamic rotational disordering of the ammonium headgroup of the chain whereas the second transition, the melting of the chains in two dimensions, is characterized by an increased conformational disorder of the methylene units of the alkyl chains. We examine these phase transitions in light of the interesting optical properties of these materials, as well as the relevance of these systems as models for phase transitions in lipid bilayers.

Tracing the source of bottled water using stable isotope techniques

The Indian Summer Monsoon (ISM) precipitation recharges ground water aquifers in a large portion of the Indian subcontinent. Monsoonal precipitation over the Indian region brings moisture from the Arabian Sea and the Bay of Bengal (BoB). A large difference in the salinity of these two reservoirs, owing to the large amount of freshwater discharge from the continental rivers in the case of the BoB and dominating evaporation processes over the Arabian Sea region, allows us to distinguish the isotopic signatures in water originating in these two water bodies. Most bottled water manufacturers exploit the natural resources of groundwater, replenished by the monsoonal precipitation, for bottling purposes. The work presented here relates the isotopic ratios of bottled water to latitude, moisture source and seasonality in precipitation isotope ratios. We investigated the impact of the above factors on the isotopic composition of bottled water. The result shows a strong relationship between isotope ratios in precipitation (obtained from the GNIP data base)/bottled water with latitude. The approach can be used to predict the latitude at which the bottled water was manufactured. The paper provides two alternative approaches to address the site prediction. The limitations of this approach in identifying source locations and the uncertainty in latitude estimations are discussed. Furthermore, the method provided here can also be used as an important forensic tool for exploring the source location of bottled water from other regions. Copyright (C) 2011 John Wiley & Sons, Ltd.