Polyaniline modified electrodes for detection of dyes

Polyaniline (PANI) is one of the most extensively used conjugated polymers in the design of electrochemical sensors. In this study, we report electrochemical dye detection based on PANI for the adsorption of both anionic and cationic dyes from solution. The inherent property of PANI to adsorb dyes has been explored for the development of electrochemical detection of dye in solution. The PANI film was grown on electrode via electrochemical polymerization. The as grown PANI film could easily adsorb the dye in the electrolyte solution and form an insulating layer on the PANI coated electrode. As a result, the current intensity of the PANI film was significantly altered. Furthermore, PANI coated stainless steel (SS) electrodes show a change in the current intensity of Fe2+/Fe3+ redox peaks due to the addition of dye in electrolyte solution. PANI films coated on both Pt electrodes and non-expensive SS electrodes showed the concentration of dye adsorbed is directly proportional to the current intensity or potential shift and thus can be used for the quantitative detection of textile dyes at very low concentrations. (C) 2011 Elsevier B.V. All rights reserved.

Thermodynamic properties of the calcium ferrites CaFe2O4 and Ca2Fe2O5

The chemical potentials of CaO in the two-phase fields Fe2O3 + CaFe2O4 and CaFe2O4 + Ca2Fe2O5 of the pseudobinary system CaO - Fe2O3 have been measured in the temperature range from 975 to 1275 K, relative to pure CaO as the reference state, using solid state galvanic cells incorporating single-crystal CaF2 as the solid electrolyte. The cell was operated under pure oxygen at ambient pressure. The standard Gibbs energies of formation of calcium ferrites, CaFe2O4 and Ca2Fe2O5, were derived from the reversible emfs. The results can be summarized by the following equations:CaO + Fe2O3 --> CaFe2O4;Delta G degrees = - 37,480 + 1.16 T (+/- 250) J/mol 2 CaO + Fe2O3 --> Ca2Fe2O5;Delta G degrees = - 45, 280 - 13.51 T (+/- 275) J/mol These values are compared with thermodynamic data reported in the literature. The results of this study are in excellent agreement with heat capacity data, and in reasonable agreement with earlier measurements of enthalpy and Gibbs energy of formation, but suggest significant revision of enthalpies of formation of calcium ferrites given in current thermodynamic compilations.

Total peroxidase activity and peroxidase isoforms as modified by salt stress in two cultivars of fox-tail millet with differential salt tolerance

The effect of NaCl on total peroxidase activity, induction of isoperoxidases and lipid peroxidation in 5-day-old seedlings of two contrasting genotypes of Setaria italica L. (Prasad, a salt tolerant cultivar and Lepakshi, a salt susceptible cultivar), was studied. Total peroxidase activity increased under NaCl salinity and the degree of elevation in the activity was salt concentration dependent. Nevertheless, a greater activity was recorded in the tolerant cultivar (cv Prasad) compared to the susceptible (cv Lepakshi) one in all days of sampling. Further, the pattern of isoperoxidases was modified during stress conditions as evident from the electrophoregrams. Although, five acidic isoforms were detected in both cultivars, differences were found between the cultivars. Furthermore, it was observed that acidic isoperoxidases were strongly expressed and an acidic isoperoxidase, A(3p) (27 kDa) is specifically found in the tolerant cultivar (cv Prasad) under NaCl stress. This isoform was partially purified and found to be thermostable with pr 5.5 and the optimum pH 7.4. A close correlation exists between the rate of lipid peroxidation in terms of malonaldehyde (MDA) content and total peroxidase activity per gram fresh weight with salt tolerance of the two cultivars. The tolerant cultivar (cv Prasad) had low MDA content and high total peroxidase activity than the susceptible variety (cv Lepakshi) during salinity stress. (C) 1999 Published by Elsevier Science Ireland Ltd. All rights reserved.

A differential-geometric analysis of singularities of point trajectories of serial and parallel manipulators

In this paper, we present a differential-geometric approach to analyze the singularities of task space point trajectories of two and three-degree-of-freedom serial and parallel manipulators. At non-singular configurations, the first-order, local properties are characterized by metric coefficients, and, geometrically, by the shape and size of a velocity ellipse or an ellipsoid. At singular configurations, the determinant of the matrix of metric coefficients is zero and the velocity ellipsoid degenerates to an ellipse, a line or a point, and the area or the volume of the velocity ellipse or ellipsoid becomes zero. The degeneracies of the velocity ellipsoid or ellipse gives a simple geometric picture of the possible task space velocities at a singular configuration. To study the second-order properties at a singularity, we use the derivatives of the metric coefficients and the rate of change of area or volume. The derivatives are shown to be related to the possible task space accelerations at a singular configuration. In the case of parallel manipulators, singularities may lead to either loss or gain of one or more degrees-of-freedom. For loss of one or more degrees-of-freedom, ther possible velocities and accelerations are again obtained from a modified metric and derivatives of the metric coefficients. In the case of a gain of one or more degrees-of-freedom, the possible task space velocities can be pictured as growth to lines, ellipses, and ellipsoids. The theoretical results are illustrated with the help of a general spatial 2R manipulator and a three-degree-of-freedom RPSSPR-SPR parallel manipulator.

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.

Study of thickness dependence on electrical properties of (Pb,La)TiO3 thin films for memory applications

Lead-lanthanum-titanate (Pb0.72La0.28)TiO3 (PLT) is one of the interesting materials for DRAM applications due to its room temperature paraelectric nature and its higher dielectric permittivity. PLT thin films of different thickness ranging from 0.54- 0.9 mum were deposited on Pt coated Si substrates by excimer laser ablation technique. We have measured the voltage (field) dependence, the thickness dependence, temperature dependence of dc leakage currents and analysis is done on these PLT thin films. Current- voltage characteristics were measured at different temperatures for different thick films and the thickness dependence of leakage current has been explained by considering space charge limited conduction mechanism. The charge transport phenomena were studied in detail for films of different thicknesses for dynamic random access memory applications.

Modified kinetic flux vector splitting (m-KFVS) method for compressible flows

To resolve many flow features accurately, like accurate capture of suction peak in subsonic flows and crisp shocks in flows with discontinuities, to minimise the loss in stagnation pressure in isentropic flows or even flow separation in viscous flows require an accurate and low dissipative numerical scheme. The first order kinetic flux vector splitting (KFVS) method has been found to be very robust but suffers from the problem of having much more numerical diffusion than required, resulting in inaccurate computation of the above flow features. However, numerical dissipation can be reduced by refining the grid or by using higher order kinetic schemes. In flows with strong shock waves, the higher order schemes require limiters, which reduce the local order of accuracy to first order, resulting in degradation of flow features in many cases. Further, these schemes require more points in the stencil and hence consume more computational time and memory. In this paper, we present a low dissipative modified KFVS (m-KFVS) method which leads to improved splitting of inviscid fluxes. The m-KFVS method captures the above flow features more accurately compared to first order KFVS and the results are comparable to second order accurate KFVS method, by still using the first order stencil. (C) 2011 Elsevier Ltd. All rights reserved.

Calcium-Decorated Carbyne Networks as Hydrogen Storage Media

Among the carbon allotropes, carbyne chains appear outstandingly accessible for sorption and very light. Hydrogen adsorption on calcium-decorated carbyne chain was studied using ab initio density functional calculations. The estimation of surface area of carbyne gives the value four times larger than that of graphene, which makes carbyne attractive as a storage scaffold medium. Furthermore, calculations show that a Ca-decorated carbyne can adsorb up to 6 H(2) molecules per Ca atom with a binding energy of similar to 0.2 eV, desirable for reversible storage, and the hydrogen storage capacity can exceed similar to 8 wt %. Unlike recently reported transition metal-decorated carbon nanostructures, which suffer from the metal clustering diminishing the storage capacity, the clustering of Ca atoms on carbyne is energetically unfavorable. Thermodynamics of adsorption of H(2) molecules on the Ca atom was also investigated using equilibrium grand partition function.

Calcium ruthenates: Determination of Gibbs energies of formation using electrochemical cells

Metallic Ru has been found to coexist separately with CaO, RuO2, and the interoxide phases, Ca2RuO4, Ca3Ru2O7, and CaRuO3, present along the pseudobinary system CaO-RuO2. The standard Gibbs energies of formation (Df((ox))G(o)) of the three calcium ruthenates from their component oxides have been measured in the temperature range 925-1350 K using solid-state cells with yttria-stabilized zirconia as the electrolyte and Ru+RuO2 as the reference electrode. The standard Gibbs energies of formation (Deltaf((ox))G(o)) of the compounds can be represented by Ca2RuO4:Deltaf((ox))G(o)/J mol(-1)=-38,340-6.611 T (+/-120), Ca3Ru2O7 : Df((ox))G(o)/J mol(-1)=-75,910-11.26 T (+/-180), and CaRuO3 : Deltaf((ox))G(o)/J mol(-1)=-35,480-3.844 T(+/-70). The data for Ca2RuO4 corresponds to the stoichiometric composition, which has an orthorhombic structure, space group Pbca, with short c axis ("S'' form). The structural features of the ternary oxides responsible for their mild entropy stabilization are discussed. A three-dimensional oxygen potential diagram for the system Ca-Ru-O is developed as a function of composition and temperature from the results obtained. Using the Neumann-Kopp rule to estimate the heat capacity of the ternary oxides relative to their constituent binary oxides, the standard enthalpies of formation of the three calcium ruthenates from the elements and their standard entropies at 298.15 K are evaluated. (C) 2003 The Electrochemical Society.

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

Defining the ‘modified Griffin plot’ in vortex-induced vibration: revealing the effect of Reynolds number using controlled damping

In the present work, we study the transverse vortex-induced vibrations of an elastically mounted rigid cylinder in a fluid flow. We employ a technique to accurately control the structural damping, enabling the system to take on both negative and positive damping. This permits a systematic study of the effects of system mass and damping on the peak vibration response. Previous experiments over the last 30 years indicate a large scatter in peak-amplitude data ($A^*$) versus the product of mass–damping ($\alpha$), in the so-called ‘Griffin plot’. A principal result in the present work is the discovery that the data collapse very well if one takes into account the effect of Reynolds number ($\mbox{\textit{Re}}$), as an extra parameter in a modified Griffin plot. Peak amplitudes corresponding to zero damping ($A^*_{{\alpha}{=}0}$), for a compilation of experiments over a wide range of $\mbox{\textit{Re}}\,{=}\,500-33000$, are very well represented by the functional form $A^*_{\alpha{=}0} \,{=}\, f(\mbox{\textit{Re}}) \,{=}\, \log(0.41\,\mbox{\textit{Re}}^{0.36}$). For a given $\mbox{\textit{Re}}$, the amplitude $A^*$ appears to be proportional to a function of mass–damping, $A^*\propto g(\alpha)$, which is a similar function over all $\mbox{\textit{Re}}$. A good best-fit for a wide range of mass–damping and Reynolds number is thus given by the following simple expression, where $A^*\,{=}\, g(\alpha)\,f(\mbox{\textit{Re}})$: \[ A^* \,{=}\,(1 - 1.12\,\alpha + 0.30\,\alpha^2)\,\log (0.41\,\mbox{\textit{Re}}^{0.36}). \] In essence, by using a renormalized parameter, which we define as the ‘modified amplitude’, $A^*_M\,{=}\,A^*/A^*_{\alpha{=}0}$, the previously scattered data collapse very well onto a single curve, $g(\alpha)$, on what we refer to as the ‘modified Griffin plot’. There has also been much debate over the last three decades concerning the validity of using the product of mass and damping (such as $\alpha$) in these problems. Our results indicate that the combined mass–damping parameter ($\alpha$) does indeed collapse peak-amplitude data well, at a given $\mbox{\textit{Re}}$, independent of the precise mass and damping values, for mass ratios down to $m^*\,{=}\,1$.

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.

The inactive X chromosome in the human female is enriched in 5-methylcytosine to an unusual degree and appears to contain more of this modified nucleotide than the remainder of the genome

By employing a procedure that combines ELISA and photoacoustic spectroscopy, we have examined the content of 5-methylcytosine (m(5)C) in DNA of individuals who differed from one another in the number of X chromosomes in their genomes. The results show that the human inactive X chromosome (Xi) contains very high amounts of this modified nucleotide. We estimate that in the 46,XX female there is more m(5)C in Xi (similar to3.6 x 10(7)) than in all the remaining chromosomes put together (similar to2.1 x 10(7)). Our results also suggest that nearly one-fifth of all cytosines in Xi are methylated and that, in addition to CpG methylation, there is extensive non-CpG methylation as well.