Activation-controlled outer-sphere electron transfer reactions: reduction of heteropoly 11-tungstovanadophosphate and heteropoly 10-tungstodivanado phosphate by thiourea in aqueous acid medium

The kinetics of reduction of heteropoly 11-tungstovanadophosphate, [PV^VW₁₁O₄₀]⁴⁻, (HPA1) and heteropoly 10-tungstodivanadophosphate, [PV^VV^VW₁₀O₄₀]⁵⁻, (HPA2) by thiourea has been investigated in HClO₄/phthalate/acetate buffer solutions spectrophotometrically at 25 °C in aqueous medium. The stoichiometry of the reaction is 1:1 in both cases. The HPAs are converted into the corresponding one-electron reduced heteropoly blues, namely, [PV^IVW₁₁O₄₀]⁵⁻ and [PV^IVV^VW₁₀O₄₀]⁶⁻, and thiourea is oxidised to formamidine disulphide. The reaction shows first-order dependence in both [HPA] and [thiourea] at constant pH. The rate–pH profile shows the participation of both the neutral and deprotonated forms of thiourea in the reaction. The reaction proceeds through an outer sphere electron transfer mechanism in which activation-controlled electron transfer is the rate-determining step. Self-exchange rate constants for the couples [PV^VW₁₁O₄₀]⁴⁻/[PV^IVW₁₁O₄₀]⁵⁻, [PV^VV^VW₁₀O₄₀]⁵⁻/[PV^IVV^VW₁₀O₄₀]⁶⁻ and H₂NCSNH₂/H₂NCS^·+NH₂ have been evaluated by Marcus theory.     

Neutrino condensate as origin of dark energy

We propose a new solution to the origin of dark energy. We suggest that it was created dynamically from the condensate of a singlet neutrino at a late epoch of the early Universe through its effective self-interaction. This singlet neutrino is also the Dirac partner of one of the three observed neutrinos, hence dark energy is related to neutrino mass. The onset of this condensate formation in the early Universe is also related to matter density and offers an explanation of the coincidence problem of why dark energy (70%) and total matter (30%) are comparable at the present time. We demonstrate this idea in a model of neutrino mass with (right-handed) singlet neutrinos and a singlet scalar.     

Application of a genetic algorithm to optimal lay-up of shells made of composite laminates

The orientation of fiber direction in layers and the number of layers of composites play the major role in determining the strength and stiffness. Thus, the basic design problem is to determine the optimum stacking sequence of the composite laminate. Many methods are available at present for the design optimization of structural systems. However, these methods are based on mathematical programming techniques involving the gradient search and the direct search. These methods assume that the variables are continuous. In this paper, a different search and optimization algorithm, known as a Genetic Algorithm (GA), has been successfully applied to obtain the optimum fiber orientation of multilayered shells, which considers the angle of fiber orientation as a discrete variable. The principle of GA is applied to obtain optimum layers and the orientation of fibers of stiffened shells for both the symmetric and antisymmetric orientations of fibers for dynamic analysis. Shells composed of two to nine layers without stiffeners, with one stiffener, and with two stiffeners for a single as well as different materials are analyzed and the maximum frequency for each population is computed using the FEAST-C software. Submitted to the 11th International Conference on Mechanics of Composite Materials (Riga, June 11–15, 2000). Published in Mekhanika Kompozitnykh Materialov, Vol. 36, No. 2, pp. 271–278, March–April, 2000.     

Characterization and Diagnosis of Cancer by Native Fluorescence Spectroscopy of Human Urine

Urine is one of the diagnostically important bio fluids, as it has different metabolites in it, where many of them are native fluorophores. Native fluorescence characteristics of human urine samples were studied using excitation–emission matrices (EEMs) over a range of excitation and emission wavelengths, and emission spectra at 405 nm excitation, to discriminate patients with cancer from the normal subjects. The fluorescence spectra of urine samples of cancer patients exhibit considerable spectral differences in both EEMs and emission spectra with respect to normal subjects. Different ratios were calculated using the fluorescence intensity values of the emission spectra and they were used as input variables for a multiple linear discriminant analysis across different groups. The discriminant analysis classifies 94.7% of the original grouped cases and 94.1% of the cross‐validated grouped cases correctly. Based on the fluorescence emission characteristics of urine and statistical analysis, it may be concluded that the fluorophores nicotinamide adenine dinucleotide (NADH) and flavins may be considered as metabolomic markers of cancer.     

Critical current density of a sample of melt grown Y1.2Ba1.8Cu2.4O x

Melt grown samples of Y_1.2Ba_1.8Cu_2.4O _x have been prepared and studied for their current carrying capacity. The composition was chosen to include Y₂BaCuO₅ (211) particles in the YBa₂Cu₃O _x (123) phase. The critical current density (J _c) of these samples was studied as a function of magnetic field using magnetization technique. The micrographic investigation shows well aligned grains in this material. The magnetic hysteresis measurements were done using a MPMS SQUID magnetometer up to the fields of 5.5 T. TheJ _c was estimated from the remanent magnetization using Bean model. Isothermal magnetization hysteresis loops at low fields reveal the presence of only one kind of hysteresis loops (corresponding to intragrain magnetizations). This is a valid proof that the weak links are greatly eliminated in these samples prepared by MG process. TheJ _c behaviour as a function of magnetic field has two components, a rapidly decaying exponential function of field and the other component that predominates at higher fields. This could be explained if we assume that the sample contains two phases of superconductors, one having a lowH _c2 becoming normal at fairly medium fields of the order of a few kilogauss will act as pinning centres for the other phase having higherH _c2 and hence higherJ _c at high fields.     

Growth aspects,spectral, thermal and hardness studies of rare earth cerium(III)nitrate doped zinc(tris) thiourea sulphate single crystals

Single crystals of pure and cerium(III)nitrate doped zinc(tris) thiourea sulphate (ZTS) were grown from aqueous solution by slow evaporation method. The cell parameters of the grown crystals were determined by single crystal X-ray diffraction analysis. Powder X-ray diffraction patterns were recorded and indexed for the structural confirmation. The presence of functional group in the compound has been confirmed by FTIR analysis. UV–vis absorption spectrum has been recorded to determine the cut-off wavelength of the crystal. TGA/DTA studies show thermal stability of the grown crystals. SEM-EDX analysis revealed the incorporation of the impurity (Ce³⁺) into ZTS crystals. The microhardness study reveals that the hardness number (H_v) increases with load for all the grown crystals of this work. From the values of work hardening coefficients, it was concluded that pure and cerium nitrate doped ZTS crystals belong to the category of soft materials. The second harmonic generation of cerium(III)nitrate doped ZTS crystals was confirmed by Kurtz–Perry powder method using Nd:YAG laser.     

Thermal and optical studies on induced smectic phases of inter molecular hydrogen bonded liquid crystals between decyloxy benzoic acid and citric acid

Hydrogen bonded liquid crystal complex (HBLC) is prepared from mesogenic 4-decyloxy benzoic acid (10OBA) and aliphatic nonmesogenic citric acid (CA). Liquid crystal (LC) phases are investigated by polarizing optical microscopy (POM), differential scanning calorimetry (DSC) studies. Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy (NMR) validate the intermolecular complementary, cyclic type of hydrogen bond (HB) and molecular environment in the designed HBLC complex. Mesomorphic phases like nematic, smectic X (Sm X) and smectic G (Sm G) are characterized by various textures and using different techniques such as POM, DSC and optical tilt angle measurements. Thermal span width and thermal stability factor for the observed phase is calculated. The complexes are prepared in different mole ratio and their corresponding influences on the phase transitions are discussed. Also it is observed that the HB units play a vital role in stabilizing the new Sm X phase. The variation in thermal stability of smectic phases due to the influence of aromatic cores and length of end chain in the different mole ratio of the present HBLC complexes are also discussed. The variation of tilt angle with respect to temperature in the smectic phase has been experimentally calculated and analyzed. The lowered melting and clearing transition temperatures and extended thermal span width in the Sm X phase are also reported.     

Spectroscopic,Computational, Antimicrobial,DNA Interaction,In Vitro Anticancer and Molecular Docking Properties of Biochemically Active Cu(II) and Zn(II) Complexes of Pyrimidine-Ligand

Biochemically active Cu(II) and Zn(II) complexes [CuL(ClO₄)₂(1) and ZnL(ClO₄)₂(2)] have been synthesized from N,N donor Schiff base ligand L derived from4,6-dichloropyrimdine-5-carboxaldehyde with 4-(2-aminoethyl)morpholine. The L, complexes 1 and 2 have been structurally characterized by elemental analysis, ¹H-NMR, FTIR, MS, UV-Visible and ESR techniques. The results obtained from the spectral studies supports the complexes 1 and 2 are coordinated with L through square planar geometry. DFT calculations results supports, the ligand to metal charge transfer mechanism can occur between L and metal(II) ions. The antimicrobial efficacy results have been recommended that, complexes 1 and 2 are good anti-pathogenic agents than ligand L. The interaction of complexes 1 and 2 with calf thymus (CT) DNA has been studied by electronic absorption, viscometric, fluorometric and cyclic voltammetric measurements. The calculated K_b values for L, complexes 1 and 2 found from absorption titrations was 4.45?×?10⁴, L; 1.92?×?10⁵, 1 and 1.65?×?10⁵, 2. The Ksv values were found to be 3.0?×?10³, 3.68?×?10³and 3.52?×?10³ for L, complexes 1 and 2 by using competitive binding with ethidium bromide (EB). These results suggest that, the compounds are interacted with DNA may be electrostatic binding. The molecular docking studies have been carried out to confirm the interaction of compounds with DNA. Consequently, in vitro anticancer activities of L, complexes 1 and 2 against selected cancer (lung cancer A549, liver cancer HepG2 and cervical carcinoma HeLa) and normal (NHDF) cell lines were assessed by MTT assay.     

Colour gluons and scaling in a unified gauge model

Deep inelastic weak and electromagnetic processes are considered within the parton framework taking the partons to be integrally charged quarks and coloured gluons. Despite the participation of the spin-one gluons in these processes, scaling is shown to be maintained by treating the problem in a unified gauge model based on the groupSU (3)_colour⊗SU _L (2)⊗U(1). This is a consequence of the vector-dominance type of couplings between the gluons and the weak or electromagnetic vector bosons which are induced by the spontaneous breakdown of gauge symmetry. As a further consequence it is found that in the asymptotic region far above the gluon masses the colour octet parts of the weak and electromagnetic currents of the quarks are damped so that, in particular, the integrally charged quarks behave as fractionally charged quarks in this region.