Solid state Mössbauer,e.p.r., magnetic properties and thermally induced stereochemical studies on double complex salts of cyclic diamine containing cationic copper(II) complexes and a hexacyanoferrate(III) anion

Summary Double complex salts containing cationic Cu^II having cyclic ligand piperazine (pipz), N-methylpiperazine (mpipz) and N,N-dimethylpiperazine (dmpipz) and hexacyanoferrate(III) ion have been synthesized and characterized by elemental analyses, i.r. and electronic spectra, and magnetic moment measurements. Mössbauer spectra at room temperature and at 80 K, were recorded in order to evaluate the metal-metal charge transfer and the impact of the cyclic ligand present in cationic moiety of the double complex salt upon the Mössbauer spectra of the hexacyanoferrate(III) ion. Evidence for metal-metal charge transfer is supported by electronic spectra and magnetic susceptibilities. Variable temperature e.p.r. spectra were recorded in order to determine the distortion of crystal system. Thermally induced stereochemical studies have been carried out with the help of i.r. spectral data. Kinetics of thermochemical reactions have also been studied. Activation energies (E _infa ^sup* ) and inception temperatures for the thermochemical reactions show the order of stability of the double complex salts follows the trend: dmpipz > mpipz > pipz, which indicates that the + I effect is more pronounced than steric effect.     

Apparent Molar Heat Capacities and Apparent Molar Volumes of Aqueous Nicotinamide at Different Temperatures

Specific heat capacities and apparent molar heat capacities of aqueous nicotinamide have been determined from 25.0 to 55.0°C using microdifferential scanning calorimetry in the molality range of 0.07433 to 1.50124 mol-kg^–1. Densities and apparent molar volumes have also been determined for aqueous nicotinamide from 10.30 to 34.98°C using a digital densimeter in the molality range 0.07804–2.02435 mol-kg^–1. The results of these measurements have been used to calculate the following partial molar quantities and temperature derivatives for aqueous nicotinamide as a function of temperature: C _p,2,m ^o, (C _p,2,m ^o/T)_p, (²C_p,2,m ^o/T ²)_p, V _2,m ^o, ( V _2,m ^o/T)_p, and (² V _2,m ²/T ²)_p. The results are discussed in terms of the changes in the packing of nicotinamide molecules in the crystal, interactions in the aqueous form, and its structure-promoting ability with rise in temperature.     

Synthesis of Pyrimidine Annelated Heterocycles [1]. Regioselective Heterocyclization of 6-Cyclopent-2-enyl-5-hydroxy-1,3-dimethyl-pyrimidine-2,4( 1H, 3H)-dione and 5-Cyclopent-2-enyl-6-hydroxy-1,3-dimethylpyrimidine-2,4( 1H, 3H)-dione

Two hitherto unreported pyrimidine annelated heterocycles were synthesized from 6-cyclopent-2-enyl-5-hydroxy-1,3-dimethylpyrimidine-2,4(1H,3H)-dione and 5-cyclopent-2-enyl-6-hydroxy-1,3-dimethylpyrimidine-2,4(1H,3H)-dione by reaction with pyridine hydrotribromide or hexamethylenetetramine hydrotribromide. The first one was also obtained by reaction with concentrated sulfuric acid.     

One- and two-photon spectra of some selected molecules: A comparative study

The complementarity of one- and two-photon spectroscopy has been utilised for throwing light on the following problems of chemical interest: (1) Weak interaction between identical chromophores separated by insulating bridges gives rise to split states of different symmetries. Two-photon spectroscopy (TPA), in conjunction with one-photon absorption (OPA), has been used to identify the states and hence to estimate the magnitude of interaction in bimolecules and trimolecules. From the shifts between the one- and the two-photon spectra, the splittings have been estimated. Calculations confirm that the dominant interaction is the through-bond one. (2) The second type of problem is the identification ofg andu vibrations in molecules. We have initiated studies on three molecules in jet-cooled conditions: 9,10-dihydro-anthracene (DHA). 9,10-dihydro-phenanthrene (DHP) and octa-fluoronaph-thalene (OFN). Only the one-photon fluorescence excitation spectra have so far been obtained by us and the TPA spectra are under investigation. (3) The third class of molecules discussed here are the Ln³⁺ complexes wheref ⁿ⇒ fⁿ transitions are intrinsically two-photon allowed. We have studied two GD³⁺ single crystals. The CF-splittings, observed clearly in TPA, have been fitted with a parametric model. Some of our observations on the variations of TPA intensity patterns from crystal to crystal, such as circular:linear polarisation ratios, relative intensities of transitions to differentJ-states, do not quite fit in with the Axe-Judd-Downer model. The discrepancies call for a reappraisal of the role of ligand in the TPA process.     

Polymer–filler interactions in sol–gel derived polymer/silica hybrid nanocomposites

The effect of polymer–filler interaction on solvent swelling and dynamic mechanical properties of the sol–gel derived acrylic rubber (ACM)/silica, epoxidized natural rubber (ENR)/silica, and poly (vinyl alcohol) (PVA)/silica hybrid nanocomposites has been described for the first time. Tetraethoxysilane (TEOS) at three different concentrations (10, 30, and 50 wt %) was used as the precursor for in situ silica generation. Equilibrium swelling of the hybrid nanocomposites in respective solvents at ambient condition showed highest volume fraction of the polymer in the swollen gel in PVA/silica system and least in ACM/silica, with ENR/silica recording an intermediate value. The Kraus constant (C) also followed a similar trend. In dynamic mechanical analysis, the storage modulus dropped at higher strain (>1%), which indicated disengagement of polymer segments from the filler surfaces. This drop was maximum in ACM/silica, intermediate in ENR/silica, and minimum in PVA/silica, both at 50 and 70 °C. The drop in modulus with theoretical volume fraction of silica (ϕ) was interpreted with the help of a Power law model ΔE′ = a₁ϕ, where a₁ was a constant and b₁ was primarily a filler attachment parameter. Strain dependence of loss modulus was observed in ACM/silica hybrid nanocomposites, while ENR/silica and PVA/silica nanocomposites showed almost strain‐independent behavior. The storage modulus showed sharp increase with increasing frequency in ACM/silica system, while that was lower in both ENR/silica (at higher frequency) and PVA/silica systems (in the entire frequency spectrum). The increase in modulus with ϕ also followed similar model ΔE′ = a₂ϕ proposed in the strain sweep mode. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2399–2412, 2005     

Collective dynamics of delay-coupled limit cycle oscillators

Coupled limit cycle oscillators with instantaneous mutual coupling offer a useful but idealized mathematical paradigm for the study of collective behavior in a wide variety of biological, physical and chemical systems. In most real-life systems however the interaction is not instantaneous but is delayed due to finite propagation times of signals, reaction times of chemicals, individual neuron firing periods in neural networks etc. We present a brief overview of the effect of time-delayed coupling on the collective dynamics of such coupled systems. Simple model equations describing two oscillators with a discrete time-delayed coupling as well as those describing linear arrays of a large number of oscillators with time-delayed global or local couplings are studied. Analytic and numerical results pertaining to time delay induced changes in the onset and stability of amplitude death and phase-locked states are discussed. A number of recent experimental and theoretical studies reveal interesting new directions of research in this field and suggest exciting future areas of exploration and applications.     

Yang-Baxter algebra and generation of quantum integrable models

We discover an operator-deformed quantum algebra using the quantum Yang-Baxter equation with the trigonometric R-matrix. This novel Hopf algebra together with its q→1 limit seems the most general Yang-Baxter algebra underlying quantum integrable systems. We identify three different directions for applying this algebra in integrable systems depending on different sets of values of the deforming operators. Fixed values on the whole lattice yield subalgebras linked to standard quantum integrable models, and the associated Lax operators generate and classify them in a unified way. Variable values yield a new series of quantum integrable inhomogeneous models. Fixed but different values at different lattice sites can produce a novel class of integrable hybrid models including integrable matter-radiation models and quantum field models with defects, in particular, a new quantum integrable sine-Gordon model with defect. __________ Translated from Teoreticheskaya i Matematicheskaya Fizika, Vol. 151, No. 3, pp. 470–485, June, 2007.     

Bayesian inference and life testing plans for generalized exponential distribution

Recently generalized exponential distribution has received considerable attentions. In this paper, we deal with the Bayesian inference of the unknown parameters of the progressively censored generalized exponential distribution. It is assumed that the scale and the shape parameters have independent gamma priors. The Bayes estimates of the unknown parameters cannot be obtained in the closed form. Lindley’s approximation and importance sampling technique have been suggested to compute the approximate Bayes estimates. Markov Chain Monte Carlo method has been used to compute the approximate Bayes estimates and also to construct the highest posterior density credible intervals. We also provide different criteria to compare two different sampling schemes and hence to find the optimal sampling schemes. It is observed that finding the optimum censoring procedure is a computationally expensive process. And we have recommended to use the sub-optimal censoring procedure, which can be obtained very easily. Monte Carlo simulations are performed to compare the performances of the different methods and one data analysis has been performed for illustrative purposes. This work was partially supported by a grant from the Department of Science and Technology, Government of India     

Silicon assisted diversified reaction of a β-silylmethylene malonate with dimethylsulfoxonium methylide

Reaction of dimethylsulfoxonium methylide with a β-silylmethylene malonate gives diversified products, cyclopropane, cyclobutane or allyl and homoallyl silanes depending upon the stoichiometry of the reactants and reaction conditions. Contrary to this, reaction of a β-arylmethylene malonate gives only the cyclopropane product. The product(s) formed are unique and the silicon group played a crucial role either by assisting and/or by participating in the process.     

The Effect of High Fat Diet on Cerebrovascular Health and Pathology: A Species Comparative Review

In both humans and animal models, consumption of a high-saturated-fat diet has been linked to vascular dysfunction and cognitive impairments. Laboratory animals provide excellent models for more invasive high-fat-diet-related research. However, the physiological differences between humans and common animal models in terms of how they react metabolically to high-fat diets need to be considered. Here, we review the factors that may affect the translatability of mechanistic research in animal models, paying special attention to the effects of a high-fat diet on vascular outcomes. We draw attention to the dissociation between metabolic syndrome and dyslipidemia in rodents, unlike the state in humans, where the two commonly occur. We also discuss the differential vulnerability between species to the metabolic and vascular effects of macronutrients in the diet. Findings from animal studies are better interpreted as modeling specific aspects of dysfunction. We conclude that the differences between species provide an opportunity to explore why some species are protected from the detrimental aspects of high-fat-diet-induced dysfunction, and to translate these findings into benefits for human health.