Synthesis, characterisation, and DC conductivity of polyaniline-lead oxide composites

The polyaniline-PbO composites of various mass fractions were prepared by in situ polymerisation. The prepared samples were characterised by FTIR, and the dominant peaks confirmed the formation of polyaniline-PbO composites. The SEM study shows a granular agglomerated morphology, and increases with an increase in the lead oxide mass % in polyaniline. Direct current (DC) conductivity (σ _DC) was studied as a function of temperature (T). From these studies, it was found that conductivity increased at higher temperatures due to the polarons hopping from one localised state to another. DSC studies reveal, the decrease in peak temperature from 273°C (pure PANI) to 169.2°C, 193.5°C, 218.4°C, 235.2°C, and 224.2°C, respectively for the various mass fractions (10 %, 30 %, 20 %, 40 %, and 50 %) of polyaniline-PbO composites.     

Electronic spectra of C<Subscript>6</Subscript>H<Superscript>+</Superscript> and C<Subscript>6</Subscript>H<Stack><Subscript>3</Subscript><Superscript>+</Superscript></Stack> in the gas phase

Measurement of the ³Π-³Π transition of C₆H⁺ in the gas phase near 19486 cm⁻¹ is reported. The experiment was carried out with a supersonic slit-jet expansion discharge using cavity ringdown absorption spectroscopy. Partly resolved P lines and observation of band heads permitted a rotational contour fit. Spectroscopic constants in the ground and excited-state were determined. The density of ions being sampled is merely 2×10⁸ cm⁻³. Broadening of the spectral lines indicates the excited-state lifetime to be ≈100 ps. The electronic transition of HC₆H₂⁺ at 26402 cm⁻¹ assumed to be ¹A₁-X¹A₁ in C_2v symmetry could not be rotationally resolved.     

Guanidinate-stabilized monomeric hafnium amide complexes as promising precursors for MOCVD of HfO2

Novel guanidinato complexes of hafnium [Hf{eta2-(iPrN)2CNR2}2(NR2)2] (R2 = Et2, 1; Et, Me, 2; Me2, 3), synthesized by insertion reactions of N,N'-diisopropylcarbodiimide into the M-N bonds of homologous hafnium amide complexes 1-3 and {[mu2-NC(NMe2)2][NC(NMe2)2]2HfCl}2 (4) using a salt metathesis reaction, are reported. Single-crystal X-ray diffraction analysis revealed that compounds 1-3 were monomers, while compound 4 was found to be a dimer. The observed fluxional behavior of compounds 1-3 was studied in detail using variable-temperature and two-dimensional NMR techniques. The thermal characteristics of compounds 1-3 seem promising for HfO2 thin films by vapor deposition techniques. Metal-organic chemical vapor deposition experiments with compound 2 as the precursor resulted in smooth, uniform, and stoichiometric HfO2 thin films at relatively low deposition temperatures. The basic properties of HfO2 thin films were characterized in some detail.     

A convenient synthesis of partially reduced benzo[c]phenanthrenes, its ketals and ketones

A concise and convenient synthesis of various partially reduced 6-sec-amino-1,2,3,4,7,8-hexahydro-, 6-sec-amino-1,2,7,8-tetrahydrobenzo[c]phenanthrene-5-carbonitriles, 6-sec-amino-3,4,7,8-tetrahydro-1H-benzo[c]phenanthrene-2-one-5-carbonitrile cycloalkene ketals, pendant with electron donor and acceptor substituents has been described through base catalyzed ring transformation of 2-oxo-4-sec-amino-5,6-dihydro-2H-benzo[h]chromene-3-carbonitriles by cyclohexanone, 2-cyclohexen-1-one, 1,4-cyclohexanedione monocycloalkene ketals. The acid catalyzed deketalation of 6-sec-amino-3,4,7,8-tetrahydro-1H-benzo[c]phenanthrene-2-one-carbonitrile ketals led to yield 6-sec-amino-3,4,7,8-tetrahydro-1H-benzo[c]phenanthrene-3-carbonitrile-2-ones in excellent yield. We also performed the X-ray studies of the molecules 3d and 6a to know the degree of non-planarity.     

Linear and nonlinear rheology of wormlike micelles

Several surfactant molecules self-assemble in solution to form long, cylindrical, flexible wormlike micelles. These micelles can be entangled with each other leading to viscoelastic phases. The rheological properties of such phases are very interesting and have been the subject of a large number of experimental and theoretical studies in recent years. We shall report our recent work on the macrorheology, microrheology and nonlinear flow behaviour of dilute aqueous solutions of a surfactant CTAT (Cetyltrimethylammonium Tosilate). This system forms elongated micelles and exhibits strong viscoelasticity at low concentrations (∼0.9 wt%) without the addition of electrolytes. Microrheology measurements of G(θ) have been done using diffusing wave spectroscopy which will be compared with the conventional frequency sweep measurements done using a cone and plate rheometer. The second part of the paper deals with the nonlinear rheology where the measured shear stress σ is a nonmonotonic function of the shear rate . In stress-controlled experiments, the shear stress shows a plateau for larger than some critical strain rate, similar to the earlier reports on CPyCl/NaSal system. Cates et al have proposed that the plateau is a signature of mechanical instability in the form of shear bands. We have carried out extensive experiments under controlled strain rate conditions, to study the time-dependence of shear stress. The measured time series of shear stress has been analysed in terms of correlation integral and Lyapunov exponent to show unambiguously that the behaviour is typical of low dimensional dynamical systems.     

The Kac Model Coupled to a Thermostat

In this paper we study a model of randomly colliding particles interacting with a thermal bath. Collisions between particles are modeled via the Kac master equation while the thermostat is seen as an infinite gas at thermal equilibrium at inverse temperature \(\beta \) . The system admits the canonical distribution at inverse temperature \(\beta \) as the unique equilibrium state. We prove that any initial distribution approaches the equilibrium distribution exponentially fast both by computing the gap of the generator of the evolution, in a proper function space, as well as by proving exponential decay in relative entropy. We also show that the evolution propagates chaos and that the one particle marginal, in the large system limit, satisfies an effective Boltzmann-type equation.     

On the Zagreb indices of the line graphs of the subdivision graphs

The aim of this paper is to investigate the Zagreb indices of the line graphs of the tadpole graphs, wheel graphs and ladder graphs using the subdivision concepts.     

Three-level depletion by cavity ringdown absorption spectroscopy: proof of concept

Theoretical quantitative considerations as well as experimental data are presented based on absorption population depletion coupled with cavity ringdown spectroscopy. The absorbing number densities inside the cavity are determined by numerical integration of the coupled rate equations. The number of photons involved in absorption, cavity losses due to mirror reflectivity and stimulated emission are taken into account. The principle is to monitor a first transition by cavity ringdown spectroscopy while a second transition, with a state in common, is resonantly excited by the decaying radiation of different frequency also trapped inside the optical cavity. A numerical example is given for atomic lines of neon and the measurements carried out in a supersonic slit-jet expansion discharge demonstrate the feasibility of the technique. The technique is also proven to work with two resonant transitions of C₂. Translational velocity of the jet modifying the rate equations is included in the model.     

Optically transparent and thermally stable nonlinear optic chromophores featuring a thieno[2,3-b]thiophene donor

A thieno[2,3-b]thiophene core has been utilized as a π-donor component to design two series of push-pull thienothiophenes by introducing various acceptor groups either via olefinic or aza-spacers. The molecules show a UV-visible cut-off wavelength below the second harmonic generation (SHG) at λ/2 of 532 nm, thereby conforming to the nonlinearity-transparency trade-off. Second order molecular nonlinearity, β measured by Hyper-Rayleigh scattering technique was found in the range of 9.58-47.66×10⁻³⁰ esu, while the Kurtz powder technique produced signals of the order of 0.43-1.02 U. Thermal decomposition temperatures measured by differential scanning calorimetry revealed decomposition temperatures≥275 °C, indicating high thermal stability.     

Amphiphilic silicones prepared from branched PEO‐silanes with siloxane tethers

Amphiphilic silicones were prepared by the covalent incorporation of branched polyethylene oxide (PEO) via a siloxane tether. This was achieved by using six novel branched PEO‐silanes with varying siloxane tether lengths and PEO molecular weight (M_n). Each PEO‐silane was crosslinked via acid‐catalyzed sol–gel condensation with α,ω‐bis(Si‐OH)polydimethylsiloxane (PDMS) (M_n = 3000 g/mol) to yield six amphiphilic silicone films. Film surface hydrophilicity increased with siloxane tether length, particularly after exposure to an aqueous environment, indicating that the PEO segments were more readily driven to the surface. This effect was more pronounced for films prepared with PEO‐silanes containing lower M_n PEO segments. AFM was used to study surface reconstruction of films upon exposure to an aqueous environment. Adsorption of bovine serum albumin (BSA) and human fibrinogen (HF) proteins decreased with siloxane tether length, particularly after first exposing films to an aqueous environment. For a given siloxane tether length, relatively less BSA adsorbed onto films prepared with PEO‐silanes with lower M_n PEO segments whereas less HF adsorbed onto films prepared with PEO‐silanes with higher M_n PEO segments. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4108–4119, 2010