Optical, electrochemical and morphological investigations of poly (3,4-propylenedioxythiophene)-sultone (PProDOT-S) thin films

In this paper, we have carried out thin film characterization of poly(3,4-propylenedioxythiophene)-sultone (PProDOT-S), a derivative of electrochromic poly(3,4-propylenedioxythiophene) (PProDOT). PProDOT-S was deposited onto transparent conducting oxide coated glass substrates by solution casting method. Single wavelength spectrophotometry is used to monitor the switching speed and contrast ratio at maximum wavelength (lambda (max)). The percentage transmittance at the lambda (max) of the neutral polymer is monitored as a function of time when the polymer film is repeatedly switched. This experiment gives a quantitative measure of the speed with which a film is able to switch between the two states i.e. the coloured and the bleached states. PProDOT-S films were switched at a voltage of 1 center dot 9 V with a switching speed of 2 s at lambda (max) of 565 nm and showed a contrast of similar to 37%. Cyclic voltammetry performed at different scan rates have shown the characteristic anodic and cathodic peaks. The structural investigations of PProDOT-S films by IR spectra were in good agreement with previously reported results. Raman spectra of PProDOT-S showed a strong Raman peak at 1509 cm (-aEuro parts per thousand 1) and a weak peak at 1410 cm (-aEuro parts per thousand 1) due to the C = C asymmetric and symmetric stretching vibrations of thiophene rings. The morphological investigations carried out by using scanning electron microscope (SEM) of polymer films have shown that these polymers are found to be arranged in dense packed clusters with non-uniform distribution having an average width and length of 95 nm and 160 nm, respectively.

Nonequilibrium arrhythmic states and transitions in a mathematical model for diffuse fibrosis in human cardiac tissue

We present a comprehensive numerical study of spiral-and scroll-wave dynamics in a state-of-the-art mathematical model for human ventricular tissue with fiber rotation, transmural heterogeneity, myocytes, and fibroblasts. Our mathematical model introduces fibroblasts randomly, to mimic diffuse fibrosis, in the ten Tusscher-Noble-Noble-Panfilov (TNNP) model for human ventricular tissue; the passive fibroblasts in our model do not exhibit an action potential in the absence of coupling with myocytes; and we allow for a coupling between nearby myocytes and fibroblasts. Our study of a single myocyte-fibroblast (MF) composite, with a single myocyte coupled to N-f fibroblasts via a gap-junctional conductance G(gap), reveals five qualitatively different responses for this composite. Our investigations of two-dimensional domains with a random distribution of fibroblasts in a myocyte background reveal that, as the percentage P-f of fibroblasts increases, the conduction velocity of a plane wave decreases until there is conduction failure. If we consider spiral-wave dynamics in such a medium we find, in two dimensions, a variety of nonequilibrium states, temporally periodic, quasiperiodic, chaotic, and quiescent, and an intricate sequence of transitions between them; we also study the analogous sequence of transitions for three-dimensional scroll waves in a three-dimensional version of our mathematical model that includes both fiber rotation and transmural heterogeneity. We thus elucidate random-fibrosis-induced nonequilibrium transitions, which lead to conduction block for spiral waves in two dimensions and scroll waves in three dimensions. We explore possible experimental implications of our mathematical and numerical studies for plane-, spiral-, and scroll-wave dynamics in cardiac tissue with fibrosis.

Projecting low-dimensional chaos from spatiotemporal dynamics in a model for plastic instability

We investigate the possibility of projecting low-dimensional chaos from spatiotemporal dynamics of a model for a kind of plastic instability observed under constant strain rate deformation conditions. We first discuss the relationship between the spatiotemporal patterns of the model reflected in the nature of dislocation bands and the nature of stress serrations. We show that at low applied strain rates, there is a one-to-one correspondence with the randomly nucleated isolated bursts of mobile dislocation density and the stress drops. We then show that the model equations are spatiotemporally chaotic by demonstrating the number of positive Lyapunov exponents and Lyapunov dimension scale with the system size at low and high strain rates. Using a modified algorithm for calculating correlation dimension density, we show that the stress-strain signals at low applied strain rates corresponding to spatially uncorrelated dislocation bands exhibit features of low-dimensional chaos. This is made quantitative by demonstrating that the model equations can be approximately reduced to space-independent model equations for the average dislocation densities, which is known to be low-dimensionally chaotic. However, the scaling regime for the correlation dimension shrinks with increasing applied strain rate due to increasing propensity for propagation of the dislocation bands.

Subdiffusion in hair bundle dynamics: The role of protein conformational fluctuations

The detection of sound signals in vertebrates involves a complex network of different mechano-sensory elements in the inner ear. An especially important element in this network is the hair bundle, an antenna-like array of stereocilia containing gated ion channels that operate under the control of one or more adaptation motors. Deflections of the hair bundle by sound vibrations or thermal fluctuations transiently open the ion channels, allowing the flow of ions through them, and producing an electrical signal in the process, eventually causing the sensation of hearing. Recent high frequency (0.1-10 kHz) measurements by Kozlov et al. Proc. Natl. Acad. Sci. U. S. A. 109, 2896 (2012)] of the power spectrum and the mean square displacement of the thermal fluctuations of the hair bundle suggest that in this regime the dynamics of the hair bundle are subdiffusive. This finding has been explained in terms of the simple Brownian motion of a filament connecting neighboring stereocilia (the tip link), which is modeled as a viscoelastic spring. In the present paper, the diffusive anomalies of the hair bundle are ascribed to tip link fluctuations that evolve by fractional Brownian motion, which originates in fractional Gaussian noise and is characterized by a power law memory. The predictions of this model for the power spectrum of the hair bundle and its mean square displacement are consistent with the experimental data and the known properties of the tip link. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4768902]

Nonlinear dynamic analysis of dragonfly inspired piezoelectrically driven flapping and pitching wing

The nonlinear equations for coupled elastic flapping-twisting motion of a dragonfly in- spired smart flapping wing are used for a flapping wing actuated from the root by a PZT unimorph in the piezofan configuration. Excitation by the piezoelectric harmonic force generates only the flap bending motion, which in turn, induces the elastic twist motion due to interaction between flexural and torsional vibrations modes. An unsteady aerodynamic model is used to obtain the aerodynamic forces. Numerical simulations are performed using a wing whose size is the same as the dragonfly Sympetrum Frequens wing. It is found that the value of average lift reaches to its maximum when the smart flapping wing is excited at a frequency closer to the natural frequency in torsion. Moreover, consideration of the elastic twisting of flapping wing leads to an increase in the lift force. It is also found that the flapping wing generates sufficient lift to support its own weight and carry a small pay- load. Therefore, the piezoelectrically actuated smart flapping wing based on the geometry of Sympetrum Frequens wing and undergoing flapping-twisting motions may be considered as a potential candidate for use in MAV applications.

Estimation of electric stress and surface potential for traction insulators

Traction insulators are solid core insulators widely used for railway electrification. Constant exposure to detrimental effects of vandalism, and mechanical vibrations begets certain faults like shorting of sheds or cracks in the sheds. Due to fault in one/two sheds, stress on the remaining healthy sheds increases, owing to atmospheric pollution the stress may lead to a flashover of the insulator. Presently due to non availability of the electric stress data for the insulators, simulation study is carried out to find the potential and electric field for most widely used traction insulators in the country. The results of potential and electric field stress obtained for normal and faulty imposed insulators are presented.

Vibration spectrum analyzer using stretched membranes of polymer piezoelectrics for sensor networks

The key problem tackled in this paper is the development of a stand-alone self-powered sensor to directly sense the spectrum of mechanical vibrations. Such a sensor could be deployed in wide area sensor networks to monitor structural vibrations of large machines (e. g. aircrafts) and initiate corrective action if the structure approaches resonance. In this paper, we study the feasibility of using stretched membranes of polymer piezoelectric polyvinlidene fluoride for low-frequency vibration spectrum sensing. We design and evaluate a low-frequency vibration spectrum sensor that accepts an incoming vibration and directly provides the spectrum of the vibration as the output.

Infrared spectrum of formamide in the solid phase

Infrared spectra of solid formamide are reported as a function of temperature. Solid formamide samples were prepared at 30 K and then annealed to higher temperatures (300 K) with infrared transmission spectra being recorded over the entire temperature range. The NH2 vibrations of the formamide molecule were found to be particularly very sensitive to temperature change. The IR spectra revealed a phase change occurring in solid formamide between 155 and 165 K. Spectral changes observed above and below the phase transition may be attributed to a rearrangement between formamide dimers and the formation of polymers is proposed at higher temperatures.

A multifold reduction in the transition Reynolds number, and ultra-fast mixing, in a micro-channel due to a dynamical instability induced by a soft wall

A dynamical instability is observed in experimental studies on micro-channels of rectangular cross-section with smallest dimension 100 and 160 mu m in which one of the walls is made of soft gel. There is a spontaneous transition from an ordered, laminar flow to a chaotic and highly mixed flow state when the Reynolds number increases beyond a critical value. The critical Reynolds number, which decreases as the elasticity modulus of the soft wall is reduced, is as low as 200 for the softest wall used here (in contrast to 1200 for a rigid-walled channel) The instability onset is observed by the breakup of a dye-stream introduced in the centre of the micro-channel, as well as the onset of wall oscillations due to laser scattering from fluorescent beads embedded in the wall of the channel. The mixing time across a channel of width 1.5 mm, measured by dye-stream and outlet conductance experiments, is smaller by a factor of 10(5) than that for a laminar flow. The increased mixing rate comes at very little cost, because the pressure drop (energy requirement to drive the flow) increases continuously and modestly at transition. The deformed shape is reconstructed numerically, and computational fluid dynamics (CFD) simulations are carried out to obtain the pressure gradient and the velocity fields for different flow rates. The pressure difference across the channel predicted by simulations is in agreement with the experiments (within experimental errors) for flow rates where the dye stream is laminar, but the experimental pressure difference is higher than the simulation prediction after dye-stream breakup. A linear stability analysis is carried out using the parallel-flow approximation, in which the wall is modelled as a neo-Hookean elastic solid, and the simulation results for the mean velocity and pressure gradient from the CFD simulations are used as inputs. The stability analysis accurately predicts the Reynolds number (based on flow rate) at which an instability is observed in the dye stream, and it also predicts that the instability first takes place at the downstream converging section of the channel, and not at the upstream diverging section. The stability analysis also indicates that the destabilization is due to the modification of the flow and the local pressure gradient due to the wall deformation; if we assume a parabolic velocity profile with the pressure gradient given by the plane Poiseuille law, the flow is always found to be stable.

Projecting low and extensive dimensional chaos from spatio-temporal dynamics

We review the spatio-temporal dynamical features of the Ananthakrishna model for the Portevin-Le Chatelier effect, a kind of plastic instability observed under constant strain rate deformation conditions. We then establish a qualitative correspondence between the spatio-temporal structures that evolve continuously in the instability domain and the nature of the irregularity of the scalar stress signal. Rest of the study is on quantifying the dynamical information contained in the stress signals about the spatio-temporal dynamics of the model. We show that at low applied strain rates, there is a one-to-one correspondence with the randomly nucleated isolated bursts of mobile dislocation density and the stress drops. We then show that the model equations are spatio-temporally chaotic by demonstrating the number of positive Lyapunov exponents and Lyapunov dimension scale with the system size at low and high strain rates. Using a modified algorithm for calculating correlation dimension density, we show that the stress-strain signals at low applied strain rates corresponding to spatially uncorrelated dislocation bands exhibit features of low dimensional chaos. This is made quantitative by demonstrating that the model equations can be approximately reduced to space independent model equations for the average dislocation densities, which is known to be low-dimensionally chaotic. However, the scaling regime for the correlation dimension shrinks with increasing applied strain rate due to increasing propensity for propagation of the dislocation bands. The stress signals in the partially propagating to fully propagating bands turn to have features of extensive chaos.

Anomalous optical phonons in Cs-0.9(NH4)(0.1)H2AsO4: a temperature-dependent Raman study

We determine the nature of coupled phonons in mixed crystal of Cs-0.9(NH4)(0.1)H2AsO4 using inelastic light scattering studies in the temperature range of 5 K to 300 K covering a spectral range of 60-1100 cm(-1). The phase transition in this system are marked by the splitting of phonon modes, appearance of new modes and anomalies in the frequency as well as linewidth of the phonon modes near transition temperature. In particular, we observed the splitting of symmetric (v(1)) and antisymmetric (v(3)) stretching vibrations associated with AsO4 tetrahedra below transition temperature (T-c(*) similar to 110 K) attributed to the lowering of site symmetry of AsO4 in orthorhombic phase below transition temperature. In addition, the step-up (hardening) and step-down (softening) of the AsO4 bending vibrations (v(4) (S9, S11) and v(2) (S6)) below transition temperature signals the rapid development of long range ferroelectric order and proton ordering. The lowest frequency phonon (S1) mode observed at similar to 92 cm(-1) shows anomalous blue shift (similar to 12 %) from 300 K to 5 K with no sharp transition near T-c(*) unlike other observed phonon modes signaling its potential coupling with the proton tunneling mode. (C) 2013 Author(s).

C-13-H-1 dipolar couplings for probing rod-like hydrogen bonded mesogens

Hydrogen bonding is the most important non-covalent interaction utilised in building supramolecular assemblies and is preferred often as a means of construction of molecular, oligomeric as well as polymeric materials that show liquid crystalline properties. In this work, a pyridine based nematogenic acceptor has been synthesized and mixed with non-mesogenic 4-methoxy benzoic acid to get a hydrogen bonded mesogen. The existence of hydrogen bonding between the pyridyl unit and the carboxylic acid was established using FT-IR spectroscopy from the observation of characteristic stretching vibrations of unionized type at 2425 and 1927 cm(-1). The mesogenic acceptor and the complex have been investigated using C-13 NMR in solution, solid and liquid crystalline states. Together with the 2D separated local field NMR experiments, the studies confirm the molecular structure in the mesophase and yield the local orientational order parameters. It is observed that the insertion of 4-methoxy benzoic acid not only enhances the mesophase stability but also induces a smectic phase due to an increase in the core length of the hydrogen bonded mesogen.

Ionothermal synthesis of TiO2 nanoparticles: Photocatalytic hydrogen generation

Rutile phase TiO2 nanoparticles have been successfully prepared at 120 degrees C for one day via the ionothermal method using imidazolium based functionalized ionic liquid. The obtained products have been characterized by various techniques. XRD pattern shows rutile phase with crystallite size similar to 15 nm. FTIR shows a band at similar to 410 cm(-1) assigned to Ti-O-Ti stretching vibrations and few other bands due to the presence of ionic liquid. UV-vis studies show maximum absorbance at similar to 215 nm due to the imidazolium moiety and a band at 316 nm due to TiO2 nanoparticles. TEM images show that the size of particle is similar to 30 nm. TG-DTA shows weight loss corresponding to the formation of stable TiO2 nanoparticles. The rutile TiO2 nanoparticle is a promising material for hydrogen generation through photocatalysis. (C) 2013 Elsevier B.V. All rights reserved.

Vibrational spectra of fluorene, 1-methylfluorene and 1,8-dimethylfluorene

In this paper, we report the gas phase infrared spectra of fluorene and its methylated derivatives using a heated multipass cell and argon as a carrier gas. The observed spectra in the 4000-400 cm(-1) range have been fitted using the modified scaled quantum mechanical force field (SQMFF) calculation with the 6-311G** basis. The advantage of using the modified SQMFF method is that it scales the force constants to find the best fit to the observed spectral lines by minimizing the fitting error. In this way we are able to assign all the observed fundamental bands in the spectra. With consecutive methyl substitutions two sets of bands are found to shift in a systematic way. The set of four aromatic C-H stretching vibrations around 3000 cm(-1) shifts toward lower frequencies while the single most intense aromatic C-H out-of-plane bending mode around 750 cm(-1) shifts toward higher frequencies. The reason for shifting of aromatic C-H stretching frequency toward lower wave numbers with gradual methyl substitution has been attributed to the lengthening of the C-H bonds due to the +I effect of the methyl groups to the ring current as revealed from the calculations. While the unexpected shifting of the aromatic C-H out-of-plane bend toward higher wave numbers with increasing methyl substitution is ascribed to the lowering of the number of adjacent aromatic C-H bonds on the plane of the benzene ring with gradual methyl substitutions. (C) 2013 Elsevier B.V. All rights reserved.

Linear and nonlinear optical studies on 3,6-bis (2 pyridyl) pyridazine

3,6-Bis (2 pyridyl) pyridazine has been synthesized and characterized by NMR, XRD and elemental analyses. The vibrational studies were carried out by using FTIR and Raman spectroscopy and the modes of vibrations were analysed and compared with the theoretically calculated values. The nonlinear optical property of the title compound was examined by Kurtz-Perry method and Hyper Raleigh scattering with the fundamental wavelength of 1064nm. This compound possesses less SHG efficiency but large first hyperpolarizability. (C) 2013 Elsevier GmbH. All rights reserved.