Interfacial tension and critical wetting phenomena of the binary liquid mixture cyclohexane-acetonitrile near the critical solution temperature

The determination of the capillary parameter for the partially miscible binary liquid system acetonitrile + cyclohexane has been reported. The system has closely matched densities and the data points are affected by gravity only when the fractional change of the temperature from the critical temperature is about 10^–6. The system also exhibits very interesting wetting properties. The interfacial tension has been fitted to a power law =0.061 (T_c-T)^1.26. The effect of doping with water and the instability of the wetting layer, which crucially depends on the interfacial tension, are studied.     

Synthesis and characterization of stable thiazolylazo anion radical complexes of ruthenium(II)

Two stable thiazolylazo anion radical complexes of ruthenium(II), [Ru(L1^•−)(Cl)(CO)(PPh₃)₂] (1) and [Ru(L2^•−)(Cl)(CO)(PPh₃)₂] (2) (where L1 = 2′-Thiazolylazo-2-imidazole and L2 = 4-(2′-Thiazolylazo)-1-n-hexadecyloxy-naphthalene), have been synthesized and characterized by spectroscopic and electrochemical techniques. The radical nature of the complexes has been confirmed from their room temperature magnetic moments and X-band ESR spectra. The radical complexes display a moderately intense (ε ~ 10⁴ M⁻¹ cm⁻¹) and relatively broad band in 430–460 nm region. In the microcrystalline state, complexes (1) and (2) display strong ESR signals at g = 1.951 and g = 1.988, respectively. In CH₂Cl₂ solution, complexes (1) and (2) show a quasireversible one-electron response near −0.64 and −0.59 V, respectively, versus Ag/AgCl due to the radical redox couple [Ru^II(L)(Cl)(CO)(PPh₃)₂]/[Ru^II (L^•−)(Cl)(CO)(PPh₃)₂].     

MAPLE-deposited polymer films for improved organic device performance

Matrix-assisted pulsed-laser evaporation (MAPLE) provides a mechanism for layer-by-layer growth to control the polymer–dielectric interface in organic metal–insulator–semiconductor (MIS) diodes and field-effect transistors (FETs). MAPLE-deposited copolymers of polyfluorene (PF) and polythiophene maintain their structural and optical properties, as determined by Raman spectroscopy, absorption, and photoluminescence. These films are further utilized in MIS and FET structures with SiO₂ and other polymer dielectrics. Since common polymer dielectrics prevent spin coating of solution processable polymers due to solubility effects, MAPLE is one of the only deposition techniques for investigating all polymer semiconductor-insulator interfaces. In this paper we present optical and electrical studies of MAPLE-deposited PF and polythiophene films in FETs and MIS structures. The FET carrier mobilities of these devices compare well with spin-coated devices. Capacitance–voltage and conductance–voltage from MIS structures with MAPLE-deposited PF copolymer films yield interface trap densities in the low 10¹² eV⁻¹ cm⁻² range.     

Theoretical aspects of single pulse induced modulation of cell-cell interactions favoring iso-electrofusion.

A single pulse-mediated electrofusion of freely suspending widely separated cells could reduce steps in the protocol. Prediction of such electrofusion is still unsolved. In pre-pulse condition, quantitative estimation with three-layered model cell surface reveals electrostatic repulsion (due to negative surface charge) is the major hindrance to membrane-to-membrane contact. On theoretical grounds we predict that designed single high voltage pulsing on widely separated model cell surface can counteract the non-specific repulsive interaction and favor approach of two apposed membranes. But hydrodynamic modulation of pulse exposed cell surface interaction can hamper approach of membranes contact when cells are held at a gap of more than approximately 450 A.     

Using massively parallel simulation and Markovian models to study protein folding: examining the dynamics of the villin headpiece

We report on the use of large-scale distributed computing simulation and novel analysis techniques for examining the dynamics of a small protein. Matters addressed include folding rate, very long time scale kinetics, ensemble properties, and interaction with water. The target system for the study, the villin headpiece, has been of great interest to experimentalists and theorists both. Sampling totaled nearly 500 mus-the most extensive published to date for a system of villin's size in explicit solvent with all atom detail-and was in the form of tens of thousands of independent molecular dynamics trajectories, each several tens of nanoseconds in length. We report on kinetics sensitivity analyses that, using a set of short simulations, probed the role of water in villin's folding and sensitivity to the simulation's electrostatics treatment. By constructing Markovian state models (MSMs) from the collected data, we were able to propagate dynamics to times far beyond those directly simulated and to rapidly compute mean first passage times, long time kinetics (tens of microseconds), and evolution of ensemble property distributions over long times, otherwise currently impossible. We also tested our MSM by using it to predict the structure of villin de novo.     

Chain morphologies in semicrystalline polyfluorene: evidence from Raman scattering

The beta phase in di-octyl substituted polyfluorene (PF8) exhibits a surprising level of conformational order at nanometer length scales compared to other phases. We present Raman scattering studies of PF8 as a function of thermal cycling, which establishes a connection between the conformational isomers and the side and main chain morphology. Density-functional calculations of the vibrational spectra of single chain oligomers in conjunction with the experimental results demonstrate the incompatibility of the beta phase with the overall alpha crystalline phase in PF8.     

Effect of γ-dose rate and total dose interrelation on the polymeric hydrogel: A novel injectable male contraceptive

Functional necessity to use a particular range of dose rate and total dose of γ-initiated polymerization to manufacture a novel polymeric hydrogel RISUG^® (reversible inhibition of sperm under guidance) made of styrene maleic anhydride (SMA) dissolved in dimethyl sulphoxide (DMSO), for its broad biomedical application explores new dimension of research. The present work involves 16 irradiated samples. They were tested by fourier transform infrared spectroscopy, matrix assisted laser desorption/ionization–TOF, field emission scanning electron microscopy, high resolution transmission electron microscopy, etc. to see the interrelation effect of gamma dose rates (8.25, 17.29, 20.01 and 25.00 Gy/min) and four sets of doses (1.8, 2.0, 2.2 and 2.4 kGy) on the molecular weight, molecular weight distribution and porosity analysis of the biopolymeric drug RISUG^®. The results of randomized experiment indicated that a range of 18–24 Gy/min γ-dose rate and 2.0–2.4 kGy γ-total doses is suitable for the desirable in vivo performance of the contraceptive copolymer.     

Polarized Hessian covariant: Contribution to pattern formation in the Föppl–von Kármán shell equations

We analyze the structure of the Föppl–von Kármán shell equations of linear elastic shell theory using surface geometry and classical invariant theory. This equation describes the buckling of a thin shell subjected to a compressive load. In particular, we analyze the role of polarized Hessian covariant, also known as second transvectant, in linear elastic shell theory and its connection to minimal surfaces. We show how the terms of the Föppl–von Kármán equations related to in-plane stretching can be linearized using the hodograph transform and relate this result to the integrability of the classical membrane equations. Finally, we study the effect of the nonlinear second transvectant term in the Föppl–von Kármán equations on the buckling configurations of cylinders.     

Topological alterations in human spermatozoa associated with the polyelectrolytic effect of RISUG

A new method of male contraception has been developed which results in long-term infertility and has the potential advantage of being reversible. The contraceptive, given the name RISUG (an acronym for Reversible Inhibition of Sperm Under Guidance) is a polyelectrolytic compound and when injected into the lumen of the vas deferens, induces a surface charge imbalance on the sperm membrane system leading to its destabilization. In the present study, morphological and topological alterations in human spermatozoa induced by RISUG have been investigated using atomic force microscopy (AFM). Complete disintegration of the plasma membrane with subsequent rupture and dispersion of the acrosomal contents is observed on treatment with RISUG in vitro. Considerable damage to the midpiece region with significant clustering of the mitochondria and its fusion with the head region is also observed. These observations are in agreement with the significant increase in the volume of RISUG-treated sperm-head region. Topological alterations in the flagellar and midpiece region of RISUG-treated spermatozoa have also been studied.     

Fatigue life prediction of welded cruciform joints using strain energy density factor approach

The influences of two welding processes, namely, shielded metal arc welding (SMAW) and flux cored arc welding (FCAW), on fatigue life of cruciform joints containing lack of penetration (LOP) defects have been analyzed by using the strain energy density factor (SEDF) approach. Load carrying cruciform joints were fabricated from ASTM 517 ‘F’ grade steel. Fatigue crack growth experiments were carried out in a mechanical resonance vertical pulsator (SCHENCK 200 kN capacity) with a frequency of 30 Hz under constant amplitude loading (R=0). It was found that the fatigue lives of the cruciform joints fabricated by SMAW process were relatively higher than the FCAW counterpart. Moreover, fracture mechanics equations have been developed to predict the fatigue life of the cruciform joints fabricated by the above-mentioned two processes.