Synthesis and vesicle formation from dimeric pseudoglyceryl lipids with (CH2)(m) spacers: pronounced m-value dependence of thermal properties, vesicle fusion, and cholesterol complexation

Eight new dimeric lipids, in which the two Me2N+ ion headgroups are separated by a variable number of polymethylene units [-(CH2)(m)-], have been synthesized. The electron micrograph (TEM) and dynamic light scattering (DLS) of their aqueous dispersions confirmed the formation of vesicular-type aggregates. The vesicle sizes and morphologies were found to depend strongly on the m value, the method, and thermal history of the vesicle preparation. Information on the thermotropic properties of the resulting vesicles was obtained from microcalorimetry and temperature-dependent fluorescence anisotropy measurements. Interestingly, the T-m values for these vesicles revealed a nonlinear dependence on spacer chain length (m value). These vesicles were able to entrap riboflavin. The rates of permeation of the OH- ion under an imposed transmembrane pH gradient were also found to depend significantly on the m value. X-Ray diffraction of the cast films of the lipid dispersions elucidated the nature and the thickness of these membrane organizations, and it was revealed that these lipids organize in three different ways depending on the m value. The EPR spin-probe method with the doxylstearic acids 5NS, 12NS, and 16NS, spin-labeled at various positions of stearic acid, was used to establish, the chain-flexibility gradient and homogeneity of these bilayer assemblies. The apparent fusogenic propensities of these bipolar tetraether lipids were investigated in the presence of Na2SO4 with fluorescence-resonance energy-transfer fusion assay. Small unilamellar vesicles formed from 1 and three representative biscationic lipids were also studied with fluorescence anisotropy and H-1 NMR spectroscopic techniques in the absence and the presence of varying amounts of cholesterol.

Pd-coated Ni nanoparticles by the polyol method: an efficient hydrogenation catalyst

Pd-coated Ni nanoparticles of 50 +/- 15 nm size are prepared by the polyol method and characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and thermogravimetry analysis. Surface coverage of Pd on Ni particles is less than a monolayer for 0.5 and 1 at% Pd-coated Ni. Quantitative conversion of nitrobenzene to aniline is observed over these Pd-coated Ni particles at 27degreesC under one atmospheric pressure of hydrogen. 0.5 and 1 at% Pd-coated Ni exhibits 10 times greater activity than that of typical colloidal palladium and platinum catalysts and 2.5 times higher activity than commercial 5 wt% Pd/C.

Fluorescence quenching of biologically active carboxamide by aniline and carbon tetrachloride in different solvents using Stern-Volmer plots

Fluorescence quenching of biologically active carboxamide namely (E)-2-(4-chlorobenzylideneamino)-N-(2-chlorophenyl)-4,5,6,7-tetrahydrobe nzo[b]thiophene-3-carboxamide [ECNCTTC] by aniline and carbon tetrachloride (CCl(4)) quenchers in different solvents using steady state method and time resolved method using only one solvent has been carried out at room temperature to understand the role of quenching mechanisms. The Stern-Volmer plot has been found to be linear for all the solvents studied. The probability of quenching per encounter p (p') was determined in all the solvents and was found to be less than unity. Further, from the studies of rate parameters and life time measurements in n-heptane and cyclohexane with aniline and carbon tetrachloride as quenchers have been shown that, the phenomenon of quenching is generally governed by the well-known Stern-Volmer (S-V) plot. The activation energy E(a) (or E(a)') of quenching was determined using the literature values of activation energy of diffusion E(d) and the experimentally determined values of p (or p'). It has been found that, the activation energy E(a) (E(a)') is greater than the activation energy for diffusion E(d) in all solvents. Hence, from the magnitudes of E(a) (or E(a)') as well as p (or p') infer that, the quenching mechanism is not solely due to the material diffusion, but there is also contribution from the activation energy. (C) 2011 Elsevier B.V. All rights reserved.

Non Identical Duplicate Video Detection using SIFT Method

Non-Identical Duplicate video detection is a challenging research problem. Non-Identical Duplicate video are a pair of videos that are not exactly identical but are almost similar.In this paper, we evaluate two methods - Keyframe -based and Tomography-based methods to determine the Non-Identical Duplicate videos. These two methods make use of the existing scale based shift invariant (SIFT) method to find the match between the key frames in first method, and the cross-sections through the temporal axis of the videos in second method.We provide extensive experimental results and the analysis of accuracy and efficiency of the above two methods on a data set of Non- Identical Duplicate video-pair.

Preparation, characterization and magnetic studies of Bi0.5X0.5(X=Ca,Sr)MnO3 nanoparticles

Nanoparticles (dia ~ 5 - 7 nm) of Bi0.5X0.5(X=Ca,Sr)MnO3 are prepared by polymer assisted sol-gel method and characterized by various physico-chemical techniques. X-ray diffraction gives evidence for single phasic nature of the materials as well as their structures. Mono dispersed to a large extent, isolated nanoparticles are seen in the transmission electron micrographs. High resolution electron microscopy shows the crystalline nature of the nanoparticles. Superconducting quantum interferometer based magnetic measurements from 10K to 300K show that these nanomanganites retain the charge ordering nature unlike Pr and Nd based nanomanganites. The CO in Bi based manganites is thus found to be very robust consistent with the observation that magnetic field of the order of 130 T are necessary to melt the CO in these compounds. These results are supported by electron magnetic resonance measurements.

Direct evidence of redox interaction between metal ion and support oxide in Ce(0.98)Pd(0.02)O(2-delta) by a combined electrochemical and XPS study

A combined electrochemical method and X-ray photo electron spectroscopy (XPS) has been utilized to understand the Pd(2+)/CeO(2) interaction in Ce(1-x)Pd(x)O(2-delta) (x = 0.02). A constant positive potential (chronoamperometry) is applied to Ce(0.98)Pd(0.02)O(2-delta) working electrode which causes Ce(4+) to reduce to Ce(3+) to the extent of similar to 35%, while Pd remains in the +2 oxidation state. Electrochemically cycling this electrode between 0.0-1.2 V reverts back to the original state of the catalyst. This reversibility is attributed to the reversible reduction of Ce(4+) to Ce(3+) state. CeO(2) electrode with no metal component reduces to CeO(2-y) (y similar to 0.4) after applying 1.2 V which is not reversible and the original composition of CeO(2) cannot be brought back in any electrochemical condition. During the electro-catalytic oxygen evolution reaction at a constant 1.2 V for 1000 s, Ce(0.98)Pd(0.02)O(2-delta) reaches a steady state composition with Pd in the +2 states and Ce(4+) : Ce(3+) in the ratio of 0.65 : 0.35. This composition can be denoted as Ce(0.63)(4+)Ce(0.35)(4+)Pd(0.02)O(2-delta-y) (y similar to 0.17). When pure CeO(2) is put under similar electrochemical condition, it never reaches the steady state composition and reduces almost to 85%. Thus, Ce(0.98)Pd(0.02)O(2-delta) forms a stable electrode for the electro-oxidation of H(2)O to O(2) unlike CeO(2) due to the metal support interaction.

Combustion synthesis, characterization and Raman studies of ZnO nanopowders

Spherical shaped ZnO nanopowders (14-50 nm) were synthesized by a low temperature solution combustion method in a short time <5 min. Rietveld analysis show that ZnO has hexagonal wurtzite structure with lattice constants a = 3.2511(1) angstrom, c = 5.2076(2) angstrom, unit cell volume (V) = 47.66(5) (angstrom)(3) and belongs to space group P63mc. SEM micrographs reveal that the particles are spherical in shape and the powders contained several voids and pores. TEM results also confirm spherical shape, with average particle size of 14-50 nm. The values are consistent with the grain sizes measured from Scherrer's method and Williamson-Hall (W-H) plots. A broad UV-vis absorption spectrum was observed at similar to 375 nm which is a characteristic band for the wurtzite hexagonal pure ZnO. The optical energy band gap of 3.24 eV was observed for nanopowder which is slightly lower than that of the bulk ZnO (3.37 eV). The observed Raman peaks at 438 and 588 cm(-1) were attributed to the E(2) (high) and E(1) (LO) modes respectively. The broad band at 564 cm(-1) is due to disorder-activated Raman scattering for the A(1) mode. These bands are associated with the first-order Raman active modes of the ZnO phase. The weak bands observed in the range 750-1000 cm(-1) are due to small defects. (C) 2011 Elsevier B.V. All rights reserved.

The Co Cr S ternary diagram at 1223 K and applications to corrosion

Ternary phase relations in the Co-Cr-S system at 1223 K were determined using microprobe analysis of quenched samples. The results are consistent with the data available on the binary systems. A complete solid solution exists between cobalt monosulfide and chromium monosulfide. The CoCr2S4 thiospinel is the only ternary compound formed. A sulfur potential diagram was constructed for the region involving equilibrium between alloy and monosulfide based on thermodynamic data on the Co-Cr, Co-S, and Cr-S binary systems and the ternary information obtained in this study. The sulfidation behavior of Co-Cr alloys reported in the literature is discussed in light of the sulfur potential diagram.

Weakening of charge order and antiferromagnetic to ferromagnetic switch over in Pr0.5Ca0.5MnO3 nanowires

We have prepared crystalline nanowires (diameter ∼ 50 nm, length ∼ a few microns) of the charge-ordering manganite Pr0.5Ca0.5MnO3 using a low reaction temperature hydrothermal method and characterized them using x-ray diffraction, transmission electron microscopy, superconducting quantum interference device (SQUID) magnetometry and electron magnetic resonance measurements. While the bulk sample shows a charge ordering transition at 245 K and an antiferromagnetic transition at 175 K, SQUID magnetometry and electron magnetic resonance experiments reveal that in the nanowires phase, a ferromagnetic transition occurs at ∼ 105 K. Further, the antiferromagnetic transition disappears and the charge ordering transition is suppressed. This result is particularly significant since the charge order in Pr0.5Ca0.5MnO3 is known to be very robust, magnetic fields as high as 27 T being needed to melt it.

Seismic reliability assessment of internal stability of reinforced soil walls using the pseudo-dynamic method

The study focuses on probabilistic assessment of the internal seismic stability of reinforced soil structures (RSS) subjected to earthquake loading in the framework of the pseudo-dynamic method. In the literature, the pseudo-static approach has been used to compute reliability indices against the tension and pullout failure modes, and the real dynamic nature of earthquake accelerations cannot be considered. The work presented in this paper makes use of the horizontal and vertical sinusoidal accelerations, amplification of vibrations, shear wave and primary wave velocities and time period. This approach is applied to quantify the influence of the backfill properties, geosynthetic reinforcement and characteristics of earthquake ground motions on reliability indices in relation to the tension and pullout failure modes. Seismic reliability indices at different levels of geosynthetic layers are determined for different magnitudes of seismic acceleration, soil amplification, shear wave and primary wave velocities. The results are compared with the pseudo-static method, and the significance of the present methodology for designing reinforced soil structures is discussed.

Biosorption of heavy metal ions from aqueous and cyanide solutions using fungal biomass

A waste fungal biomass containing killed cells of Aspergillus niger was efficiently used in the removal of toxic metal ions such as nickel, calcium, iron and chromium from aqueous solutions. The role of different parameters such as initial metal ion concentration, solution pH and biomass concentration on biosorption capacity was established. The maximum metal uptake was found to be dependent on solution pH and increased with biomass loading upto 10g/L. The adsorption densities for various metal ions could be arranged as Ca>Cr (III)>Ni>Fe>Cr (VI). The effect of the presence of various metal ions in binary, ternary and quaternary combinations on biosorption was also assessed. Ni uptake was significantly affected, while that of Cr (VI) the least, in the presence of other metal ions. Uptake of base metals from an industrial cyanide effluent was studied using different species of fungi such as Aspergillus niger, Aspergillus terreus and Penicillium funiculosum and yeast such as Saccharomyces cerevisiae which were isolated from a gold mine. Traces of gold present in the cyanide effluent could be efficiently recovered. Among the four base metal contaminants present in the cyanide effluent, zinc was found to be most efficiently biosorbed, followed by iron, copper and lead. The role of both living and dead biomass on biosorption was distinguished and probable mechanisms illustrated.

Time and Frequency Domain Finite Element Models for Axial Wave Analysis in Hyperelastic Rods

The propagation of axial waves in hyperelastic rods is studied using both time and frequency domain finite element models. The nonlinearity is introduced using the Murnaghan strain energy function and the equations governing the dynamics of the rod are derived assuming linear kinematics. In the time domain, the standard Galerkin finite element method, spectral element method, and Taylor-Galerkin finite element method are considered. A frequency domain formulation based on the Fourier spectral method is also developed. It is found that the time domain spectral element method provides the most efficient numerical tool for the problem considered.

Photo, thermal, and ultrasonic degradation of EGDMA-crosslinked poly(acrylic acid-co-sodium acrylate-co-acrylamide) superabsorbents

Superabsorbent polymers (SAPs) based on acrylic acid (AA), sodium acrylate (SA), and acrylamide (AM) were synthesized by inverse suspension polymerization using ethylene glycol dimethacrylate as the crosslinking agent. The equilibrium swelling capacities and the rates of swelling of SAPs varied with the AM content and followed first-order kinetics. The photodegradation of SAPs in their equilibrium swollen state was carried out by monitoring their swelling capacity and the residual weight fraction. The SAPs degraded in two stages, wherein the swelling capacity increased to a maximum and then subsequently decreased. Thermogravimetric analysis of the SAPs indicated that the copolymeric superabsorbents had intermediate thermal stability between the homopolymeric superabsorbents. The activation energies of SAPs with 0, 20, and 100 mol % AM content were determined by Kissinger method and were found to be 299, 248, and 147 kJ mol-1, respectively. The ultrasonic degradation of the superabsorbents was carried out in their equilibrium swollen state, and the change in the viscosity with ultrasonication time was used to quantify the degradation. The ultrasonic degradation of AA/SA superabsorbent was also investigated at various ultrasound intensities. The degradation rate coefficients were found to increase with the intensity of ultrasound. The ultrasonic degradation of AA/SA/AM (20% AM) was also carried out, and degradation rate was found to be more than that of the AA/SA superabsorbent. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Finite Element Method For A Nonlocal Problem Of Kirchhoff Type

The nonlocal term in the nonlinear equations of Kirchhoff type causes difficulties when the equation is solved numerically by using the Newton-Raphson method. This is because the Jacobian of the Newton-Raphson method is full. In this article, the finite element system is replaced by an equivalent system for which the Jacobian is sparse. We derive quasi-optimal error estimates for the finite element method and demonstrate the results with numerical experiments.

A Numerical Scheme for Three-Dimensional Front Propagation and Control of Jordan Mode

As an example of a front propagation, we study the propagation of a three-dimensional nonlinear wavefront into a polytropic gas in a uniform state and at rest. The successive positions and geometry of the wavefront are obtained by solving the conservation form of equations of a weakly nonlinear ray theory. The proposed set of equations forms a weakly hyperbolic system of seven conservation laws with an additional vector constraint, each of whose components is a divergence-free condition. This constraint is an involution for the system of conservation laws, and it is termed a geometric solenoidal constraint. The analysis of a Cauchy problem for the linearized system shows that when this constraint is satisfied initially, the solution does not exhibit any Jordan mode. For the numerical simulation of the conservation laws we employ a high resolution central scheme. The second order accuracy of the scheme is achieved by using MUSCL-type reconstructions and Runge-Kutta time discretizations. A constrained transport-type technique is used to enforce the geometric solenoidal constraint. The results of several numerical experiments are presented, which confirm the efficiency and robustness of the proposed numerical method and the control of the Jordan mode.