Conformational Dynamics in Alkyl Chains of an Anchored Bilayer: A Molecular Dynamics Study

Molecular dynamics (MD) simulations are reported for an anchored bilayer formed by the intercalation of cetyl trimethyl ammonium (CTA) and CH3(CH2)15N+(CH3) ions in a layered solid, CdPS3. The intercalated CTA ions are organized with the cationic headgroups tethered to the inorganic sheet and the hydrocarbon tails arranged as bilayers. Simulations were performed at three temperatures, 65, 180, and 298 K, using an isothermal−isobaric ensemble that was subsequently switched once macroscopic parameters had converged to a canonical isothermal−isochoric ensemble. The simulations are able to reproduce the experimental features of this system, including the formation of the bilayer and layer-to-layer separation distance. An analysis of the conformation of the chains showed that at all three temperatures a fraction of the alkyl chains retained a planar all-trans conformation, and that gauche bonds occurred as part of a “kink” (gauche+−trans−gauche−) sequence and not as isolated gauche bonds. Trans−gauche isomerization rates for the alkyl chains in the anchored bilayer are slower than those in lipid bilayers at the same temperature and show a progressive increase as the torsion numbers approach the tail. A two-dimensional periodic Voronoi tessellation analysis was performed to obtain the single-molecular area of an alkyl chain in the bilayer. The single-molecular area relaxation times are an order of magnitude longer than the trans−gauche isomerization times. The results indicate that the trans−gauche isomerization is associated with the creation and annihilation of a kink defect sequence. The results of the present MD simulation explain the apparent conflicting estimates of the gauche disorder in this system as obtained from infrared and 13C nuclear magnetic resonance measurements.

Thermodynamics of ligand (substrate end product) binding to endoxylanase from Chainia sp. (NCL-82-5-1): isothermal calorimetry and fluorescence titration studies

The binding of xylo-oligosaccharides to Chainia endoxylanase resulted in a decrease in fluorescence intensity of the enzyme with the formation of 1:1 complex. Equilibrium and thermodynamic parameters of ligand binding were determined by fluorescence titrations and titration calorimetry. The affinity of xylanase for the oligosaccharides increases in the order X-2 < X-3 < X-4 less than or equal to X-5. Contributions from the enthalpy towards the free energy change decreased with increasing chain length from X-2 to X-4, whereas an increase in entropy was observed, the change in enthalpy and entropy of binding being compensatory. The entropically driven binding process suggested that hydrophobic interactions as well as hydrogen bonds play a predominant role in ligand binding.

Adenosine-5'-carboxylic Acid

The two molecules in the asymmetric unit of adenosine-5'-carboxylic acid, C10H11N5O5, exist as zwitterions with N1 protonated and the carboxyl groups ionized. Both molecules are in an anti conformation with glycosyl torsion angles of -161.4(3) and -155.5(3)degrees. The ribose moieties adopt a C3-endo-C2-exo twist conformation. The pseudo-rotation parameters are P = 0.01(1) and 6.58(1)degrees, and tau(m) = 36.2(2) and 34.6(2)degrees, for molecules A and B, respectively. The carboxyl groups of A and B are not in the standard g(+), g(-) or t conformations. Both Watson-Crick sites, N1 and N6, of the adenine bases are involved in a pair of hydrogen bonds with the dissociated carboxyl groups, forming a cyclic tetramer. The adenine base of molecule A stacks on the ribose O4' atom of a symmetry-related B molecule at a distance of 2.88 Angstrom; the adenine base of B stacks in an analogous way at a distance of 2.91 Angstrom.

2.5-dimensional solution of the advective accretion disk:a self-similar approach

We provide a 2.5-dimensional solution to a complete set of viscous hydrodynamical equations describing accretion- induced outflows and plausible jets around black holes/compact objects. We prescribe a self-consistent advective disk-outflow coupling model, which explicitly includes the information of vertical flux. Inter-connecting dynamics of an inflow-outflow system essentially upholds the conservation laws. We provide a set of analytical family of solutions through a self-similar approach. The flow parameters of the disk-outflow system depend strongly on the viscosity parameter α and the cooling factor.

Zeeman effect of chlorine nuclear quadrupole resonance and hydrogen bonding in 2,6-, 2,5- and 3,5-dichlorophenols

The Zeeman effect of chlorine nuclear quadrupole resonance in polycrystalline samples of 2,6-, 2,5 and 3,5-dichlorophenol has been investigated at room temperature in order to study the effect of hydrogen bonding on the electric field gradient asymmetry parameter n. While the two n.q.r. lines in 3,5-dichlorophenol gave an asymmetry parameter of 10%, those in 2,6- and 2,5-dichlorophenol gave different values of n for the two chlorines. The chlorine atom which is ortho to the OH group and involved in hydrogen bonding (i.e., corresponding to the low frequency line) gave an asymmetry parameter of 0.21 in 2,6-dichlorophenol and 0.17 in 2,5-dichlorophenol while the other chlorine (i.e., corresponding to the high frequency line) gave a lower value of 0.12 in 2,6-dichlorophenol and 0.11 in 2,5-dichlorophenol. These values of n are discussed in terms of hydrogen bonding and bond parameters.

Estimation of cosmological parameters from neutral hydrogen observations of the post-reionization epoch

The emission from neutral hydrogen (HI) clouds in the post-reionization era (z <= 6), too faint to be individually detected, is present as a diffuse background in all low frequency radio observations below 1420MHz. The angular and frequency fluctuations of this radiation (similar to 1 mK) are an important future probe of the large-scale structures in the Universe. We show that such observations are a very effective probe of the background cosmological model and the perturbed Universe. In our study we focus on the possibility of determining the redshift-space distortion parameter beta, coordinate distance r(nu), and its derivative with redshift r(nu)('). Using reasonable estimates for the observational uncertainties and configurations representative of the ongoing and upcoming radio interferometers, we predict parameter estimation at a precision comparable with supernova Ia observations and galaxy redshift surveys, across a wide range in redshift that is only partially accessed by other probes. Future HI observations of the post-reionization era present a new technique, complementing several existing ones, to probe the expansion history and to elucidate the nature of the dark energy.

Optical Properties of Nanocrystalline Potassium Lithium Niobate in the Glass System (100-x) TeO2-x(1.5K(2)O-Li2O-2.5Nb(2)O(5))

Optically clear glasses of various compositions in the system (100-x) TeO2-x(1.5K(2)O-Li2O-2.5Nb(2)O(5)) (2 <= x <= 12, in molar ratio) were prepared by the melt-quenching technique. The glassy nature of the as-quenched samples was established via differential scanning calorimetry (DSC). The amorphous and the crystalline nature of the as-quenched and heat-treated samples were confirmed by the X-ray powder diffraction and transmission electron microscopic (TEM) studies. Transparent glasses comprising potassium lithium niobate (K3Li2Nb5O15) microcrystallites on the surface and nanocrystallites within the glass were obtained by controlled heat-treatment of the as-quenched glasses just above the glass transition temperature (T-g). The optical transmission spectra of these glasses and glass-crystal composites of various compositions were recorded in the 200-2500 nm wavelength range. Various optical parameters such as optical band gap, Urbach energy, refractive index were determined. Second order optical non-linearity was established in the heat-treated samples by employing the Maker-Fringe method.

Study of Friction and Transfer Layer Formation in Copper-Steel Tribo-System: Role of Surface Texture and Roughness Parameters

In the present investigation, experiments were conducted on a tribological couple-copper pin against steel plate-using an inclined pin-on-plate sliding tester to understand the role of surface texture and roughness parameters of the plate on the coefficient friction and transfer layer formation. Two surface characteristics of the steel plates-roughness and texture-were varied in the tests. It was observed that the transfer layer formation and the coefficient of friction along with its two components, namely, the adhesion and plowing, are controlled by the surface texture of the plate. The plowing component of friction was highest for the surface texture that promotes plane strain conditions while it was lowest for the texture that favors plane stress conditions at the interface. Dimensionless quantifiable roughness parameters were formulated to describe the degree of plowing and hence the plane strain/stress type deformations taking place at the asperity level.

Intermolecular charge-transfer complexes of macrocyclic polyethers with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone

The interactions of benzo-15-crown-5, dibenzo-18-crown-6, and dibenzo-24-crown-8 with 2,3-dichloro-5,6-dicyano- 1,4-benzoquinone have been studied in methylene chloride by using spectroscopic methods. These crown ethers from 1:l molecular complexes with the acceptor. The magnitudes of association constants and thermodynamic parameters of complexation are indicative of cooperative interaction of oxygens with the acceptor.

An approximate mathematical procedure for the determination of characteristic parameters for a general case in three dimensional photoelasticity

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Comparison of performance parameters of poly(3,4 ethylenedioxythiophene) (PEDOT) based electrochromic device on glass with and without counter electrode

Conjugated polymers are promising materials for electrochromic device technology. Aqueous dispersions of poly(3,4-ethylenedioxythiophene)-(PEDOT) were spin coated onto transparent conducting oxide (TCO) coated glass substrates. A seven-layer electrochromic device was fabricated with the following configuration: glass/transparent conducting oxide (TCO)/PEDOT (main electrochromic layer)/gel electrolyte/prussian blue (counter electrode)/TCO/glass. The device fabricated with counter electrode (Prussian blue) showed a contrast of 18% and without counter electrode showed visible contrast of 5% at 632 nm at a voltage of 1.9 V. The comparison of the device is done in terms of the colouration efficiency of the devices with and without counter electrode.

Effect of process parameters on transport phenomena during solidification in the presence of electromagnetic stirring

In the present work, a numerical study is performed to predict the effect of process parameters on transport phenomena during solidification of aluminium alloy A356 in the presence of electromagnetic stirring. A set of single-phase governing equations of mass, momentum, energy and species conservation is used to represent the solidification process and the associated fluid flow, heat and mass transfer. In the model, the electromagnetic forces are incorporated using an analytical solution of Maxwell equation in the momentum conservation equations and the slurry rheology during solidification is represented using an experimentally determined variable viscosity function. Finally, the set of governing equations is solved for various process conditions using a pressure based finite volume technique, along with an enthalpy based phase change algorithm. In present work, the effect of stirring intensity and cooling rate are considered. It is found that increasing stirring intensity results in increase of slurry velocity and corresponding increase in the fraction of solid in the slurry. In addition, the increasing stirring intensity results uniform distribution of species and fraction of solid in the slurry. It is also found from the simulation that the distribution of solid fraction and species is dependent on cooling rate conditions. At low cooling rate, the fragmentation of dendrites from the solid/liquid interface is more.

ErbB-2 expression and its association with other biological parameters of breast cancer among Indian women

Overexpression of the epidermal growth factor receptor family genes, which include ErbB-1, 2, 3 and 4, has been implicated in a number of cancers. We have studied the extent of ErbB-2 overexpression among Indian women with sporadic breast cancer. Methods: Immmunohistochemistry and genomic polymerase chain reaction (PCR) were used to study the ErbB2 overexpression. ErbB2 status was correlated with other clinico-pathological parameters, including patient survival. Results: ErbB-2 overexpression was detected in 43.2% (159/368) of the cases by immunohistochemistry. For a sub-set of patients (n = 55) for whom total DNA was available, ErbB-2 gene amplification was detected in 25.5% (14/55) of the cases by genomic PCR. While the ErbB2 overexpression was significantly higher in patients with lymphnode (χ2 = 12.06, P≤ 0.001), larger tumor size (χ2 = 8.22, P = 0.042) and ductal carcinoma (χ2 = 15.42, P ≤ 0.001), it was lower in patients with disease-free survival (χ2 = 22.13, P ≤ 0.001). Survival analysis on a sub-set of patients for whom survival data were available (n = 179) revealed that ErbB-2 status (χ2 =25.94, P ≤ 0.001), lymphnode status (χ2 = 12.68, P ≤ 0.001), distant metastasis (χ2 = 19.49, P ≤ 0.001) and stage of the disease (χ2 = 28.04, P ≤0.001) were markers of poor prognosis. Conclusions: ErbB-2 overexpression was significantly greater compared with the Western literature, but comparable to other Indian studies. Significant correlation was found between ErbB-2 status and lymphnode status, tumor size and ductal carcinoma. ErbB-2 status, lymph node status, distant metastasis and stage of the disease were found to be prognostic indicators.

Impedance parameters and the state-of-charge. III. Zinc-manganese dioxide and magnesium-manganese dioxide dry batteries

The problem of non-destructive determination of the state-of-charge of zinc- and magnesium-manganese dioxide dry batteries is examined experimentally from the viewpoint of internal impedance and open-circuit voltage at equilibrium. It is shown that the impedance is mainly charge-transfer controlled at relatively high states-of-charge and progressively changes over to diffusion control as the state-of-charge decreases in the case of zinc-manganese dioxide dry batteries. On the other hand, the impedance is mainly diffusion controlled for undischarged batteries but becomes charge-transfer controlled as soon as there is some discharge in the case of magnesium-manganese dioxide batteries. It is concluded that the determination of state-of-charge is not possible for both types of batteries by the measurement of impedance parameters due to film-induced fluctuations of these parameters. The measurement of open-circuit voltage at equilibrium can be used as a state-of-charge indicator for Zn-MnO2 batteries but not for Mg-MnO2 batteries.