Probing potential energy surfaces in confined systems: behavior of mean-square displacement in zeolites

Time evolution of mean-squared displacement based on molecular dynamics for a variety of adsorbate-zeolite systems is reported. Transition from ballistic to diffusive behavior is observed for all the systems. The transition times are found to be system dependent and show different types of dependence on temperature. Model calculations on a one-dimensional system are carried out which show that the characteristic length and transition times are dependent on the distance between the barriers, their heights, and temperature. In light of these findings, it is shown that it is possible to obtain valuable information about the average potential energy surface sampled under specific external conditions.

Synthesis, glucose uptake activity and structure-activity relationships of some novel glitazones incorporated with glycine, aromatic and alicyclic amine moieties via two carbon acyl linker

Three series of novel glitazones were designed and prepared by using appropriate synthetic schemes to incorporate glycine, aromatic and alicyclic amines via two carbon linker. Compounds were synthesized both under conventional and microwave methods. Nineteen out of twenty four synthesized compounds were evaluated for their in vitro glucose uptake activity using isolated rat hemi-diaphragm. Compounds, 6, 9a, 13a, 13b, 13c, 13f and 13h exhibited significant glucose uptake activity. Illustration about their synthesis and in vitro glucose uptake activity is described along with the structure activity relationships. (C) 2010 Elsevier Masson SAS. All rights reserved.

Characterization of aerosol black carbon over a tropical semi-arid region of Anantapur, India

Black carbon (BC) aerosol mass concentrations measured using an aethalometer at Anantapur, a semi-arid tropical station in the southern part of peninsular India, from August 2006 to July 2007 are analyzed. Seasonal and diurnal variations of BC in relation to changes in the regional meteorological conditions have been studied along with the mass fraction of BC to the total aerosol mass concentration (M-t) and fine particle mass (FPM) concentration in different months. The data collected during the study period shows that the annual average BC mass concentration at Anantapur is 1.97 +/- 0.12 mu g m(-3). Seasonal variations of BC aerosol mass concentration showed high during the dry (winter and summer) seasons and low during the post-monsoon followed by the monsoon seasons. Diurnal variations of BC aerosols attain a gradual build up in BC concentration from morning and a sharp peak occurs between 07:00 and 09:00 h almost an hour after local sunrise and a broad nocturnal peak from 19:00 to 21:00 h with a minimum in noon hours. The ratio of BC to the fine particle mass concentration was high during the dry season and low during the monsoon season. The regression analysis between BC mass concentration and wind speed indicates that, with increase in wind speeds the BC mass concentrations would decrease and vice-versa. Aerosol BC mass concentration shows a significant positive correlation with total mass concentration (M-t) and aerosol optical depth (ACID, tau(p)) at 500 nm. (C) 2010 Elsevier B.V. All rights reserved.

Surface-ray tracing on hybrid surfaces of revolution for UTD mutual coupling analysis

An angle invariance property based on Hertz's principle of particle dynamics is employed to facilitate the surface-ray tracing on nondevelopable hybrid quadric surfaces of revolution (h-QUASOR's). This property, when used in conjunction with a Geodesic Constant Method, yields analytical expressions for all the ray-parameters required in the UTD formulation. Differential geometrical considerations require that some of the ray-parameters (defined heuristically in the UTD for the canonical convex surfaces) be modified before the UTD can be applied to such hybrid surfaces. Mutual coupling results for finite-dimensional slots have been presented as an example on a satellite launch vehicle modeled by general paraboloid of revolution and right circular cylinder.

Chemical and microstructural modifications in LiPON thin films exposed to atmospheric humidity

Lithium phosphorus oxynitride (LiPON), the widely used solid electrolyte for thin film microbatteries, is not compatible with the ambient humid temperatures. The reasons for reduction in ionic conductivity of LiPON thin films from 2.8 x 10(-6) Scm(-1) to 9.9 x 10(-10) Scm(-1) when exposed to air are analyzed with the aid of AC impedance measurements, SEM, XPS and stylus profilometry. Initially, particulate-free film surfaces obtained soon after rf sputter deposition in N-2 ambient conditions becomes covered with microstructures, forming pores in the film when exposed to air. LiPON films are deposited on Ti coated silicon in addition to bare silicon, ruling out the possibility of stress-related rupturing from the LiPON/Si interface. The reduction of nitrogen, phosphorus, and increased presence of lithium, oxygen and carbon over the film surface lowers the ionic conductivity of LiPON films when exposed to air. (c) 2011 Elsevier B.V. All rights reserved.

Applicability of Butler's equation in interpreting the thermodynamic behavior of surfaces and adsorption in Fe-S-O melts

Expressions for various second-order derivatives of surface tension with respect to composition at infinite dilution in terms of the interaction parameters of the surface and those of the bulk phases of dilute ternary melts have been presented. A method of deducing the parameters, which consists of repeated differentiation of Butler's equations with subsequent application of the appropriate boundary conditions, has been developed. The present investigation calculates the surface tension and adsorption functions of the Fe-S-O melts at 1873 and 1923 K using the modified form of Butler's equations and the derived values for the surface interaction parameters of the system. The calculated values are found to be in good agreement with those of the experimental data of the system. The present analysis indicates that the energetics of the surface phase are considerably different from those of the bulk phase. The present research investigates a critical compositional range beyond which the surface tension increases with temperature. The observed increase in adsorption of sulfur with consequent desorption of oxygen as a function of temperature above the critical compositional range has been ascribed to the increase of activity ratios of oxygen to sulfur in the surface relative to those in the bulk phase of the system.

C-13 MAS NMR spectra of cis,cis-mucononitrile in liquid-crystalline media and in the solid state. Orientation of the carbon chemical-shift tensors

The spinning sidebands observed in the C-13 MAS NMR spectra of cis,cis-mucononitrile oriented in liquid-crystalline media and of the neat sample in the solid state are studied. There are differences in the sideband intensity patterns in the two cases. These differences arise because the order parameters which characterize the orientation of the solute in the liquid-crystalline media differ for different axes. It is shown that, in general, the relative intensities of the sidebands contain information on the sign and magnitude of an effective chemical-shift parameter which is a function of the sum of the products of the principal components of the chemical-shift tensor and the corresponding order parameters with respect to the director. A method for obtaining the orientation of the carbon chemical-shift tensor is proposed. The carbon chemical-shift tensors obtained from gauge-including atomic orbital calculations are also presented for comparison. (C) 1996 Academic Press, Inc.

Carbon-13 and proton relaxation study of backbone dynamics of poly(vinyl acetate) in solution

The dynamics of poly(vinyl acetate) in toluene solution has been examined by C-13 and proton relaxation. C-13 spin-lattice relaxation time and nuclear Overhauser enhancement measurements were carried out as a function of temperature at 50.3 and 100.6 MHz. The spin-lattice relaxation times for backbone protons were measured at different temperatures at 200 MHz. The relaxation data have been analyzed using the Hall-Weber-Helfand (HWH) model, which describes backbone dynamics in terms of conformational transitions and the Dejean-Laupretre-Monnerie (DLM) model, which includes bond librations in addition to conformational transitions. The parameters obtained from the analysis of C-13 relaxation data were utilized to predict the proton relaxation data. The DLM model was found to be more successful in reproducing the experimental results. To study the influence of libration further, proton relaxation data for poly(vinyl acetate) over a wider range of temperature reported in the literature were analyzed by these two models. The DLM model could reproduce the experimental data at all temperatures whereas the HWH model was found to be successful only in accounting for the experimental data at high temperatures. The results demonstrate the importance of including the librational mode in the description of the backbone dynamics in polymers.

Carbon-13 relaxation study of chain segmental motion and side-chain internal rotations of poly(isobutyl methacrylate) in solution

The dynamics of poly(isobutyl methacrylate) in toluene solution has been examined by C-13 spin-lattice relaxation time and NOE measurements as a function of temperature. The experiments were performed at 50.3 and 100.6 MHz. The backbone carbon relaxation data have been analyzed using the Dejean-Laupretre-Monnerie (DLM) model, which describes the dynamical processes in the backbone in terms of conformational transitions and bond librations. The relaxation data of the side chain nuclei have been analyzed by assuming different motional models, namely, unrestricted rotational diffusion, three site jumps, and restricted rotational diffusion. The different models have been compared for their ability to reproduce the experimental spin-lattice relaxation times and also to predict the behavior of NOE as a function of temperature. Conformational energy calculations have been carried out on a model compound by using the semiempirical quantum chemical method, AM1, and the results confirm the validity of the motional models used to describe the side-chain motion.

Conductivity and structural studies on disordered amorphous conducting carbon films

Amorphous carbon films are prepared by the pyrolysis of Tetra Chloro Phthalic Anhydride (TCPA) at different temperatures (700 degrees C to 900 degrees C). DC Conductivity measurements are done on the films in the temperature range 300K to 4.2K. It shows an activated temperature dependence with a small activation energy (0.02eV to 0.003eV). Variable range hopping is observed at low temperatures. The films are characterised by XRD, SEM, TEM, AFM and microRaman. The electronic structure of the film is used to explain the electrical behaviour.

Local polynomial convexity of the union of two totally-real surfaces at their intersection

We consider the following question: Let S (1) and S (2) be two smooth, totally-real surfaces in C-2 that contain the origin. If the union of their tangent planes is locally polynomially convex at the origin, then is S-1 boolean OR S-2 locally polynomially convex at the origin? If T (0) S (1) a (c) T (0) S (2) = {0}, then it is a folk result that the answer is yes. We discuss an obstruction to the presumed proof, and provide a different approach. When dim(R)(T0S1 boolean AND T0S2) = 1, we present a geometric condition under which no consistent answer to the above question exists. We then discuss conditions under which we can expect local polynomial convexity.

Interaction of single-walled carbon nanotubes with poly(propyl ether imine) dendrimers

We study the complexation of nontoxic, native poly(propyl ether imine) dendrimers with single-walled carbon nanotubes (SWNTs). The interaction was monitored by measuring the quenching of inherent fluorescence of the dendrimer. The dendrimer-nanotube binding also resulted in the increased electrical resistance of the hole doped SWNT, due to charge-transfer interaction between dendrimer and nanotube. This charge-transfer interaction was further corroborated by observing a shift in frequency of the tangential Raman modes of SWNT. We also report the effect of acidic and neutral pH conditions on the binding affinities. Experimental studies were supplemented by all atom molecular dynamics simulations to provide a microscopic picture of the dendrimer-nanotube complex. The complexation was achieved through charge transfer and hydrophobic interactions, aided by multitude of oxygen, nitrogen, and n-propyl moieties of the dendrimer. (C) 2011 American Institute of Physics. doi:10.1063/1.3561308]

Thermodynamics of water entry in hydrophobic channels of carbon nanotubes

Experiments and computer simulations demonstrate that water spontaneously fills the hydrophobic cavity of a carbon nanotube. To gain a quantitative thermodynamic understanding of this phenomenon, we use the recently developed two phase thermodynamics method to compute translational and rotational entropies of confined water molecules inside single-walled carbon nanotubes and show that the increase in energy of a water molecule inside the nanotube is compensated by the gain in its rotational entropy. The confined water is in equilibrium with the bulk water and the Helmholtz free energy per water molecule of confined water is the same as that in the bulk within the accuracy of the simulation results. A comparison of translational and rotational spectra of water molecules confined in carbon nanotubes with that of bulk water shows significant shifts in the positions of the spectral peaks that are directly related to the tube radius. (C) 2011 American Institute of Physics.