Theoretical study of unimolecular rearrangements of vinylidenes to acetylenes

The rearrangement of vinylidene to acetylene has been studied in detail by the density functional method, using Becke's three‐parameter exchange functional and the gradient‐corrected functional of Lee, Yang, and Parr. The rearrangement of the anion, as well as that of fluoro‐substituted systems, has also been investigated, in order to determine the effect of fluorine substitution on the activation barrier to the 1,2‐hydrogen shift, as well as the relative migratory aptitudes of hydrogen and fluorine. Natural bond orbital analysis is invoked to gain insight into the mechanisms of the rearrangements. Basis size effects are also discussed, particularly in relation to anionic systems. The need to include diffuse functions in geometry optimizations of anionic systems is reinforced by the present calculations. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Mirror image nanostructures

Chiral molecules that self-assemble to form chiral supramolecular structures exhibit interesting structural features reminiscent of tertiary and quaternary structures of proteins and have applications in catalysis and nonlinear optics. Often, these structures are hierarchical, with their chiral structure difficult to interpret on the molecular scale. In this communication, we observe chiral assembling molecules that form well-defined helices with a pitch of 28 nm. We observe the behavior in both R- and S-enantiomers of the molecule, forming mirror image nanostructures. The molecular chirality is determined by the dimethyloctyl alkyl coil of the molecule and is located more than 4 nm from the hydrogen-bonding segment. The nanostructures observed are not hierarchical, which could be a result of the significant separation between the stereocenter and hydrogen-bonding dendron. The subtle structural modification at the periphery of the molecule biases the supramolecular assembly, which is driven primarily by strong hydrogen-bonding and pi-pi stacking interactions.     

Enantioselective separation on a naturally chiral surface

Kinked-stepped, high Miller index surfaces of metal crystals are chiral and, therefore, exhibit enantiospecific properties. Previous temperature-programmed desorption (TPD) spectra have shown that the desorption energies of R-3-methylcyclohexanone (R-3-MCHO) on the chiral Cu(643)(R) and Cu(643)(S) surfaces are enantiospecific (J. Am. Chem. Soc. 2002, 124, 2384). Here, a comparison of the TPD spectra from Cu(111), Cu(221), Cu(533), Cu(653)(R&S), and Cu(643)(R&S) surfaces reveals that the enantiospecific desorption occurs from the chiral kink sites on the Cu(643) surfaces. Titration of the chiral kink sites with I atoms confirms this assignment of desorption features in the TPD spectra. Finally, the enantiospecific difference in the desorption energies of R- and S-3-MCHO has been used as the basis for demonstration of an enantioselective, kinetic separation of racemic 3-MCHO into its purified components during adsorption and desorption on the Cu(643)(R&S) surfaces.     

Highly Selective and Sensitive Graphene Based Electrochemical Sensor for Quantification of Receptor Agonist Rizatriptan

A highly selective and sensitive electrochemical sensor has been developed by modification of a glassy carbon electrode (GCE) with graphene (GRP) for quantification of Rizatriptan. The significant increase of the peak current and the improvement of the oxidation peak potential indicate that the electrochemical sensor facilitates the electron transfer of Rizatriptan. The oxidation peak current was proportional to the Rizatriptan concentration in the range from 100 to 600 µg/mL with detection (LOD) and quantification limit (LOQ) of 36.52 and 121.73 µg/mL, respectively. The developed method was successfully employed for quantification of Rizatriptan in pharmaceutical formulations. The sensor shows great promise for simple, sensitive and quantitative detection of Rizatriptan.     

Comparison of two theories during self-focusing of Gaussian laser beam in thermal conduction-loss predominant plasmas

In the present paper, self-focusing phenomenon occurring as a result of non-linear interaction of intense laser beam with thermal conduction-loss predominant plasmas is studied by following both approaches viz. paraxial theory approach and moment theory approach. Non-linear differential equations for the beam width parameters of laser beam have been set up and solved numerically in both cases to study the variation of beam width parameters with normalized distance of propagation. Effects of laser intensity as well as plasma density on the beam width parameters have also been analyzed. It is observed from the analysis that in case of moment theory approach, strong self-focusing of laser beam is observed as compared to paraxial theory approach.     

High-rate and high-density gas separation adsorbents and manufacturing method

High-rate and high-density gas separation adsorbents used in vacuum pressure swing adsorption (VPSA) processes are described. Agglomerated zeolite Li–LSX compositions made using colloidal silica binding agents and having improved nitrogen pore diffusivity compared to like compositions prepared with traditional clay binders, are also described. Preparation methods for the colloidal silica-bound adsorbents are described together with their characterization by mercury (Hg) porosimetry, scanning electron microscopy (SEM) and low dead-volume breakthrough testing, from which the pore diffusivity is obtained. In this article, we show how the location and dispersion of the colloidal silica binding agent within the agglomerated zeolite particle yields pore-architectures that resemble “state-of-the-art” binderless adsorbents. In addition, we use VPSA process simulations to show that the best process performance is achieved by the combination of high-rate and high-density adsorbent properties.     

Electrochemical determination of thermodynamic properties of DyRhO3 and phase relations in the system Dy-Rh-O

Thermodynamic properties of Dysprosium rhodite (DyRhO₃) are measured in the temperature range from 900 to 1,300 K using a solid-state electrochemical cell incorporating yttria-stabilized zirconia as the electrolyte. The standard Gibbs free energy of formation of DyRhO₃ with O-type perovskite structure from its components binary oxides, Dysprosia with C-rare earth structure and β-Rh₂O₃ with orthorhombic structure, can be represented by the equation: $$ {{{\varDelta G_{{f\left( {ox} \right)}}^o\left( {\pm 182} \right)}} \left/ {{{\mathrm{J} ~ \mathrm{mo}}{{\mathrm{l}}^{{ - 1}}}}} \right.} = - 52710 + 3.821\left( {{{T} \left/ {\mathrm{K}} \right.}} \right). $$ By using the thermodynamic data for DyRhO₃ from experiment and auxiliary data for other phases from the literature, the phase relations in the system Dy-Rh-O are computed. Thermodynamic data for intermetallic phases in the binary system Dy-Rh, required for constructing the chemical potential diagrams, are evaluated using calorimetric data available in the literature for three intermetallics and Miedema’s model, consistent with the phase diagram. The results are presented in the form of Gibbs triangle, oxygen potential–composition diagram, and three-dimensional chemical potential diagram at 1,273 K. Temperature–composition diagrams at constant oxygen partial pressures are also developed. The decomposition temperature of DyRhO₃ is 1,732 (±2.5) K in pure oxygen and 1,624 (±2.5) K and in air at standard pressure.     

Synthesis and thermal evaluation of novel mono- and bis-adamantylated resorcinol-based phthalonitrile resins with enhanced solubility

Journal of Thermal Analysis and Calorimetry - Phthalonitrile (PN) resins are high-temperature-resistant thermosetting polymers which find applications in military as well as aerospace owing to...     

Lossy mode resonance-based uniform core tapered fiber optic sensor for sensitivity enhancement

A lossy mode resonance (LMR)-supported fiber optic sensor in which a uniform fiber core is placed among two identical tapered regions, is investigated numerically. Indium tin oxide (ITO) and aluminum-doped zinc oxide (AZO) are considered as LMR active materials used to excite several lossy modes and gold and silver are used as surface plasmon resonance (SPR) active materials. In this probe design, a central uniform core coated with ITO/AZO is the active sensing region, whereas tapered regions are meant for bringing the incident angle close to the critical angle. The sensitivity of the present fiber optic bio-sensor is evaluated for first two LMRs utilizing both ITO and AZO separately, along with its variation with the taper ratio (TR). For ITO, the maximum sensitivity values are observed to be 18.425 μm RIU⁻¹ (refractive index unit) and 0.825 μm RIU⁻¹, corresponding to the first and second LMRs, respectively, at a TR of 1.6 and for AZO, equivalent values are 0.79 μm RIU⁻¹ and 0.35 μm RIU⁻¹, respectively, at a TR of 2.0. The results illustrate that the first LMR is more sensitive than the second LMR and the ITO-coated probe possesses greater sensitivity than the AZO-coated probe for both LMRs. Similarly, for the fiber optic SPR sensor, the maximum value of sensitivity is 5.6425 μm RIU⁻¹, in the case of gold and 5.0615 μm RIU⁻¹ in the case of silver, at a TR of 1.6. Hence, the result shows that the sensor with the present fiber optic probe design has around a 3-fold enhancement in sensitivity compared with conventional SPR sensors. This study will have applications in many sensing schemes where the requirement of large sensitivity is vital.