Molecular valence calculations on cyclohexasulfur,cycloheptasulfur, and cyclooctasulfur

A theoretical study of homocyclic sulfur species S₆, S₇, and S₈ was carried out using a molecular valence method involving stepwise approximations for orthogonality and core-valence interactions. The valence shell orbitals are described at the minimal basis level. The geometries of the molecules are predicted well as compared with other theoretical studies and the experimental values. The slight overestimation of the SS bond length is typical to the nonpolarized basis sets. The energies of the valence orbitals are well in accord with the conventional all-electron ab initio results. The trend in the stabilities of the three molecules is discussed. The present method provides an attractive possibility to study homocyclic and heterocyclic systems involving heavier chalcogens with no increase of the computing time.     

A time-differential measurement of the hyperfine structure of the 6.13 MeV state in highly ionized 16O atoms

A time-differential technique has been developed which makes possible the observation of time dependent effects produced by hyperfine interactions in highly ionized atoms during recoil into vacuum. Theoretical and experimental considerations of the technique are discussed and a value for |g_I| of 0.55 ± 0.03 has been obtained for the 6.13 MeV (3^?) state of ¹⁶O.     

Core-shell nanoparticles: characterization and study of their use for the encapsulation of hydrophobic fluorescent dyes

Core-shell nanocapsules intended to be used as drug scavengers were prepared using a surfactant mixture containing octadecyltrimethoxysilane (OTMS) as a reactive amphiphile, to form spherical templates. A siloxane shell was grown on the surface of the templates by reacting tetramethoxysilane (TMOS) with the silanol groups obtained after the hydrolysis and condensation of OTMS. Dynamic light scattering (DLS) showed that particles with diameters in the range of 100-200 nm were obtained, with core and shell sizes controlled by varying component compositions. Atomic force microscopy (AFM) was used to study the effect of the silica coating of the templates on their robustness after deposition on a substrate. Subsequently, we present studies on the encapsulation of two hydrophobic fluorescent dyes, which are sensors of polarity and rigidity. Steady-state fluorescence spectroscopy was used to examine the fluorescence response of the dyes before and after shell growth. Changes in the emission of the encapsulated dyes were related to changes in the polarity and rigidity of the microenvironment where the dyes were located and correlated to the AFM results. Finally, dye-free core-shell particles were used to sequester the dyes from aqueous suspensions. Fluorescence of the sequestered species was compared to the dye-loaded particles to determine the final fate of the fluorophores in the nanoparticles.     

Quantifying the fraction of glycine and alanine in beta-sheet and helical conformations in spider dragline silk using solid-state NMR

Solid-state two-dimensional refocused INADEQUATE MAS NMR experiments resolve distinct helical and beta-sheet conformational environments for both alanine and glycine in Nephila clavipes dragline silk fibers; the fraction of alanine and glycine in beta-sheet structures is determined to be 82% +/- 4% and 28% +/- 5%, respectively.     

Charge-transfer complex formation between p-chloranil and 1,n-dicarbazolylalkanes

Dimer model compounds of polyvinylcarbazoles (1,n-di(N-carbazolyl)alkanes, when n=1-5) were synthesized to model the effects of distance and orientation between carbazole groups in polymeric systems. Charge-transfer (CT) complexes of carbazole, N-ethylcarbazole and 1,n-di(N-carbazolyl)alkanes with p-chloranil (p-CHL) have been investigated spectrophotometrically in dichloromethane. The colored products are measured spectrophotometrically at different wavelength depending on the electronic transition between donors and acceptor. The formation constants of the CT complexes were determined by the Benesi-Hildebrand equation. The thermodynamic parameters were calculated by Van't Hoff equation. Stochiometries of the complexes formed between donors and acceptor were defined by the Job's method of the continuous variation and found in 1:1 complexation with donor and acceptor at the maximum absorption bands.     

Hydrocarbon fuel effects in solid-oxide fuel cell operation: an experimental and modeling study of n-hexane pyrolysis

Pyrolysis experiments of n-hexane were performed and the product distribution and fuel consumption were measured as a function of temperature. The experimental temperatures ranged from 550-675 degrees C, with a pressure of approximately 1 atm, and residence times of approximately 5 s. N-Hexane was used as a model compound to represent the linear alkanes that might be found in practical hydrocarbon fuels. Under these conditions, high fuel conversion was observed at the higher temperatures and a wide range of products were formed. The experimental observations were compared to predictions from a plug-flow model using a reaction mechanism consisting of 205 species and 1403 reactions. The hydrogen abstraction and isomerization rate coefficients in this model were based on CBS-QB3 calculations. The only model modification was adjustment of the A-factor of the initiation rates to match conversion at one temperature. This model was able to successfully predict the observed trends in both product selectivities as well as fuel conversion over the temperature range. The mechanism was also used to capture the trends previously observed in n-butane pyrolysis under similar experimental conditions. Significant differences in the sensitivity coefficients for the hexane and butane systems are discussed in terms of the competition between beta-scission and isomerization of the initial radicals formed. The kinetic model predicts that n-hexane will be completely converted within 0.1 s in the higher temperature environment ( approximately 800 degrees C) of the anode channel of a solid-oxide fuel cell (SOFC). This result clearly illustrates the need to explicitly account for gas-phase reactions in SOFC models for those cases where hydrocarbons, especially those larger than methane, are fed directly to an SOFC.     

Structural acoustic control of plates with variable boundary conditions: design methodology

A method for optimizing a structural acoustic control system subject to variations in plate boundary conditions is provided. The assumed modes method is used to build a plate model with varying levels of rotational boundary stiffness to simulate the dynamics of a plate with uncertain edge conditions. A transducer placement scoring process, involving Hankel singular values, is combined with a genetic optimization routine to find spatial locations robust to boundary condition variation. Predicted frequency response characteristics are examined, and theoretically optimized results are discussed in relation to the range of boundary conditions investigated. Modeled results indicate that it is possible to minimize the impact of uncertain boundary conditions in active structural acoustic control by optimizing the placement of transducers with respect to those uncertainties.     

Polystyrene-block-poly(ethylene oxide) stars as surface films at the air/water interface

Star diblock copolymers containing polystyrene (PS) and poly(ethylene oxide) (PEO) were investigated as surface films at the air/water interface. Both classic and dendritic-like stars were prepared containing either a PS core and PEO corona or the reverse. The investigated polymers, consisting of systematic variations in architectures and compositions, were spread at the air/water interface, generating reproducible surface pressure-area isotherms. All of the films could be compressed to higher pressures than would be possible for pure PEO. For stars containing 20% or more PEO, three distinct regions appeared. At higher areas, the PEO absorbs in pancakelike structures at the interface with PS globules sitting atop. Upon compression, a pseudoplateau transition region appeared. Both regions strongly depended on PEO composition. The pancake area and the pseudoplateau width and pressure increased in a linear fashion with an increasing amount of PEO. In addition, minimum limits of PEO chain length and mass percentage were determined for observing a pseudoplateau. At small areas, the film proved less compressible, producing a rigid film in which PS dominated. Here, the film area increased with both molecular weight and the amount of PS. Comparison with pure linear PS showed the stars spread more, occupying greater areas. Among the stars, the PEO-core stars were more compact while the PS-core stars spread more. The influence of architecture in terms of the core/corona polymers and branching were also examined. The effects of architecture were subtle, proving less important than PEO chain length or mass percentage.