What does pressure decide to cook with orientationally disordered plastic phase of cubane: an orientational glass or crystal?

The effect of pressure on the structure and reorientational motion of molecules in orientationally disordered (OD) crystalline phase of cubane has been investigated in detail using variable shape molecular simulations in constant-pressure constant-temperature ensemble. Complete orientational ordering occurs at a pressure of 1.0 GPa and the OD phase transforms to an orientationally ordered phase at this pressure. The transition is associated with a kink in the variation of structural parameters such as cell parameters, unit-cell volume, and interaction energy. This transition is also associated with an anomaly in specific heat. Above this transition pressure, the structural quantities display only smaller changes with further increase in pressure. The structure of high-pressure orientationally ordered (HPOO) phase has been characterized using radial distribution functions and orientational distribution function. From detailed analysis of the structure of HPOO phase we conclude that it is isostructural with low-temperature orientationally ordered phase. The OD phase has four times larger compressibility than the HPOO phase.     

Adsorption of comb copolymers on weakly attractive solid surfaces

In this work continuum and lattice Monte Carlo simulation methods are used to study the adsorption of linear and comb polymers on flat surfaces. Selected polymer segments, located at the tips of the side chains in comb polymers or equally spaced along the linear polymers, are attracted to each other and to the surface via square-well potentials. The rest of the polymer segments are modeled as tangent hard spheres in the continuum model and as self-avoiding random walks in the lattice model. Results are presented in terms of segment-density profiles, distribution functions, and radii of gyration of the adsorbed polymers. At infinite dilution the presence of short side chains promotes the adsorption of polymers favoring both a decrease in the depletion-layer thickness and a spreading of the polymer molecule on the surface. The presence of long side chains favors the adsorption of polymers on the surface, but does not permit the spreading of the polymers. At finite concentration linear polymers and comb polymers with long side chains readily adsorb on the solid surface, while comb polymers with short side chains are unlikely to adsorb. The simple models of comb copolymers with short side chains used here show properties similar to those of associating polymers and of globular proteins in aqueous solutions, and can be used as a first approximation to investigate the mechanism of adsorption of proteins onto hydrophobic surfaces.     

Computer simulation study of probe-target hybridization in model DNA microarrays: effect of probe surface density and target concentration

We use lattice Monte Carlo simulations to study the thermodynamics of hybridization of single-stranded "target" genes in solution with complementary "probe" DNA molecules immobilized on a microarray surface. The target molecules in our system contain 48 segments and the probes tethered on a hard surface contain 8-24 segments. The segments on the probe and target are distinct, with each segment representing a sequence of nucleotides that interacts exclusively with its unique complementary target segment with a single hybridization energy; all other interactions are zero. We examine how surface density (number of probes per unit surface area) and concentration of target molecules affect the extent of hybridization. For short probe lengths, as the surface density increases, the probability of binding long stretches of target segments increases at low surface density, reaches a maximum at an intermediate surface density, and then decreases at high surface density. Furthermore, as the surface density increases, the target is less likely to bind completely to one probe; instead, it binds simultaneously to multiple probes. At short probe lengths, as the target concentration increases, the fraction of targets binding completely to the probes (specificity) decreases. At long probe lengths, varying the target concentration does not affect the specificity. At all target concentrations as the probe length increases, the fraction of target molecules bound to the probes by at least one segment (sensitivity) increases while the fraction of target molecules completely bound to the probes (specificity) decreases. This work provides general guidelines to maximizing microarray sensitivity and specificity. Our results suggest that the sensitivity and specificity can be maximized by using probes 130-180 nucleotides long at a surface density in the range of 7 x 10(-5)- 3 x 10(-4) probe molecules per nm(2).     

Survey of the quasi-ternary system La0.8Sr0.2MnO3–La0.8Sr0.2CoO3–La0.8Sr0.2FeO3

An overview on the variation of the thermal expansion, the electrical conductivity as well as non-stoichiometry of the oxide content as a function of composition within the quasi-ternary system La_0.8Sr_0.2MnO_3−δ–La_0.8Sr_0.2CoO_3−δ–La_0.8Sr_0.2FeO_3−δ in air is presented. The various powders were synthesized under identical conditions. The DC electrical conductivity values of the compositions at 800 °C in air vary in a wide range from 15 to 1338 S cm⁻¹. The magnitude of electrical conductivity of the perovskites is mainly determined by the percentage of cobalt in the compositions. A similar behaviour was observed for the measured thermal expansion coefficients between room temperature and 1000 °C in air, increasing from 10.9 to 19.4 × 10⁻⁶ K⁻¹ as a function of cobalt content. Changes in the oxygen stoichiometry of the materials were characterized by temperature-programmed oxidation measurements.     

Carbon/titanium oxide supported bimetallic platinum/iridium nanocomposites as bifunctional electrocatalysts for lithium-air batteries

Platinum (Pt) and iridium (Ir) catalysts are well known to strongly enhance the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics, respectively. Pt–Ir-based bimetallic compounds along with carbon-supported titanium oxides (C–TiO₂) have been synthesized for the application as electrocatalysts in lithium oxygen batteries. Transition metal oxide-based bimetallic nanocomposites (Pt–Ir/C–TiO₂) were prepared by an incipient wetness impregnation technique. The as-prepared electrocatalysts were composed of a well-dispersed homogenous alloy of nanoparticles as confirmed by X-ray diffraction patterns and Fourier transform scanning electron microscopy analyses. The electrochemical characterizations reveal that the Pt–Ir/C–TiO₂ electrocatalysts were bifunctional with high activity for both ORR and OER. When applied as an air cathode catalyst in lithium-air batteries, the electrocatalyst improved the battery performance in terms of capacity, reversibility, and cycle life compared to that of cathodes without any catalysts.     

A closed-loop logistics model for remanufacturing

Recoverable product environments are becoming an increasingly important segment of the overall push in industry towards environmentally conscious manufacturing. Integral to the recoverable product environment is the recoverable manufacturing system that focuses on recovering the product and extending its life through remanufacture or repair. Remanufacturing provides the customer with an opportunity to acquire a product that meets the original product standards at a lower price than a new product. The flow of materials and products in this environment occurs both from the customer to the remanufacturer (reverse flow), and from the remanufacturer to the customer (forward flow). Since most of the products and materials may be conserved, essentially this forms a closed-loop logistics system. We present a 0–1 mixed integer programming model that simultaneously solves for the location of remanufacturing/distribution facilities, the transshipment, production, and stocking of the optimal quantities of remanufactured products and cores. We also discuss the managerial uses of the model for logistics decision-making.     

Ion-exchange displacement chromatography of proteins Dextran-based polyelectrolytes as high affinity displacerss

Dextran-based polyelectrolyte displacers were successfully employed for the displacement purification of proteins in ion-exchange displacement systems. The effect of molecular mass was investigated by examining the efficacy of DEAE-dextran and dextran sulfate displacers of various molecular masses in cation- and anion-exchange systems, respectively. Induced salt gradients produced during these displacement experiments were measured in order to study their effect on the protein separations. The unique characteristics of these displacements were well predicted by simulations obtained from a steric mass action (SMA) ion-exchange model. These displacements differ from the traditional vision of displacement chromatography in several important ways: the isotherm of the displacer does not necessarily lie above the feed component isotherms; the concentration of the displaced proteins can sometimes exceed that of the displacer; higher-molecular-mass displacers are not necesarily more efficacious than lower-molecular-mass compounds; and the salt gradients induced by the adsorption of the displacer produce different salt micro-environments for each displaced protein.     

Diboramacrocycles: reversible borole dimerisation–dissociation systems

We report that the outcome of the tin–boron exchange reaction of a mixed thiophene-benzo-fused stannole with aryldibromoboranes is associated with the steric bulk of the aryl substituent of the borane reagent, leading to either boroles or large diboracycles as products. NMR spectroscopic studies indicate that the two products can reversibly interconvert in solution, and mechanistic density functional theory (DFT) calculations reveal boroles to be intermediates in the formation of the diboracyclic products. The addition of Lewis bases to the diboracycles leads to the corresponding borole adducts, demonstrating that they react as “masked” boroles. Additionally, the reaction of the title compounds with a series of organic azides affords complex heteropropellanes, formally 2 : 1 borole-azide adducts, that deviate from the usual BN aromatic compounds formed via nitrogen atom insertion into the boroles.

Diboramacrocycles are a new form of borole dimers, participating in various addition reactions as “masked” boroles. The reaction of a less crowded diboramacrocycle with organic azides affords unprecedented complex heteropropellanes.     

Spectral,BVS, and Thermal Studies on Bisdithiocarbamates of Divalent Zn,Cd, and Their Adducts: Single Crystal X-Ray Structure Redetermination of (Diiodo) (Tetraethylthiuramdisulfide)mercury(II), [Hg(tetds)I2]

The current article describes the TG and DT analyses of divalent Zn, Cd, and Hg dithiocarbamato (dtc) complexes and their adducts (dchdtc = N,N-dicyclohexyldithiocarbamate anion, 4-mpzdtc = 4-methylpiperazinecarbodithioato anion, padtc = N,N′-(iminodiethylene)bisphthalimidedithiocarbamate anion, pipdtc = piperidinecarbodithioate anion, 1,10-phen = 1,10-phenanthroline, and 2,2′-bipy = 2,2′-bipyridine) along with the structural reinvestigation of [Hg(tetds)I ₂ ], where tetds = tetraethylthiuramdisulfide. In the case of Zn(II) and Cd(II) dithiocarbamates and their nitrogenous adducts, thermal decomposition of the nitrogenous bases is followed by the decay of dithiocarbamate leading to the formation of ZnS or CdS as residue. The interaction of iodine with [Hg(dedtc) ₂ ] in CHCl ₃ results in the oxidation of diethyldithiocarbamate leading to the formation of [Hg(tetds)I ₂ ], and the structure was redetermined because the earlier determination was by a Polaroid crystallographic technique with a higher R value. The S-Hg-I bond angles [105.09(3); 105.59(3); 109.26(3), and 100.99(3)°] indicate the near tetrahedral environment around the metal ion. ¹ H and ¹³ C NMR spectra of the complex were analyzed. Whether the product formed upon oxidation is a disulfide or an iodo-substituted product, in the present investigation, is clearly decided by the bulkiness of the substituent attached to the nitrogen. Interestingly, the steric influence is a deciding factor only in the case of mercury compounds and the dithiocarbamates involving Zn, Cd forms of the disulfide complexes.     

Solvothermal synthesis of hierarchically porous CeO2 nanopalm leaves and their photocatalytic properties

Hierarchically porous CeCO₃OH palm leaves were synthesized by using a facile solvothermal method at 180 °C utilizing cerium nitrate and ethylene glycol. Polycrystalline CeO₂ palm leaves were obtained from the thermal decomposition-oxidation process of the CeCO₃OH nanostructures. CeCO₃OH and CeO₂ palm leaves were characterized by X-ray diffraction pattern, scanning electron microscopy image, energy dispersive X-ray analyses, and ultraviolet (UV)–visible spectroscopy images. The CeO₂ palm leaves exhibited a significant photocatalytic performance in degrading azo dye acid orange II in an aqueous solution under an UV radiation. The formation mechanisms of the CeCO₃OH/CeO₂ nanostructures were described on the basis of the experimental results.