Computer simulations of time-dependent suppression of EOF by polymer coatings

We use molecular dynamics simulations in order to investigate the time evolution of the effect of adsorbed polymer coatings on the electro-osmotic flow (EOF) in a capillary. Weakly adsorbed coatings show no time-dependent performance, but they do not strongly reduce the EOF. On the other hand, strongly adsorbed coatings made of longer polymer chains are often quenched in non-equilibrium conformations that can strongly reduce the EOF over extremely long periods of time. For intermediate adsorption strengths, we observe that the EOF increases as a function of time due to the relaxation of the coating layer. The concentration of polymers in solution and the length of the polymer chains also affect the time-dependence of the EOF. These results show that the quality of electrophoretic separations can depend on the waiting time between the formation of the coating and the beginning of the separation. We conclude by suggesting experimental tests of our predictions.     

Vortex rings and the superfluid λ-transition

A vortex-ring formulation of the₄He -transition provides a clear physical picture of the superfluid transition. The thermally excited rings are dipoles which orient in an applied flow field, and their net backflow cancels part of the applied flow, reducing the superfluid density. At the -point rings of infinite size drive the superfluid density to zero as a power law of the reduced temperature, with an exponent of 0.672. By fitting to the experimental superfluid amplitude the core energy of the smallest rings is found to be 6.1K at T and their diameter is 2.3 Å. It is proposed that these can be identified as the roton excitations of the Landau model. The vortex theory also yields new insights into topics such as boundary effects at a wall, finite-size effects, and the dynamics of the transition.     

Steric stabilization of Stöber silica dispersions using organosilanes

Organosilanes of the general formula R _x Si(OR)_4–x (where R is an alkyl group and R = CH₃ or CH₂CH₃) were used to sterically stabilize hexane dispersions of submicrometre silica spheres. The dispersions were characterized according to sediment volume results. For 0.5m silica particles, the sediment density increased by more than a factor of three up to 50 to 55% of theoretical in the presence of organosilanes with 12 or more carbons in the R group. Solid-state¹³C nuclear magnetic resonance was used to characterize the powder-dispersant interaction; this technique can distinguish between carbons in the R group of the organosilane and residual organic groups in the silica. Scanning electron micrographs of filter compacts were used to further characterize the dispersions and indicated the presence of primary particles as well as small agglomerates.     

Validation of a Gas Chromatography-Mass Spectrometry Method for the Measurement of the Redox State Metabolic Ratios Lactate/Pyruvate and β-Hydroxybutyrate/Acetoacetate in Biological Samples

The metabolic ratios lactate/pyruvate and β-hydroxybutyrate/acetoacetate are considered valuable tools to evaluate the in vivo redox cellular state by estimating the free NAD+/NADH in cytoplasm and mitochondria, respectively. The aim of the current study was to validate a gas-chromatography mass spectrometry method for simultaneous determination of the four metabolites in plasma and liver tissue. The procedure included an o-phenylenediamine microwave-assisted derivatization, followed by liquid-liquid extraction with ethyl acetate and silylation with bis(trimethylsilyl)trifluoroacetamide:trimethylchlorosilane 99:1. The calibration curves presented acceptable linearity, with a limit of quantification of 0.001 mM for pyruvate, β-hydroxybutyrate and acetoacetate and of 0.01 mM for lactate. The intra-day and inter-day accuracy and precision were within the European Medicines Agency’s Guideline specifications. No significant differences were observed in the slope coefficient of three-point standard metabolite-spiked curves in plasma or liver and water, and acceptable recoveries were obtained in the metabolite-spiked samples. Applicability of the method was tested in precision-cut liver rat slices and also in HepG2 cells incubated under different experimental conditions challenging the redox state. In conclusion, the validated method presented good sensitivity, specificity and reproducibility in the quantification of lactate/pyruvate and β-hydroxybutyrate/acetate metabolites and may be useful in the evaluation of in vivo redox states.     

A Novel DUF569 Gene Is a Positive Regulator of the Drought Stress Response in Arabidopsis

In the last two decades, global environmental change has increased abiotic stress on plants and severely affected crops. For example, drought stress is a serious abiotic stress that rapidly and substantially alters the morphological, physiological, and molecular responses of plants. In Arabidopsis, several drought-responsive genes have been identified; however, the underlying molecular mechanism of drought tolerance in plants remains largely unclear. Here, we report that the “domain of unknown function” novel gene DUF569 (AT1G69890) positively regulates drought stress in Arabidopsis. The Arabidopsis loss-of-function mutant atduf569 showed significant sensitivity to drought stress, i.e., severe wilting at the rosette-leaf stage after water was withheld for 3 days. Importantly, the mutant plant did not recover after rewatering, unlike wild-type (WT) plants. In addition, atduf569 plants showed significantly lower abscisic acid accumulation under optimal and drought-stress conditions, as well as significantly higher electrolyte leakage when compared with WT Col-0 plants. Spectrophotometric analyses also indicated a significantly lower accumulation of polyphenols, flavonoids, carotenoids, and chlorophylls in atduf569 mutant plants. Overall, our results suggest that novel DUF569 is a positive regulator of the response to drought in Arabidopsis.     

Employing fractals and FEM for detailed variation analysis of non-rigid assemblies

Many studies on non-rigid assemblies, or assemblies of non-rigid components, suggest that the component variation affects the assembly dimensional quality. However, little is known about how the variation of surface micro-geometry of assembly components influences the assembly dimensional quality. In this paper, a new method based on the fractal geometry and finite element method (FEM) is proposed to study such an influence. In the new method, a special fractal function, named the Weierstrass–Mandelbrot (W–M) function, is used to extract and represent the characteristics of surface micro-geometry of assembly components. FEM is applied to analyze the deformation of non-rigid assemblies by integrating the variation of component micro-geometry. The sensitivity matrix between the component variation and assembly variation is obtained by using the existing influence coefficients method. It is found that contributions of the surface micro-geometry of assembly components to the final variation of non-rigid assemblies could be substantial under certain conditions. The proposed method is illustrated through a case study on an assembly of two flat sheet metal components under different fixture-releasing conditions.     

Silicon Nitride Derived from an Organometallic Polymeric Precursor: Preparation and Characterization

Partially crystalline Si₃N₄, with nanosized crystals and a specific surface area greater than 200 m²/g, is obtained by pyrolysis of a commercially available vinylic polysilane in a stream of anhydrous NH₃ to 1000°C. This polymer does not contain N initially. Crystallization to high-purity α-Si₃N₄ proceeds with additional heating above 1400°C under N₂. The changes in crystallinity, powder morphology, infrared spectra, and elemental compositions, for samples annealed from 1000° to 1600°C under N₂, are consistent with an amorphous-to-crystalline transformation. Although macroscopic consolidation and local densification occur at 1400°C, volatilization and accompanying weight loss limit bulk densification. The effect of temperature on specific surface area is examined and related to the sintering process. These results are applicable to pyrolysis, decomposition, and crystallization studies of ceramics synthesized by polymeric precursor routes.     

Fourier transform infrared study of high-purity maceral types

A suite of density-differentiated macerals from several coals was analysed by Fourier transform infrared spectroscopy to obtain information on the nature and magnitude of the variations exhibited by the various maceral fractions. The most characteristic change between maceral groups was the variation in aliphatic hydrogen content, with exinite ? vitrinite ? inertinite. Since the separation technique (density gradient centrifugation) generally provided a number of fractions within a maceral group region, some of these were also analysed. In a series of density fractions from a low rank vitrinite, it was found that the aliphatic hydrogen content decreased as the density increased. The inertinites also exhibited a decrease in aliphatic hydrogen. The inertinite C—O bands had extinction coefficients different from those of vitrinites or exinites. The data suggest that quite profound variations in organic structure as determined by FT-i.r. spectroscopy can exist within a maceral group, so that for the most critical work on coals it is necessary to take this into account.     

Enlargement of the micropores of a caking bituminous coal by controlled oxidation

In a study of the enlargement of pores of coals it has been found that treatment of a bituminous coal (PSOC No. 371, from the Pennsylvania State University Coal Section) with a 5:95 O₂:N₂ stream 4 h at 400 °C increases the surface area as measured by nitrogen adsorption at 77K by a factor of at least 50 to a value 52 m² g^?1. The increase in pore size was accompanied by a 9.7% weight loss. Simultaneously, the area as measured by carbon dioxide at 195K increased from 61 to 136 m² g^?1 and that measured by carbon dioxide at room temperature increased from 125 to 237 m² g^?1. Attempts to enlarge the pores by oxidation with hydrogen peroxide or ozone were unsuccessful. A Pittsburgh coal subject to a small percentage of oxygen in nitrogen or steam at 300 to 400 °C showed a surface area as measured by nitrogen adsorption of less than 1 m² g^?1 both before and after such pretreatment. This same coal with a 5:95 O₂:N₂ stream for 4 h at 450 °C showed a surface area of 110 m² g^?1 measured by nitrogen adsorption at 77K.     

Cuticular hydrocarbons ofReticulitermes virginicus (Banks) and their role as potential species- and caste-recognition cues

The cuticular hydrocarbon components of four castes ofReticulitermes virginicus (Banks) have been identified and quantitated. Components identified includen-alkanes; 2-, 3-, 11-, 13-, and 15-methyl-alkanes; 11,15-dimethylalkanes, (Z)-9-alkenes; (Z,Z)-7,9-dienes; and (E/Z)-6,9-dienes ranging in carbon number from C₂₁ to C₄₀. All caste forms ofR.virginicus contained the same components, but showed caste-specific proportions. Comparison of these hydrocarbons with those of the sympatric termiteR. flavipes (Kollar) suggest that cuticular hydrocarbons might serve as species- and caste-recognition cues. A bioassay was developed to test this species-recognition hypothesis, with the experimental results supporting the hypothesis.Isoptera: Rhinotermitidae.