Thermodynamics of Chromium(VI) Anionic Species Sorption onto Surfactant-Modified Montmorillonite Clay

Batch sorption experiments performed on Cr(VI) species sorption showed a significantly enhanced removal of inorganic hexavalent chromium anionic species from aqueous solution by montmorillonite clays modified with quaternary amine, hexadecyltrimethylammonium (HDTMA) bromide. Unmodified clay had no affinity for chromium(VI) species. The sorption of Cr(VI) species has been carried out as a function of pH, contact time, adsorbate concentration (4.14x10(-5) to 8.62x10(-3) M), and temperature (5-45 degrees C). The surfactant-modified clay surface was stable when exposed to extremes in pH. The optimum pH for maximum sorption of Cr(VI) species was found to be at pH 1 and was constant between pH 2 and pH 6. The sorption data obtained was well described by DKR and Langmuir sorption isotherms. Sorption energy (E) for (i) surfactant sorption by montmorillonite clay and (ii) sorption of chromium(VI) species by surfactant modified clay have been computed from the DKR equation. Sorption energy evaluated for the sorption of both surfactant and Cr(VI) species showed that an ion-exchange mechanism was operative. The mechanism of retention appears to be replacement of counterion of the surfactant by Cr(VI) anionic species. Adsorbent capacity for the sorption of Cr(VI) species has been evaluated from the Langmuir sorption isotherm data. Thermodynamic parameters (Delta H degrees, Delta S degrees and Delta G degrees ) for surfactant sorption on montmorillonite clay and Cr(VI) sorption by modified clay have been evaluated. The specific rate constant for sorption of Cr(VI) species on modified montmorillonite was rapid during the first 10 min and equilibrium was found to be attained within 30 min. The sorption of Cr(VI) species onto modified montmorillonite clay followed first-order rate kinetics. Copyright 2000 Academic Press.     

Influence of the sample preparation method on the serotonin determination in plasma and platelets

Plasma or platelet serotonin concentration is commonly used to provide information about the serotonergic activity in various psychiatric or neurological diseases. Some difficulties have been described in the measurement of serotonin (5-HT) levels in plasma or platelets. We describe an isocratic liquid-chromatographic assay with amperometric detection for determination of 5-HT in the platelet pellet and in platelet-rich and platelet-poor plasma (PRP and PPP) in sample sizes of 100 microL of plasma. The method uses an RP(18) column and an amperometric detector with a thin-layer type electrochemical fl ow cell, with glassy carbon electrode maintained at a potential of +0.600 V vs an Ag/AgCl reference electrode. Determinations were performed in the presence or in the absence of plasma, since the biological matrix may affect the results. Different validation parameters were analysed: selectivity, accuracy, precision, linearity and stability. Reference values for 5-HT concentration in healthy adults (n = 12) were 6.6 nmol/10(9) platelets, for the platelet pellet, and 5.5 nmol/10(9) platelets, for PRP. The 100 microL sample volume used for the preparation of PPP did not make possible the determination of 5-HT levels with accuracy and precision.     

Synthesis and self-assembly of glycal-based bolaforms

Glycal-based bolaforms serve as synthetically flexible components of molecular self-assembly. The compounds are prepared in good yield by a Ferrier reaction between triacetylglucal or -galactal or diacetylxylal and a long chain alpha,omega-diol, followed by deacetylation under Zemplen conditions. The reactions are stereoselective and preferentially afford the alpha-diastereomer. The bolaforms undergo self-assembly in water or water/dioxane solution to give a variety of nanostructures. In solution, bolaforms with C8 or C10 chains between glucal headgroups form nanoscale vesicles. In contrast, bolaforms with C12 chains exhibit lower solubility and a dynamic self-assembly, forming several different nanoscale structures. However, the solid-state structures of C12 bolaform isomers adopt shapes very similar to those of bolaforms possessing more extensive hydrogen-bonding networks, indicating that multiple hydrogen bonds in solution are important to formation of stable, discrete nanostructures but that only a few key intermolecular interactions between bolaform headgroups are necessary to determine the structure in the solid state. The diversity and differentiation of the functional groups present in glycal-based bolaforms suggest that they could be useful probes of the various noncovalent forces controlling the structure of new nanomaterials.     

The Compressible Viscous Surface-Internal Wave Problem: Nonlinear Rayleigh–Taylor Instability

This paper concerns the dynamics of two layers of compressible, barotropic, viscous fluid lying atop one another. The lower fluid is bounded below by a rigid bottom, and t he upper fluid is bounded above by a trivial fluid of constant pressure. This is a free boundary problem: the interfaces between the fluids and above the upper fluid are free to move. The fluids are acted on by gravity in the bulk, and at the free interfaces we consider both the case of surface tension and the case of no surface forces.We are concerned with the Rayleigh–Taylor instability when the upper fluid is heavier than the lower fluid along the equilibrium interface. When the surface tension at the free internal interface is below the critical value, we prove that the problem is nonlinear unstable.     

Ginzburg‐Landau vortex dynamics driven by an applied boundary current

In this paper we study the time‐dependent Ginzburg‐Landau equations on a smooth, bounded domain Ω ? ?², subject to an electrical current applied on the boundary. The dynamics with an applied current are nondissipative, but via the identification of a special structure in an interaction energy, we are able to derive a precise upper bound for the energy growth. We then turn to the study of the dynamics of the vortices of the solutions in the limit ε → 0. We first consider the original time scale in which the vortices do not move and the solutions undergo a “phase relaxation.” Then we study an accelerated time scale in which the vortices move according to a derived dynamical law. In the dynamical law, we identify a novel Lorentz force term induced by the applied boundary current. © 2010 Wiley Periodicals, Inc.     

Naturally occurring organic matter as a chemical trap to scan an ecosystem for natural products

A model is proposed that tests an ecosystem for natural products (NPs) using a nonpolar extract of naturally occurring organic matter (NOM), which we demonstrate to be an efficient chemical trap for relatively nonpolar organic molecules. To test the model we collected twenty-six samples of NOM from various locations on the Suwannee River, from its headwaters in the Okeefenokee Swamp to the Gulf of Mexico. We have tentatively identified stearic acid, DDT, chincodine, and a potential precursor to bryostatin. Our data provide evidence that NOM can trap, hold for several decades, concentrate, and transport NP in the environment.     

Sorption of inorganic nanoparticles in woven cellulose fabrics

Titanium dioxide was deposited from aqueous suspension onto cellulosic surfaces.Titania was sourced from Degussa (P25TM,70:30 anatase:rutile).Dry uptake of particles was shown to be rapid and dominant with one-third of the deposition occurring in less than 30 s and over one-half in the first minute.Isotherms were recorded to compare the rate of titanium deposition on dry and pre-wetted cotton.In the dry case uptake reached a maximum in 30 min whereas in the pre-wetted case the uptake was seen to continue beyond 180 min.A broad trend of higher deposition occurring at lower pH was seen,corresponding to the region where surface charges were opposite and thus attractive.Dry pickup was less significant at high pH.The response to varying ionic strength was complex and was attributed to the combined effect of charge screening,particle aggregation and consequent particle entrapment or occlusion.Titania deposition into the interstices of woven cotton sheets resulted in the formation of inorganic,nanoparticulate skeletons which could be isolated by controlled combustion of the cellulose and thus cotton was suggested to have potential for the templated synthesis of high surface area semiconductor materials.