Overpressured thin-layer chromatography

The properties, apparatus and applications of overpressured thin-layer chromatography (OPTLC) have been reviewed. In the Introduction planar chromatography has been briefly characterized, with particular attention to TLC. The general properties of OPTLC and methods of development of chromatograms in this technique have been then given. The construction of chambers and equipment for OPTLC has been described, paying attention to two-dimensional columns. The properties of chambers for OPTLC have been characterized considering the flow of eluent, sorbent-eluent interactions and the efficiency of various systems. OPTLC, TLC and HPTLC have been compared and also a comparison between OPTLC with a constant (linear) eluent flow-rate and with a decreasing eluent flow-rate has been made. Analytical applications of OPTLC have been described and examples of separations of mixtures have been given.     

Alpha-cyclodextrin functionalized CdS nanocrystals for fabrication of 2/3 D assemblies

Different types of cyclodextrins (CDs) have been tested as mediators for the water phase transfer of organic-capped CdS nanocrystals (NCs), and alphaCD has been demonstrated to be the most effective system. The formation of a complex based on alphaCDs and colloidal NCs has been considered to be responsible for the phase transfer process and extensively investigated by optical, structural, and calorimetric measurements, as a function of the experimental parameters (pH and NC and CD concentration). A mechanism for the complexation phenomena has been suggested. The fabrication of 2/3 D supramolecular architectures has been proposed according to two different strategies. First, a layer-by-layer procedure has been used to obtain multilayered structures where polyelectrolyte layers have been intercalated with negatively charged alphaCD-CdS NC complexes by exploiting electrostatic interaction between polyelectrolyte and cyclodextrin OH groups. Second, a monolayer of CdS NCs has been deposited onto a self-assembled monolayer of sulfated CDs, thus combining the use of an electrostatic-force-based approach and host-guest chemistry. The important role played by host-guest interactions has then been revealed.     

Viscoelastic response of elastomers in large deformations

A simple nonlinear theory of viscoelasticity has been developed for application to elastomers. The interpretation of nonlinear viscoelastic responses based on Gibbs-DiMarzio theory has been identified at a molecular level and hence structural understanding has been established. The introduced model is applied to strain imposed conditions. From this, a relaxation process has been revealed for the resultant stress, where a dependence of relaxation time on the state of strain has been established.     

Preparation and polymerization of a diisocyanate from the Diels-Alder adduct of levopimaric acid and acrylic acid

Starting from tetrahydroabietic acid the model compounds tetrahydroabietoyl chloride, 2-aminoethyltetrahydroabietate hydrochloride, and 2-isocyanatoethyltetrahydroabietate have been prepared. Carbamate and urea derivatives of the isocyanate have been prepared. A Diels-Alder adduct of levopimaric acid and acrylic acid has been prepared and converted to its diacid chloride. The β-aminoethyl ester hydrochloride has been synthesized and converted to a diisocyanate which has been polymerized with poly(tetramethylene glycol) and also with p-phenylenediamine. Dimerex resin, a technical polymerized rosin, has been similarly converted to a diisocyanate. This isocyanate has not proven to be useful as a polymer-forming intermediate.     

Transport of excitation energy in a three-dimensional doped molecular crystal. IV. Fourth-order propagation,exciton clothing,and exciton diffusion

The problem of excitons in interaction with phonons in a molecular crystal has been reinvestigated as a continuation of our earlier work. The exciton-phonon interaction has been taken to be linear in lattice displacements. The external medium, the phonon assembly, has been considered to be in thermal equilibrium. Following Simons, we have incorporated the effects of the medium on the exciton dynamics into a time-dependent effective potential that contains the equilibrium average exciton-phonon interaction as well as terms arising from the fluctuations in the medium's coordinates about their equilibrium values. A correlation function that represents the probability of exciton transfer has been given in the interaction picture. The time evolution of this correlation function has been determined by following Kubo's technique of cumulant expansion. The zeroth-, second-, and fourth-order contributions to the correlation function have been calculated in this way. The second- and fourth-order contributions have been diagrammatically represented. The second-order contribution has been explicitly calculated in different physical limits, namely, the slow exciton and the slow phonon limits at high and low temperatures and for very large and very small time. A few simple formulas for the transfer probability of a bare exciton in a molecular crystal of cubic symmetry have been derived from the Debye approximation for the dispersion of phonons. It has been specifically shown that the sum over phonon modes in the large time dynamics leads to a fully destructive interference in second order at a very low temperature and gives rise to a diffusive transport at a high enough temperature. A natural way of clothing the excitons has been considered and the clothed exciton has been represented diagrammatically. The dressing requires the correlation function to be redefined in terms of the clothed states and the clothed operators. The clothed exciton correlation function that represents the probability of transfer of excitons fully clothed by the phonons in thermal equilibrium turns out to be identical with the bare exciton correlation function. This attaches a novel interpretation to the correlation function which was originally defined by Simons. Transfer probabilities for a clothed exciton in a cubic crystal has been explicitly worked out for different physical limits under the Debye model of phonon dispersion. From these results a few expressions for the macroscopic diffusion coefficient of the clothed exciton have been obtained. A few critical comments have been incorporated. © 1996 John Wiley & Sons, Inc.     

On the thermodynamic theory of the strength of solids: 5. Energetic characteristics of a crack with a meniscus and ultimate solid strength

The thermodynamic relations describing the formation work of a crack with a meniscus inside it have been analyzed for capillary condensation and evaporation processes. The conformal and depth mechanisms of crack growth have been discussed. It has been shown that the capillary forces alone cannot cause the fracture of a solid upon the formation of a meniscus in a crack. Criteria have been established for the strength upon the brittle fracture, and corrections related to the presence of a meniscus in a crack have been calculated. As a rule, the formation of a meniscus reduces the ultimate strength.     

Electron microtomography: A new method for studying the spatial structure of catalysts

The spatial arrangement of active component (Pt) particles on the surface of a support (Sibunit globule) has been studied by bright-field electron tomography. A tomographic attachment for a standard specimen holder and tomographic grids have been designed. The tomographic procedure has been refined, and adequate tilt series alignment and tomographic reconstruction algorithms have been chosen. The 3D distribution of the active component in the catalyst grain has been studied: particles hidden in micropores have been directly observed, and the size of the pores connecting internal cavities with the exterior has been estimated.     

On the electrochemical characterization of ion-selective cellulose acetate membranes with and without stigmasterol liquid membranes

Stigmasterol, a plant product, has been used as a surfactant to generate liquid membranes supported on a cellulose acetate matrix. Electrochemical characterization of the membrane has been attempted with a view to simulating its behavior with natural membranes by measuring membrane potentials and membrane conductance. The selectivity of cellulose acetate membrane kept in contact with magnesium chloride solutions of different mean concentrations has been found to change from anion to cation. Transport numbers have been estimated from membrane potential data. Permselectivity and fixed charge density values for the cellulose acetate membrane with and without stigmasterol have been determined from transport numbers. The variation of these parameters with concentration and pH has also been examined.     

Determination of the surface potential for hollow-fiber membranes by the streaming-potential method

A procedure has been proposed for measuring the surface potential of hollow-fiber membranes by the streaming-potential method under the conditions of a tangential flow of a solution. The zeta-potential and surface charge of nanofiltration hollow-fiber polyacrylonitrile membranes have been measured. The measurements have been performed for membranes with different porosities, which were obtained by partial drying of initial humid membranes. The porosity has been determined from the electrical conductivity of a membrane. An equation has been proposed for calculating the charge transfer by a solution flow in a porous layer. It has been shown that the use of the proposed equation makes it possible to obtain more correct values of the membrane surface potential.     

Synthesis of Hydrogenated Graphene during Acetylene Conversion in Helium Plasma Jet

Hydrogenated graphene has been synthesized in one step by acetylene conversion in a helium plasma jet. A dc plasma torch with a diverging anode channel and a power up to 45 kW has been used to generate plasma. The obtained graphene materials have been studied by scanning electron microscopy, Raman spectroscopy, and elemental analysis. Hydrogen desorption from the samples synthesized has been studied by thermal analysis as a function of temperature. It has been found that during annealing in vacuum, the synthesis products change their morphology because of hydrogen release.     

Continuous chromatographic separation process: simulated moving bed allowing simultaneous withdrawal of three fractions

Continuous counter-current chromatographic separation has been carried out in a simulated moving bed system (SMB). We have worked with a SMB pilot plant (8 columns, 4.4 litres of resin each) which allows the continuous withdrawal of two different fractions. A mixture of glucose-fructose has been separated. To calculate the concentration profile within the separator an axial dispersed plug flow model and an equilibrium stage model have been employed; software has been created to simulate the behaviour of the separator. The necessary parameters of the mode: the adsorption equilibrium constant, the height equivalent to a theoretical plate and the bed voidage, have been acquired experimentally from elution chromatography measurements. The results calculated by simulation give a good representation of the experimental concentration profiles; other separations like xylitol-arabitol have been simulated. The influence of some factors like desorbent flow-rate, feed flow-rate and the bed voidage have been studied using the software. Once the system has worked in a two withdrawal way, an extension of the pilot plant has been constructed so as to obtain a third one. The necessary parameters of the three withdrawal model will be studied.     

A fluorimetric and circular dichroism study of hemoglobin--effect of pH and anionic amphiphiles

In this work, bovine hemoglobin (Hb) has been studied mainly by the fluorescence method. pH has been found to exert a profound effect on Hb structure. This has been confirmed by fluorescence and circular dichroism (CD) studies. The pH-induced change in quaternary structure of Hb indirectly affects its secondary structure. This in turn affects ligand binding to Hb at various pH. The binding of two amphiphiles, a bile salt and a surfactant, have been investigated. The pH-induced structural modification of Hb has been confirmed by studies with the well-known denaturant urea and the polarity probe ANS, which has been used as an extrinsic fluorophore.     

FLASH PHOTOLYSIS OF AQUEOUS TRYPTOPHAN, ALANYL TRYPTOPHAN AND TRYPTOPHYL ALANINE

Abstract— Tryptophan has been flash photolysed in deoxygenated and air equilibrated solutions. The kinetics of the subsequent reactions of the tryptophyl radical and the hydrated electron have been elucidated. Oxygen has been found to reduce the primary photoionization yield, indicating a triplet state precursor, but no evidence has been found for a biphotonic process. Appreciable differences in the photoionization quantum yields have been found for tryptophan, alanyl tryptophan and tryptophyl alanine.     

Kinetics and mechanism of the production of higher olefins from stearic acid in the presence of an alumina-supported nickel sulfide catalyst

A nickel sulfide catalyst which efficient in the decarbonylation of fatty acids to olefins and dienes has been obtained for the first time by treating alumina-supported nickel sulfate with hydrogen, and its properties have been studied. In its presence, the olefin selectivity of the reaction can exceed 90%. The kinetics of stearic acid deoxygenation to heptadecenes has been investigated, a kinetic model has been constructed, and a mechanism has been proposed for the reaction over this catalyst. Olefin oligomerization is the dominant side reaction. Kinetic evidence for the catalytic inhibition of oligomerization by nickel hydrides formed on the catalyst has been obtained. The compositions of active site–reactant adsorption complexes have been discussed.     

Separation of carbon dioxide/methane mixtures by adsorption on a basic resin

In this work, the separation of carbon dioxide/methane mixtures by PSA using a basic resin (Amberlite IRA-900) has been studied. Adsorption equilibrium and kinetics of carbon dioxide and methane on a fixed-bed of this adsorbent have been measured, and a binary adsorption equilibrium isotherm has been obtained. The adsorbent deactivation with the number of adsorption-desorption cycles, and its regeneration, have also been analysed. A model based on the LDF approximation has been used to describe the experimental breakthrough curves. The applicability of the basic resin to the separation of carbon dioxide/methane mixtures has been studied in an experimental PSA setup using a single bed. The validity of the model used in the fixed-bed study for simulating a PSA system has been checked by comparing the simulated and the experimental performance of the proposed PSA cycle.     

Phase structure of silanol-modified ethylene-vinyl acetate copolymers

For (ethylene-vinyl acetate copolymer)-tetraethoxysilane and (ethylene-vinyl acetate copolymer)-polydimethylsiloxane systems, the solubility of components has been studied in a wide range of temperatures and compositions. Phase diagrams have been constructed, pair interaction parameters have been calculated, and diffusion coefficients and activation energies of diffusion have been estimated. The temperature and concentration ranges of a change in solubility related to chemical interactions between the components have been revealed, and the structure of the modified copolymers has been studied. On the basis of the kinetic data on the movement of isoconcentration planes in diffusion zones of component mixing, time intervals corresponding to the onset of the chemical reaction between the components have been determined and the apparent activation energies of the process have been computed. Complex-shaped binodal and boundary curves have been interpreted within the framework of the classical Flory-Huggins theory.     

Ethanol loading in an inductively coupled plasma

Changes to the fundamental and analytical parameters of a plasma have been investigated when ethanol has been added to aqueous or organic solutions. Excitation temperature, electron number density, and intensity of the H(alpha) line increased when ethanol has been added to aqueous solutions, while an electron density decrease and signal reduction have been found when ethanol has been added to xylene. The sensitivity has been improved for all ethanol concentrations when water has been the solvent, but the reverse has been found for xylene solutions.     

A comparative study on direct and indirect electrochemical oxidation of polyaromatic compounds

This study has been performed to investigate the treatment of an industrial wastewater containing naphthalene- and anthraquinone-sulfonic acids, by direct and indirect electrolyses. The direct electrochemical oxidation has been carried out using boron-doped diamond and lead dioxide anodes, while the indirect electrolyses has been mediated by active chlorine electrogenerated on a platinum anode, or by hydrogen peroxide electrogenerated on a graphite felt cathode. For each type of electrolyses the effects of operating parameters, such as anode material, current density, chloride concentration, ferrous ions concentrations have been also investigated. Measurements of Chemical Oxygen Demand (COD) and colour fading have been used to compare the results of different electrolyses. Experimental data showed that the complete COD and colour removals have been obtained only by direct oxidation or by active chlorine mediated electrolyses. On the contrary using electrogenerated hydrogen peroxide the solution has been presented a residual COD and colour. In particular, it found that faster oxidation rate has been obtained by direct oxidation using a boron-doped diamond anodes at low current density.     

Synthesis,characterization, and curing of hyperbranched allyl ether–maleate functional ester resins

A model two-step synthesis of a saturated hyperbranched hydroxyl-terminated ester has been developed to show a synthesis route. Three different series of hyperbranched esters with different terminations have been synthesized to relate some of their properties to their structures. This route has then been used to synthesize three different allyl ethermaleate functional hyperbranched ester resins in a two-step procedure. The resins have been characterized with respect to rheology, structure, and properties, and the differences are discussed. The allyl ether-maleate functional resins have also been studied with respect to curing performance and final film properties. © 1993 John Wiley & Sons, Inc.     

Electromembrane extraction from biological fluids

Electro-assisted extraction of ionic drugs from biological fluids through a supported liquid membrane (SLM) and into an aqueous acceptor solution was recently introduced as a new sample preparation technique termed electromembrane extraction (EME). The applied electrical potential across the SLM has typically been in the range of 1-300 V. Successful extractions have been demonstrated even with common batteries (9 V) instead of a power supply. The chemical composition of the SLM has been crucial for the selectivity and for the recoveries of the extraction. Compared to other liquid-phase microextraction techniques (LPME), extraction times have been reduced by a factor of 6-17, and successful extractions have been obtained at extraction times of 1-5 min, and even down to a few seconds with online microfluidic EME devices. The technique has provided very efficient sample clean-up and has been found well suited for the extraction of sample sizes in the low μL range. Extractions have been performed with both rod-shaped hydrophobic porous fibers and with flat hydrophobic porous sheets as SLM support. The technique has been successfully downscaled into the micro-chip format. The nature of the SLM has been tuned for extraction of drugs with different polarity allowing extractions to be tailored for specific applications depending on the analyte of interest. The technique has been found to be compatible with a wide range of biological fluids and extraction of drugs directly from untreated human plasma and whole blood has been demonstrated. EME selectively extracts the compounds from the complex biological sample matrix as well as allowing concentration of the drugs. With home-built equipment fully acceptable validation results have been obtained.