Peculiarities of the coagulation mechanism of a nanocrystalline cellulose hydrosol and a latex

Dynamic light scattering has been employed to study the coagulation kinetics of colloidal dispersion of nanocrystalline cellulose and SKS-27 ARK synthetic latex under the action of sodium chloride. It has been found that, when a system being coagulated is exposed to a mechanical action, aggregates almost cease to grow at some moment. It has been assumed that the first stage of coagulation is caused by the formation of strong contacts between primary particles and their agglomeration, while the second stage is realized via the interaction of residual hydration layers. It has been shown that, as the density of surfactant adsorption layers on the surface of latex particles is enhanced, the duration of the first stage increases, while the average hydrodynamic particle size decreases.     

Monte Carlo study of the translocation of a polymer chain through a hole

The translocation of a polymer chain through a narrow hole in a rigid obstacle has been studied by the static Monte Carlo simulations. A modified self-avoiding walk on a cubic lattice has been used to model the polymer in an athermal solution. The entropy of the chain before, in the course, and after the translocation process has been estimated by the statistical counting method. The thermodynamic generalized forces governing the translocation have been calculated. The influence of the system geometry on the entropic barrier landscape is discussed.     

Micellar extraction of a tin complex of phenylfluorone into a cetylpyridinium chloride-based liquid phase

Optimal conditions have been found for the modification of compact liquid phases based on a cationic surfactant, cetylpyridinium chloride, with salicylic acid. On the example of the system tin-phenylfluorone we have shown the applicability of such phases to the preconcentration of multiply charged ions readily hydrolyzed metals. The influence of concentrations on the absorbance and composition of the complex has been studied; the optimal conditions of its extraction have been found. The developed spectrophotometric procedure of tin determination with phenylfluorone using micellar-extraction preconcentration has been tested for the analysis of canned vegetables and brines.     

Stability of two-dimensional growth of a packed body of proteins on a solid surface

Adsorption of proteins from the bulk is at times accompanied by a rearrangement which leads to the formation of closed packed bodies, that may or may not be crystalline. Mass transfer of protein molecules on a surface is modeled. Forced diffusion by van der Waals and electrostatic forces leads to segregation, which is eventually a different phase that is assumed to be thermodynamically favored. The net effective force in two-dimensions has been modeled approximately and shown to be much stronger and more long ranged than in the bulk: that is, under the same conditions, the protein molecules may not aggregate in the bulk they may aggregate on a surface. These forces have been used only indirectly but equivalently as an adsorption-desorption step at the interline. Eventually, a linear stability analysis of the growing body shows it to be unstable and would give rise to whiskers that are one molecule thick. This is what is observed experimentally. The conditions that give rise to the instability have been determined. The reverse case of rinsing of the protein molecules has also been studied experimentally and has been analyzed using the same mechanisms. Here it is seen that thicker inroads into the packed body cause the interline to take on a spongy appearance. It is conjectured that eventually islands will appear as seen in the experiments.     

Molecular ordering of a cyano compound at a displacive transition temperature: a statistical analysis based on quantum mechanics and computer simulations

A statistical analysis has been carried out to determine the configurational preference of a pair of 4-cyanophenyl 4-n-pentylbenzoate (CPPB) molecules with respect to translatory and orientational motions. The CNDO/2 method has been employed to evaluate the net atomic charge and atomic dipole components at each atomic centre of the molecule. Configurational energy has been computed using the Rayleigh—Schodinger perturbation method. The total interaction energy values obtained through these computations were used to calculate the probability of each configuration at the phase transition temperature using the Maxwell—Boltzmann formula. An attempt has been made to identify the most probable configuration at the phase transition temperature. Further, the flexibility of various configurations has been studied in terms of variation of probability due to small departures from the most probable configuration. On the basis of stacking, in-plane and terminal interaction energy calculations, all possible geometrical arrangements of the molecular pair have been considered. The results are discussed in the light of experimental as well as theoretical observations. The nature of the mesophase has been correlated with the parameter introduced in this paper.     

Molecular ordering of a cyano compound at a displacive transition temperature: a statistical analysis based on quantum mechanics and computer simulations

A statistical analysis has been carried out to determine the configurational preference of a pair of 4-cyanophenyl 4- n -pentylbenzoate (CPPB) molecules with respect to translatory and orientational motions. The CNDO/2 method has been employed to evaluate the net atomic charge and atomic dipole components at each atomic centre of the molecule. Configurational energy has been computed using the Rayleigh-Schodinger perturbation method. The total interaction energy values obtained through these computations were used to calculate the probability of each configuration at the phase transition temperature using the Maxwell-Boltzmann formula. An attempt has been made to identify the most probable configuration at the phase transition temperature. Further, the flexibility of various configurations has been studied in terms of variation of probability due to small departures from the most probable configuration. On the basis of stacking, in-plane and terminal interaction energy calculations, all possible geometrical arrangements of the molecular pair have been considered. The results are discussed in the light of experimental as well as theoretical observations. The nature of the mesophase has been correlated with the parameter introduced in this paper.     

Platinum solubility of a substance designed as a model for emissions of automobile catalytic converters

Automobile catalytic converters emit nanocrystalline platinum attached to alumina particles. For investigations about the bioavailability of Pt from these particles a model substance with approx. 5% Pt on alumina has been prepared and characterized by physical methods (ESCA, XRD, TEM, DTA, TG). Measuring the platinum solubility of these samples in different solvents revealed high amounts that can be explained assuming a corrosion process. The portion of soluble platinum is dependent on the particle size distribution. For a comparative study platinum black has been used. In general the platinum determination has been carried out by electrothermal atomic absorption spectrometry (ET-AAS). The comparison of ET-AAS results with determinations by adsorptive voltammetry (formazone method) allowed to distinguish between elemental and ionic platinum; in solution samples only ionic platinum has been present. UV spectra of extracts have been used for the semi-quantitative platinum speciation in solutions.     

Development of a Novel Chemiluminescent Probe with a Higher Efficiency than LucigeniiT

A many efforts have been made to take advantage of the chemiluminesce of lucigenin and acridine derivatives, especially for analytical purposes. Aryl acridinium esters have been used as labels for the immunoassay of both large and small molecules. Lucigenin is more stable and higher quantum yield than acridinium ester,but it has not been used as labels in immunoassay and DNA probes,because it dose not have a label moiety group, so for.     

Electrophoretic Mobility of a Polyelectrolyte Capsule

The electrophoretic motion of a polyelectrolyte capsule has been considered in a uniform electric field. The capsule carries a uniformly distributed charge and is permeable to ions of different natures. An electrolyte identical to a dispersion medium is located inside the capsule. The flow in the porous layer of the capsule has been described by the Brinkman equations taking into account the effect of electrostatic forces. The distribution of ions in the vicinity of the capsule has been determined, and its electrophoretic mobility has been found in a linear approximation. The mobility of the capsule has been studied as depending on its geometric characteristics, permeability, and charge density. In particular, a complex extremal character of variations in the mobility as depending on the solid phase fraction in the capsule has been revealed at different ratios between the thicknesses of the electrical double layer and the Brinkman filtration layer.     

Location of a branch in a saturated carbon chain

Oxidative degradation by chromic acid in glacial acetic acid has been developed as an effective method for location of a branch in a saturated carbon chain. Detection of cleavage products by use of gas phase chromatography allows convenient application of the method to samples of 3–10 mg. Several branched-chain acids and a branched-chain hydrocarbon have been found to yield the expected cleavage products; however, selective attack on a branch located alpha, beta or gamma to carboxyl is not significant. The mechanism of the oxidation and the protective influence of carboxyl are discussed.     

Infrared near-field detection of a narrow resonance due to molecular vibrations in a nanoparticle

Di-iron nonacarbonyl particles on a gold surface have been imaged using an apertureless near-field scanning infrared microscopy. First and second harmonic detection, with and without an auto-homodyning option, have been used to collect the near-field spectrum of a single vibrational mode of the bridging carbonyls in di-iron nonacarbonyl nanocrystalline flakes on a gold surface. The experimental results have been compared to two theoretical models, a static image-dipole effective medium and an image dipole modified by a Fresnel coefficient for the appropriate observation angle. The calculations have taken into account the roughness of the gold film. The phase dependence of the near-field contrast has been investigated using broadband and tunable CO2 lasers. Particle size effects on contrast and spatial resolution have been studied to determine the limits of applicability of the half-space approximation.     

Miscibility of a polyarylate with a liquid crystalline copolyester

The miscibility has been investigated for binary blends of a polyarylate (PAr) with a liquid crystalline copolyester of p-hydroxybenzoate and ethylene terephthalate units in a 6/4 molar ratio (PET/PHB). The binary blends were prepared by solution precipitation. The transitions of the PET/PHB have been measured with a rheometrics dynamic spectrometer. The phases in blends have been studied with a differential scanning calorimeter, by ther-mogravimetry and with a polarizing optical microscope. The blends exhibit two glass transitions (T_gs) over the composition range 10–90 wt %. The amorphous PET phase from the PET-PHB is found to be partially miscible with PAr, which leads to a decrease of the PAr T_g. The amount of this partially miscible portion of PET has been estimated by the Couch-man equation. On heat treatment of the blends at 250 to 300°C, transesterficiation takes place, as judged by the shift of the higher of the two T_gs. © 1993 John Wiley & Sons, Inc.     

Radical cyclizations of unsaturated moieties bearing a stereogenic sulfur center: a new type of radical acceptor

Optically active vinylsulfoxides and N--sulfinimines have been submitted to radical cyclization conditions. Corresponding carbocycles have been prepared in good yields. Complexation by Lewis acids has been examined, allowing an enhancement of the stereoselectivities.     

Platinum solubility of a substance designed as a model for emissions of automobile catalytic converters

Automobile catalytic converters emit nanocrystalline platinum attached to alumina particles. For investigations about the bioavailability of Pt from these particles a model substance with approx. 5% Pt on alumina has been prepared and characterized by physical methods (ESCA, XRD, TEM, DTA, TG). Measuring the platinum solubility of these samples in different solvents revealed high amounts that can be explained assuming a corrosion process. The portion of soluble platinum is dependent on the particle size distribution. For a comparative study platinum black has been used. In general the platinum determination has been carried out by electrothermal atomic absorption spectrometry (ET-AAS). The comparison of ET-AAS results with determinations by adsorptive voltammetry (formazone method) allowed to distinguish between elemental and ionic platinum; in solution samples only ionic platinum has been present. UV spectra of extracts have been used for the semi-quantitative platinum speciation in solutions.     

Experimental study of a diffusion-controlled reaction involving a chain molecule with terminal reactive sites

Diffusion-controlled reaction of electron transfer from diphenylsilane radical anions to the series of α- and α,ω-bromoalkanes with alkane chain length up to 18 atoms has been studied in n-dodecane solutions. At room temperature, reaction rate constants have been determined and corresponding reaction radii have been evaluated. It has been shown that a not-too-long chain molecule, which contains two terminal reaction sites and participates in the diffusion-controlled reaction, may be considered as a rapidly rotating pair of reacting sinks with a distance between their centers equal to the mean-square end-to-end distance of the molecule.     

On the formation and properties of a high-temperature resin from a bisphthalonitrile

When 4,4'-bis (3,4-dicyanophenoxy) biphenyl is heated with small amounts of aromatic amine or amidine salts, a highly crosslinked polytriazine is obtained. This polymer has been shown to be the same as that reported when bisphthalonitriles are heated with amines. Salts promote this reaction more readily and the glass transition temperature of the polymer after post-cure at 315°C is generally 30°C higher than when free bases are used. The fracture properties and elasticity of the salt-cured polymer have been measured at temperatures up to 250°C. As a model system, the self reaction of phthalonitrile promoted by amines and their salts has been studied. In both cases, poly[4-(2-cyanophenyl)-1,3,5-triazine-2,6-diyl-1,2-phenylene] is produced, and more efficiently using the salts. A reaction mechanism for this polymerization has been proposed. © 1994 John Wiley & Sons, Inc.     

Cation-exchange properties of pumice: Taking a sip from a volcanic cocktail

The search for the telltale signs of volcanic eruptions in easily dateable (biological) material like tree rings or speleothems has been going on for a very long time. Even though the reactions of tree rings to cataclysmic events are fairly well understood, there has not been a satisfactory method to distinguish volcanic from other climatically active events. Recent findings of differing Ba-contents in soil and the unexpected mobility of Ba during volcanic eruptions strongly suggest that tephra changes the concentrations of trace elements in the surrounding topsoil. To better understand the mechanics of this enrichment, leaching experiments with volcanic ashes have been performed that show that pumice acts as a cation-exchanger. Neutron activation analysis (NAA) with its reasonably simple sample preparation and the possibility to distinguish volcanic ashes from contamination of solvents by using activated ashes offers a hands on approach to the problem above. Several samples of known composition of volcanic ashes have been activated and leached with different solvents and solutions, aiming to both recreate a realistic situation comparable to natural leaching due to rain fall and obtain quantifiable results.     

Cooperativity during binding of a ligand to a multidentate oligomer

A matrix method to describe the equilibrium binding of a ligand by a multidentate oligomer with a system of binding centers differing in the affinity for the binding ligand has been proposed. The example of a complexation process simulating the formation of a complex between an oligonucleotide and zinc phthalocyanine ZnPc is considered. With the use of the proposed method, diagrams of the relative contents of different forms of DNA-ligand complexes have been constructed and analyzed. It is shown that the cooperativity of complexation has a considerable effect on the equilibrium of the ligand with the system of nonequivalent centers of binding. The experimental data on changes in the intensity of luminescence in the course of binding between zinc tetrakis(diisopropylguanidinio)phthalocyanine and a DNA molecule with the nucleotide sequence GTTA(GAGTTA)4GG have been analyzed.     

DMTA study of a nickel-titanium wire

The nickel-titanium alloys are usually known as Shape Memory alloys because of their ability to return to some previously defined shape or size when subjected to the appropriate thermal procedure. Mechanical properties of a nickel titanium wire were investigated by DMTA using cylindrical tension mode. The Young"s modulus, the maximum strain and residual deformation have been calculated. Recovery of previously deformed samples was observed in constant stress temperature ramp tests. Relaxation stress behaviour at temperatures above the austenitic transformation has been studied. The strain and frequency ranges of linear response have been determined by dynamic experiments. Strain amplitude of 0.1% and frequency of 1 Hz have been chosen for the temperature ramp dynamic experiments. A big change between 65 and 95°C is observed in the storage modulus. The values of E' at temperatures below and above the transition are essentially constant. Finally, the effects of the frequency at different temperatures have been examined. This revised version was published online in July 2006 with corrections to the Cover Date.     

Removal of PCR inhibitors using dielectrophoresis as a selective filter in a microsystem

Diagnostic PCR has been used to analyse a wide range of biological materials. Conventional PCR consists of several steps such as sample preparation, template purification, and PCR amplification. PCR is often inhibited by contamination of DNA templates. To increase the sensitivity of the PCR, the removal of PCR inhibitors in sample preparation steps is essential and several methods have been published. The methods are either chemical or based on filtering. Conventional ways of filtering include mechanical filters or washing e.g. by centrifugation. Another way of filtering is the use of electric fields. It has been shown that a cell will experience a force when an inhomogeneous electric field is applied. The effect is called dielectrophoresis (DEP). The resulting force depends on the difference between the internal properties of the cell and the surrounding fluid. DEP has been applied to manipulate cells in many microstructures. In this study, we used DEP as a selective filter for holding cells in a microsystem while the PCR inhibitors were flushed out of the system. Haemoglobin and heparin - natural components of blood - were selected as PCR inhibitors, since the inhibitory effects of these components to PCR have been well documented. The usefulness of DEP in a microsystem to withhold baker's yeast (Saccharomyces cerevisiae) cells while the PCR inhibitors haemoglobin and heparin are removed will be presented and factors that influence the effect of DEP in the microsystem will be discussed. This is the first time dielectrophoresis has been used as a selective filter for removing PCR inhibitors in a microsystem.