Development and validation of a gas chromatography/mass spectrometry procedure for confirmation of para-toluenesulfonamide in edible fish fillet tissue

Chloramine-T is a disinfectant being developed as a treatment for bacterial gill disease in cultured fish. As part of the drug approval process, a method is required for the confirmation of chloramine-T residues in edible fish tissue. The marker residue that will be used to determine the depletion of chloramine-T residues from the edible tissue of treated fish is para-toluenesulfonamide (p-TSA), a metabolite of chloramine-T. The development and validation of a procedure for the confirmation of p-TSA is described. Homogenized fish tissue is dried by mixing with anhydrous sodium sulfate, and the mixture is extracted with methylene chloride. The extract is passed through a silica gel solid-phase extraction column, from which p-TSA is subsequently eluted with acetonitrile. The acetonitrile extract is evaporated, and the oily residue is dissolved in hexane. The hexane solution is shaken with fresh acetonitrile. The acetonitrile solution is evaporated and the residue is redissolved in dilute potassium hydroxide solution. The aqueous solution is extracted with methylene chloride to further remove more of the fat co-extractive. The aqueous solution is reacted with pentafluorobenzyl bromide in presence of tetrabutylammonium hydrogensulfate. The resulting di-(pentafluorobenzyl) derivative of p-TSA is analyzed by gas chromatography/mass spectrometry. This method permits the confirmation of p-TSA in edible fish tissue at 20 ppb.     

Measuring the electrophoretic mobility of concentrated suspensions in nonaqueous media

We present a new method of measuring the electrophoretic mobility of a particle in a concentrated suspension. The method is used to measure the electrophoretic mobility of PMMA particles (diameter 10 microm) suspended in a mixture of liquid hydrocarbons. The particle volume fraction of the suspension is varied from 0 up to 0.30 and the resulting variation of the electrophoretic mobility is discussed. The suspending liquid is such that its refractive index is very close to that of the particles. Thus the suspension is almost transparent and it is possible to follow through a microscope the motion of one particle. The suspension is subjected to a low-frequency electric field (0.5 Hz). The cell containing the suspension is mounted on a piezoelectric crystal. The displacement that compensates for the particle motion (when the particle image is steady) is determined.     

Recombination of ions of a dense ion plasma in a fluorine atmosphere

A new effect leading to the slowing of recombination in a weakly nonideal ion plasma is considered. The solvation of ions is included in the explanation of the results from studying a gas discharge afterglow in a fluorine atmosphere. It is shown that recombination in such a system is slowed in comparison to the standard relationships for ideal plasma. The formation and composition of cluster ions in such a medium are considered. The relationship between the variation in the kinetics of recombination and the course of the process according to a complicated mechanism with the intermediate formation of metastable cluster pairs is established. A quantitative model is built and a formula allowing us to describe the recombination rate over a wide range of parameters of the medium is obtained. It is shown that the proposed model is in good agreement with the experimental data.     

Time correlation functions and chemical reaction rates

The relation between time-dependent density correlation functions and chemical reaction rates is investigated. The case of a simple two-atom reaction in a fluid system is studied in detail. It is found that the reaction is obtainable from a three-density correlation function, taken in the long-time, long-wavelength limit. This result is analogous to the well known relation between the diffusion rate and the two-density correlation in a fluid. The present calculation is valid in an arbitrary fluid system, and is applicable in particular to reactions in a catalytic medium.     

Experimental investigation of contact angle, curvature, and contact line motion in dropwise condensation and evaporation

Image-analyzing interferometry is used to measure the apparent contact angle and the curvature of a drop and a meniscus during condensation and evaporation processes in a constrained vapor bubble (CVB) cell. The apparent contact angle is found to be a function of the interfacial mass flux. The interfacial velocity for the drop during condensation and evaporation is a function of the apparent contact angle and the rate of change of radius of curvature. The dependence of velocity on the apparent contact angle is consistent with Tanner's scaling equation. The results support the hypothesis that evaporation/condensation is an important factor in contact line motion. The main purpose of this article is to present the experimental technique and the data. The equilibrium contact angle for the drop is found experimentally to be higher than that for the corner meniscus. The contact angle is a function of the stress field in the fluid. The equilibrium contact angle is related to the thickness of the thin adsorbed film in the microscopic region and depends on the characteristics of the microscopic region. The excess interfacial free energy and temperature jump were used to calculate the equilibrium thickness of the thin adsorbed film in the microscopic region.     

Determination of formaldehyde in frozen fish with formaldehyde dehydrogenase using a flow injection system with an incorporated gel-filtration chromatography column

A flow injection analysis (FIA) system for determination of formaldehyde in frozen fish products is described. The system provides a rapid and selective determination of formaldehyde in aqueous fish extracts by the combination of a deproteinization procedure and a stopped-flow enzymatic approach in a FIA system. The FIA system is furnished with a gel-filtration chromatography column for on-line removal of the proteins from the extract before the enzymatic analysis is performed. Compared with the standard methods for determination of formaldehyde in fish products the present method is much faster and less affected by interferences. The limit of detection for the proposed method is 2.5 mg/l of formaldehyde. The sampling frequency is about 10 determinations per hour.     

Numerical simulation of phase separation of immiscible polymer blends on a heterogeneously functionalized substrate

The spinodal phase decomposition of an immiscible binary polymer blend system is investigated with numerical models in two-dimensional and three-dimensional (3D). The effect of the elastic energy is included. The mechanism of the evolution of the phase separation is studied and the characteristic length R(t) is shown to be proportional to t(13). In the case when the phase separation is directed by a heterogeneously functionalized substrate, the increase in the characteristic length is divided into two stages by a critical time. The R(t) approximately t(13) diagram can be fitted with a straight line in both the first and second stages. The slope of the fitting line significantly decreases after the critical time. The compatibility of the resulting pattern to the substrate pattern is also measured by a factor C(S). It is observed that there is also a critical time in the evolution of the compatibility for the cases with and without elastic energy. The critical time of C(S) is identical with the respective critical time of R(t). The lateral and vertical composition profiles functionalized substrate is observed with the 3D model. The difference mechanism of the cases with and without elastic energy is discussed.     

Fluorimetric method for the determination of uranium in natural waters

A method is described for the fluorimetric determination of uranium in natural waters. The limit of detection is 0.3 ppM. Ion-exchange is used to preconcentrate the uranium by a factor of 22 and separate it from quenching ions in the sample. The fluorescence is measured in a medium that is 1.35M in both sulphuric and phosphoric acids. The uranyl ions are excited by radiation of wavelength 280 nm and bandwidth 40 nm. The emitted signal is scanned from 470 to 510 nm. After spiking of the sample solution with a small volume of standard uranium solution, the fluorescence signal is scanned again and the uranium content of the sample calculated from the two readings. The coefficient of variation is 8.5% for determinations of U in a synthetic water sample having a uranium content of 1.9 ppM. Destruction of organic matter in the eluates gives 0.1 ppM detection limit.     

On the signal collection in laser enhanced ionization spectrometry

A theoretical model is developed which relates the experimentally observed signal to the charged species produced in laser enhanced ionization. The model is based on a general equation, which describes the electric field in a flame confined between electrodes at fixed potentials, and a relation for the charge induced on these electrodes. A complete analytical solution is found in a one-dimensional geometry. The signal corresponding to the laser induced electrons is described accurately by the model. The ionic part of the signal, although in most cases negligible, is influenced significantly by dynamic screening in the flame, and requires a more complete model. The theory is applied to an experimental situation, and relations for optimal signal collection are derived. Then the predictions from the theory in a cylindrical geometry are compared to results from a graphite furnace experiment. The temporal behaviour of the signal is further used for a determination of the electron mobility in a flame.     

Statistical Modeling of Water Structure in a Near-Electrode Layer

The structure of water near the electrode surface is studied by a molecular dynamics method, the electrode is assumed to be a structureless conducting surface, a cell of 216 water molecules is used. It is shown that the structure of water in a near-electrode area formed under the electric field influence differs greatly from that in the bulk. The effect of anisotropy of water structure normally to the surface is found. The effect consists of a lower diffusion mobility of molecules in this direction, quantitatively depends on the surface charge density, and decays with increasing distance from the surface. The main role in forming the water structure in the near-electrode layer is played by electrostatic interaction.     

Atomic charges based on spherical harmonics expansion at the atomic centers

Molecular orbitals are expanded in spherical harmonics functions around atomic centers. The expansion coefficient is a function of the distance from the nucleus and the quotient between this function and a corresponding atomic orbital is almost constant in the core region. The square of the quotient is used as a definition of an atomic charge component. The erratic dependence on the type of basis functions in the Mulliken method is thereby avoided. The relationship between the new charge and the Mulliken population is investigated and a new invariant Mulliken population is suggested.     

Flow injection analysis of sulphite by gas-phase molecular absorption UV/VIS spectrophotometry

A flow injection gas-phase molecular absorption spectrophotometric method is described for the determination of sulphite in aqueous solution. The sulphite solution, 200 microl, is introduced into a stream of distilled water. The carrier stream containing a sulphite zone is reacted, in the first mixing coil, with a stream of sulphuric acid (1 M). The evolved sulphur dioxide is purged to the segments of nitrogen flow through the second mixing coil. The gaseous phase is separated from the liquid stream by the use of a purpose built gas-liquid separator and then is swept into a purpose built flow-through cell. The absorbance of the gaseous phase is measured at 200 nm using a UV/VIS spectrophotometer. Up to 440 microg of sulphite is determined. The limit of detection is 0.8 microg and the R.D.S. for the determination of 70 and 220 microg of sulphite are 1.02 and 0.76%, respectively. Up to 40 samples h(-1) can be analyzed. The effect of several anions and cations on the determination of sulphite was studied and the results showed that the method is relatively free from interferences. The proposed method was applied to the determination of sulphite in a synthetic sample, water sample and lemon juice.     

An automated submicrogram determination of selenium in vegetation by quartz-tube furnace atomic-absorption spectrophotometry

An automated method for the determination of submicrogram amounts of selenium in vegetation is described. A weighed sample of vegetation is digested with a 4:1 nitric-perchloric acid mixture, and made up to a known volume. The digested sample is placed in a Technicon sampler and reacted with sodium borohydride solution. The selenium converted into the gaseous hydride is swept by an argon stream into a gas-liquid separator. The mixed gas stream is passed through a heated quartz cell, positioned in the light-path of an atomic-absorption spectrophotometer. The absorption by the atomized selenium is recorded. The method is capable of analysing 50 samples a day by the use of a calibration curve or 25 a day by the standard addition technique. A relative standard deviation of better than 10% and a detection limit of 0.025 microg/g were obtained.     

A lubricated stagnation point flow of nanofluid with heat and mass transfer phenomenon: Significance to hydraulic systems

The improved thermal association of heat transfer is considerably observed due to interaction of nanoparticles in recent days. The lubrication phenomenon with heat and mass transfer effects plays a key role in the hydraulic systems. In current research, the thermal impact of nanofluid over a lubricated stretching surfaces near a stagnation point analytical has been studied. A thin layer of lubricating fluid with a variable thickness provides lubrication. The inspection of thermophoresis and Brownian motion phenomenon is illustrated via Boungrino model. The analytical finding of refurbished boundary layer ordinary differential equations is obtained by a reliable and proficient technique namely variational iteration method (VIM). The Lagrange Multiplier is a potent tool in proposed technique to reduce the computational work. In addition, a numerical comparison is presented to show the effectiveness of this study. The range of flow parameters is based on theoretical flow assumptions. Physical inspection of involved parameters on velocities, temperatures, concentrations, and other quantities of interest when lubrication is presented. The current results present applications in polymer process, manufacturing systems, heat transfer and hydraulic systems.     

On the theory of the radical radiation formation in a solid host

The calculation of the radical formation rate constant in solid organic compounds is carried out. This formation is a result of the cleavage of the hydrogen atom from the carbon atom via a radiationless electronic transition in an electronically excited molecule. The electronic transition is supposed to be stipulated by the nonadiabaticity operator and the perturbation theory with respect to this operator is supposed to be applicable. The vibrational interaction of an electronically excited molecule with the host environment is assumed not to be small. The calculation is carried out within the framework of a model in which the whole molecule is represented by a CH group this being treated as a Morse oscillator. The specific features of the different substances in such a model are simulated by different values of the CH bond parameters.     

An action principle for biopolymer foldingin vitro: A new perspective on the design of expeditiously-folded RNA molecules

The exploration of conformation space performed by a biopolymer becomes rapidly biased towards a confined region and takes place under a stringent schedule incompatible with the thermodynamic limit. The theoretical underpinnings of such properties have been missing to a considerable extent. By introducing anaction principle in the space of folding pathways, we show how folding is guided expeditiously within realistic time frames. The variational principle is constructed in three stages: (a) An appropriate space of folding histories is defined. (b) The space is endowed with a measure and, in this way, an ensemble is defined. (c) This measure induces a Lagrangian which, in turn, defines the underlying action principle. The theory is specialized to account for the expeditious folding of an RNA species resolved to the level of secondary structure. Thus, using the Lagrangian, a time-dependent Base-Pair Probability Matrix (BPPM) is generated. This representational tool is introduced to display all RNA structures contributing to the cross section of the ensemble of pathways at each instant in time. The BPPM is contrastedvis-a-vis experimental information on biologically-competent RNA conformations. The results reveal that the statistical weight is concentrated on a very limited domain of folding pathways which yield the biologically-relevant destination structure within realistic timescales. To conclude, we assess in a preliminary fashion the potential of the action principle as a tool to aid the design of RNA species capable of folding within experimental timeframes.     

Stepwise creep in polyethylenes of trademarked pipes in the premelting temperature mode

The stepwise creep in polyethylenes of the trademarked pipes Hostalen 4731b and Dowlex 2388 is compared to that of standard HDPE and LDPE. With the aim to study the deformation of the interlamellar macromolecules, a temperature of 100°C is chosen. At this temperature, the destruction of the interlamellar aggregates results in their easy deformation with the preservation of the integrity of the main crystalline framework. The process is performed under a light load, as a result of which there is deformation relaxation to some limiting value, and then the loading is repeated. The ordering of the lamellar structuring in the annealed samples leads to a sharp decrease in deformability of the interlamellar molecules, unlike what is observed in quenched samples. The shortening of samples is established after stepwise unloading similar to the loading. The Dowlex 2388 copolymer exhibits a sharp increase in tear resistance at 115°C accompanied by a local rise in the orientation stretching of the interlamellar molecules, whose subsequent breakage leads to a significant increase in the slot width after tearing at 115 ± 5°C, i.e., at exactly the maximum resistance.     

Role of the cure kinetics in morphology control at phase separation of curing multicomponent thermosets and a criterion of equilibrium

The formation of heterophase polymers via phase separation in the course of curing reaction in a blend of a thermosetting oligomer with a rubber modifier is considered. The interference of thermodynamic and kinetic factors that define the morphology of the material being formed is discussed. The need for a kinetic theory of cure-induced phase separation is established, and an approach of this kind is proposed. On the basis of this approach a simple quantitative criterion of deflection of the phase-separating system from the thermodynamic equilibrium is given.     

Specific determination of cysteine and penicillamine through cyclization to 2-thioxothiazolidine-4-carboxylic acids

A very simple and highly specific method for the determination of cysteine and penicillamine is presented. Treatment with 1,1'-thiocarbonyldiimidazole in slightly basic solutions converts cysteine rapidly and quantitatively to a very stable derivative, 2-thioxothiazolidine-4-carboxylic acid, which is not formed by thiols or amines. The cyclic derivative has a characteristic UV spectrum with a maximum at 272 nm and it can be quantified by one of two ways. (1) When only inorganic ions and common additives are present, a spectrophotometer or a plate reader capable of handling multiple samples is sufficient to estimate cysteine in the concentration range of 2-150 muM. Penicillamine is determined similarly by cyclization to 5,5-dimethyl-2-thioxothiazolidine-4-carboxylic acid. The method is also applicable to derivatives of cysteine modified only at the carboxyl group. (2) To determine cysteine in complex mixtures, a liquid chromatograph connected to a UV detector is used. The elution is rapid with well-separated peaks for the thiazolidine derivatives. The detection limit is 2 pmole of cysteine or penicillamine per injection and the detector response is linear up to 1 nmole. The usefulness of the method is demonstrated by determining cysteine and penicillamine in capsules and by measuring cysteine in a dietary supplement.     

Anodic dissolution of gold in a solution of 1,3-diaminopropane with the formation of a cathodic deposit and a colloidal solution of Au

The corrosion of a Au anode in a solution of 1,3-diaminopropane (DAP) is studied by means of gravimetry. It is found that the products of corrosion of Au electrode in galvanostatic conditions are reduced on a Pt cathode with the formation of either an electrolytic Au deposit or a colloidal solution of metallic Au, depending on the current strength. The kinetics of the dissolution of Au in the presence of DAP is investigated. The formation of a complex of Au with DAP is observed, and a structure for it is proposed.