Investigation of the role of the C-PCM solvent effect in reactivity indices

It has been shown recently, how the coupling between electronic degrees of freedom and vibrational modes is reflected in the properties of molecules. The necessary derivatives have been analyzed and their thermodynamic relations were demonstrated. This present work is focused on the analysis of a molecular system, under the influence of C-PCM induced solvent effect. The analysis is based on reactivity indices derived from DFT. The shift of frequency for diatomic molecules has been obtained. It has been identified as chemical force effect. The role of nuclear reactivity indices has been emphasized. This concept has been extended to obtain regional chemical potential values within C-PCM model for polyatomic molecules.     

Selective Potentiometric Measurement of Physiologically Significant Thiols

The reaction of benzoquinone with reduced thiol species has been investigated using potentiometric techniques. The specificity of this reaction for thiol functionality has been briefly assessed and the nature of the electrode response has been elucidated. The system has been characterized in terms of selectivity, sensitivity and the efficacy of using the system for the quantification of thiol containing pharmaceuticals has been demonstrated. The simplicity of the detection methodology is shown to markedly contrast alternative thiol detection strategies. The transfer of the technology to a mass production format through the adoption of screen print electrode formats has been achieved and the efficacy of the approach demonstrated. Recovery experiments using captopril and penicillamine in tissue culture as a model analyte system were performed.     

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.     

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.     

In situ study of electrocopolymerization of acrylamide,formaldehyde, and N,N′-methylenebisacrylamide

An apparatus and procedure for real-time in situ investigations of monomer electropolymerization in solution using optical microscopy with differential interference and phase contrast have been designed. The kinetics of electropolymerization of an acrylamide-formaldehyde monomer mixture in aqueous solution has been studied. An induction period of electropolymerization was fixed and evaluated for the first time. Growth of the polymer film after disconnection has been visualized. The dynamics of this phenomenon is evaluated, and possible reasons are discussed. Anisotropic mechanical stresses, arising in the polymer film during electropolymerization, have been found and characterized. The mechanism that is responsible for the formation of a dense near-cathode layer has been revealed. The formation of a zinc sublayer during electropolymerization has been examined. Reasons for the roughness of the near-electrode surface of the polymer film and for high adhesion of the electrodeposited polymer film to the metal have been established.     

Investigation of the extraction equilibrium of ion-association complexes of molybdenum (VI) with some polyphenols and thiazolyl blue. extraction-spectrophotometric determination of molybdenum

The extraction process of ternary ion-association complexes of molybdenum (VI) with some polyphenols (4-nitrocatechol, 2,3-dihydroxy naphthalene) and thiazolyl blue has been investigated by using an extraction-spectrophotometric method. The optimum conditions for their quantitative preparation in aqueous medium and subsequent extraction into an organic solvent have been found. The extraction, distribution and association constants, and the recovery factors have been calculated. The composition of the complexes has been determined. A precise, sensitive and simple extraction-spectrophotometric method for determination of molybdenum in products from ferrous metallurgy has been developed.     

活性炭的Zeta电位对其吸附达旦黄规律的影响

The effect of pH on the adsorption of anionic dye Titan yellow on the activated carbon from aqueous solution has been studied. It has been found that the Zeta potential of the activated carbon has a great effect on adsorption capacity of Titan yellow. The kinetic and the thermodynamic parameters of adsorption as a function of pH has been evaluated. The mechanism for adsorption of anionic dye Titan yellow on the activated carbon has also been discussed.     

Spectrophotometric determination of tin with stilbazo in the presence of poly(sulfonylpiperidinylmethylene hydroxide)

The best complexing conditions have been determined for the tin-stilbazo-poly(sulfonylpiperidi nylmethylene hydroxide) system. The ratio between the components in the complex has been found, and the mechanism of complexation has been examined. A rapid procedure for the determination of tin has been developed and tested in the analysis of standard reference samples of bronzes.     

模糊聚类-因子分析法解析稀土配合物吸收峰的研究

将模糊聚类分析与因子分析相结合,对地质样品中吸收光谱严重重叠的稀土多组份体系进行解析,较好地解决了计算光度分析中校准模型的优化问题。对数据库的建立、聚类参数选择等问题进行了讨论。对地质样品中15个稀土元素进行了同时测定,标准偏差小于1.2。     

Accurate theoretical prediction of optical properties of BODIPY dyes

Boron-dipyrromethene dyes (BODIPY) are of great interest nowadays mostly due to their valuable optical properties. Nevertheless, no systematic research of the optical property dependence on the structure of dyes has been performed yet. In this work, analysis of the available quantum-chemical methods for BODIPY optical property calculations has been carried out. The accuracy of eight DFT functionals has been studied. The solvation effects upon excitation have been considered within two schemes. The methods that predict the absorption and emission spectra of BODIPY derivatives with high accuracy have been proposed. Using the suggested methods, the influence of nature of substituents and their position in the BODIPY core on the optical spectra of the dyes has been studied. A complex pattern of red- and blue-shifts in optical spectra in dependence of nature and position of substituents has been revealed. The results of this work provide the way for efficient design of BODIPY derivatives with desired optical properties.     

Fixed-bed adsorption of carbon dioxide/methane mixtures on silicalite pellets

The adsorption of carbon dioxide and methane on silicalite pellets packed on a fixed bed has been studied. Equilibrium and kinetic measurements of the adsorption of carbon dioxide and methane have been performed, and a binary adsorption isotherm for carbon dioxide/methane mixtures has been obtained. A model based on the LDF approximation for the mass transfer has been used to describe the breakthrough curves obtained experimentally. A PSA cycle has been proposed for obtaining methane with purity higher than 98% from carbon dioxide/methane mixtures containing 38% and 50% methane, and its performance has been simulated using the proposed model. The simulation results show that silicalite can be a suitable adsorbent for employment in a PSA separation process for carbon dioxide removal from coalseam and landfill gases.     

Solvent extraction of Sb(III) with malachite green into chloroform

A rapid and selective method for the solvent extraction of Sb(III) using malachite green (C. I. Basic green 4) has been described. Effect of different parameters affecting the extraction coefficient value of Sb(III) such as acidity, time of equilibration, KI concentration, solvents, anions, etc. has been studied. For various elements the separation factor has been evaluated. The stoichiometry of the extracted species has been determined by the method of substoichiometric extraction. The decontamination factor for some elements using substoichiometric quantities of the extracting agent has been evaluated. Radiotracers were employed for the extraction studies. The method elaborated has been employed for the quantitative determination of antimony in normal, benign and cancerous tissues of the human brain.     

An enzymatic method for the detection of esters

An enzymatic method for the detection of esters has been developed. The use of various esterases as an analytical tool has been examined. It has been found that lipase can be used for the detection of esters under specified conditions. The relative rates of hydrolysis observed in the case of various esters have been explained on the basis of the generally accepted mechanism. The enzymatic method has been compared with the hydroxamic acid test.     

The Synergistic Effect of a Mixed Surfactant (Tween 80 and SDBS) on Wettability Alteration of the Oil Wet Quartz Surface

The synergistic effect of a new combination of Tween 80 and sodium dodecylbenzenesulfonate (SDBS) surfactants has been studied for wettability alteration of a reservoir rock. The contact angle decreased substantially for the aqueous solution of the mixed surfactant on a crude oil aged quartz substrate when compared to water and individual surfactants viz. SDBS and Tween 80. This established synergism between anionic and non-ionic surfactants. The optimal salinity for reduction of the contact angle has been figured out. The rheological effect of the mixed surfactant solution on the wettability alteration has been investigated. Adsorption of crude components at the solid–fluid interfaces has been observed to visualize the activity at the micro scale. Quantification of adsorption for the mixed surfactant on sand has been studied to meet the economical aspect. Reaction aspects of the mixed surfactant–quartz–crude oil system have been interpreted from FTIR. Functional groups present in the system have also been enquired.     

Optimization of silicon dioxide surface functionalization protocol for designing the receptor layer of a biosensor for detecting explosives

The development of the receptor layer of the biosensor for detecting explosive compounds is described. The covalent modification has been chosen for immobilizing E. coli nitroreductase on the gate oxide of the ion-sensitive field effect transistor (ISFET) that is comprised of silicon dioxide. The self-assembled monolayer technique has been used for immobilization. This method assumes the usage of different silanes and spacer molecules for activating the surface of SiO₂. Two different immobilization strategies have been compared, one using asymmetric spacers (3-maleimidobenzoic acid N-hydroxysuccinimide ester (MBS) and 4-(4-maleimidophenyl)butyric acid N-hydroxysuccinimide ester (SMPB)) and another using a symmetric glutaric dialdehyde linker both accompanied by appropriate silanes. For the first method, the dependence of functionalization efficiency on silane concentration has been studied. The sufficient density of enzyme molecules on the surface of SiO₂ has been achieved at a concentration of silane of 0.0015%. The type of asymmetric linker has no influence on immobilization efficiency. The method implying glutaric dialdehyde results in higher activity of the immobilized enzyme. For this method, the immobilization procedure has been optimized. The method has been adapted for immobilization of E. coli nitroreductase inside the channel of a microfluidic system on the surface of ISFET. For this purpose, (3-aminopropyl)triethoxysilane (APTES) has been changed to the corresponding silatrane, and the concentration of the enzyme has been increased to 30 μg/mL. The optimized procedure has been successfully used to develop a biosensor for detecting explosives.     

Influence of the heating rate on the temperature profiles and on the conversion rate of powdery cellulose and pine sawdust

An experimental study of the thermal decomposition of powdered cellulose and pine sawdust has been performed. The influence of the heating rate on the temperature profiles in the sample and on the solid conversion rate has been studied. A mathematical model without adjustable parameters has been used to calculate the temperature at different points in the solid bed and the average total solid conversion. The experimental results have been compared with those calculated by the model. A good agreement has been obtained for sawdust. Some differences are observed for cellulose at high heating rates, and the influence of the thermal conductivity and the reaction heat on the results has been analysed.     

Ionization probability of the hydrogen atom suddenly released from confinement

The problem of the stability of a confined atom when it is extracted from the confining cavity has been investigated, modeled by a spherical hard wall potential. The ionization probability when the atom is released from confinement has been obtained. The dependence of the ionization probability on the confinement radius and on the quantum numbers of the initial confined state has been studied. The probability density function of the ionization energy of the ejected electron has been obtained for the different cases considered. The oscillatory structure of this distribution function, with a principal maximum located in the neighborhood of the energy of the initial state and minima very close to zero has been elucidated. The sudden approximation has been applied and the analytic continuation method has been used to calculate the different stationary states.     

On the solution of one classical problem in vibrational spectroscopy

The identification of the structure of molecules from their vibrational spectra has been considered as an inverse spectral problem. A statement of the problem has been formulated and an algorithm has been treated for its solution. Conditions for obtaining a unique solution have been analyzed. An attempt has been made to evaluate the possibility of distinguishing isomers by calculating their vibrational spectra.     

The influence of the concentration and size of silver nanoparticles on the conductivity of ring-shaped deposits resulting from evaporation of colloidal solution droplets

The conductivity of ring-shaped deposits formed at the periphery of evaporating droplets of silver nanoparticle colloidal solutions has been studied. The dependence of the resistance of the ring-shaped deposits on nanoparticle size has been shown to exhibit a percolation transition. The specific conductivity of the deposits has been estimated in relation to their geometric shapes. The conductivity has been established to nonmonotonically depend on nanoparticle sizes. It has been noted that, in rather strong fields, the conductivity of the composite layers dramatically increases after some induction period. The X-ray spectra of silver have been revealed to alter for samples the conductivity of which has increased under the action of an external electric field.     

Studying the Adsorption of an Iron(II) Complex of 1,10-Phenanthroline on Laboratory Glassware Using Thermal Lens Spectrometry

The adsorption of iron(II) tris(1,10-phenanthroline) on the glass surface of laboratory ware from solutions has been studied by thermal lens spectrometry at a level of nanogram amounts. The effect of glass pretreatment on the fraction of the adsorbed substance has been studied, and the most appropriate variant of the pretreatment has been selected. The kinetics of iron(II) tris(1,10-phenanthroline) adsorption on the surface of laboratory glass has been studied, and an adsorption isotherm has been constructed for nanogram chelate contents of the solution. The process is most closely approximated by the Freundlich equation. Based on the obtained data, a procedure has been proposed for the preparation of solutions for constructing calibration relationships that can be used in thermal lens measurements of trace amounts of analytes. This procedure takes into account the loss of substances at the surface of laboratory glassware.