Transport properties of materials based on MF-4SC membranes and silica manufactured by a casting method

Composites based on MF-4SC perfluorinated cation-exchange membranes were manufactured by casting from a polymer solution with a precursor for subsequent use in the synthesis of hydrous silica. Their proton conductivity was studied as a function of composition, temperature, and relative humidity. Modification of MF-4SC with small dopant amounts increases the water content and ion conductivity, in a reduced humidity, too. Materials containing 3% SiO₂ by weight have a maximal conductivity.     

Diffusion properties of bilayer membranes based on MC-40 and MF-4SC modified with silicon and zirconium oxides

MC-40 membrane samples modified with a thin MF-4SC layer containing inorganic oxide particles have been synthesized. Deposition of an MF-4SC layer raises the diffusion permeability of the membrane. Insertion of ZrO₂ or SiO₂ nanoparticles into this layer enhances the ion transport selectivity in terms of the cation transport number. The best results are obtained with oxide particles synthesized in the pores of the deposited layer.     

Effect of modification of the MF-4SC membranes in the potassium form with acid salts of heteropolyacids on membrane properties and characteristics of dp sensors based on them

Hybrid materials based on perfluorinated sulfo cation-exchange MF-4SC membrane and nanoparticles of cesium hydrogen phosphotungstate and silicotungstate heteropolyanions were obtained. These membranes with a gradual dopant distribution along the length were used to develop potentiometric sensors for determination of amino-containing organic cations in aqueous solutions at pH < 7. A relationship between the membrane transport characteristics and sensing properties was elucidated.     

Preparation of MF-4SC composite membranes with the anisotropic distribution of polyaniline and ion-transport asymmetry

A method of preparing MF-4SK membranes with the anisotropic distribution of aniline over the thickness is developed. The processes of aniline polymerization in the matrix of the MF-4SC sulfocationite membrane are investigated via electronic-absorption and IR spectroscopy. The processes of ion transport in the obtained composite membranes are studied via impedance spectroscopy, voltammetry, and potentiometry.     

Polarographic determination of phenylalanine,tyrosine, methionine,glutamic acid and histidine with a dropping copper amalgam electrode

The anions of the phenylalanine, tyrosine, methionine and glutamic acid give an anodic wave when a dropping copper amalgam electrode is oxidized in their presence, approximately at the same half-wave potential of that of the glycine anion (?0.28 V vs. SCE). The height of these waves depends on pH and amino acid concentration and can be utilized for the polarographic determination of these substances using the same procedure as that described previously for the determination of glycine. The polarographic behaviour of histidine is somewhat different because the zwitterion of this amino acid reacts with the Cu²⁺ and the anion forms a more stable complex. The polarographic determination of histidine can be also carried out with the same procedure.     

Mechanism of ion transport in hybrid materials based on MF-4SC perfluorinated sulfonation-exchange membranes and acid zirconium phosphate nanoparticles

The relationship between the transport properties of various salt forms (H⁺, Li⁺, Na⁺, Cs⁺) of MF-4SC hybrid membranes containing nanoparticles of crystalline acid zirconium phosphate Zr(HPO₄)₂ at various relative humidities are investigated with the use of impedance studies and NMR spectroscopy. Modification of the membranes leads to a marked increase in ion mobility, and the maximum effect is observed under reduced humidity conditions. The conductivity of a modified membrane at a relative humidity of 10% is 1.6 × 10^?4 Ω^?1 cm^?1, that is, almost 1.5 orders of magnitude greater than the conductivity of an initial membrane under the same conditions.     

Photoacoustic spectroscopy study of neodymium complexes with alanine,valine, phenylalanine and tryptophan

Neodymium complexes with amino acids: Nd(Ala)(3)Cl(3).3H(2)O, Nd(Val)(3)Cl(3).3H(2)O, Nd(Phe)Cl(3).5H(2)O and Nd(Trp)(3)Cl(3).3H(2)O (Ala: L-alanine, Val: L-valine, Phe: L-phenylalanine, Trp: L-tryptophan) are synthesized and their photoacoustic (PA) spectra are reported. The nephelauxetic ratio beta, bonding parameter b(1/2) and Sinha parameter delta are calculated based on their PA spectra. The variation of these parameters and correlation of them with the nature of metal-ligand bonding are discussed. The PA intensity analysis of the f-f transitions of neodymium ion is carried out by calculating the intensity branching vector. The environmental effect on the f-f transitions of neodymium ion is also studied. The branching vectors of the f-f transitions of Nd(Ala)(3)Cl(3).3H(2)O and Nd(Val)(3)Cl(3).3H(2)O are similar, which indicates the perturbation of the two ligand fields is similar. The branching vectors of energy levels 4G(5/2)+(2)G(7/2) of Nd(Phe)Cl(3).5H(2)O and Nd(Trp)(3)Cl(3).3H(2)O increase remarkably compared with those of Nd(Ala)(3)Cl(3).3H(2)O and Nd(Val)(3)Cl(3).3H(2)O. As the degree of covalency increases, the oscillator strength of the hypersensitive transition exhibits a corresponding increase. The relaxation process of Nd(Ala)(3)Cl(3).3H(2)O is established through its PA and electron absorption spectroscopy (EAS). A method used to resolve the PA amplitude spectrum is suggested. With the phase spectrum, PA absorption bands of Nd(Trp)(3)Cl(3).3H(2)O are resolved well in the region of ligand absorption.     

Ionselective electrodes based on adamantylthiacalix[4]arenes for alkali cations determination

The possibility of using three derivatives of p-R-thiacalix[4]arene: tetraethyl ester of p-(1-adamantyl)thiacalix[4]arene acid (I) and asymmetric p-tert-buthylcalix[4]-p-R-thiacalix[4]arene “molecular tubes” [R = tert-Bu(II), 1-adamantyl(III)] as ionophores in PVC-membrane ISEs for the determination of Na⁺, K⁺ and Rb⁺ ions was studied. It was found that an electrode based on thiacalix[4]arene (I) exhibited high selectivity toward Na⁺ ions, and electrodes with (II) and (III) demonstrated a good potentiometric response of the Rb⁺ ion; Rb⁺ can be determined in the presence of excess amounts Na⁺ and K⁺.     

Electrotransport properties and morphology of MF-4SK membranes after surface modification with polyaniline

The method of template synthesis is used for the surface modification of MF-4SK membranes with polyaniline. The influence of the time of polyaniline synthesis in the surface layer of a perfluorinated MF-4SK membrane on its morphology and electrotransport properties is investigated. It is established that under the synthesis conditions, a gradient distribution of polyaniline develops across the thickness of the membrane, and as a result of this, an anisotropic composite structure is formed. It is shown that the specific electrical conductivity and the electroosmotic and diffusion permeability exhibit an extremal character as functions of the time of polyaniline synthesis. When the orientation of these composite membranes is changed with respect to electrolyte flow, an asymmetry effect in their diffusion characteristics is found. With the application of the bilayer fine porous membrane model, the modified-layer thickness is estimated, and the determining influence of the difference in absolute values of effective fixed-charge volume densities on the development of the asymmetry effect is found.     

Sorption and conducting properties of perfluorinated MF-4SC membranes in aqueous solutions containing phenylammonium ions

A comparative study of the sorption effect is performed for nitrogen-containing ammonium, phenylammonium (PhA⁺), and tetrabutylammonium (TBA⁺) cations on conducting and hydrophilic properties of protonic form of perfluorinated sulfocationite MF-4SC membrane. Conductometric method was used to study thermodynamic equilibria in the systems of perfluorinated MF-4SC membrane—aniline in the acid solutions of variable composition (PhA⁺/HCl and PhA⁺/H₂SO₄). Concentration constants of ion-exchange equilibrium are calculated for a MF-4SC membrane on the basis of these data. These constants in the solutions of aniline with HCl and H₂SO₄ are 10.3 and 27.0, accordingly. The choice of sulfuric acid as background electrolyte for matrix polyaniline synthesis is substantiated.     

Preparation and characterization of PVDF microporous membrane with highly hydrophobic surface

Using the mixture of triethyl phosphate (TEP) and N,N‐dimethylacetamide (DMAc) as solvent, PVDF microporous membranes with highly hydrophobic surface were prepared by a modified NIPS method with a dual coagulation process. The effects of the exposure time on these membranes before being immersed into the coagulation bath and the composition in the coagulation bath on precipitation rate, membrane morphology, membrane hydrophobicity, membrane mechanical property, and membrane performance were studied. The morphologies and hydrophobicities of PVDF microporous membranes were investigated by scanning electron microscopy (SEM) and contact angle (CA) measurement. The precipitation processes were observed by light transmittance measurement. The pore size distribution was determined by liquid permeation technique. PVDF microporous membrane obtained by passing evaporation period of 60 min before being immersed into the water bath showed a high water CA of 122.1°. Using ethanol (EtOH) as coagulation bath, the water CAs of the top surface and bottom surface of the membrane increased to 125.9 and 132.6°, respectively. To further improve PVDF membrane hydrophobicity, a dual coagulation process was used and the mixed solvent (TEP–DMAc) was added into the first coagulation bath for 30 sec. Increase in the TEP–DMAc content led to the change in the morphology type of the membrane, that is, from an asymmetric structure with a dense top surface to a symmetric structure with a skinless top surface, and the pore size distribution widened greatly. By increasing the mass ratio of TEP to DMAc, the denseness of the membrane surface decreased significantly. Adding 60 wt% of TEP–DMAc to the first coagulation bath and the mass ratio of TEP to DMAc was 60:40, the CA reached to a maximum as high as 136.6°, and PVDF microporous membrane showed a high porosity of 80% and an excellent mechanical property of 3.14 MPa tensile strength and 61.79% elongation ratio. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of modification of ion-exchange membrane MF-4SK on its polarization characteristics

Modifications of perfluorinated membrane MF-4SK are studied by a membrane voltammetry method. Various techniques used for physicochemical modification of the membrane (variation of conditions of its chemical conditioning, insertion of tetrabutylammonium cations) exert predicted action on its structural and electrotransport properties. Correlation is established between variations in the slope of the ohmic segment of a voltammetric curve, the magnitude of the limiting electrodiffusion current, and the potential of the system’s conversion into an overlimiting state and the electrotransport properties of membranes and their structural characteristics that are obtained by independent methods of impedance conductimetry and standard porosimetry. The increase in the limiting current for membranes subjected to a thermal oxidizing treatment is explained by a change in the content and state of water in the membrane bulk. Effects of acceleration of the occurrence of an overlimiting state of the membrane saturated with tetrabutylammonium cations is discovered and possible reasons for this phenomenon are discussed. For membranes saturated with tetrabutylammonium cations, a correlation is established between the limiting current and electroosmotic phenomena.     

Adsorption of codeine on hydrophilic silica and silica surface modified by hydrophobic groups in the presence of electrolytes

The adsorption of codeine from aqueous solution onto colloidal silica and silica surface-modified with chemiadsorbed octadecyl dimethyl silane (ODDMS) or dimethyl silane (DMS) groups was studied in the presence of neutral electrolytes at different pH values. From codeine-hydrochloride solutions codeine cations are strongly bound to negatively charged silica surfaces. Inorganic salts (NaCl, NaNO₃) reduce the adsorption of the organic cation. On silica modified by ODDMS (10% of surface silanol groups are occupied), codeine cations are adsorbed to a higher extent at pH 6, while at pH 8 the adsorbed amounts are lower than on the bare silica surface. Neutral electrolytes reduce codeine adsorption on the ODDMS modified silica. On the hydrophobic silica, completely covered by DMS groups, codeine adsorption is considerably lower than on the bare silica, but neutral salts increase the adsorption. The adsorption of codeine is compared with the adsorption of aggregating surfactant ions. Common and different features of their interactions with silica surfaces are outlined.     

Nanosized carriers for hydrophobic compounds based on mesoporous silica: synthesis and adsorption properties

Russian Chemical Bulletin - MCM-41 type mesoporous silica particles were obtained using a template method in an alkaline medium and cetyltrimethylammonium bromide as a matrix. The structural and...     

Ion-selective electrodes for determination of phenylalanine based on uranyl complexes of phosphoryl-containing podands

The possibility of phenylalanine determination using membrane ion-selective electrodes based on uranyl complexes with phosphoryl-containing podands was shown. The variation of the procedure of membrane preparation (either entrapping the preliminarily synthesized uranyl-podand complex in the membrane phase or conditioning of the podand-containing membrane in the uranyl solution) was found to have practically no effect on the electrode properties. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1729–1732, October, 2000.     

Application of thermal analysis for determination of film pressure and film surface energy on silica gel surface

The results of dynamic and quasi-isothermal thermodesorption of water from a silica gel surface at low furnace heating rates in the temperature range 20–125° are presented. From the experimental results, the water film pressure π on silica gel surface, the activation energy ΔE and the evaporation heat ΔH were calculated. An interpretation of π changes in relation to the film thickness and wetting process has been proposed. It is concluded that the characteristic film pressure values correspond to the work of spreading, and immersional, adhesional and adhesional-cohesional wetting. From the determined film pressure values, the average value of the silica gel polar component, γ _s ^P , was calculated to be 114.67 mJ/m².     

Spectrofluorimetric determination of phenylalanine based on fluorescence enhancement of europium ion immobilized with sol-gel method

The analysis of phenylalanine (Phe) in serum is widely performed for the screening of newborn phenylketonuria (PKU). In this work, a novel spectrofluorimetric method for the determination of Phe was developed based on the fluorescence enhancement of Ruhemann's purple, the reaction product between Phe and ninhydrin, upon coordination with Eu(3+). A filter paper disc containing immobilized reactants (ninhydrin and Eu(3+)) was fabricated by sol-gel method. The experimental parameters affecting the determination of Phe, such as the concentrations of immobilized reagents, the pH value, the reaction time and temperature were optimized. Under optimum conditions, the fluorescence intensity of Phe-ninhydrin-Eu(3+) system was linearly proportional to the concentration of Phe in the range from 5×10(-5) to 2×10(-3) mol L(-1), and the limit of detection was found to be 5.2×10(-6) mol L(-1). The relative standard deviation was 2.6% for ten replicate measurements of 1.5×10(-4) mol L(-1) of Phe. The method has merits of sensitivity, simplicity and low cost, and has been applied to the determination of Phe in artificial serum.