The interphase between mercury and acetone+ nitromethane mixtures with KPF6 as a supporting electrolyte

Differential capacity and interfacial tension measurements were carried out on mercury for acetone+nitromethane mixtures with KPF₆ as a supporting electrolyte. On the basis of Gibbs adsorption equation and Guggenheim's model of the surface phase the composition of the surface layer was estimated for different acetone contents and different charges on the mercury electrode. The results obtained indicate that the positive acetone adsorption is marked at negative charges with maximum at σ_m=?0.07 C m^?2, but is practically non-existent at zero and positive charges.     

Electrokinetic studies on testosterone/aqueous electrolyte interface : Part 1. Electro-osmosis,electrophoresis, streaming potential and streaming current

The electrical properties of testosterone interfaces were investigated. For this purpose, measurements of electro-osmosis, hydrodynamic permeation, streaming potential and streaming currents of metabolically important solutions of the electrolytes NaCl, KCl and MgCl₂ (in the concentration range 10^?4?10^?3 mol/l) across a testosterone plug were carried out. Electrophoretic mobility of testosterone particles suspended in these electrolyte solutions was also studied. The data were analysed from the viewpoint of nonequilibrium thermodynamics. Phenomenological coefficients were evaluated from the linear transport equations and Saxen's relationship was verified. Dependence of phenomenological coefficients on electrolyte concentration was examined. Electro-osmotic and electrophoretic transport coefficients were found to vary linearly with concentration, whereas hydrodynamic permeation and membrane conductance coefficients show non-linear variation. The results are explained on the basis of structural modifications occurring during the passage of the permeating species through the membrane. The nature of the electrical double layer formed at the testosterone/solution interface was ascertained on the basis of the direction of electro-osmotic permeation and electrophoretic migration of testosterone particles.Zeta potentials were estimated in order to obtain a plausible picture of the electrical double layer at the testosterone/solution interfaces. Dependence of zeta potentials on concentration was examined and membrane parameters calculated. The double layer thickness was estimated, which reveals that the diffuse double layer is more compact in the case of MgCl₂ than in that of KCl.     

Adsorption of naphthalene on bismuth electrode from ethanol

Adsorption of naphthalene on a polarized bismuth electrode was studied from the ethanolic solutions of LiClO₄ by means of differential capacity measurements. Two regions of adsorption of naphthalene (13.2 and ?1.3 μC cm^?2) corresponding to different orientations of naphthalene molecules at the electrode surface were discovered. A sharp capacity maximum at far positive charges indicates that formation of a polymolecular adsorption layer consisting of the adsorbed naphthalene molecules in flat orientation occurs. By use of the Gibbs equation and of double layer theory the surface excess of naphthalene, adsorption energy, potential drop across the inner layer and some other adsorption parameters have been calculated for a wide range of charges. The π-oribital interaction energy of naphthalene with the bismuth surface has been estimated for various charges. A comparison of the adsorption behaviour of naphthalene in ethanolic and aqueous solutions was made.     

Irreversible adsorption of latex particles on fibrinogen covered mica

Physicochemical properties of bovine plasma fibrinogen (Fb) in electrolyte solutions were characterized. These comprised the diffusion coefficient (hydrodynamic radius), determined by the DLS method, electrophoretic mobility and the isoelectric point. The hydrodynamic radius of Fb was 12 nm for pH<5. The number of uncompensated (electrokinetic) charges on the protein N _c was calculated from the electrophoretic mobility data. It was found that for pH<5.8 the electrokinetic charge was positive, independently of the ionic strength and negative for pH>5.8. For pH=3.5 the value of N _c , was 26 for 10^?3 M. Similar electrokinetic measurements were performed for the mica substrate using the streaming potential cell. It was shown that for pH=3.5 and 10^?3 M, the zeta potential of mica remained negative (?50 mV). This promoted an irreversible, electrostatically driven adsorption of Fb, which was confirmed in experiments carried out under diffusion-controlled transport. The surface concentration of Fb on mica was determined directly by AFM counting. By adjusting the time of adsorption, Fb monolayers of desired coverage were produced. Independently, the presence of Fb on mica was determined quantitatively by the colloid enhancement method, in which negatively charged latex particles were used, having the diameter of 800 nm. It was found that for Fb coverage below 0.05 the method was more sensitive than other indirect methods. The experimental data obtained in latex deposition experiments were adequately interpreted in terms of the random site model used previously for polyelectrolytes. It was shown that adsorption sites consisted of a cluster of two Fb molecules. It was concluded that the colloid enhancement method can be successfully used for detecting the presence of proteins at solid substrates and to determine the uniformity of monolayers in the nanoscale.     

Electric and adsorption properties of pharmaceutical polymers. Part I: Electrokinetics of Aquacoat

The characterization of the electrical surface properties of Aquacoat, a polymer latex of great interest in pharmaceutical sciences, is described. The technique used is electrophoresis. Analysis was carried out of the effect of pH, electrolyte and surfactant concentration on the electrophoretic mobility of the latex particles. Increasing the pH of the dispersion medium provokes a monotonous increase in the value of the negative mobility. The electrolytes LiCl, KCl and NaCl give rise to larger mobilities when their concentration in solution is increased up to ca. 10^–3 M, and a similar behavior is found in the presence of Na₂SO₄. The effect of raising the concentration of CaCl₂ is to decrease the absolute value of the mobility as a consequence of double layer compression. Sodium dodecyl sulphate seems to adsorb on the particle surface increasing its negative charge, but when its concentration is close to 10^–3 M saturation of the surface appears to take place, and an approximately constant mobility is suggested by data, whatever the pH of the medium. Finally, the mobility variations with LaCl₃ concentration indicate adsorption of the La³⁺ cation when it is hydrolyzed (pH5), whereas non-hydrolyzed lanthanum has little effect on the particle charge.     

Electrokinetic properties of aluminum oxide nanodispersions in NaCl solutions

Using a Zetasizer Nano analyzer, electrophoretic mobility and particle sizes are studied as depending on the pH (3–11) and concentration (10^?3–10^?1 M) of NaCl background solutions for two samples of aluminum oxide, namely, γ-oxide of the Degussa brand and a sample synthesized by aluminum chloride hydrolysis. The values of the electrokinetic ζ potential are calculated through the Smoluchowski equation and with allowance for the effect of the polarization of electrical double layer on the electrophoretic mobility within the framework of the Overbeek-Boes-Wiersema model (ζ_W). It is established that, in the region of the isoelectric point (IEP), at (pH-pH_IEP) = ±1.5, the |ζ_W|-pH dependences are linear and their slopes are almost equal for both aluminum oxide samples. The difference between the positions of IEPs for γ-oxide and synthesized oxide sample may be related to different degrees of their surface hydration.     

聚吡咯薄膜的电特性

含有不同的链长的w-吡咯烷基二甲基氯硅烷作为粘合剂通过自组装（SAMs）吸附于二氧化硅表面,然后聚吡咯膜化学沉积于该粘合剂修饰的表面。化学沉积的聚吡咯膜的表面形貌用扫描电镜（SEM）及原子力显微镜（AFM）表征。除短链外不同链长的粘合剂对聚吡咯膜的厚度影响不大。聚吡咯膜的电特性用电流-电压表征。结果显示电流与粘合剂的链长无关。电特性表明载流子迁移率为1.4 ´ 10-4 cm2×V-1.s –1。     

Precipitation membranes — A review

Precipitation membranes are generated exclusively by diffusion-controlled precipitation. They form an asymmetrical barrier with an electrical polarity. Their electrical charges, which are charges of adsorbed ions, are not fixed and can easily and reversibly be desorbed. In the conditioned state a relatively large potential difference develops, the membranes rectify electrical current and display specific ion permeabilities. A unique property of these membranes allows determination of the permeability of single ionic species. The permeability of OH^? was thus found to be markedly greater than that of H⁺, Precipitation membrane effects may be involved in rectification phenomena in biological membranes such as the frog skin.     

Colloido-chemical characteristics of porous glasses with different compositions in KNO3 solutions. 1. Structural and electrokinetic characteristics of membranes

The structural (specific surface area, liquid-filtration coefficient, average pore radius, volume porosity, and structural-resistance coefficient) and electrokinetic (counterion transport numbers, specific electrical conductivity, and electrokinetic potential) characteristics of porous glasses with different compositions have been determined in potassium nitrate solutions with concentrations of 10^?3–10^?1 M. All the membranes under investigation have been shown to exhibit the dependences of efficiency coefficients and counterion transport numbers on electrolyte concentration and pore size that are predicted by the theory of an electrical double layer. It has been established that, at a constant electrolyte concentration, the absolute values of electrokinetic potential increase with the average pore radius because of variations in the slipping-plane position.     

Adsorption of Tri‐n‐Butyl Phosphate (TBP) from NaClO4 Aqueous Solution on Hg Electrode

The adsorption of TBP on Hg electrode from aqueous NaClO₄ media has been studied using differential capacity and chronocoulometric measurements. TBP adsorbs in two steps, the first corresponding to a flat and second to a perpendicular orientation. Both orientations were observed in the entire investigated potential range. The maximal measured surface concentration (Γ_max) of TBP reaches a value of 1.55×10^?10 mol cm^?2, which corresponds to the theoretical value for densely packed molecules in perpendicular orientation. Γ value of the first isotherm step plateau is about 7 to 15% smaller than Γ_max and decreases strongly at potentials more negative than ?0.9 V due to the repelling of negative charges between the electrode and the phosphate group. The standard Gibbs energy of adsorption was found to reach the value of ?34 kJ mol^?1.     

Electrophoretic mobility of latex spheres in the presence of divalent ions: experiments and modeling

Electrophoretic mobilities (EPM) of negatively charged latex spheres were measured as a function of salt type and salt concentration. The measured values of EPM were analyzed using a standard electrokinetic model that includes double layer relaxation and the Poisson–Boltzmann model of diffuse double layer. Calculated values of EPM were in good agreement with experimental data taken in simple 1:1 (KCl) and 1:2 (Na₂SO₄) electrolyte solutions without using any fit parameters. For 2:1 electrolytes (CaCl₂ and MgCl₂), however, the magnitude of EPM calculated by the model was higher than the measured values of EPM at higher electrolyte concentrations. The difference between measured and calculated EPM was reduced by assuming the distance of slipping plane x _s?=?0.25 nm or by assuming the decrease of the magnitude of surface charge density from ?0.07 to ?0.025 C/m². These are probably due to the accumulation of divalent counterions in the vicinity of a particle’s surface.     

Nanocomposite thin film structures based on polyarylenephthalide with SWCNT and graphene oxide fillers

Investigations of nanocomposite thin films based on polyarylene- phthalide, single-walled carbon nanotubes and graphene oxide have been carried out. Using these films as a transport layer, field-effect transistors were assembled and their output and transfer characteristics were measured. The mobility of charge carriers was estimated and the obtained values are as follows: μ_PAP/GO = 0.020 cm² V^?1 s^?1 and μ_PAP/SWCNT = 0.071 cm² V^?1 s^?1.     

Changes in electrokinetic properties of natural rubber latex after surface chemical modifications

High-ammonia latex concentrate prepared from doubly-concentrifuged fieldHevea latex was exhaustively dialyzed to remove any residual water-soluble non-rubber constituents. The specially purified latex was then treated with specific chemical reagents to modify the surface ionogenic groupings originally present on the latex particle surface. The electrophoretic mobility of the modified latexes was investigated as a function of pH. The change in electrokinetic properties of the surface-modified latex was explained in terms of chemical modification to the ionogenic groups of the adsorbed layer of proteins and long chain fatty acid soaps on the latex particle surface, the negative charges of which are primarily responsible for the colloidal stability of the latex. For comparison direct extraction of the long-chain fatty acid soaps from the specially purified latex by solvent was also carried out. Present results indicate that the number of carboxyl groups from the adsorbed long-chain fatty acid soaps plays a major role in the stabilization of the latex concentrate. In comparison the contribution of negative charges from the adsorbed proteins towards the stability of the latex is of less importance.     

Electrokinetic and light scattering properties of pea and Chlamydomonas reinhardtii thylakoid membranes: effect of phytohemagglutinin

The effects of phytohemagglutinin (PHA) and illumination on the surface charge densities and 90 degrees light scattering properties of pea and Chlamydomonas reinhardtii thylakoids were investigated. The electrophoretic mobility (EPM) of pea thylakoids decreased after treatment by various concentrations of PHA at ionic strengths of I = 0.01 and I = 0.02, while that of C. reinhardtii thylakoids remained stable except for a drop after treatment by PHA at a concentration of 6 ng/mL in a medium with an ionic strength of I = 0.01. Illumination did not influence the EPM of untreated thylakoids. However, if the EPM of thylakoids had been retarded by pretreatment with PHA, light exposure stimulated a recovery of the reduced negative surface charge density up to at least the initial values. In addition to reducing EPM, PHA also induced a decrease of the basal light scattering property of pea thylakoids, which is an indicator of thylakoid aggregation. The physiological role of the membrane surface charges of thylakoid particles in lectin regulated processes of thylakoid stacking and activity is discussed.     

Structure de la couche double sur les électrodes d'or: Détermination des composants de charge

The components of the charge q_±^Au at the interface polycrystalline gold electrode—NaF, KCl or KBr solutions and the charge due to specifically adsorbed Cl^? or Br^? anions have been determined by thermodynamical analysis of differential capacity—potential curves, using the two sets of variables q^M, μ (Grahame and Soderberg's method) and E_?, μ (Esin—Markov effect). In the absence of specific adsorption (NaF), variations of charges q_±^Au with potential are in good agreement with those provided by the diffuse layer theory in the negative charge region of the metal. With specific adsorption of Cl^? or Br^? anions, both q_±^Au(q^Au), (q_?¹)^Au(q^Au) curves obtained by the two methods fit well. Determination of components of charge was made in the whole negative charge region and in part of the positive charge region of the electrode.     

Synthesis and proton conductivity of adsorption-saturated and solvated porous hydroxyethylated cyclam layers on the surface of PVC-coated cellulose fabric

Porous layers of associates of adsorption-saturated and benzene- and hexane-solvated chloride and sulfate of hydroxyethylated cyclams with acid aqua complexes were synthesized on the surface of PVC-coated cellulose fabric. The porous structure of the layers includes a system of internal pores connected with the external pores via the diamine rings of the common walls of the hydroxyethylated cyclam nets; the internal pores are filled with the associates; the solvent molecules are adsorbed on the developed surface of the layers or solvate it. The H⁺ motion rate in a layer placed in solvent vapors or liquid solvents was measured; the layers were found to be nonlinear H⁺ conductors. The potential of H⁺ transition from the acid solution into the layer, the H⁺ mobility constant, and the field variation constant of the H⁺ mobility of the layer depend on the layer composition. The adsorption and solvation are accompanied by the formation of host-guest molecular complexes between the diamine rings of the cyclam nets and the benzene or hexane molecules, affecting the resistance of the associates to the incorporation of H⁺ ions and the H⁺ mobility in the associates.     

Electrophoresis of large colloidal particles with surface charge layers. Position of the slipping plane and surface layer thickness

A theory is proposed for the electrophoresis of a large colloidal particle with a surface charge layer. The slipping plane is assumed to be located within the surface layer but may not be located at the boundary between the surface layer and the particle core. In previous studies, the depth of the slipping plane is assumed to coincide with the surface layer thickness. The present theory makes it possible to examine the separate dependence of the electrophoretic mobility on the position of the slipping plane and on the surface layer thickness. It is shown that, at constant amount of particle-fixed charges in the surface layer, the mobility increases as the depth of the slipping plane (d _s ) increases, while it decreases as the surface layer thickness (d _c ) increases, causing a mobility maximum in some cases ifd _s =d _c . Several approximate analytic expressions for the mobility are presented.     

Comparative Study of Hypophosphite H2PO2^- Adsorption on Ni（111） and Ag（111） Surfaces by DFT

Surface structures and electronic properties of hypophosphite H2PO2^- on Ni（111） and Ag（111） surfaces were investigated by means of density functional theory at B3LYP/6-31 ＋ ＋G（d,p） level. The most stable structure was that in which the H2PO2^- adsorbs with its two P--O bonds faced to the substrate surface. The results of the Mulliken population analysis showed that because of the subtle difference of electron configuration, the adsorption energy was larger on the Ni surface than on the Ag surface, and the amounts of both donation and back donation were larger on the Ni（111） surface than on the Ag（111） surface. There were more negative Mulliken charge transfer from H2PO2^- to substrate clusters on Ni surface than on Ag surface and more positive Mulliken charges on P atom in Ni4H2PO2^- than in Ag4H2PO2^-, which means that P atom in Ni4H2PO2^- is easily attacked by a nucleophile such as OH . Thus, H2PO2^- is more easily oxidated on Ni（111） surface than on Ag（111） suface. These results indicated that the silver surface is inactive for the oxidation reaction of the hypophosphite anion.     

Surface analysis of plasma‐treated polydimethylsiloxane by x‐ray photoelectron spectroscopy and surface voltage decay

Surface states of polydimethylsiloxane (PDMS) treated by plasma were investigated by x‐ray photoelectron spectroscopy and surface voltage decay. X‐ray photoelectron spectroscopy confirmed the formation of a silica‐like (SiO_x, x = 3–4) oxidative surface layer. This layer increased in thickness with increasing exposure duration of plasma. Plasma exposure lowers the surface resistivity from 1.78 × 10¹⁴ to 1.09 × 10¹³ Ω □^?1 with increasing plasma treatment time. By measuring the decay time constant of surface voltage, the calculated surface resistivity was compared with the value measured directly by a voltage–current method; good agreement between the two methods was obtained. It was observed that plasma treatment led to a decrease in the thermal activation energy of the surface conduction from 31.0 kJ mol^?1 for an untreated specimen to 21.8 kJ mol^?1 for a plasma‐treated specimen for 1 h. Our results allow the examination of effects of plasma on the electrical properties of PDMS. Copyright © 2003 John Wiley & Sons, Ltd.     

New Polymers for Optimizing Organic Photovoltaic Cell Performances

The performance of an organic solar cell critically depends on the materials used in the active layer. Desirable characteristics of active layer materials include an intense optical absorption covering broad range of the solar spectrum to maximize photon capture, the ability to effectively separate charges upon photo‐excitation, high charge mobility to allow efficient charge transport to the electrodes, and suitable HOMO and LUMO levels to ensure a high device voltage. In order to optimize these properties simultaneously, we have designed and synthesized conjugated polymers containing alternating electron‐donating and electron‐accepting units. Based on one of the low band gap polymers we designed and synthesized previously, poly[2,6‐(4,4‐bis‐(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene)‐alt‐4,7‐(2,1,3‐benzothiadiazole)], we carried out both side chain and main chain modifications in order to improve performance even further. By incorporating fluorene repeating units into the main chain, it is possible to adjust the absorption characteristics of the polymers while maintaining a desirable HOMO level and good charge carrier mobility. The solubility profile of the polymer can be adjusted by modifying the side chains, and soluble polymer with mobility as high as 7×10^?2 cm²/Vs is realized when a combination of 2‐ethylhexy and hexyl groups are used as side chains. These polymers should be promising candidates for high performance solar cells according to a recently published model (3).