A review on experimental studies of surfactant adsorption at the hydrophilic solid-water interface

The progresses of understanding of the surfactant adsorption at the hydrophilic solid-liquid interface from extensive experimental studies are reviewed here. In this respect the kinetic and equilibrium studies involves anionic, cationic, non-ionic and mixed surfactants at the solid surface from the solution. Kinetics and equilibrium adsorption of surfactants at the solid-liquid interface depend on the nature of surfactants and the nature of the solid surface. Studies have been reported on adsorption kinetics at the solid-liquid interface primarily on the adsorption of non-ionic surfactant on silica and limited studies on cationic surfactant on silica and anionic surfactant on cotton and cellulose. The typical isotherm of surfactants in general, can be subdivided into four regions. Four-regime isotherm was mainly observed for adsorption of ionic surfactant on oppositely charged solid surface and adsorption of non-ionic surfactant on silica surface. Region IV of the adsorption isotherm is commonly a plateau region above the CMC, it may also show a maximum above the CMC. Isotherms of four different regions are discussed in detail. Influences of different parameters such as molecular structure, temperature, salt concentration that are very important in surfactant adsorption are reviewed here. Atomic force microscopy study of different surfactants show the self-assembly and mechanism of adsorption at the solid-liquid interface. Adsorption behaviour and mechanism of different mixed surfactant systems such as anionic-cationic, anionic-non-ionic and cationic-non-ionic are reviewed. Mixture of surface-active materials can show synergistic interactions, which can be manifested as enhanced surface activity, spreading, foaming, detergency and many other phenomena.     

应用扫描电化学显微镜研究电子在室温离子液体与1,2-二氯乙烷混合溶液/水相界面上的转移反应

应用扫描电化学显微镜研究了室温离子液体(Omim·Tf2N)与1,2-二氯乙烷(DCE)混合溶液/水界面上的电子转移反应. 在保持共同离子(Tf2N-)的浓度比恒定及异相电子转移反应由界面电势差所决定的条件下, 研究了离子液体和DCE混合溶液中二茂铁(Fc)与水相中亚铁氰化钾[K4Fe(CN)6]之间异相电子转移反应. 探讨了混合溶液中离子液体的体积分数(xRTIL)的变化对混合溶液/水界面上电子转移反应的影响. 结果表明, 随着xRTIL的减小(从1减小到0.1), Fc在混合溶液中的扩散系数单调递增(从2.730×10-7 cm2·s-1增加到9.131×10-6 cm2·s-1); 而异相电子转移反应速率常数(k)则先逐渐减小(从8.0 mol-1·cm·s-1减小到0.32 mol-1·cm·s-1), 之后又略有增大(从0.32 mol-1·cm·s-1增大到0.48 mol-1·cm·s-1). 对这种现象可能的原因进行了较详细探讨.     

Adsorption of oligooxypropylenated amines at the aqueous solution—air interface: Homologous series of piperidine and morpholine derivatives

The surface tension isotherms for pure oligooxypropylenated piperidine and morpholine at the aqueous solution—air interface were determined and interpreted. The surface excess concentration, Γ, the surface area per molecule, A, and the standard free energy of adsorption, ΔG°, were calculated according to a new empirical adsorption equation. The standard free energy contribution for the oxypropylene group (PO) in morpholine derivatives,ΔG° (PO) = −3.34 kJ mol⁻¹, is substantially lower than that for the PO group located in the piperidine derivatives, i.e. ΔG° (PO)= −3.12 kJ mol⁻¹.     

Dynamic surface elasticity of polymer solutions

The surfaces of surfactant solutions exhibit viscoelastic dilational behavior which may be investigated by modern optical and mechanical methods. The present study focuses on the dynamic dilational properties of the polymer solution — gas interface. Linear flexible polymer chains at the surface are considered as consisting of trains, lying on the surface, and loops and tails that protrude into the liquid. The Rouse model is used to describe the inner dynamics of the trains, whereas their motion relative to their neighbors on the surface can be described with the help of the reptation conception. An expression for the complex dynamic dilational surface elasticity has been derived. Although, in general, the relaxation of the surface tension is characterized by an infinite series of relaxation times, it is shown that for many systems the dynamics of the surface layer can be described approximately by only two main relaxation times. The dispersion equation, which was obtained earlier for solutions of conventional surfactants, is shown to be fulfilled for polymer solutions also.     

Influence of nano-structure on electrolytic properties in CeO2 based system

Doped ceria (CeO₂) compounds are fluorite type oxides that show oxygen ionic conductivity higher than yttria stabilized zirconia, in oxidizing atmosphere. In order to improve the conductivity, the effective index was suggested to maximize the oxygen ionic conductivity in doped CeO₂ based oxides. In addition, the true microstructure of doped CeO₂ was observed at atomic scale for conclusion of conduction mechanism. Doped CeO₂ had small domains (10-50 nm) with ordered structure in a grain. It is found that the electrolytic properties strongly depended on the nano-structural feature at atomic scale in doped CeO₂ electrolyte. This revised version was published online in August 2006 with corrections to the Cover Date.     

Aggregation effects on evaporation and the air/water interface of dodecyltrimethylammonium hydroxide solutions

 The system dodecyltrimethylammonium hydroxide (DTAOH)–water was studied by surface tension, ion-selective electrodes and evaporation in an electrobalance. Results confirmed earlier conclusions about a stepwise aggregation mechanism in DTAOH solutions. The aggregation process started at a total concentration C _T=(2.51±0.10)×10^-4 mol dm^-3) which probably corresponds to the formation of dimers. At C _T= (1.300±0.041)×10^-3 mol dm^-3 there was a change in the surface and evaporation behavior, corresponding to the formation of small, fully ionized aggregates which grew with increasing concentration. At C _T= (1.108±0.010)×10^-2 mol dm^-3 the formation of true micelles with hydroxide counterions in the Stern layer did not change significantly the evaporation and adsorption behavior. This means that between this concentration and C _T=(3.02±0.28)× M28.8n10^-2 mol dm^-3, the changes in structure were gradual. At the latter concentration there was a sudden change in the monolayer state at the air/water interface, with a strong surfactant desorption, and a major change in evaporation behavior. The changes are compatible with the formation of few, large aggregates reducing the total concentration of kinetically independent solute units, which in turn increased the activity of the solvent. This phenomenon is in agreement with literature information. The reduction in the evaporation rate of water was mainly due to the reduction of the water activity, caused by colligative effects. The reduction of the effective area available for evaporation had only a slight effect in water evaporation. Received: 9 January 1997 Accepted: 19 October 1997     

Simultaneous quantitative measurement of a new platelet activating factor antagonist (BN 50730) and its two main metabolites in human plasma and urine by LC-MS

Summary A simple and sensitive assay has been developed for the quantitative measurement of a new platelet activating factor antagonist (BN50730), and its two main metabolites (BN50727 and BN50922), at the picomole level in human plasma and urine. The three compounds of interest and the internal standard (BN50765) were measured by combined LC-negative chemical ionization MS. A simple solid-liquid extraction procedure was used to isolate the parent drug and the two metabolites. The MS was tuned to monitor the intense ionm/z 333 generated in the ion source by a dissociative capture process. The assay was on 1 ml plasma or 0.1 ml urine and the quantitation limit was calculated as 1 ng·ml^–1. The very low relative standard deviations and mean percentages of error calculated for within-day or between-day repeatability assays demonstrate the ruggedness of the technique for routine determination in biological fluids. Some preliminary results on the pharmacokinetics of the parent drug and its two main metabolites illustrate the applicability of this method.     

Interface interactions in modulated phases,and upsilon points

Certain features in Frenkel-Kontorova and other models of phases with a one-dimensional modulation can be analyzed by assuming parallel interfaces separating sets of lattice planes belonging to two different phases, and treating the free energy to create interfaces, as well as the interaction of two, three, or more interfaces, as phenomenological parameters. A strategy employed by Fisher and Szpilka for interacting defects can be extended to the case of interfaces, allowing a systematic study of the phase diagram by ignoring all interface interactions, and then successively taking into account pair, triple, and higher-order terms. The possible phase diagrams which can occur near the point where =0 include: various sorts of endpoints analogous to critical endpoints, an accumulation point of first-order transitions and triple points, and a self-similar structure which we call an upsilon point, which turns out to be an accumulation point of an infinite number of segments of first-order transition lines, each of which terminates in two upsilon points.     

Microstructural and physicochemical study of the buried Fe/AlGaAs(100) interface by transmission electron microscopy and x‐ray emission spectroscopy

Among the magnetic metal/semiconductor contacts, the Fe/GaAs system has been widely studied owing to its potential applications in electronic devices. In contrast, there are not many studies concerning the Fe/Al_xGa_1?xAs contact, and in particular there are no reports concerning the changes induced in the interfacial zone by the presence of Al. In this work, thin polycrystalline iron films were deposited by ion beam sputtering at room temperature on a 300 nm thick Al_0.25Ga_0.75As layer grown by molecular beam epitaxy onto GaAs(001). X‐ray diffraction analysis showed that the iron films are polycrystalline, and indications of a (002) texture of the film were observed. The fine scale analysis of the interface was achieved by high‐resolution transmission electron microscopy (HRTEM) observations, the results of which are compared with the physicochemical information obtained from electron‐induced x‐ray emission spectroscopy, by analysing the Al 3p valence states at the Fe/Al_xGa_1?xAs interface. The HRTEM experiments on cross‐section samples indicate that the interfacial zone between iron and AlGaAs is limited to <1.5 nm in thickness. X‐ray emission spectroscopy showed the presence of Al atoms in an FeAl‐like environment at the interface, and the existence of wrong bonds and point defects. The estimated width of the perturbed interface (2.0 ± 0.5 nm) is in agreement with the HRTEM results. Copyright © 2003 John Wiley & Sons, Ltd.     

Adsorption at liquid interfaces: The generalized Frumkin isotherm and interfacial structure

The thermodynamics of adsorption of amphiphilic surface-active compounds at the interface between two immiscible liquids is considered. At the interface, these molecules are supposed to replace a few of the adsorbed molecules of both solvents. Classical isotherms of adsorption (Frumkin, Frumkin-Damaskin, Langmuir, Henry) were based on the model of non-penetrable interface, where an adsorbate can substitute only molecules of one solvent. At the interface between two immiscible electrolytes, nonpolar oil/water interfaces, and liquid membranes amphiphilic molecules can substitute molecules of both solvent and classic isotherms cannot be used. The generalization of Frumkin isotherm for permeable and non-permeable interfaces, known as the Markin-Volkov isotherm, gives the possibility to analyze adsorption in a general case. The adsorption isotherms of pentafluorobenzoic acid at the octane/water interface at different pHs were measured by the drop-weight method. The thermodynamic parameters of pentafluorobenzoic acid (PFBA) adsorption at octane/water interface were determined. From the measurements of PFBA adsorption, the structure of the octane/water interface was determined. Substitution of one adsorbed octane molecule requires approximately three adsorbed PFBA molecules. This result shows that the orientation of solvent molecules at the interface is different from the bulk. Adsorbed octane molecules have a lateral orientation with respect to the interface. Gibbs free energy of adsorption equilibrium and thermodynamic parameters of PFBA adsorption show that the adsorption of PFBA at the octane/water interface is accompanied by a reduction in the attraction between adsorbed PFBA molecules as the pH decreases to the acidic region. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 10, pp. 1194–1200. The text was submitted by the authors in English.