生物基表面活性剂七叶皂素的界面行为

以天然三萜皂苷七叶皂素为研究对象, 分别采用吊片法、 悬滴法和高速摄像机动态拍摄法探究了七叶皂素分子在气-液、 液-液、 固-液界面的界面行为. 考察了以七叶皂素为乳化剂制备乳液的性质, 以及七叶皂素对液滴在疏水固体表面润湿铺展行为的调控规律, 并从分子层次角度分析了作用机理. 结果表明, 七叶皂素能在气-液界面发生吸附, 将水的表面张力降低至42.1 mN/m, 临界胶束浓度为5×10^?4 mol/L. 七叶皂素还可以在油-水界面吸附, 将亲油端插入油相, 亲水端插入水相, 形成稳定的界面膜, 降低界面张力. 以七叶皂素为乳化剂所制备的乳液, 随着浓度增大可以达到较小的粒径和较大的Zeta电势, 短时间内表现出较好的稳定性. 高浓度的七叶皂素可以很好地抑制液滴在疏水固体表面的弹跳和回缩, 达到很好的铺展效果, 有利于拓展其在诸多领域的应用.     

Determining the mechanical response of particle-laden fluid interfaces using surface pressure isotherms and bulk pressure measurements of droplets

The mechanical response of particle-laden fluid interfaces is determined by measuring the internal pressures of particle-coated drops as a function of the drop volume. The particle monolayers undergoing compression-expansion cycles exhibit three distinct states: fluid state, jammed state, and buckled state. The P-V curves are compared to the surface pressure isotherms Pi-A that are measured using a Langmuir trough and a Wilhelmy plate on a flat water-decane interface covered with the same particles. We find that in the fluid and jammed states, the water drop in decane can be described by the Young-Laplace equation. Therefore in these relatively low compression states, the bulk pressure measurements can be used to deduce the interfacial tension of the droplets and yield similar surface pressure isotherms to the ones measured with the Wilhelmy plate. In the buckled state, the internal pressure of the drop yields a zero value, which is consistent with the zero interfacial tension measured with the Wilhelmy plate. Moreover we find that the compressibility in the jammed state does not depend on the particle size.     

Interfacial dilational behaviour of adsorbed β-lactoglobulin layers at the different fluid interfaces

β-Lactoglobulin adsorption layers at the interfaces solution/air, /tetradecan and /sunflower oil were characterised by dynamic interfacial tension measurements and harmonic drop oscillation experiments in a time scale of some seconds. Axialsymmetric drop shape analysis (ADSA) was used to calculate drop volume, area and interfacial tension. Within a definite range of drop volume amplitude, the oscillation of the surface tension is harmonic and interfacial dilation parameters can be determined. Dependence of the dilational parameters on the amplitude and frequency of drop volume oscillation were determined and methodical demands are given for this special kind of ADSA application. The concentration of interfacial saturation is minimal at the interface with sunflower oil. Interfacial dilational elasticities, and viscosities are maximal at the saturation concentration of all systems investigated. The dilational viscosities are maximal in the frequency range 0.007–0.011 Hz and characterise molecular rearrangement processes in the adsorption layer. Interfacial dilational elasticity and viscosity are the largest at the interface with air. They are the smallest at the interface with sunflower oil. Similarities and differences of the systems investigated are discussed by taking into account the adsorption behaviour and the solvatation of different apolar and polar parts of the protein molecules in the neighbouring phase.     

Adsorption kinetics of asphaltenes at the oil-water interface and nanoaggregation in the bulk

Asphaltenes constitute high molecular weight constituents of crude oils that are insoluble in n-heptane and soluble in toluene. They contribute to the stabilization of the water-in-oil emulsions formed during crude oil recovery and hinder drop-drop coalescence. As a result, asphaltenes unfavorably impact water-oil separation processes and consequently oil production rates. In view of this there is a need to better understand the physicochemical effects of asphaltenes at water-oil interfaces. This study elucidates aspects of these effects based on new data on the interfacial tension in such systems from pendant drop experiments, supported by results from nuclear magnetic resonance (NMR) and dynamic light scattering (DLS) studies. The pendant drop experiments using different asphaltene concentrations (mass fractions) and solvent viscosities indicate that the interfacial tension reduction kinetics at short times are controlled by bulk diffusion of the fraction of asphaltenes present as monomer. At low mass fractions much of the asphaltenes appear to be present as monomers, but at mass fractions greater than about 80 ppm they appear to aggregate into larger structures, a finding consistent with the NMR and DLS results. At longer times interfacial tension reduction kinetics are slower and no longer diffusion controlled. To investigate the controlling mechanisms at this later stage the pendant drop experiment was made to function in a fashion similar to a Langmuir trough with interfacial tension being measured during expansion of a droplet aged in various conditions. The interfacial tension was observed to depend on surface coverage and not on time. All observations indicate the later stage transition is to an adsorption barrier-controlled regime rather than to a conformational relaxation regime.     

Interfacial characteristics of food emulsifiers (proteins and lipids) at the air-water interface

Factors affecting the interfacial characteristics (structure, stability, interfacial rheology, molecular diffusion, and rate of film formation) of food emulsifiers (polar lipids and proteins) at the air-aqueous phase interface are reviewed. The effect of interfacial and aqueous phase (water, and aqueous solutions of ethanol, glycerol, sugars, electrolytes, and pH) compositions have been analyzed as variables. Many measurement methods—such as tensiometry (Wilhelmy plate and pendant drop methods), and Langmuir- and Wilhelmy-type film balances—have been used in the experiments. The effect of the interfacial, aqueous phase composition, and operational conditions (surface density, surface pressure, and temperature) of food emulsifiers (lipids and proteins) at the air-aqueous phase interface are discussed.     

Surface activity of lysozyme and dipalmitoyl phosphatidylcholine vesicles at compressed and supercritical fluid interfaces

The surface activities of lysozyme and dipalmitoyl phosphatidylcholine (DPPC) vesicles at aqueous/compressed fluid interfaces are examined via high-pressure interfacial tension measurements using the pendant drop technique. The density and interfacial tension in compressible fluid systems vary significantly with pressure, providing a versatile medium for elucidating interactions between biomolecules and fluid interfaces and a method to elicit pressure-dependent interfacial morphological responses. The effects of lysozyme concentration (0.0008, 0.01, and 1 mg/mL) and pressure (> or = 7 MPa) on the dynamic surface response in the presence of ethane, propane, N2, and CO2 at 298 K were examined. Interfacial lysozyme adsorption reduced the induction phase and quickly led to interfacial tensions consistent with protein conformational changes and monolayer saturation at the compressed fluid interfaces. Protein adsorption, as indicated by surface pressure, correlated with calculated Hamaker constants for the compressed gases, denoting the importance of dispersion interactions. For DPPC at aqueous/compressed or aqueous/supercritical CO2 interfaces (1.8-20.7 MPa, 308 K), 2-3-fold reductions in interfacial tension were observed relative to the pure binary fluid system. The resulting surface pressures infer pressure-dependent morphological changes within the DPPC monolayer.     

Electrical oscillation at a water/octanol interface in a hydrophobic container

The electrical potential oscillation at and the shape of the water/octanol interface were investigated using hydrophobic fluoroplastic containers. The interfacial potential between a water solution containing 1.5 mM sodium dodecyl sulfate (SDS) and an octanol solution containing 5 mM tetrabutylammonium chloride oscillated with an amplitude of 50-100 mV. The potential oscillation was also observed using a transparent fluoroplastic tube. The water/octanol interface shape was unchanged and no interfacial flow was observed during the oscillation. The interface shape was convex toward the octanol phase for 1.5 mM SDS, meaning that SDS adsorption to the wall was suppressed by the hydrophobic container. Therefore, the octanol system in a hydrophobic container enabled us to elucidate the electrical oscillation without any influence from the wall effect.     

探针型表面张力测试技术的应用研究进展

表面张力是流体重要的物理性质,测定液体表面张力的方法通常包括毛细管上升法、最大气泡压力法、吊环法/吊片法、滴重法/滴体积法、旋滴法和悬滴法。本文综述了测定界面处表(界)面张力和表面压力的方法,详细介绍了基于最大拉力法(Whilhemy吊片法)改进的表面张力测试技术(Du Noüy-Padday),并且概述了这一技术近些年在生物研究、药物研发以及环境监测等领域方面的最新应用。     

小角躺滴法测定低界面张力

在测定界面张力,特别是测定低界面张力的各种方法中,躺滴法占有相当重要的位置。但一般的躺滴法都要求获得赤道半径(图1中的x_e)数据.故躺滴与基底之间的接触角必须大于90°.这在低界面张力体系中常常难以实现,致使躺滴法的应用受到限制。本文提出一种新的躺滴法,它不依赖于接触角的大小,只需测定躺滴轮廓线上两个相关点的坐标,根据所给数值表即可计算出界面张力,从而为躺滴法应用于低界面张力,特别是     

Studies on adsorption of natural and synthetic hymatomelanic acids at air–water and at oil–water interfaces

By utilizing a static method, based on slight modification of the Wilhelmy plate method, the interfacial properties of one natural and two synthetic hymatomelanic acids were studied at both the air–water and oil–water interfaces. On this basis their number-average molecular weights, flexibility and shape of the macromolecular chains at the interface, and the related thermodynamic parameters were evaluated.     

Janus cylinders at liquid-liquid interfaces

We describe the first study on the self-assembly behavior of Janus cylinders at liquid/liquid interfaces. The Janus cylinders are characterized by a phase separation along the major axis into two hemicylinders of different wettability. The pendant drop technique and microscopic imaging were used to characterize the adsorption behavior and self-assembly of Janus cylinders at perfluorinated oil/dioxane and perfluorinated oil/dimethyl sulfoxide interfaces. According to the evolution of the interfacial tension and a series of TEM images taken during the cylinder adsorption, we will specify the characteristics of early to late stages of the Janus cylinder adsorption at a liquid-liquid interface and discuss the effect of Janus cylinder length and their concentration. We also establish that the broken symmetry of the corona leads to significantly higher interfacial activity as compared to homogeneous core-shell cylinders. The adsorption is characterized by three different adsorption stages: first, free diffusion to the interface, followed by continuous adsorption of cylinders including ordering and domain formation and, finally, additional packing with a rearrangement of domains and formation of a loose multilayer system.     

Oscillating drop/bubble tensiometry: effect of viscous forces on the measurement of interfacial tension

The oscillating drop/bubble technique is increasingly popular for measuring the interfacial dilatational properties of surfactant/polymer-laden fluid/fluid interfaces. A caveat of this technique, however, is that viscous forces are important at higher oscillation frequencies or fluid viscosities; these can affect determination of the interfacial tension. Here, we experimentally quantify the effect of viscous forces on the interfacial-tension measurement by oscillating 100 and 200 cSt poly(dimethylsiloxane) (PDMS) droplets in water at small amplitudes and frequencies ranging between 0.01 and 1 Hz. Due to viscous forces, the measured interfacial tension oscillates sinusoidally with the same frequency as the oscillation of the drop volume. The tension oscillation precedes that of the drop volume, and the amplitude varies linearly with Capillary number, Ca=DeltamuomegaDeltaV/gammaa(2), where Deltamu=mu(D)-mu is the difference between the bulk Newtonian viscosities of the drop and surrounding continuous fluid, omega is the oscillation frequency of the drop, DeltaV is the amplitude of volume oscillation, gamma is the equilibrium interfacial tension between the PDMS drop and water, and a is the radius of the capillary. A simplified model of a freely suspended spherical oscillating-drop well explains these observations. Viscous forces distort the drop shape at Ca>0.002, although this criterion is apparatus dependent.     

Effects of Added Surfactant on the Dynamic Interfacial Tension Behavior of Acidic Oil/Alkaline Systems

The effects of a ready-made surfactant (sodium dodecyl sulfate) on the dynamic interfacial tension between a model acidic oil (linoleic acid dissolved in paraffin oil) and various aqueous alkaline (NaOH) systems have been studied using pendant drop tensiometry at surfactant concentrations both below and above the critical micelle concentration (CMC). Below the CMC the added surfactant contributes significantly to a further reduction of interfacial tension of the reacting acid/alkaline system, whereas above the CMC the added surfactant plays an important role in damping the dynamic trends observed for the reactive system alone. Copyright 2001 Academic Press.     

Adsorption of Alkyltrimethylammonium Bromides at the Various Interfaces

The adsorption of alkyltrimethylammonium bromide homologues has been studied at oil/water and air/water interfaces. Dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, and hexadecyltrimethylammomium bromide were used. As an oil phase the aliphatic hydrocarbons of the same chain length as that of surfactants molecules were used. The interfacial tension was measured by the drop volume method and the equilibrium values were received. The surface tension was measured by the drop weight method. The values of surface excess Gamma were calculated from the Gibbs equation. The experimental results were tested by the Langmuir isotherm as well as by the isotherm developed by E. Blomgren and J. O'M. Bockris (J. Phys. Chem. 63, 1475 (1959)). Copyright 2000 Academic Press.     

Gemini阴离子表面活性剂水溶液的界面活性

Gemini阴离子表面活性剂水溶液的界面活性;Gemini阴离子表面活性剂;表面张力;CMC;C20;界面张力     

Experimental observation and prediction of interfacial tension and viscoelastic emulsion model behavior in novel phosphate glass-polymer hybrids

The interfacial tension of hybrids composed of a tin-based phosphate glass (Pglass) and thermoplastic polymers, low-density polyethylene (LDPE), polystyrene (PS), and polypropylene (PP) was investigated using pendant drop and droplet deformation methods. High surface tension values were determined for the pure Pglass and subsequently used to obtain interfacial tension values that were found to be greater than that of most polymer blends reported in the literature. Small amplitude oscillatory shear data were fitted to the Choi-Schowalter and Palierne emulsion models in order to estimate the interfacial tension and to validate the accuracy (or lack thereof) of using a polymer emulsion model on the special Pglass-polymer systems. Although some of the hybrids showed satisfactory agreement with the emulsion models, wide ranges of interfacial tensions were obtained, suggesting that a more complicated theory that explicitly takes the Pglass-polymer interactions, shape factor, and size distributions of the dispersed Pglass phase into account may be necessary for more accurate modeling of these special hybrid systems with enhanced benefits.     

Influence of drop volume on surface tension evaluated using the pendant drop method

The pendant drop technique is one of the most accurate methods to measure surface tension of liquids. Recently, it has been found that the value of the surface/interfacial tension found using the pendant drop method might be drop-volume dependent. In this work, the surface tension of glycerol at a 25 °C and the surface tension of polypropylene at 240 °C were measured using the pendant drop method for different drop volumes. It was shown that the values of the surface tension depend on the drop size if no calibration to take into account the anisotropy in the optical enlargement is performed. However, when a calibration procedure for optical anisotropy correction is performed, the values of the surface tension obtained do not depend on the volume drop size and they corroborate the values in the literature.     

The influence of asymmetry in drop shape on an interfacial tension measurement

A requirement of the drop method for interfacial tension measurement is that the drop must have an axi-symmetry. The drop shape was measured as a function of the angle of the rod from which the drop was hanging. The deviation of the interfacial tension caused by asymmetry was calculated using the selected plane method in the pendant drop technique. A sharp maximum was seen in the interfacial tension vs angle curve when the rod was at the vertical point. The maximum value was concluded as being the true value of the interfacial tension. Both decreases in the pressure difference and in the curvature of the drop associated with an increase in the rod-angle are a counterpart with each other to satisfy the Bashforth and Adams equation. The underestimation of the interfacial tension seems to be caused by the apparent inconsistency between the decreases in the curvature and pressure difference terms. The rigorous mechanical setup demonstrated here is necessary to attain the true axi-symmetric condition, and thus obtain a reliable value for the interfacial tension.     

Dilatational rheology of beta-casein adsorbed layers at liquid-fluid interfaces

The rheological behavior of beta-casein adsorption layers formed at the air-water and tetradecane-water interfaces is studied in detail by means of pendant drop tensiometry. First, its adsorption behavior is briefly summarized at both interfaces, experimentally and also theoretically. Subsequently, the experimental dilatational results obtained for a wide range of frequencies are presented for both interfaces. An interesting dependence with the oscillation frequency is observed via the comparative analysis of the interfacial elasticity (storage part) and the interfacial viscosity (loss part) for the two interfaces. The analysis of the interfacial elasticities provides information on the conformational transitions undergone by the protein upon adsorption at both interfaces. The air-water interface shows a complex behavior in which two maxima merge into one as the frequency increases, whereas only a single maximum is found at the tetradecane interface within the range of frequencies studied. This is interpreted in terms of a decisive interaction between the oil and the protein molecules. Furthermore, the analysis of the interfacial viscosities provides information on the relaxation processes occurring at both interfaces. Similarly, substantial differences arise between the gaseous and liquid interfaces and various possible relaxation mechanisms are discussed. Finally, the experimental elasticities obtained for frequencies higher than 0.1 Hz are further analyzed on the basis of a thermodynamic model. Accordingly, the nature of the conformational transition given by the maximum at these frequencies is discussed in terms of different theoretical considerations. The formation of a protein bilayer at the interface or the limited compressibility of the protein in the adsorbed state are regarded as possible explanations of the maximum.     

Dynamic surface tension measurements on surface active materials

Surface tension measurements by the Wilhelmy plate method are being done at our laboratory using an automatic balance. Surface-active material (surfactant) is spread as a monolayer on an air-water interface and a Pt plate, suspended from a micro-balance, is brought vertically into contact with the interface. The water is contained in a trough, two opposite sides of which can move independently, one producing a large variation in surface area and the other generating a longitudinal wave in the monolayer. This set-up is a new, asymmetric variant of the Benjamins-De Feyter method. Results of measurements on visco-elastic interfacial properties of model compounds of lung surfactant are reported.