An investigation of the aggregation and water-air interfacial behaviour of a cationic tentacle molecule

The aggregation and air-water interface properties of a three-legged tentacle molecule tris (11-pyridinium undec-1-yl)benzene-1, 3, 5-tricarboxylate tribromide have been investigated by measurement of the molar conductance, , and equilibrium surface tensin,, over a wide range of bulk concentration (8×10^–6 – 0.3 M). In contrast to the single chain analogue, dodecyl pyridinium bromide, DDPB, the tentacle species shows no evidence for a conventional micellar transition in solutions up to 100 fold more concentrated than the critical micelle concentration of DDPB, though aggregation of small numbers of molecules cannot be excluded. The conductance behaviour suggests the occurrence of ion-pair (or higher) equilibria, which are likely to complicate the interpretation of the data. Also, in contrast to a previous tentacle molecule described in the literature, the present species is significantly surface active, and in the high concentration limit reduces to <30 mNm^–1, significantly lower than the values obtained for simple ionic amphiphiles. In this region the tentacle species seems to stand like a tripod at the water-air interface with both its hydrocarbon legs and its aromatic body lifted clear of the water surface. At much lower concentrations two small plateau regions in are apparent ( 60 and 52 mNm^–1). Here, the tentacle molecule occupies a much larger surface area, and seems to adopt a crab-like crouch with its aromatic body and polar ester substituents lowered into the water surface.     

A method for correcting the contact angle from the θ/2 method

The θ/2 method, a widely used technique on measuring the contact angle of a sessile drop, assumes that the drop profile is part of a sphere. However, the shape profile of a sessile drop is governed by the Young–Laplace equation and is different from a sphere, especially for drops with a large bound number (e.g. large volume or small surface tension). The spherical assumption, therefore, causes errors on evaluating the contact angles. The deviation of contact angle from the θ/2 method is evaluated from a theoretical calculation in this work. A simple means is given for correcting the measurement error. The corrected angle results from the drop volume, surface tension, liquid density and the contact angle from θ/2 method. An algorithm for finding the correct contact angle without knowing the density and surface tension is also given. At the end, two examples of pendant drops are given for the illustration.     

Effect of pressure on the adsorption and micelle formation of aqueous dodecyltrimethylammonium chloride solution-hexane system

The interfacial tension of aqueous dodecyltrimethylammonium chloride (DTAC) solution/hexane interface has been measured as a function of pressure at concentrations around the critical micelle concentration (CMC). The derivative of the interfacial tension with respect to pressure has been observed to change abruptly at the CMC as in the case of aqueous dodecylammonium chloride (DAC) solution-hexane system studied already. The volume changes associated with the adsorption of DTAC from its monomeric and micellar states have been calculated. The results have indicated that the micelle formation of surfactant is treated like the appearance of a new macroscopic phase in the system. It has also been concluded that the micelle solubilizing hexane bears resemblance to the adsorbed film in terms of the volume. The difference in the pressure dependence of the volume of micelle formation ^MW between DTAC and DAC has been attributed to a larger polar group of DTAC. The fact that the value of ^MW is larger than that estimated from the conductivity data has been explained by the solubilization of hexane into the micelle.     

钛酸钾晶须界面性质研究

通过乳液聚合的方法对钛酸钾晶须进行表面改性,获得了表面包裹聚甲基丙烯酸甲酯的钛酸钾晶须. FT-IR、SEM、EDS的表征表明,钛酸钾晶须的表面包裹了聚甲基丙烯酸甲酯膜,形成了以钛酸钾晶须为核,聚甲基丙烯酸甲酯为壳的复合粒子.研究表明,改性后的晶须表面能降低,在有机溶液中的界面张力大大降低,与聚甲基丙烯酸甲酯的界面性质相似,说明改性后的晶须基本被聚甲基丙烯酸甲酯完全包裹,因此晶须由亲水性变为疏水性,在有机溶液中的分散性显著提高.     

Action of α-cyclodextrin on phospholipid assemblies

Interactions of α-cyclodextrin (α-CD) with dimyristoylphosphatidylcholine (DMPC) and Egg phosphatidylcholine (Egg-PC) were studied (i) by analyzing surface pressure-area isotherms and surface tension of phospholipid monolayers formed at the interface between air and α-CD aqueous solutions and (ii) by X-ray diffraction performed on fully hydrated α-CD/phospholipid binary mixtures. The cyclodextrin molecules strongly interact with the two-dimension phospholipid assembly. Their addition into the aqueous sub-phase leads to the removal of part of the phospholipids from the air-water interface: the higher the α-CD concentration, the higher the phospholipid depletion. This should preferentially involve interactions between cyclodextrin and the phosphatidylcholine head group as α-CD is water-soluble and not surface-active. At the three-dimension level, the bilayer packing of the phospholipid lamellar phase appears not affected by the presence of cyclodextrin as shown by X-ray scattering at small angles whereas wide-angle diffraction patterns reveal the formation of a crystalline phase organized in a pseudo-hexagonal lattice usually characteristic of α-CD dimers. These results point out that α-CD should interact with bilayer-forming phospholipid molecules but likely according to a process that would preserve intact at least a part of the multilamellar assembly.     

A simple adsorption model for ionic surfactants

In the past, few theoretical attempts have been made to describe quantitatively the adsorption of ionic surfactants at liquid interfaces. Well-known adsorption isotherms due to Frumkin or Hill–de Boer cannot respond to the specific electrostatic and geometric properties of the surfactant molecules. Our approach is based on a combination of the Gouy–Chapman theory with a modified Frumkin isotherm. The modification implies that the system is free to choose an optimal head group area and an optimal arrangement of the surfactant molecules in the interface as a function of bulk concentration. Interaction energies between neighbouring adsorbed surfactant molecules and between surfactant and water molecules are taken into consideration. The minimum of the Gibbs free energy of the system is equivalent to a minimal interfacial tension. Thus, the thermodynamically stable isotherm can be obtained as the lower envelope of the family of σ versus ln c isotherms resulting from different choices of the model parameters, including the area per molecule. According to the Gibbs equation, the Γ versus ln c adsorption isotherm is obtained as the derivative of this envelope. By variation of the model parameters, the envelope of the calculated adsorption isotherms can be fitted to experimental data of the interfacial tension versus bulk concentration. A computer program is used to calculate the σ versus c and the Γ versus ln c curves as well as to fit the parameters. Received: 28 October 1999/Accepted: 8 February 2000     

Studies on the properties of ionic liquid EMIInCl4

This paper reports that an ionic liquid (IL) has been prepared by directly mixing InCl₃ and 1-methyl-3-ethylimidazolium chloride (EMIC) with molar ratio 1/1 under dry argon atmosphere. The densities, and surface tension of the pure IL were determined at temperature range of 293.15 to 343.15 ± 0.1 K. The volumetric properties and the properties of surface for ionic liquid based on group III were discussed by Glasser's theory and Yang's interstice model.     

Surface free energies of styrene-acrylic acid copolymer plates prepared in various frames

Styrene (St)-acrylic acid (AA) copolymer plates were synthesized in the frames made of glass, aluminum (Al) and poly(difluoroethylene) (PDFE). Surface properties of the prepared copolymer plates were characterized with regard to critical surface tension ( _C ), chemical components by IR analysis and surface energies (total energy, _S ; dispersion force components, _S ^d ; polar component, _S ^p ; hydrogen bonding component, _S ^h ) and the following results were obtained.The _C values of the copolymer plates increased with AA content and also depended on the sort of the used frame. The increasing order of the _C values of the copolymer plates corresponded to those of the used frames, namely, PDFE frame < Al frame < Glass frame.The prepared copolymer plates with low AA contents (ca. 10 mol%) were enriched in the AA moiety in the surface layer regardless of the kind of the used frame.The total and the individual components of the surface free energies of the copolymer plates were largely affected by the property of the used frame. The glass frame gave the plate with higher _S ^h values suggesting preferential orientation of the polar site of AA component.     

Effect of Neck Formation on the Measurement of Dynamic Interfacial Tension in a Drop Volume Tensiometer

Dynamic interfacial tension values obtained by drop volume tensiometry will be affected under certain experimental conditions by the formation of a neck between the drop and the capillary tip. This phenomenon must be accounted for to obtain accurate values of interfacial tension. In this work, neck formation for a water–mineral oil system is studied under conditions where hydrodynamic effects can be neglected. A model originally developed for the determination of the surface tension of a suspended drop is modified for application to dynamic interfacial tensions of surfactant-containing liquids. The model relates apparent values of interfacial tension calculated from drops possessing necks to actual values. Experiments with Span 80 (sorbitan monooleate) and sodium dodecyl sulfate (SDS) surfactants in a mineral oil–water system are used to test the validity of the developed model. For the small tip diameter used, good agreement is obtained for Span 80 up to the critical micelle concentration, and for low concentrations of SDS, when the surfactant adsorption is diffusion-limited. In both cases, the neck diameter of the growing drop can be considered constant over the range of dynamic interfacial tensions tested.     

A theory of adsorption kinetics with time delay and its application to overshoot and oscillation in the surface tension of gelatin solution

A theory of adsorption kinetics with time delay [Ohshima et al. (1992) Colloid Polym. Sci. 270:707] is developed and applied to the surface tension of a polymer solution. It is found that the general appearance of the overshoot and oscillation in the time course of the surface tension of aqueous gelatin solution observed by Sato and Ueberreiter [(1979) Makromol. Chem. 180:829, 1107; (1979) Polym. Prepr. Am. Chem. Soc. Div. Polym. Chem. 20:907) can be explained by the present theory.