Chain length dependencies of the bending modulus of surfactant monolayers

The effect of the surfactant chain length n on the bending modulus kappa of surfactant monolayers is simulated with a mesoscopic oil-water-surfactant model. We confirm a power law, kappa is proportional to np, as predicted by mean-field theory and found experimentally, and find p approximately 1.5 at a constant surface density and p approximately 1.0 at a constant interfacial tension. This agrees quite well with both mean-field theory (p=2-3, assuming constant surface density) and experiments (at constant surface tension). Our results suggest that the previously reported agreement between theory and experiment may be fortuitous and caused by the difference in surfactant types.     

Complex fluids with a yield value; their microstructures and rheological properties

Summary A general method is presented for the preparation of viscoelastic surfactant phases that consist of densely packed multilamellar vesicles in water. The phases form spontaneously when ionic surfactants are added to L_α-or L₃-phases from uncharged surfactants and cosurfactants. The dimensions and the structure of the vesicles were studied from FF-TEM micrographs for 100 mM surfactant solutions. The average diameter of the vesicles is in the range of 1 μm, the interlamellar spacing is around 800 ?. Under these conditions the vesicles are densely packed and cannot pass each other. The systems are highly viscoelastic and have a yield value. The storage and the loss moduli were determined by oscillating rheological measurements. The storage modulus was about one order of magnitude larger than the loss modulus and independent of frequency. Both parameters were determined as a function of the concentration and the chain length of the surfactant and cosurfactant, the charge density and ionic strength, the solubilization of hydrocarbon and temperature. The yield values and shear moduli increase linearly with the surfactant concentration. For constant surfactant concentration the moduli increase in a S-shaped form with the charge density and reach saturation for a mole fraction of about 7% of ionic surfactant. The storage moduli and yield values decrease with the addition of excess salt. The storage moduli depend strongly on the chain length of the surfactant. The values of the moduli are explained on the basis of a hard-sphere model in which the multilamellar vesicles are considered as hard-sphere particles. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Investigation of W/O microemulsion droplets by contrast variation light scattering

Dynamic and static light scattering experiments have been performed at various molar ratios (γ) of water to AOT and temperatures on water-in-oil (W/O) microemulsions dispersed in n-heptane, n-octane, and n-nonane. Size and shape fluctuations of microemulsion droplets are determined with very high precision because polydispersity influences the characteristic features of scattering data as well as the hydrodynamic radius withγ. Self-consistent interpretation of dynamic and static light scattering data using optical properties and packing consideration on the basis of the layered sphere model are obtained. The estimated extent of polydispersity index of 17% is found, whereas the polydispersity is independent of the alkane types. The geometrical parameters, e.g., hydrodynamic radius, area per head group of the surfactant molecule and thickness of the surfactant layer of microemulsion droplets are also estimated and compared in three different n-alkane types. The best interpretation of the temperature dependence of data has shown a transition from spherical droplets to ellipsoid aggregates with increasing temperature. Axial ratio increases with increase of temperature and the longer the alkane the larger is the axial ratio. The parameters describing the polydispersity and shape change are in agreement with theoretical and experimental results found in the literature     

Surface area per molecule in lipid/C12E n membranes as seen by fluorescence resonance energy transfer

Fluorescence resonance energy transfer (FRET) from NBD-PE to rhodamine-PE has been used to measure the average area occupied by surfactant molecules in lipid bilayers. The Foerster radius has been determined from the spectral overlap of donor fluorescence and acceptor absorption (R ₀=4.6 nm). The results of steady-state as well as of time-resolved investigations have been compared. The analysis of time-resolved fluorescence data by means of nonexponential decay functions yields an average area per lipid of 0.65 nm² in pure POPC bilayers. The area per surfactant in two-component C₁₂E _n /POPC-membranes (n=2, 4, 6) has been determined and compared with the results of X-ray investigations. The surfactant head group seems to adapt a predominantly disordered confirmation within the bilayer.     

Dispersion relation of lipid membrane shape fluctuations by neutron spin-echo spectrometry

We have studied the mesoscopic shape fluctuations in aligned multilamellar stacks of 1,2-dimyristoyl-sn-glycero-3-phoshatidylcholine bilayers using the neutron spin-echo technique. The corresponding in plane dispersion relation tau-1(q//) at different temperatures in the gel (ripple, Pbeta') and the fluid (Lalpha) phase of this model system has been determined. Two relaxation processes, one at about 10 ns and a second, slower process at about 100 ns can be quantified. The dispersion relation in the fluid phase is fitted to a smectic hydrodynamic theory, with a correction for finite qz resolution. We extract values for the bilayer bending rigidity kappa, the compressional modulus of the stacks B, and the effective sliding viscosity eta3. The softening of a mode which can be associated with the formation of the ripple structure is observed close to the main phase transition.     

Cooperative Association of p-Alkylbenzene Sulfonates Sodium Salts to Poly-2-(dimethylamino) Ethylmethacrylate-N-alkyl Quaternized at the Water/Chloroform Interface

The association of p-alkyl benzene sulfonate sodium salts with several poly-2-(dimethylamino) ethylmethacrylate-N-alkyl quaternized bromides at the water/chloroform interface was studied. High association percentages were found which increase with both the size of the sulfonate molecule and the length of the polyelectrolyte side chain: octyl, decyl, dodecyl and tetradecyl. The results fit well to the Hill's equation for the association of anionic surfactant to polyelectrolytes. Benzene sulfonate shows an anticooperative behavior for the association, whereas 4-methyl benzene sulfonate and 4-ethylbenzene sulfonate are increasingly cooperative for the association. From the association constants, the standard free energies of transfer from water to the interfacial polyelectrolytes were determined. Their values were a linear function of the number of carbon atoms of the aliphatic residue of the benzene sulfonate molecule ranging from ?15.7 kJ/mol of CH₂ groups for the octyl polyelectrolyte to ?18.9 kJ/mol of CH₂ groups for the tetradecyl derivative. These values are similar to those reported for the association of some of these sulfonates molecules with ammonium type cationic micelles. The results for the incremental free energy of transfer by mol of methylene group from water to micelles are in the same order of magnitude as those reported for p-alkyl phenoxides and p-alkylbenzoates to hexadecyltrimethyl ammonium bromide micelles. The results shows that amphipathic counterions as small as 4-ethylbenzenesulfonate are enough to induce a cooperative effect in their association to cationic polyelectrolytes.     

阳离子表面活性剂三甲基溴化铵与硝酸铵相互作用的表面和热力学研究

本文系统研究了阳离子表面活性剂三甲基溴化铵和硝酸铵盐的表面现象和自聚集行为. 采用电导法和表面张力法研究在不同温度下阳离子表面活性剂三甲基溴化铵的表面性质和热力学性质. 通过表面张力测定得到临界胶束浓度、吸附自由能、胶束化的自由能、最小分子面积和表面过量浓度. 该研究表明,胶束化过程是自发放热反应. 电导测定结果确定了临界胶束浓度、电离程度和反离子结合度. 加入硝酸铵盐至表面活性剂溶液后,临界胶束浓度降低,电离程度和反离子结合度增加,更加有利于胶束化过程的自发. 该研究对进一步理解电解质和表面活性剂之间相互作用具有重要意义.     

Weakly charged lamellar bilayer system: Interplay between thermal undulations and electrostatic repulsion

We study the interplay between thermal undulations and electrostatic interactions for weakly charged surfactant bilayers by measuring the backscattering of light from very dilute lamellar phases of the non-ionic surfactant triethylene glycol monodecyl ether (C₁₀E₃) doped with small amounts of the anionic surfactant sodium dodecyl sulphate (SDS), both with and without added electrolyte. Upon charging, the lamellar phases show a transition from undulation to electrostatic stabilization. Non-lamellar structures develop if the molar mixing ratio exceeds . Deviations from ideal swelling, , where is the lamellar repeating distance and the membrane volume fraction, were detected for all lamellar phases. Salt-free lamellar phases with charge densities below , as well as more highly charged lamellar phases at high ionic strength show a universal logarithmic deviation from ideal swelling that was analyzed using theories for undulation stabilized lamellar phases. Deviations from ideal swelling for electrostatically stabilized lamellar phases were analyzed using theories recently developed for undulations in charged lamellar phases. The fits to the various theories yield a value of for the bending modulus of the C₁₀E₃ bilayers. Received 21 June 1999 and Received in final form 25 August 1999     

Relative-thickness dependence of exchange bias in bilayers and trilayers

We consider the models of ferromagnetic (FM)/antiferromagnetic (AFM) bilayers and trilayers and perform a modified Monte Carlo method to study their exchange bias (EB) properties at low temperature after field cooling on increasing one component thickness at the expense of the other one. The results indicate that EB is insensitive to the thickness variations as the FM layer is thicker than the AFM one. Otherwise, it has a steep increase with the decrease of FM thickness, but the purely inverse proportion is no longer valid due to the dual influences of FM and AFM thicknesses. EB in trilayers should be approximately twice larger than that in bilayers because there is a double interfacial area in the trilayers compared with the bilayers, but the dispersed FM/AFM distributions may break this relation as a result of thermal destabilization. Moreover, EB is independent of FM/AFM stacking sequences probably because of the ideal interface between them. It has been clarified unambiguously that such control of EB through varying the FM/AFM dimensions in heterostructures is attractive for spintronics applications.     

A study of the properties of mixed nonionic surfactants microemulsions by NMR, SAXS, viscosity and conductivity

The pseudoternary phase behavior of the water/sucrose laurate/ethoxylated mono-di-glyceride/R (+)-limonene systems was investigated for different surfactants mixing ratios (w/w) at 25 °C. The microemulsion boundaries were determined and the surfactants content at the interface of water- R (+)-limonene was estimated. For surfactants mixing ratio (w/w) equals unity, the area of the one phase microemulsion region reaches its maximum. The system with the maximum microemulsion area was investigated using electrical conductivity, dynamic viscosity, small angle X-ray scattering, and nuclear magnetic resonance. Electrical conductivity increases as the water volume fraction increases and a percolation threshold was observed. Dynamic Viscosity varies as function of the water volume fraction in a non-monotonic way giving two-peaked plot. The characteristics of the domain size of the microemulsions called periodicity measured by small angle X-ray scattering increases with the increase in the water volume fraction. The correlation length of the domain size reaches a maximum when plotted against the water volume fraction in the microemulsions. Relative diffusion coefficients of water increase and those of oil decrease with increasing the water volume fractions in the microemulsions indicating structural transitions.     

Direct calculation from the stress tensor of the lateral surface tension of fluctuating fluid membranes

From the tangential and normal stresses associated with the Helfrich Hamiltonian, we calculate the lateral force per unit length, tau, exerted by a planar, fluctuating membrane, as a function of the membrane tension sigma and bending rigidity kappa. We unveil a confusion in the literature concerning the derivation of tau, and we argue, contrary to the present understanding, that tau should differ from the tensionlike coefficient of the fluctuation spectrum. Nontrivial implications concerning the Laplace pressure in vesicles and its relation with the excess area are discussed.     

Effect of Polyacrylic Acid on Phase State of Lipids and Diffusion in Lipid-Water System

Lipid vesicles interacting with polyanions are promising for controlled drug delivery. However, different aspects of the interaction of these polymers with lipids are far from complete understanding. In this work we studied the influence of polyacrylic acid (PAA) with small concentrations (1–4 mol%) on the change of the phase state, lateral diffusion of these lipids in lamellar phase and transmembrane water diffusion in macroscopically oriented bilayers of lipid-water systems formed by dimiristoylphosphatidylcholine (DMPC) and dioleoylphosphatidylcholine. Measurements were performed by ³¹P nuclear magnetic resonance (NMR) spectroscopy and the ¹H NMR technique with a pulsed field gradient. It was found that the presence of PAA does not change the lamellar structure of the system. However, a part of bilayers changes their originally flat geometry and forms vesicles with a higher surface curvature. Macroscopic orientation of bilayers disappeared. For DMPC the presence of PAA leads to a shift of the gel-to-liquid crystalline phase-transition temperature to higher temperatures. An increase of PAA concentration leads to a monotonous decrease in the lateral diffusion coefficient of lipids that is caused, probably, by the ordering of lipids in bilayers. The transbilayer diffusion coefficient of water increases in the presence of PAA, but it depends slightly on the PAA concentration. An increase of pH leads to a change of the lipid lateral and transbilayer diffusion coefficients to the values typical for a pure bilayer. Authors' address: Andrey Filippov, Kazan State University, Kremlevskaya ulitsa 18, Kazan 420008, Russian Federation     

Cholesterol perturbs lipid bilayers nonuniversally

Cholesterol is well known to modulate the physical properties of biomembranes. Using modern x-ray scattering methods, we have studied the effects of cholesterol on the bending modulus K(C), the thickness D(HH), and the orientational order parameter S(xray) of lipid bilayers. We find that the effects are different for at least three classes of phospholipids characterized by different numbers of saturated hydrocarbon chains. Most strikingly, cholesterol strongly increases K(C) when both chains of the phospholipid are fully saturated but not at all when there are two monounsaturated chains.     

绝缘油在水和酸共同作用下的分子动力学模拟

为探讨水分和温度对变压器油中酸扩散行为的影响,在分子模拟软件内建立了水分子、矿物油分子、甲酸分子的复合模型,水的体积分数分别为1%,3%,5%,甲酸的质量分数为3%.通过分子动力学方法模拟计算了甲酸分子在不同含水量油模型中的扩散系数、径向分布函数以及复合模型的总动能;此外,选取了水体积分数为1%的复合模型为研究对象,以温度为变量进行动力学模拟.结果表明:随着水含量的增多,甲酸的扩散系数并没有逐渐增大,甲酸分子与水分子之间的氢键数目呈逐渐减少的趋势.而随着温度的升高,油模型具有的动能越大,酸分子的扩散逐渐增强.油模型中,含水量越多,水和酸在热运动下碰撞油分子的能量越大;温度越高,相互之间的碰撞越激烈.模拟结果说明水分增加或温度增高,均对油分子的结构稳定性造成一定程度的破坏.     

单壁碳纳米管非线性力学行为的数值模拟

单壁碳纳米管的力学行为是纳米复合材料和纳米器械的基本问题之一.使用有限元方法系统地研究了单壁碳纳米管的轴压和纯弯变形，并将有限元模拟结果和分子动力学模拟结果进行了比较.研究结果表明单壁碳纳米管的轴压屈曲载荷受直径变化的影响；单壁碳纳米管在弯曲载荷作用下的屈曲和后屈曲行为强烈地依赖于管长和管径的变化，合理地选择碳纳米管的弹性模量和壁厚，有限元方法能够很好地解释碳纳米管的屈曲机理.研究大尺度的纳米力学问题时，有限元方法将会成为更加准确、快捷的数值模拟方法.     

单壁碳纳米管非线性力学行为的数值模拟

单壁碳纳米管的力学行为是纳米复合材料和纳米器械的基本问题之一.使用有限元方法系统地研究了单壁碳纳米管的轴压和纯弯变形,并将有限元模拟结果和分子动力学模拟结果进行了比较.研究结果表明单壁碳纳米管的轴压屈曲载荷受直径变化的影响;单壁碳纳米管在弯曲载荷作用下的屈曲和后屈曲行为强烈地依赖于管长和管径的变化,合理地选择碳纳米管的弹性模量和壁厚,有限元方法能够很好地解释碳纳米管的屈曲机理.研究大尺度的纳米力学问题时,有限元方法将会成为更加准确、快捷的数值模拟方法. 关键词： 单壁碳纳米管 非线性力学行为 有限元     

Behavior of adhesive boundary lubricated surfaces under shear: Effect of grafted diblock copolymers

The shear behavior and the normal interaction between mica surfaces covered by surfactant or surfactant-polymer mixtures were studied with a Surface Forces Apparatus (SFA) nanotribometer. If the surfaces are compressed while fully immersed in an aqueous surfactant solution that adsorbs in the form of flat bilayers, hemifusion can be induced. When the hemifused surfaces are subject to shear, at least five different dynamic regimes can be recognized. The general behavior may be described by a model based on the kinetics of formation and rupture of adhesive bonds between the shearing surfaces, with an additional viscous term. Once the adsorbed surfactant layer is decorated with physigrafted copolymers, the number of sliding regimes may be reduced to only one, in which the shear stress increases sublinearly with the driving velocity. The adhesion energy and the resistance to hemifusion of the adsorbed surfactant-polymer layers are also strongly modified as the grafting density increases.Received: 4 March 2004, Published online: 13 October 2004PACS: 46.55. + d Tribology and mechanical contacts - 81.40.Pq Friction, lubrication, and wear     

基于新型超低频拉曼光谱的液态水分子高温研究

液态水是地球上大多数生化过程的化学支柱,对生物的新陈代谢是必不可少的。因此,它是一个跨科学领域的关键课题。水的理化特性被认为是氢键衍生结构的结果。然而,目前还很难在实验上定量地将水分子的理化特性与氢键结构联系起来形成完整的液态水分子结构理论。拉曼光谱因其快速、无损等优点成为表征液态水分子结构及其变化规律的主要手段。目前,水分子的拉曼光谱主要研究的是其高频振动模。然而,液态水较宽的低频拉曼模是氢键及其局部结构效应的结果,包含高频峰无法表征的特征信息,而超低频拉曼特征峰仍能在高温下揭示水分子（超）结构的许多关键细节。因此,在实验上实现对水分子的新型高温超低频拉曼光谱（5～200 cm-1频率区域）,探测得到理论预测的全部四种平动特征模,包括弯曲模（51.7 cm-1）、扭转模（81.4 cm-1）、对称（154.0 cm-1）和不对称拉伸模（188.6 cm-1）,并在225.2 cm-1处额外发现了平动-旋转耦合特征模。所有特征模都被精确指认。高温超低频拉曼光谱实验发现,首先在特征峰频率上,由于高温下氢键断裂导致水分子间的平均结构关联长度（SLG）迅速缩短,当温度从0 ℃升高到400 ℃,所有四种超低频特征模的频率都随温度升高而大幅蓝移。其次在特征峰强度上,拉伸模的强度在100和200 ℃间出现明显降低。而弯曲模的强度随着拉伸模频率从高频率到低频率依次升高,这是理论研究从未涉及的。最后在斯托克斯/反斯托克斯比值（R_S/AS）上,温度在150～170 ℃时（压强约为2 kbar）,R_S/AS迅速从1.1增加到1.3;当温度高于170 ℃时,R_S/AS随温度线性变化。综上所述,通过对水分子各共振模的频率蓝移、强度变化,以及斯托克斯/反斯托克斯比值等特征进行细致研究,得到温度对水分子结构,尤其是氢键衍生特性的影响。该新型高温超低频拉曼光谱方法,填补了部分理论空白,为深入全面地理解水分子结构提供了重要的实验依据。     

Full fitting analysis of the relative intermediate form factor measured by neutron spin echo

This paper describes the dynamics of a water-in-oil microemulsion from the dilute to the dense droplet region. Using the relative intermediate form factor method for neutron spin echo data analyses [M. Nagao, H. Seto, Phys. Rev. E 78 (2008) 011507], the shape and structure fluctuations of a droplet microemulsion are successfully decoupled. In the previous paper, we used the first cumulant analysis of the shape fluctuation model, while the full fitting form of the same model is applied in this paper. The final results of the fittings using the first cumulant approximation and the full form of the model are almost identical, and therefore, the validity of the method is strengthened. The estimated bending modulus of the surfactant membrane, κ, is basically the same, within the experimental errors, in the previous and present results. The κ is not affected much by an increase of the droplet concentration. A clear dynamic slowing down of the water droplets is highlighted at the length scale corresponding to the inter-droplet distance from the structure fluctuation analysis.     

Fabrication of Poly-l-lactide Biomaterials with High Mechanical Properties Using Fiber Oriented Pressing

A new technique of dilute solution spinning to obtain poly-l-lactide (PLLA) fiber was presented. PLLA materials were fabricated by using fiber oriented pressing and the effects of pressing pressure and temperature on the mechanical properties and weight average molecular mass of PLLA were investigated. Good oriented fibers with porous structure (0.1 ～ 1 μm) were obtained by a dilute solution spinning method. Bending and shearing strength of PLLA samples first increase and then decrease with the increase of pressing temperature and pressure. The bending strength, shearing strength, and bending modulus reach 238.8 ± 6.5 MPa, 127.5 ± 3.5 MPa and 3.25 ± 0.25 GPa, respectively, if the pressing temperature is 185°C and the pressure is 130 MPa. These values are greater than conventional pressing methods. In addition, the decrease in weight average molecular mass (19.5%) that results from using oriented pressing is lower than that seen (30.0%) by using the conventional pressing method.