Electrokinetic characterization of polystyrene–non-ionic surfactant complexes

An experimental study on the electrophoretic mobility (μ_e) of polystyrene particles after the adsorption of non-ionic surfactants with different chain lengths is described. Two sulphate latexes with relatively low surface charge densities (3.2 and 4.8 μC cm⁻²) were used as solid substrate for the adsorption of four non-ionic surfactants, Triton X-100, Triton X-165, Triton X-305 and Triton X-405, each one with 9–10, 16, 30 and 40 molecules of ethylene oxide (EO), respectively. The electrophoretic mobility of the polystyrene–non-ionic surfactant complexes was studied versus the amount of adsorbed surfactant (Γ). The presence of non-ionic surfactant onto particles surface seems to produce a slight shifting of the slipping plane because the mobilities of the different complexes display a very small decreasing. The increase in the number of EO chains in the surfactant molecule seems to operate as a steric impediment which decreases the number of adsorbed large surfactant molecules. The electrophoretic mobilities of the latex–surfactant complexes with maximum adsorption were measured versus the pH and ionic strength of the dispersion. While the different complexes showed a similar qualitative behaviour compared with that of the bare latex against the pH, the adsorption of the surfactant reduces the typical maximum in the μ_e−log[electrolyte].     

Assessment of the Surface Heterogeneity of Talc Materials

The hydrophobic and hydrophilic components of the surface of talc materials in aqueous solution were determined using ionic surfactants and their polar headgroup adsorption isotherms. The hydrophilic and hydrophobic surface areas are inferred from the amount of probe molecule adsorbed and the structure of the adsorbed layer. Natural dispersion of talc shows at 298 K a pH of 9.4 and the electrophoretic measurements indicate that the particles are negatively charged. The hydrophilic surface area is estimated from the adsorption of benzyltrimethylammonium ions (BTMA(+)) through electrostatic interactions as supported by the increase of divalent ions in the bulk phase and the decrease in the exothermic displacement enthalpy. It was also observed from the adsorption isotherm of benzene sulfonate anions that the density of positive surface sites is very low and is thus neglected. The adsorption of an anionic surfactant essentially occurs through dispersive interactions between the nonpolar organic tail of the molecule and the hydrophobic surface. Furthermore, some assumptions on the structure of dodecyl sulfate surfactant aggregates at the interface allow the hydrophobic part of the talc particles to be estimated. The cationic surfactant adsorption has been investigated and found to corroborate the hydrophilic and hydrophobic area values first obtained. Copyright 2001 Academic Press.     

Wetting and adsorption: II. Adsorption of Triton X-100 and Triton X-305 onto carbon black from water and cyclohexane solutions

The adsorption isotherms of nonionic surfactants Triton X-100 and Triton X-305 from water and cyclohexane on carbon black have been determined at 15 and 30°C. The Langmuir-type and BET-type isotherms are obtained for adsorption of Triton X-100 and Triton X-305 from water and cyclohexane respectively. Both the contact angles of water for graphite/water/air and graphite/water/cyclohexane decrease monotonously with increasing surfactant concentration. From these results, it is proposed that the adsorption of Triton X-100 and Triton X-305 on carbon black or graphite from water is monolayer. For the adsorption from cyclohexane solutions, the ethyleneoxide group of the surfactant molecules may be adsorbed onto the polar spot at the surface of carbon black, and the hydrophobic group of adsorbed molecules may direct toward the liquid phase or attaches to the nonpolar surface region around the polar spot. As the concentration increases, the ethylene oxide groups of the adsorbed molecules can be aggregated with each other via polar interactions to form hemi-reversed micelle.     

Adsorption of different amphiphilic molecules onto polystyrene latices

In order to know the influence of the surface characteristics and the chain properties on the adsorption of amphiphilic molecules onto polystyrene latex, a set of experiments to study the adsorption of ionic surfactants, nonionic surfactants and an amphiphilic synthetic peptide on different latex dispersions was performed. The adsorbed amount versus the equilibrium surfactant concentration was determined. The main adsorption mechanism was the hydrophobic attraction between the nonpolar tail of the molecule and the hydrophobic regions of the latex surface. This attraction overcame the electrostatic repulsion between chains and latex surface with identical charge sign. However, the electrostatic interactions chain-surface and chain-chain also played a role. General patterns for the adsorption of ionic chains on charged latex surfaces could be established. Regarding the shape, the isotherms presented different plateaus corresponding to electrostatic effects and conformational changes. The surfactant size also affects the adsorption results: the higher the hydrophilic moiety in the surfactant molecule the lower the adsorbed amount.     

Wetting and adsorption: I. The structure of adsorbed layer of nonionic surfactants at SiO2/water and SiO2/cyclohexane interface

Based on the adsorption of Triton X-100 on silica/water and silica/cyclohexane interfaces and the adsorption of Triton X-305 on silica/water interface, two adsorption models have been proposed. On silica/cyclohexane interface, the adsorption of Triton X-100 is monomolecular layer. The molecules in the monolayer are presumed to be attached to the silica surface by their EO chain such that their hydrocarbon chain are exposed to the cyclohexane phase. On silica/water interface, the adsorption of Triton X-100 or Triton X-305 is bimolecular layer. The surfactant molecules orientated in the first layer are similar with that on the silica/cyclohexane interface. The molecules in the second layer are postulated to adsorb on those of the first in the opposite orientation, with EO chain directed toward the adsorption medium. The contact angle of quartz-water-cyclohexane (θ_W) as a function of the concentration of Triton X-100 and Triton X-305 in water has been measured with quartz plate employing the captive drop (cyclohexane) technique. The observed θ_W (measured through water) rose from < 10° to a maximum of about 120° for Triton X-100 and of about 40° for Triton X-305 as the concentration of surfactant in water increased, and then fell, as the concentration increased further. The results are consistent with the proposed adsorption models.     

Solution properties of hydrophobically modified acrylamide-based polysulfobetaines in the presence of surfactants

Polymer–surfactant interactions in aqueous solutions of a acrylamide-based, hydrophobically modified polysulfobetaine (ADS) containing 3-[N-(2-methacryloxylethyl)-N,N-dimethylammonio]-propane sulfonate and stearyl methylacrylate, with sodium dodedyl sulfate (SDS), N-dodecyl-N,N,N-trimethylammonium bromide (DTAB), and Triton X-100 were studied using surface tension, rheology, Rayleigh light scattering, and dynamic laser light scattering techniques. The purpose of this study was to highlight the influences of the surfactant structure and the nature of the surfactant head group on the polymer–surfactant interactions. The results show that the interaction and association between ADS and surfactants are distinctly varied depending on surfactant type and surfactant concentration. SDS produced the strongest interactions with ADS, while DTAB and Triton X-100 interact with ADS to a lesser degree, which is attributed to surfactant structure and the nature of the surfactant head group. For SDS and DTAB, there are two driving forces for the complexation of the polymer and surfactants, resulting from the electrostatic interaction and the hydrophobic association. However, for the nonionic surfactant Triton X-100, only hydrophobic association predominated in the interaction between ADS and the surfactant. The mechanism and reconstruction of the polymer–surfactant complexes have been evaluated and discussed.     

Properties of mixed micelles of cationic gemini surfactants and nonionic surfactant triton X-100: effects of the surfactant composition and the spacer length

The mixed micelles of cationic gemini surfactants C12C(S)C12Br2 (S=3, 6, and 12) with the nonionic surfactant Triton X-100 (TX100) have been studied by steady-state fluorescence, time-resolved fluorescence quenching, electrophoretic light scattering, and electron spin resonance. Both the surfactant composition and the spacer length are found to influence the properties of mixed micelles markedly. The total aggregation number of alkyl chains per micelle (N(T)) goes through a minimum at X(TX100)=0.8. Meanwhile, the micropolarity of the mixed micelles decreases with increasing X(TX100), while the microviscosity increases. The presence of minimum in N(T) is explained in terms of the competition of the reduction of electrostatic repulsion between headgroups of cationic gemini surfactant with the enhancement of steric repulsion between hydrophilic headgroups of TX100 caused by the addition of TX100. The variations of micropolarity and microviscosity indicate that the incorporation of TX100 to the gemini surfactants leads to a more compact and hydrophobic micellar structure. Moreover, for the C12C3C12Br2/TX100 mixed micelle containing C12C3C12Br2 with a shorter spacer, the more pronounced decrease of N(T) at X(TX100) lower than 0.8 may be attributed to the larger steric repulsion between headgroups of TX100. Meanwhile, the increase of microviscosity and the decrease of micropolarity are more marked for the C12C12C12Br2/TX100 mixed micelle, owing to the looped conformation of the longer spacer of C12C12C12Br2.     

表面活性剂对污泥脱水性能影响的机理研究:Gemini表面活性剂与聚电解质相互作用的分子动力学模拟

表面活性剂可以与污泥表面的胞外聚合物(EPS)吸附形成胶束,释放出自由水和结合水,从而达到改善污泥脱水性能的目的.本文采用粗粒化的分子动力学模拟方法,研究了Gemini表面活性剂与EPS形成复合物的过程和结构.聚电解质链的亲疏水性对吸附过程有显著影响,亲水聚电解质链与Gemini表面活性剂吸附的主要驱动力为静电吸引,Gemini表面活性剂头基吸附在链上,尾链朝向溶剂;疏水聚电解质链与Gemini表面活性剂吸附过程由静电作用与疏水作用共同促进,Gemini表面活性剂以平行于聚电解质链的构型存在.Gemini表面活性剂联结基团长度对吸附过程的影响甚微;聚电解质链的电荷密度对亲水聚电解质链的吸附产生协同作用,对疏水聚电解质链的吸附不产生作用.     

Adsorption Kinetics of Some Polyethylene Glycol Octylphenyl Ethers Studied by the Fast Formed Drop Technique

The adsorption kinetics of Triton X-100 and Triton X-405 at solution/air and solution/hexane interfaces is studied by the recently developed fast formed drop technique. The dynamic interfacial tension of Triton X-100 and Triton X-405 solutions against hexane has been measured without preequilibration of the water and oil phases. It is found that the dynamic interfacial tension of Triton X-100 solutions passes through a minimum. This strange behavior is attributed to partial solubility of the surfactant in hexane. Such minima of the dynamic interfacial tension of Triton X-405 solutions have not been observed, which correlates well with the solubilities of both surfactants in hexane reported in the literature. The dynamic surface tension of solutions of both surfactants and the dynamic interfacial tension of Triton X-405 solutions are interpreted by the Ward and Tordai model for diffusion controlled adsorption. It is shown that proper interpretation of the experimental data depends on the type of isotherm used. More consistent results are obtained when the Temkin isotherm is used instead of the Langmuir isotherm. The results obtained with Triton X-100 at the solution/air interface confirm that the adsorption of this surfactant occurs under diffusion control. The adsorption of Triton X-405 at solution/air and at solution/hexane interfaces seems to occur under diffusion control at short periods of time, but under mixed (diffusion-kinetic) control at long periods of time. A hypothesis is drawn to explain this phenomenon by changes in the shape of the large hydrophilic heads of Triton X-405 molecules. Copyright 2000 Academic Press.     

吸附与润湿II.Triton X-100和Triton x-305在炭黑/水和炭黑/环己烷界面上的吸附层结构

测定了15℃和30℃时炭黑自水和环己烷中吸附非离子型表面活性剂TritonX-100和Triton X-305的等温线;计算了吸附过程的标准热力学函数;测定了石墨/水/环己烷和石墨/水/空气的接触角与表面活性剂浓度的关系, 分析所得结果,可得结论:在炭黑/水或石墨/水界面上,Triton型表面活性分子形成单分子吸附层,分子以憎水的iso-C8H17C6H4基团附着在表面,而以亲水的聚氧乙烯链伸入水相的方式取向;在炭黑/环已烷或石墨/环己烷界面上,分子是通过聚氧乙烯链吸附到表面上的,当浓度增加时分子在表面可能通过聚氧乙烯链间的相互作用而发生聚集,即可能形成表面反式胶团。     

Effect of inorganic positive ions on the adsorption of surfactant Triton X-100 at quartz/solution interface

The electrode-separated piezoelectric sensor (ESPS), an improved setup of quartz crystal microbalance (QCM), has been employed to investigate the adsorption behavior of nonionic surfactant Triton X-100 at the hydrophilic quartz-solution interface in mineralized water medium in situ, which contained CaCl2 0.01 mol·L?1, MgCl2 0.01 mol·L?1, NaCl 0.35 mol·L?1. In a large scale of surfactant concentration, the effects of Ca2 , Mg2 and Na on the adsorption isotherm and kinetics are obviously different. In aque-ous solution containing NaCl only, adsorption of Triton X-100 on quartz-solution interface is promoted, both adsorption rate and adsorption amount increase. While in mineralized water medium, multivalent positive ions Ca2 and Mg2 are firmly adsorbed on quartz-solution interface, result in the increasing of adsorption rate and adsorption amount at low concentration of surfactant and the peculiar desorption of surfactant at high concentration of Triton X-100. The results got by solution depletion method are in good agreement with which obtained by ESPS. The "bridge" and "separate" effect of inorganic positive ions on the adsorption and desorption mechanism of Triton X-100 at the quartz- solution interface is discussed with molecular dynamics simulations (MD), flame atomic absorption spectrometry (FAAS) and atomic force microscopy (AFM) methods.     

Effect of surface composition on the adsorption of photosystem I onto alkanethiolate self-assembled monolayers on gold

We have used self-assembled monolayers (SAMs) prepared from omega-terminated alkanethiols on gold to generate model surfaces and examine the effect of surface composition on the adsorption of Photosystem I (PSI), stabilized in aqueous solution by Triton X-100. Triton-stabilized PSI adsorbs to high-energy surfaces prepared from HO- and HO2C-terminated alkanethiols but does not adsorb to low-energy surfaces. The inhibition of PSI adsorption at low-energy surfaces is consistent with the presence of a layer of Triton X-100 that adsorbs atop the hydrophobic SAM and presents a protein-resistant poly(ethylene glycol) (PEG) surface. While the presence of the PEG surface prevents the adsorption of PSI, the displacement of the inhibiting layer of Triton X-100 by dodecanol, a more active surfactant, greatly enhances the adsorption of PSI. This inhibiting effect by Triton X-100 can be extended to other protein systems such as bovine serum albumin.     

纳米SiO2与阳离子表面活性剂的相互作用及其诱导的正辛烷-水乳状液的双重相转变

研究了3种不同结构的水溶性阳离子表面活性剂对纳米二氧化硅颗粒的原位表面活性化作用, 它们分别是单头单尾的十六烷基三甲基溴化铵(CTAB)、单头双尾的双十二烷基二甲基溴化铵(di-C12DMAB)和双头双尾的Gemini型阳离子三亚甲基-二(十四酰氧乙基溴化铵)(II-14-3), 并通过测定Zeta电位、吸附等温线及接触角等参数对相关机理进行了阐述. 结果表明, 阳离子表面活性剂吸附到颗粒/水界面形成以疏水基朝向水的单分子层, 从而增强了颗粒表面的疏水性是原位表面活性化的基础. 通过吸附CTAB和II-14-3, 颗粒的疏水性适当增强, 能吸附到正辛烷/水界面稳定O/W(1)型乳状液; 而通过吸附di-C12DMAB所形成的单分子层更加致密, 颗粒的疏水性进一步增强, 进而使乳状液从O/W(1)型转变为W/O型; 当表面活性剂浓度较高时, 由于链-链相互作用, 表面活性剂分子将在颗粒/水界面形成双层吸附, 使颗粒表面变得亲水而失去活性, 但此时体系中游离表面活性剂的浓度已增加到足以单独稳定O/W(2)型乳状液的程度. 因此当采用纳米二氧化硅和di-C12DMAB的混合物作乳化剂时, 通过增加di-C12DMAB的浓度即可诱导乳状液发生O/W(1)→W/O→O/W(2)双重相转变.     

Assessment of polycrystalline graphites as sorbents for solid-phase microextraction of nonionic surfactants

Two polycrystalline graphites (pencil lead and glassy carbon) were used as sorbents for solid-phase microextraction of a nonionic alkylphenol ethoxylate surfactant (Triton X-100). Analyses were performed by reversed-phase HPLC-fluorescence detection. The presence of the benzene ring in the congeners of Triton X-100 also allowed their direct detection at lambda(ex) = 230 nm and lambda(em) = 310 nm. Variables such as time of adsorption, time of desorption and concentration of surfactant in water were evaluated. The method limit of detection was found to be 0.5 microg/l for Triton X-100, with a linear dynamic range of 0.5-150 microg/l. Results were compared to those obtained using polymeric fibers such as PDMS/DVB and Carbowax/TPR. The chemical resistance and low cost of the polycrystalline graphites are advantageous over commercially available SPME fibers.     

Foaming and foam stability for mixed polymer-surfactant solutions: effects of surfactant type and polymer charge

Solutions of surfactant-polymer mixtures often exhibit different foaming properties, compared to the solutions of the individual components, due to the strong tendency for formation of polymer-surfactant complexes in the bulk and on the surface of the mixed solutions. A generally shared view in the literature is that electrostatic interactions govern the formation of these complexes, for example between anionic surfactants and cationic polymers. In this study we combine foam tests with model experiments to evaluate and explain the effect of several polymer-surfactant mixtures on the foaminess and foam stability of the respective solutions. Anionic, cationic, and nonionic surfactants (SDS, C(12)TAB, and C(12)EO(23)) were studied to clarify the role of surfactant charge. Highly hydrophilic cationic and nonionic polymers (polyvinylamine and polyvinylformamide, respectivey) were chosen to eliminate the (more trivial) effect of direct hydrophobic interactions between the surfactant tails and the hydrophobic regions on the polymer chains. Our experiments showed clearly that the presence of opposite charges is not a necessary condition for boosting the foaminess and foam stability in the surfactant-polymer mixtures studied. Clear foam boosting (synergistic) effects were observed in the mixtures of cationic surfactant and cationic polymer, cationic surfactant and nonionic polymer, and anionic surfactant and nonionic polymer. The mixtures of anionic surfactant and cationic polymer showed improved foam stability, however, the foaminess was strongly reduced, as compared to the surfactant solutions without polymer. No significant synergistic or antagonistic effects were observed for the mixture of nonionic surfactant (with low critical micelle concentration) and nonionic polymer. The results from the model experiments allowed us to explain the observed trends by the different adsorption dynamics and complex formation pattern in the systems studied.     

Self-Assembly of Dendritic Micellar Structures Based on Triton X-100 and Branched Poly(ethylene oxide)-containing Cyclodextrins

Interaction between the branched poly(etylene oxide)-containing cyclodextrins and nonionic surfactant Triton X-100 was studied. Amphiphilic character of substituted cyclodextrins where poly(etylene oxide) fragments serve as the hydrophilic moiety and outer cyclodextrin surface, as the hydrophobic moiety. Using two groups of experimental methods, it was shown that substituted -cyclodextrin forms inclusion complexes with hydrophilic poly(ethylene oxide) fragment of Triton X-100 molecule, surfactant molecules being incorporated into a micelle composition. The first group of these methods includes viscometry of solutions and measurement of rotational diffusion coefficient, while the other group (tensiometry, gel permeation chromatography, and spectrophotometry) makes it possible to determine colloidal properties of components. The modified micelles consist of nonionic surfactant molecules, whose outer ends are strung with molecules of substituted cyclodextrins; moreover, their structure resembles that of dendrimers due to arising branchings. Note that the self-assembly method was employed to prepare such dendrimers for the first time.     

气相二氧化硅/季铵Gemini表面活性剂稳定的泡沫体系

以zeta电位法研究了季铵Gemini表面活性剂亚甲基-α, ω-双(十二烷基二甲基溴化铵) (12-s-12, s=2, 6)在水溶液中修饰气相二氧化硅(F-SiO₂)粒子。这些粒子随表面活性剂浓度C增加经历了表面从原先的亲水到疏水再重新亲水的改变,其中疏水粒子可以自发吸附在气泡液膜中,从而很好地稳定泡沫。重新亲水的粒子脱附出液膜,仅留下表面活性剂稳定气泡。强的液膜弹性对应于稳定的泡沫。联接链长度影响了Gemini在F-SiO₂粒子表面的吸附,因而也影响了液膜的弹性和对泡沫的稳定。超短s=2联接链的12-2-12由于反离子解离不完全而带有较少的正电荷,在粒子表面的初始吸附弱于12-6-12,但因此减少了吸附分子头基间的静电排斥,可以形成更致密的吸附层。由于12-2-12本身比12-6-12具有更强的界面吸附能力,F-SiO₂粒子和12-2-12的协同作用可以更好地稳定泡沫体系。     

Dispersion stability of a ceramic glaze achieved through ionic surfactant adsorption

The adsorption of cetylpyridinium chloride (CPC) and sodium dodecylbenzenesulfonate (SDBS) onto a ceramic glaze mixture composed of limestone, feldspar, quartz, and kaolin has been investigated. Both adsorption isotherms and the average particle zeta potential have been studied in order to understand the suspension stability as a function of pH, ionic strength, and surfactant concentration. The adsorption of small amounts of cationic CPC onto the primarily negatively charged surfaces of the particles at pH 7 and 9 results in strong attraction and flocculation due to hydrophobic interactions. At higher surfactant concentrations a zeta potential of more than +60 mV results from the bilayered adsorbed surfactant, providing stability at salt concentrations < or = 0.01 M. At 0.1 M salt poor stability results despite substantial zeta potential values. Three mechanisms for SDBS adsorption have been identified. When anionic SDBS monomers either adsorb by electrostatic interactions with the few positive surface sites at high pH or adsorb onto like charged negative surface sites due to dispersion or hydrophobic interactions, the magnitude of the negative zeta potential increases slightly. At pH 9 this increase is enough to promote stability with an average zeta potential of more than -55 mV, whereas at pH 7 the zeta potential is lower at about -45 mV. The stability of suspensions at pH 7 is additionally due to steric repulsion caused by the adsorption of thick layers of neutrally charged Ca(DBS)2 complexes created when the surfactant interacts with dissolved calcium ions from the calcium carbonate component.     

Surfactant-induced amorphous aggregation of tobacco mosaic virus coat protein: a physical methods approach

The interactions of non-ionic surfactant Triton X-100 and the coat protein of tobacco mosaic virus, which is an established model for both ordered and non-ordered protein aggregation, were studied using turbidimetry, differential scanning calorimetry, isothermal titration calorimetry, and dynamic light scattering. It was found that at the critical aggregation concentration (equal to critical micelle concentration) of 138 x 10(-6) M, Triton X-100 induces partial denaturation of tobacco mosaic virus coat protein molecules followed by protein amorphous aggregation. Protein aggregation has profound ionic strength dependence and proceeds due to hydrophobic sticking of surfactant-protein complexes (start aggregates) with initial radii of 46 nm. It has been suggested that the anionic surfactant sodium dodecyl sulfate forms mixed micelles with Triton X-100 and therefore reverses protein amorphous aggregation with release of protein molecules from the amorphous aggregates. A stoichiometric ratio of 5 was found for Triton X-100-sodium dodecyl sulfate interactions.