Interactions between Adsorbed Layers of a Low Charge Density Cationic Polyelectrolyte on Mica in the Absence and Presence of Anionic Surfactant

Interactions between two negatively charged mica surfaces across aqueous solutions containing various amounts of a 10% charged cationic polyelectrolyte have been studied. It is found that the mica surface charge is neutralized when the polyelectrolyte is adsorbed from a 10–50 ppm aqueous solution. Consequently no electrostatic double-layer force is observed. Instead an attractive force acts between the surfaces in the distance regime 250–100 Å. We suggest that this attraction is caused by bridging. Additional adsorption takes place when the polyelectrolyte concentration is increased to 100 and 300 ppm, and a long-range repulsion develops. This repulsive force is both of electrostatic and steric origin. The polyelectrolyte layer adsorbed from a 50 ppm solution does not desorb when the polyelectrolyte solution is replaced with an aqueous polyelectrolyte-free solution. Injection of sodium dodecyl sulfate (SDS) into the measuring chamber to a concentration of about 0.01 CMC (8.3 × 10⁻⁵M) does not affect the adsorbed layers or the interaction forces. However, when the SDS concentration is increased to 0.02 CMC (0.166 mM) the adsorbed layer expands dramatically due to adsorption of SDS to the polyelectrolyte chains. The sudden swelling suggests a cooperative adsorption of SDS to the preadsorbed polyelectrolyte layer and that the critical aggregation concentration between the polyelectrolyte and SDS at the surface is about 0.02 CMC. The flocculation behavior of the polyelectrolyte in solution upon addition of SDS was also examined. It was found that 0.16–0.32 mol SDS/mol charged segments on the polyelectrolyte is enough to make the solution slightly turbid.     

Mixed micelles formed by SDS and a bolaamphiphile with carbohydrate headgroups

The formation of micelles in aqueous mixtures of a carbohydrate-based bolaamphiphile and sodium dodecyl sulfate (SDS) is investigated by surface tension and small-angle neutron scattering. The obtained values of critical micelle concentration (CMC) are analyzed within the framework of regular solution theory. Synergetic interactions between the bolaamphiphile and SDS are observed (parameter beta is negative; a minimum in the plot CMC vs composition). SANS data are collected for mixtures containing protonated and deuterated SDS. This gives us the possibility to conclude that mixed micelles with a homogeneous distribution of surfactant molecules within the micelle are formed. The shape of the micelles is found to be slightly oblate.     

表面活性剂胶束化物理化学性质研究

通过电导法考查温度和盐浓度对十二烷基硫酸钠(SDS)临界胶束浓度(CMC)的影响,研究表面活性剂形成胶束过程的物理化学性质。根据拟相分离模型求得胶束化热力学函数,并讨论体系电导活化能随温度和SDS浓度变化关系。结果表明:SDS的CMC随温度升高而增加,随氯化钠浓度增大而减小。在热力学上SDS在水溶液中形成胶束是一个自发、放热、熵增的过程;在动力学上,SDS溶液电导率与温度关系符合Arrhenius公式,通过电导活化能信息可揭示离子型表面活性剂形成胶束的机理特征。     

Interaction of Nonionic Surfactant Triton-X-100 with Ionic Surfactants

The interaction in two mixtures of a nonionic surfactant Triton-X-100 (TX-100) and different ionic surfactants was investigated. The two mixtures were TX-100/sodium dodecyl sulfate (SDS) and TX-100/cetyltrimethylammonium bromide (CTAB) at molar fraction of TX-100, α_TX-100 = 0.6. The surface properties of the surfactants, critical micelle concentration (CMC), effectiveness of surface tension reduction (γ_CMC), maximum surface excess concentration (Γ_max), and minimum area per molecule at the air/solution interface (A _min) were determined for both individual surfactants and their mixtures. The significant deviations from ideal behavior (attractive interactions) of the nonionic/ionic surfactant mixtures were also determined. Mixtures of both TX-100/SDS and TX-100/CTAB exhibited synergism in surface tension reduction efficiency and mixed micelle formation, but neither exhibited synergism in surface tension reduction effectiveness.     

Micellar effects on the electrochemistry of dopamine and its selective detection in the presence of ascorbic acid

The electrochemistry of dopamine (3-hydroxytyramine) was studied by cyclic voltammetry at a glassy carbon electrode in the presence of cetyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) micelles at different pH. The anodic peak potential (E(pa)) and peak current (I(pa)) were found to be remarkably dependent on the charge and the concentration of the surfactant. The E(pa) and I(pa) change abruptly around the critical micellar concentration (CMC) of the surfactants and reach a plateau above the CMC. The E(pa) at the plateau shifts to more positive values in the cationic CTAB micellar solution, e.g. from 180 mV vs SCE in aqueous solution at pH 6.8 to 410 mV in CTAB micelle, whilst it shifts to less positive values in the anionic SDS micellar solution, e.g. 150 mV at pH 6.8. Therefore, the overlapped anodic peaks of dopamine and ascorbic acid in the mixture of the two compounds in aqueous solutions can be separated in CTAB micelles since the micelle shifts the E(pa) of ascorbic acid to less positive values. The two peaks are separated by ca. 400 mV at pH 6.8 in CTAB micelle, hence dopamine can be determined in the presence of 100 times excess of ascorbic acid. In SDS micelle and in the presence of ascorbic acid, the I(pa) of dopamine is greatly enhanced due to the catalytic oxidation of the latter that enables quantitative determination of both compounds.     

Electrolyte effect on mixed micelle and interfacial properties of binary mixtures of cationic and nonionic surfactants

In the present work, the adsorption behavior at the liquid-air interface and micellization characteristics of mixtures of cetyltrimethylammonium bromide (CTAB) and p-(1,1,3,3-tetramethylbutyl) polyoxyethylene (TritonX-100) in aqueous media containing different concentrations of NaBr were investigated by surface tension and potentiometry measurements. From plots of surface tension (gamma) as a function of solution composition and total surfactant concentration, we determined the critical micelle concentration (CMC), minimum surface tension at the CMC (gamma(CMC)), surface excess (Gamma(max)), and mean molecular surface area (A(min)). On the basis of regular solution theory, the compositions of the adsorbed film (Z) and micelles (X(M)) were estimated, and then the interaction parameters in the micelles (beta(M)) and in the adsorbed film phase (beta(sigma)) were calculated. For all mole fraction ratios, the results showed synergistically enhanced ability to form mixed micelles as well as surface tension reduction. Furthermore beta was calculated by considering nonrandom mixing and head group size effects. It was observed that, for both the planar air/aqueous interface and micellar systems, the nonideality decreased as the amount of electrolyte in the aqueous medium was increased. This was attributed to a decrease of the surface charge density caused by increasing the concentration of bromide ions.     

Adsorption kinetics of surfactant mixtures from micellar solutions as studied by maximum bubble pressure technique

The adsorption kinetics of micellar solutions of anionic/cationic SDS/DATB mixtures with mixing ratios of 10/1 and 10/2, respectively, are studied experimentally by means of the maximum bubble pressure method. For long adsorption times the adsorption of the highly surface-active anionic/cationic complex leads to a decrease of dynamic surface tension in comparison to the single SDS system. However, the situation is the reverse for short adsorption times where the dynamic surface tension is increased by addition of the cationic surfactant, although the overall concentration is increased. This unexpected behavior is explained by partial solubilization of free SDS molecules into micelles formed by SDS/DTAB complexes. With increasing overall concentration, when eventually the CMC of SDS is reached, the anionic/cationic complex itself is solubilized by SDS micelles. Finally, no complex micelles, which for their part can solubilize an excess of SDS molecules, are present. Hence, the dynamic properties of the solution are no longer influenced by the depletion of SDS molecules and the mixture tends to behave like a pure SDS solution.     

N,O-羧甲基壳聚糖的合成和性质研究

采用多段升温法将壳聚糖改性,合成了取代度为1.84、平均分子量为3.08×105、等电点为7.28的N,O-羧甲基壳聚糖(CMC),分别用紫外光谱、红外光谱、荧光光谱对其结构进行了表征,并对其水溶液的Zeta电位、电导率、表面张力以及水分散体系中羧甲基壳聚糖微粒的粒径分布进行了研究.结果表明, N,O-羧甲基壳聚糖具有表面活性;介质的pH值和浓度对羧甲基壳聚糖溶液的稳定性有很大的影响.     

Modification of molecular properties of some dyes in sodium dodecyl sulphate (SDS) micellar aqueous solution

The influence of SDS upon the molecular properties of proflavine (3,6-diaminoacridine), acridine yellow (2,7-dimethyl-3,6-diaminoacridine) and methylene blue (3,7-bis-dimethylamino-phenothiazine) was studied comparatively to their properties in that of aqueous media. The absorption and emission spectra of the three dyes in SDS aqueous solution (1-100 mmol/l) were recorded. The spectroscopic data also allowed the evaluation of the critical micellization concentration (CMC), acidity constants in fundamental (pk(a)) and excited (pK(*)(a)) states, and lifetimes of excited singlet states.     

Solubility of ethylene in aqueous solution of sodium dodecyl sulfate at ambient temperature and near the hydrate formation region

The solubility of ethylene in aqueous solutions of sodium dodecyl sulfate (SDS) at different concentrations was measured at temperature 298.2 K and near the hydrate formation region. The effect of SDS on the gas solubility was studied and the solubilities of ethylene in a single micelle under different conditions were evaluated. It was found that the micelle solubilization was obvious, especially in the region near hydrate formation conditions. The CMC of SDS solution was also evaluated based on the solubility vs SDS concentration curves and it was found that it decreased with decreasing temperature.     

Solubilization of Nile Red in Micelles and Protomicelles of Sodium Dodecyl Sulfate

A spectrophotometric study of the solubilization and aggregation of the Nile red dye (NR) in premicellar and micellar aqueous solutions of sodium dodecyl sulfate (SDS) was carried out. The experiments were conducted both with saturated solutions of NR under conditions of thermodynamic equilibrium of the solution with a dye precipitate, and at a constant concentration of NR in a homogeneous solution. In the first case, it was proved theoretically and verified experimentally that with an increase in the SDS concentration, the NR concentration always increases, and at the limit of low concentrations, the dependence is linear. In both cases, the concentration of NR dimers as a function passes through a maximum in the premicellar region. There are no dimers in the micellar region. The extinction coefficients of NR monomers in SDS solutions were determined both below and above the critical micelle concentration (CMC) of SDS. A solubilization curve with branches for the premicellar and micellar regions was constructed, the intersection of which was used to find the CMC value in the system under study. The state of deep supersaturation of the NR solution in the metastable state upon dilution of the micellar system with water was studied. It was found that, in addition to dimers, molecular aggregates of higher orders were also formed.     

十二烷基硫酸钠/聚氧乙烯体系饱和蒸汽压和表面张力

表面活性剂／聚合物体系具有多种工业用途，尤其在提高石油采收率方面具有广泛的应用前景。另外，此类体系中存在复杂而特殊的相互作用．因此，聚合物／表面活性剂体系物理化学性质的研究具有十分重要的理论和实际意义．文献中对此方面的研究已有不少报导[1－6]．1967年，Jones     

Ionic liquid-induced changes in the properties of aqueous sodium dodecyl sulfate solution: effect of acidic/basic functional groups

The effects of ionic liquids 1-(2-aminoethyl)-3-methylimidazolium chloride ([MimAE]Cl), 1-carboxylmethyl-3-methylimidazolium chloride ([MimCM]Cl), 1-(2-hydroxylethyl)-3-methylimidazolium chloride ([MimHE]Cl), and 1-ethyl-3-methylimidazolium chloride ([Emim]Cl) on the physicochemical properties of aqueous sodium dodecyl sulfate (SDS) solutions were studied. Compared with [Emim]Cl, the presence of amino group can further facilitate the micellization of SDS, while the opposite result is observed as carboxyl group is imparted. No obvious changes in critical micelle concentration (CMC) and $ {\gamma_{\mathrm{CMC}}} $ values are induced by the neutral hydroxyl group. Only the addition of [MimAE]Cl drastically increases the micellar size. Significant decrease in CMC and increase in micellar size were observed with decreasing pH of [MimAE]Cl solution. The increase in pH of [MimCM]Cl solution results in a slight increase in CMC and decrease in micellar size. ¹H NMR spectra revealed the amino groups are adsorbed at the micellar surface, while the carboxyl groups/carboxylate ions and hydroxyl groups tend to point towards bulk water.     

A new method for the determination of the critical micelle concentration of Triton X-100 in the absence and presence of beta-cyclodextrin by resonance Rayleigh scattering technology

A new method for the determination of the critical micelle concentration (CMC) of Triton X-100 in aqueous solution and beta-cyclodextrin solution by resonance Rayleigh scattering (RRS) has been developed. The method is based on the measurement of the RRS intensity of different concentration of Triton X-100 in aqueous solution and beta-cyclodextrin solution (6.0 x 10(-4) mol l(-1)). When the RRS intensities were plotted against the concentration of Triton X-100, an inflection point appeared at the Triton X-100 concentration of 5.0 x 10(-4) mol l(-1) in aqueous solution and 1.1 x 10(-3) mol l(-1) in beta-cyclodextrin solution, respectively. These values of concentration corresponded to the CMC of Triton X-100 in aqueous solution and beta-cyclodextrin solution, which also agreed closely with the results reported by surface tension and UV-Vis absorption spectrophotometry. Therefore, the present RRS method is very convenient, rapid and accurate and can be used as a new technology for the determination of CMC values of surfactants without any probe. The relationship between the RRS intensity and the concentration, aggregate state and the aggregate molecular size of Triton X-100 has been primarily discussed.     

Modification of molecular properties of some dyes in sodium dodecyl sulphate (SDS) micellar aqueous solution

The influence of SDS upon the molecular properties of proflavine (3,6-diaminoacridine), acridine yellow (2,7-dimethyl-3,6-diaminoacridine) and methylene blue (3,7-bis-dimethylamino-phenothiazine) was studied comparatively to their properties in that of aqueous media. The absorption and emission spectra of the three dyes in SDS aqueous solution (1–100 mmol/l) were recorded. The spectroscopic data also allowed the evaluation of the critical micellization concentration (CMC), acidity constants in fundamental (pk_a) and excited (pK^*_a) states, and lifetimes of excited singlet states.     

Photoisomerization of merocyanine 540 in polymer-surfactant aggregate

Photoisomerization of merocyanine 540 (MC540) in a polymer-surfactant aggregate is studied using picosecond time resolved emission spectroscopy. The aggregate consists of the polymer, poly(vinylpyrrolidone) (PVP) and the surfactant, sodium dodecyl sulphate (SDS). With increase in the concentration of SDS in an aqueous solution of MC540 containing PVP, the emission quantum yield and lifetime of MC540 increase markedly. This indicates marked retardation in the nonradiative photoisomerization process of MC540, when it binds to the polymer-surfactant aggregate. The critical association concentration of SDS for binding to PVP has been found to be 0.5 mM. This is about 16 times lower than the CMC of SDS in pure water (8 mM).     

Synthesis and surface-active properties of the fatty acid N-methylethylolamides and their phosphate derivatives

N-Methylethylolamides have been synthesized on the basis of vegetable oils (corn, coconut, canola, olive, cotton-seed, and palm) and modified with orthophosphoric acid. The structure of the synthesized N-methylethylolamides and their phosphate derivatives has been identified by IR and NMR spectroscopies. Surface activity of the N-methylethylolamides and their derivatives at the water–air border has been determined and their colloidal-chemical parameters (maximum surface excess concentration and minimum area per molecule at the aqueous solution–air interface, surface pressure at the critical micellization concentration (CMC), standard thermodynamic parameters of adsorption and micellization) have been calculated. The character of influence of the surfactants structure on their colloidal-chemical parameter has been clarified. The petroleum-collecting and petroleum-dispersing capacities of the synthesized surfactants have been studied on the surface of the water of various mineralization degrees.     

Spectroscopic and tensiometric considerations on anionic surfactants (SDS) and ascorbic acid/ascorbates interactions

The cosmetics and personal care products market is developing dynamically and the formulations of products are subject to numerous modifications due to consumer expectations and market trends. An increase in demand for products containing ascorbic acid or its more stable forms has been observed for several years. In this study, the correlation between SDS and ascorbic acid or its derivatives in aqueous solutions was assessed using spectroscopic and tensiometric methods. The influence of SDS interactions on the total antioxidant capacity of ascorbic acid/ascorbic acid derivatives was analyzed. The highest FRAP values of SDS-AA2G and SDS-EAC systems (0.17 and 2.71 mmol Fe²⁺/g, respectively) were at SDS concentration of 0.40 mM and were much higher than the ones of pure ascorbic acid derivatives. Based on the surface tension isotherms and Szyszkowski's equation, it was found that for the tested SDS/ascorbic acid, ascorbyl glucoside and 3-O-ethyl ascorbic acid systems, the CMC values were: 3.85, 2.54 and 3.31 mmol/dm³. There was also an influence on the values of the adsorption parameters, i.e. the surface excess at the saturated interface, the minimum molecular area in the adsorption layer at the saturated interface and the Gibbs free energy of adsorption. Moreover, in most of the analyzed cases, the tested systems had better wetting properties, which resulted in lower values of the contact angle than in the case of pure SDS solution.     

Interfacial and bulk behavior of sodium dodecyl sulfate in isopropanol-water and in isopropanol-poly(vinylpyrrolidone)-water media

The surface activity of isopropanol (IP) and poly(vinylpyrrolidone) (PVP) at the air/water interface has been studied. The self-aggregation of sodium dodecyl sulfate (SDS) in IP-water as well as in IP-PVP-water media has been investigated using physical methods, viz., tensiometry, conductometry, calorimetry, and viscometry. The interaction of SDS with PVP in IP-water medium as well as its self-aggregation (or micellization) in the presence of PVP has been assessed. The results reveal a fair degree of surface activity of IP in aqueous medium, which is only moderate for PVP. The critical micellar concentration (CMC) of SDS passes through a minimum at (v/v) % IP = 6.62. SDS interacts with PVP, yielding a critical aggregation concentration (CAC) at a low [SDS], independent of IP content in the medium. At a higher [SDS], free micelle formation takes place in solution, which is lower in mixed solvent than in water and is independent of solvent composition by tensiometry, but not by conductometry and calorimetry. The viscosity of micelle-interacted PVP in solution takes a long time to stabilize, whereas, for non-interacting additives, such as NaCl and cetyltrimethylammonium bromide (CTAB), it is time independent.     

多相光催化分解H2S中阴离子表面活性剂对半导体催化剂CdS表面的影响

研究了在H₂S碱性溶液中,CdS粉末催化剂存在时,光催化分解H₂S释氢和生成硫反应。考察了阴离子表面活性剂——十二烷基硫酸钠(SDS)对催化剂的表面性质和催化活性的影响。通过模拟该反应体系,用电化学方法测定了单晶CdS电极在上述反应体系中加入SDS(浓度低于临界胶团浓度CMC值)后的平带电位的变化。结果表明:单晶CdS电极的平带电位,由于该体系加入SDS而正移,与n型多晶半导体CdS在加入SDS的H₂S碱性溶液中,光催化分解H₂S的释氢量减少相一致。并探讨了在该体系中,由于表面活性剂的阴离子与S^2-在单晶CdS电极表面上的竞争吸附,而引起单晶CdS电极的平带电位正移。