Bordeaux-R interactions with surfactants: thermochromic investigations of proton ionisation in cationic, nonionic and anionic surfactant solutions

Apparent thermodynamic parameters for the hydroxy proton ionisation of Bordeaux-R were obtained in micellar solutions using the thermochromic method. The effect of addition of the surfactants CTAB, TX-100 and SDS was investigated in buffered solutions in the pH range of 6–13. Ionisation constants in water and in the presence of surfactants were determined spectrophotometrically and the p K ' of Bordeaux-R in water was found to be 10.90 in the absence of surfactant. However, at concentrations above critical micelle concentration, p K ' dropped to 10.14 with CTAB, increased to 11.29 with TX-100 but was insensitive to SDS addition. Standard enthalpies and entropies of ionisation were obtained using the thermochromic method. This method, in conjunction with p K and spectral measurements and comparison with different azo dyes, has been shown to provide detailed information on the mechanism of dye–surfactant interaction.     

表面活性剂对孪尾缔合聚合物水溶液表观黏度的影响

用黏度法研究了孪尾疏水缔合水溶性聚合物聚（丙烯酰胺／丙烯酸钠／N,N-二己基丙烯酰胺）[P（AM／NaAA／DiC6AM）]与十二烷基硫酸钠（SDS）、十六烷基三甲基溴化铵（CRAB）、OP-10的相互作用。结果表明,水溶液的表观黏度随SDS、CTAB质量浓度的增加急剧上升,超过一定浓度后水溶液黏度又急剧下降;黏度上升的幅度随疏水单体用量的增加、表面活性剂与疏水单体的摩尔比率（SMR值）的减小而增大;随水解度的增加,黏度上升的幅度较小。P（AM／NaAA／DiC6AM）的临界缔合浓度cac约为30g/mL,当加入SDS、CTAB时,能显著地降低。随OP-10质量浓度的增加,水溶液表观黏度几乎不变。表明P（AM／NaAA／DRAM）与SDS、CTAB的疏水缔合作用较强,而与OP-10的疏水缔合作用较弱。     

GSS362/TX-100复配体系在水中的溶液行为研究

研究了1,3-丙二醇双子琥珀酸二异辛酯磺酸钠(GSS362)和辛基酚聚氧乙烯醚(TX-100)复配物在水中的表面性质和胶束化行为,并对理想混合临界胶束浓度以及混合体系中各组分在表面吸附层和胶束中的组成、相互作用参数和热力学参数进行分析计算。结果表明,复配物在水溶液中不存在协同效应,但是TX-100的加入明显降低了GSS362的临界胶束浓度,混合胶束的形成为自发过程,胶束中GSS362与TX-100分子具有较弱的相互作用,胶束中富含非离子表面活性剂TX-100。     

Aqueous dispersion of surfactant-modified multiwalled carbon nanotubes and their application as an antibacterial agent

The dispersing power of different surfactant-modified multiwalled carbon nanotubes (MWCNTs) and their effect on the antibacterial activity were examined. Three surfactants, including hexadecyltrimethylammonium bromide (CTAB), triton X-100 (TX-100) and sodium dodecyl sulfate (SDS) were tested. UV–vis absorbance, transmission electron microscopy and Fourier transform infrared spectroscopy were used to characterize the dispersion of MWCNTs in the aqueous phase, showing that the surfactant molecules had been adsorbed onto the MWCNTs’ surface. Among the three surfactants, TX-100 and CTAB provided maximum and minimum dispersion, respectively. The surfactant-modified MWCNTs exhibited different antibacterial activities to Streptococcus mutans. The fluorescence images showed that the surfactant-modified MWCNTs were not only capable of capturing bacteria and forming cell aggregates, but also killing them. Under the same concentration and treatment time, the CTAB-modified MWCNTs exhibited the strongest antibacterial activity compared to the TX-100 and SDS-modified MWCNTs. The optical density growth curves and viable cell number determined by the plating method suggested that the antibacterial activity of all surfactant-modified MWCNTs was both concentration- and treatment time-dependent.     

Spectroscopic and conductometric studies on the interactions of thionine with anionic and nonionic surfactants

In this study, the interaction of thionine, a cationic dye, with anionic [sodium dodecyl sulphate (SDS), lithium dodecyl sulphate (LiDS), and sodium dodecylbenzene sulphonate (SDBS)], nonionic (Tween 20 and Triton X‐100), and binary mixtures of anionic and nonionic surfactants was studied by conductometric and spectrophotometric measurements. The degree of ionisation, the counterion binding parameters, and the equilibrium constants in the premicellar region were obtained from conductivity data. Binding constants of thionine to anionic, nonionic, and mixtures of anionic and nonionic micelles were determined by spectrophotometric measurements. The binding tendency of thionine to anionic micelles followed the order SDBS > SDS > LiDS. The presence of nonionic surfactants increased significantly the binding affinity of thionine to anionic micelles, and the highest binding constant was calculated in the presence of Tween 20. The results obtained from conductometric studies correlated with those obtained from spectroscopic studies. Data concerning dye–surfactant interaction are important for a fundamental understanding of the performance of single and mixed surfactants and for their industrial application.     

表面活性剂对疏水改性丙烯酰胺共聚物增粘性能的影响

采用自由基胶束聚合法合成丙烯酰胺/丁基苯乙烯疏水缔合水溶性共聚物(PSAM),所用的十二烷基硫酸钠(SDS)、辛基酚聚氧乙烯醚(OP-10)和十六烷基三甲基溴化铵(CTAB)能显著影响疏水单体在聚合产物中的含量,从而影响聚合物的溶液粘度,其中以SDS合成得到的产物的溶解性及增粘性能最好。另外,少量表面活性剂的加入能显著地提高聚合物亚浓溶液的粘度,在十二烷基苯磺酸钠(SDBS)、SDS和CTAB中,SDBS对聚合物亚浓溶液粘度的影响最大,其浓度为0.7 mmol/L时,0.3 g/dL PSAM溶液的表观粘度从237 mPa.s上升到981 mPa.s。     

Synthesis and Surface Active Properties of Gemini Cationic Surfactants and Interaction with Anionic Azo Dye (AR52)

A homologous series of new gemini cationic surfactants were synthesized and characterized using micro elemental analysis, FTIR, ¹H-NMR and mass spectra. The surface activities of these amphiphiles were determined based on the data of surface tension. Critical micelle concentration, effectiveness of the surface tension reduction, efficiency of adsorption, maximum surface excess, minimum surface area and critical packing parameter were evaluated. The effect of cationic micelles on solubilization of anionic azo dye, sulforhodamine B (Acid Red 52) in aqueous micellar solution of the synthesized gemini cationic surfactants was studied at pH 6.9 ± 0.5 and 25 °C. The results showed that the solubility of dye rose with increasing surfactant concentration as a consequence of some association between the dye and the micelles. It was also observed that the aggregation of surfactant and dye takes place at a surfactant concentration below the CMC of the individual surfactant. The partition coefficients between the bulk water and surfactant micelles as well as the Gibbs energies of distribution of dye between the bulk water and surfactant micelles were calculated using a pseudo-phase model. The effect of the hydrophobic chain length of Gemini cationic surfactants on the distribution parameters was also reported. The results show favorable solubilization of dye in cationic micelles.     

Wetting and adsorption properties of cetyltrimethylammonium bromide and Triton X-100 mixture with short-chain alcohol in polymer–solution–air system

Measurements of the contact angle of the aqueous solutions of Triton X-100 (TX-100) and cetyltrimethylammonium bromide (CTAB) mixture with methanol or propanol on the polytetrafluoroethylene (PTFE) and nylon-6 surfaces were made. On the basis of the obtained results, the Gibbs surface excess concentration of alcohol and TX-100 + CTAB mixture at the polymer–solution and polymer–air interfaces was calculated and compared to that at the solution–air one. The standard Gibbs free energy of alcohol adsorption was determined by different methods. For TX-100 and CTAB mixture, this energy was calculated using the values of critical micelle concentration (CMC) of that mixture, the surface tension and contact angle of aqueous solution of alcohol as well as the surface tension and contact angle of the aqueous solution of TX-100 and CTAB mixture with alcohol at CMC. The polymer–solution interfacial tension, the adhesion tension, and the adhesion work of the studied solutions to the polymer surface were also determined. From the obtained data, it results that the studied solutions can wet completely only the nylon-6 surface and that below alcohol critical aggregation concentration the adsorption of surfactants and alcohols at the polymer–water and water–air interfaces is similar for PTFE and different for nylon-6.     

表面活性剂水溶液池热核沸腾传热的试验研究

对表面活性剂SDS、CTAB、Triton X-114和Triton X-100水溶液物性及其池核沸腾传热进行了试验,重点探讨了表面活性剂分子结构参数和溶液物性对沸腾传热的影响。结果表明：表面活性剂溶液沸腾传热效果、表面活性剂相对分子质量对表面活性剂溶液沸腾传热的影响规律都与表面活性剂的电离特性密切相关,离子型表面活性剂SDS与CTAB溶液的沸腾传热系数比值与相对分子质量的比值成－0.22的指数关系,而非离子表面活性剂Triton X-114和Triton X-100溶液不存在指数关系。动态表面张力和热流密度相等时,SDS和CTAB溶液沸腾传热特性差异主要受相对分子质量和平衡接触角的影响,而Triton X-100和Triton X-114溶液则受质量分数、EO基团数、浊点和动力黏度的综合作用。     

Surfactant-Induced Wettability Alteration of Oil-Wet Sandstone Surface: Mechanisms and Its Effect on Oil Recovery

Different analytical methods were utilized to investigate the mechanisms for wettability alteration of oil-wet sandstone surfaces induced by different surfactants and the effect of reservoir wettability on oil recovery. The cationic surfactant cetyltrimethylammonium bromide (CTAB) is more effective than the nonionic surfactant octylphenol ethoxylate (TX-100) and the anionic surfactant sodium laureth sulfate (POE(1)) in altering the wettability of oil-wet sandstone surfaces. The cationic surfactant CTAB was able to desorb negatively charged carboxylates of crude oil from the solid surface in an irreversible way by the formation of ion pairs. For the nonionic surfactant TX-100 and the anionic surfactant POE(1), the wettability of oil-wet sandstone surfaces is changed by the adsorption of surfactants on the solid surface. The different surfactants were added into water to vary the core surface wettability, while maintaining a constant interfacial tension. The more water-wet core showed a higher oil recovery by spontaneous imbibition. The neutral wetting micromodel showed the highest oil recovery by waterflooding and the oil-wet model showed the maximum residual oil saturation among all the models.     

Effect of Self-Assemblies on the Dynamics of the Briggs–Rauscher Reaction

The study involves the dynamic evolution of the Briggs–Rauscher (BR) reaction in the presence of various surfactants—SDS (sodium dodecyl sulphate) as anionic, CTAB (cetyl trimethylammonium bromide) as cationic and TritonX‐100 [4‐(1,1,3,3‐(tetramethylbutyl) phenyl polyethylene glycol] as a neutral one in single as well as mixed mode conditions (SDS + TX‐100 and CTAB + TX‐100). The reaction has been monitored potentiometrically at 30 °C under CSTR conditions. These surfactants affect the reaction dynamics to an extent which depends on the nature and concentration of the surfactant and the formation of their self‐assemblies. The experimental findings indicate that the oscillatory behavior of the BR reaction in the presence of surfactants is due to the efficacy of organized surfactant assemblies to selectively distribute the key species involved in the reaction, and their interaction with the counter ions in cases of ionic micelles. The study reveals that the evolution of oscillatory behavior is a characteristic feature of the surfactant.     

Solubilisation of dyes by surfactant micelles. Part 4: Influence of dye fixatives

Dye loss from unfixed dyed fabrics has been found to be insensitive to change in surfactant type or concentration. There was accompanying dye transfer to white fabric but this was reduced by Synperonic A7 in the case of fabrics dyed with CI Direct Green 26, due to solubilisation of the dye in nonionic micelles. The anionic surfactant, SDS, selectively displaced dye from fixed dyed fabrics, paralleling its behaviour with water soluble polymers. Similarly, dye loss was related to concentration of surfactant monomer, the effect increasing with SDS concentration up to its critical micelle concentration. Other anionic surfactants have been found to exhibit a similar trend, the effect increasing with their increasing surface activity. The commercial polymeric fixatives, Tinofix ECO and Indosol E50, were the most effective of those studied and the single-chain cationic surfactant, CTAB, was the least effective.     

Influence of breakup and reformation of micelles on surfactant diffusion in pure and mixed micellar systems

Pulsed field gradient (PFG) NMR technique was used to study diffusion of surfactant ions in the following two micellar systems: (i) aqueous solution of an anionic surfactant sodium dodecyl sulfate (SDS), and (ii) aqueous solution of a mixture of SDS and a small amount of the cationic surfactant N-dodecyltrimethylammonium bromide (C₁₂TAB). PFG NMR measurements provided separate sets of data on diffusion of SDS and C₁₂TAB surfactant ions for a broad range of diffusion times. For each type of surfactants at least two components with different effective diffusivities were observed at sufficiently small diffusion times. The faster component was assigned to the surfactants that experience breakup or reformation of micelles during the diffusion time of the PFG NMR measurement, while the slower component was assigned to the surfactants that did not participate in such events during the diffusion time. The observed changes of the fractions and diffusivities of these components with increasing diffusion time were found to be in a qualitative agreement with such assignment. Fundamental understanding of surfactant diffusion in micellar system is important due to an increasing use of such systems for synthesis of porous materials where micelles are used as templates as well as for many other applications.     

Adsorption and Aggregation Activity of Sodium Dodecyl Sulfate and Rhamnolipid Mixture

Measurements of the surface tension, density and viscosity of sodium dodecyl sulfate (SDS) and rhamnolipid (RL) mixtures were carried out in aqueous solution. From the obtained results, composition of mixed surface layer at the water–air interface, mixed micelles, parameter of intermolecular interactions, activity of SDS and RL in the surface layer and micelles, Gibbs standard free energy of adsorption and micellization as well as Gibbs free energy of SDS and RL mixing in the surface layer and micelles were established. These parameters were discussed in the light of independent adsorption of SDS and RL and the size of their molecules as well as the area in contact with water molecules. A correlation between the number of water molecules in contact with those of SDS and RL and standard free energy of adsorption as well as micellization of these surfactants was observed. A correlation between the apparent and partial molar volumes of RL and SDS in their mixture and size of surfactant molecules as well as the average distance between molecules was also found. The parameter of intermolecular interactions indicates that there is a synergetic effect in the reduction of water surface tension and micelle formation.     

Interactions between dyes and surfactants in inkjet ink used for textiles

Optimal preparation of inkjet ink should be possible through the elucidation of the relationship between dye/additive interactions and ink performance. In the present study, the interactions between the dyes and surfactant additives were investigated. To investigate the physical properties of the surfactants used, the critical micelle concentration (cmc) and the aggregation number (N) were determined using electron spin resonance, static light-scattering, and fluorescence spectroscopy. On the basis of the cmc and N values, the visible absorption spectra of aqueous acid dye solutions (C. I. Acid Red 88, 13, and 27) containing surfactants (i.e., Surfynol 465 (S465), octaethylene glycol monododecyl ether (OGDE), and sodium dodecyl sulfate (SDS)) were measured. From the dependence of the spectra on the surfactant concentration, the binding constants, K(bind), of the acid dyes with the surfactant micelles were calculated: the K(bind) values decreased in the order of C. I. Acid Red 88 > C. I. Acid Red 13 > C. I. Acid Red 27, which correlates with the number of sulfonate groups. For all the dyes, the K(bind) values with the nonionic surfactants, S465 and OGDE, were much larger than those with the anionic surfactant, SDS. The thermodynamic parameters of the binding, i.e., the enthalpy change, ΔH(bind), and entropy change, ΔS(bind), were determined via the temperature dependence of the binding constants. The positive ΔH(bind) value for S465 indicates an endothermic binding process, while the negative ΔH(bind) values for SDS and OGDE indicate exothermic binding processes.     

Studies on aggregation of AOT and NaDEHP via the energy transfer between AO and RB molecules

The aggregation behaviours of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and sodium bis(2-ethylhexyl)phosphate (NaDEHP) solutions are studied via the energy transfer of acridine orange (AO) and rhodamine B(RB) molecules. The approximate apparent energy transfer efficiency (ϕ_a) of the dye molecules reaches its maximum value when the concentrations of AOT and NaDEHP are far lower than their cmc. This might be caused by the formation of surfactant–dye mixtures. The anionic surfactants (SDS, AS, AOT and NaDHEP), cationic surfactant (CTAB) and nonionic surfactant (Triton-X-100) are chosen to investigate the effect of the structure of surfactant on the ϕ_a between AO and RB molecules. The results indicate that the effective energy transfer may occur in the anionic surfactant systems and it is not obvious in the nonionic and cationic surfactant systems.     

Effect of tartrazine dye on micellisation of cationic surfactants: conductometric,spectrophotometric, and tensiometric studies

The interactions between anionic dye (tartrazine) and cationic surfactants (dodecyltrimethylammonium bromide and cetyltrimethylammonium bromide) have been studied by conductometric, spectrophotometric, and tensiometric techniques. The conductance and surface tension of dodecyltrimethylammonium bromide and cetyltrimethylammonium bromide in pure water as well as in aqueous tartrazine when plotted with surfactant concentration gave values of the critical micelle concentration at different temperatures. As well as increasing the length of the carbon chain of surfactants, the presence of tartrazine reduces the critical micelle concentration. From specific conductivity data, the counterion dissociation constant, standard free energy, enthalpy, entropy of micellisation, surface excess concentration, surface tension at critical micelle concentration, minimum area per molecule, surface pressure at critical micelle concentration, and Gibbs energy of adsorption were evaluated. Spectroscopic studies reveal that the binding of dye to micelles brings a bathochromic shift in dye absorption spectra that indicates dye–surfactant interaction.     

Surface protection of copper in acid medium by azoles and surfactants

The influence of derivatives of 1,2,4 triazole, 3-amino 1,2,4-traizole (ATA), 3-amino 5-mercapto 1,2,4 triazole (AMT) and 3-amino 5-methylthio 1,2,4 triazole (AMTT) and ionic surfactants cetyl trimethyl ammonium bromide (CTAB) and sodium dodecyl sulphate (SDS) on the corrosion control of copper in acidic solution was investigated by gravimetric and electrochemical methods. The combined effect of triazoles and surfactants was also evaluated. Electrochemical parameters like corrosion potentials corrosion current density, corrosion rates and inhibition efficiencies were determined. The results reveal the fact that of all triazoles AMTT shows best inhibition and anionic surfactant SDS protects the surface better than the cationic surfactant CTAB. The polarisation data reveal that all inhibitors behave as a mixed type inhibitor. Adsorption of these inhibitors on the surface of copper is found to obey the Langmuir adsorption isotherm. A marked inhibition synergism effect is shown by all the combinations of triazole and surfactant.     

Effect of different additives on the phase separation behavior and thermodynamics of p-tert-alkylphenoxy poly (oxyethylene) ether in absence and presence of drug

Cloud point(CP) determinations of 4-(1,1,3,3-tetramethylbutyl)phenyl-polyethylene glycol(TX-100(nonionic surfactant)) was carried out in aqueous as well as in the attendance of drug(ceftriaxone sodium trihydrate(CFT))/(CFT + different inorganic salts) and discussed thoroughly. Nonionic surfactants are employed extensively in different formulations. In aqueous solution, the values of CP of TX-100 are obtained to increase by means of enhancing of their concentration in the solution. The CP values of TX-100 solutions were found to decrease in the presence of drug and their values decrease more with rising concentrations of the drug. The values of CP of CFT and TX-100 mixtures were found to further decrease in the attendance of inorganic salts in comparison to their absence. The effect of different sodium salts in decreasing CP values of TX-100 was achieved in the following order: NaCO_3 Na_2SO_4 Na Cl. However, in the case of potassium and ammonium salts, the decreasing order obtained is K_2SO_4 KCO_3 KCl and(NH4)2 SO_4 Na_2CO_3 NH_4Cl respectively. Various thermodynamic parameters for example standard free energy(ΔG_c~Θ), standard enthalpy(ΔH_c~Θ) as well as standard entropy(Δ Sc?)changes of phase separation were also evaluated and discussed in detail on the basis of their behavior.     

Properties of hydrophobically modified polyacrylamide with low molecular weight and interaction with surfactant in aqueous solution

Hydrophobically modified polyacrylamide (HMPAM), with a molecular weight of 10⁴ g/mol, was studied using a range of rheological methods and dynamic light scattering (DLS). DLS measurements indicate that the association of the modified polymer begins at low concentration. The modified polymer with high substitution forms transient networks below the critical concentration, but the networks are disrupted by the micelles formed by the polymer itself, and the networks do not contribute to viscosity enhancement. The modified polymers exhibited surface activity, and so they may be regarded as nonionic polymeric surfactants rather than thickeners. On the other hand, HMPAM is shown to interact with the surfactant SDS while PAM is inert to SDS. In the hydrophobic domains, it undergoes a surfactant‐induced association process; in the hydrophobe‐surfactant transition regions, the surfactant binds to the polymer in a noncooperative way and forms a polymer–surfactant complex. Contracted polymer chains begin to extend because of electrostatic repulsion, which can overcome the association at surfactant domains. The conformation of HMPAM polymer chains could be controlled by adding a specific amount of surfactant. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4348–4360, 2006