Interaction of Azo Dye with Cationic Surfactant Under Different pH Conditions

The aggregation induced by Alizarin Yellow R (AYR) in the cationic surfactant, cetyltrimethylammonium bromide (CTAB), was investigated by measuring their UV–visible absorption spectra. Conductance measurements as a function of surfactant concentration below and above the critical micelle concentration (CMC) were studied. CTAB aggregation takes place at the concentration far below its normal CMC in the presence of AYR. Both hydrophobic and electrostatic interactions affect the aggregation process in aqueous solution. The dye effect on the CMC of CTAB was noted by a specific conductivity method as well. AYR–CTAB binding constant (K_s) and water–micelle partition co-efficient (K_x) were quantified with the help of mathematical models employed to determine the partitioning of organic additives in the micellar phase. The number of dye molecules per micelle was estimated at particular CTAB concentrations above CMC, during this study.     

Determination of critical micelle concentrations of some nonionic surfactants by Keto-Enol tautomerism of benzoylacetoanilide

The absorbances of benzoylacetoanilide, keto-enol tautomer, dissolved in aqueous solution of several concentration ranges below and above the CMC of the incorporating surfactants. Below the CMC, the absorbance of the band at 250 nm due to the ketonic form showed hardly any change and that of the band at 320 nm due to the enolic form could not be observed. In contrast, above the CMC, the spectral band of the enolic form appeared, and the absorbance increased abruptly and that due to the ketonic form decreased gradually. The changes at the CMC in absorbance for these nonionic surfactants were distinctly observed by plotting the absorbance at 250 and 320 nm as a function of the concentration of surfactants. These changes at the CMC were very noticeable with nonionic surfactants as well as with ionic surfactants. The concentrations corresponding to break points for these surfactants were in fairly good agreement with the published data of the CMC of each surfactant. This method of keto-enol tautomerism using benzoylacetoanilide has been confirmed CMC for most anionic, cationic, and nonionic surfactants.     

Kinetics of precipitation of surfactants. I. Anionic surfactants with calcium and with cationic surfactants

Isoperibol calorimetry was used to measure the rates of precipitation for aqueous solutions of several anionic surfactants with calcium and of anionic and cationic surfactants. A monomer concentration-dependent supersaturation ratio was used to describe the relative rates of precipitation for the surfactant systems studied. This supersaturation ratio allows for the relative rates of precipitation of any surfactant solution to be compared whether micelles are present in solution or not. In general, as the supersaturation ratio increases, the rate of precipitation decreases and the induction time decreases, bot above and below the critical micelle concentration (CMC). The rate of precipitation of sodium dodecyl sulfate (SDS) with dodecyl pyridinium chloride is much slower than the rate of precipitation of the anionic surfactants with calcium for similar supersaturation ratios. The rate of precipitation of SDS with calcium is slightly faster than the rate of precipitation of sodium octyl benzene sulfonate for similar supersaturation ratios. Studies of precipitate crystals, conducted using image analysis, showed that size and shape dependent on the initial supersaturation, the precipitating surfactant molecule, and the extent of aging (until an equilibrium size and shape was reached). Also, differences in the appearance of crystals formed from solutions above and below the CMC were observed. These were most likely due to the difference in supersaturation of these solutions. The crystals formed due to precipitation of SDS with calcium at a concentration above the CMC formed flat trapezoidal, rhombic and hexagonal shapes. These aged into clusters by 1 wk. For a solution that was precipitated at concentrations beginning below the CMC, the crystals began as elongated and rhombic flat plates and aged into trapezoidal, rhombic, and needle-like structures.     

烷基苯磺酸盐Gemini表面活性剂的结构与界面性质

以烷基酰氯为原料,经傅克酰基化反应、格林反应、催化氢化还原及磺化、中和等步骤,合成了10-4-10、12-4-12和10-6-10(10和12代表疏水基碳数,4和6代表连接基团碳数)3种不同结构的双烷基双苯双磺酸盐Gemini表面活性剂,并用核磁共振氢谱和电喷雾质谱对产物进行了结构鉴定。用旋滴法测定了其水溶液与正庚烷的界面张力,发现磺酸盐Gemini表面活性剂的CMC比对应的传统的表面活性剂的CMC低两个数量级,并且随着疏水基碳数或连接基团碳数的增加而降低。10-4-10、12-4-12和10-6-10的饱和吸附面积(Amin)分别为0.23、0.35和0.97 nm2,饱和吸附量(Γmax)分别为7.37×10-10、4.65×10-10和1.72×10-10mol/cm2,临界胶束浓度下的界面张力(γCMC)分别为3.60、3.06和1.89 mN/m。     

2-羟基-3-辛基-5-长链烷基苯磺酸钠的合成及表面活性

以脂肪酸、苯酚为原料,经酰化反应、酯化反应、Fries重排、氢化还原反应、磺化以及中和反应等步骤,合成出了2-羟基-3-辛基-5-长链烷基苯磺酸钠表面活性剂。两相滴定法测定了产物的质量分数均大于99%;用核磁共振氢谱、傅立叶红外光谱和质谱对产物进行了结构鉴定。用悬挂滴法测定了30℃时该系列表面活性剂的表面张力。实验发现,纯水溶液中表面活性剂的临界胶束浓度(CMC)达到10-6mol/L数量级,临界胶束浓度下的表面张力(γCMC)均小于28 mN/m;随着苯环上长链烷基碳数(n=8,10,12)的增加,CMC降低,分别为1.06×10-5,3.35×10-6,2.65×10-6mol/L;而γCMC变化不明显,分别为26.77,26.89,27.22 mN/m。结果表明,此类表面活性剂具有比较好的表面活性。     

Relationship between foaming properties and solution properties of protein/nonionic surfactant mixtures

The foaming properties of bovine serum albumin (BSA), in the absence and presence of Triton X-100 (TX-100), have been investigated using shaking tests. The results showed that increases in the TX-100 bulk concentration rapidly reduced both foam height and foam stability at TX-100 concentrations below about 0.25 mM, but increased foam height and foam stability at TX-100 concentration above 0.3 mM. The interaction between BSA and TX-100 has been studied using fluorescence spectroscopy. The surfactant appeared to bind to BSA with a low molar ratio (about one surfactant molecule per protein molecule) at concentrations below the critical micelle concentration (CMC); the binding became weaker at concentrations above the CMC. It was confirmed that protein-protein or protein-surfactant interactions had significant influence upon foaming properties of mixed protein/surfactant system.     

Fluorescence anisotropy and rotational diffusion of two kinds of 4-n-alkyl-4'-cyanobiphenyls in glycerol

Absorption and fluorescence spectra, fluorescence lifetimes, and steady-state and time-resolved fluorescence anisotropies were measured for 4-methyl-4'-cynanobiphenyl (1CB) and 4-hexyl-4'-cynanobiphenyl (6CB) in glycerol at various temperatures. The energies and intensities of the absorption and emission spectra for 1CB and 6CB were almost equally observed, and the fluorescence lifetimes around 1.0 ns were also almost equally obtained and did not depend on temperature. However, the time-resolved fluorescence anisotropies measured in glycerol solution indicated that the molecules of 1CB rotate more rapidly than those of 6CB: the rigid-sphere radii for 1CB and 6CB obtained by using the pulsed exciting light were evaluated as 1.3x10(-10) m (1CB) and 1.8 x 10(-10) m (6CB) in the low temperature region (2-10 degrees C), whereas those evaluated in the high temperature regions (20-60 degrees C for 1CB and 30-60 for 6CB) were 2.7 x 10(-10) m (1CB) and 3.6 x 10(-10) m (6CB). These radii evaluated in the high temperature region were in good agreement with those obtained by using steady-state exciting light, 2.9 x 10(-10) m (1CB) and 3.4x10(-10) m (6CB). It is noted that the increase of radius was observed across an intermediate temperature region (10-30 degrees C for 1CB or 10-40 degrees C for 6CB), and was more remarkable for 6CB than for 1CB. This implies that the movements of hexyl-chain are much more enhanced at high temperature, and are effectively reflected to the increase in radius of rotational diffusion. The changing phenomenon of movements of peripheral alkyl-chain in liquid-crystal molecules is important for the phase transition between liquid crystal and isotropic liquid phases: the changing to less vigorous movements of the alkyl-chain in 6CB is thought enough to contribute to the liquid-crystal formation of 6CB molecule.     

Mechanism of micelle formation in sodium dodecyl sulfate and cetyltrimethylammonium bromide

pH changes as a function of concentration for sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) were observed by addition of 1 N HCl and 1 N KOH. pH values increased up to the critical micellar concentration (CMC) for the SDS/HCl system and decreased for the CTAB/KOH system. In the SDS/HCl and CTAB/KOH systems, the micellar phase had a fixed composition and was homogeneous and monodisperse above the CMC. However, in the SDS/KOH and CTAB/HCl systems, pH values increased continuously and gradually below and above the CMC, and the properties of the micellar phase changed as a function of concentration, giving rise to inhomogeneity and polydispersity.     

Surface active properties of combinations of soap and lime soap dispersing agents

Surface tension versus log concentration curves were obtained for combinations of a variety of lime soap dispersing agents (LSDA) with sodium oleate. Salient features of the curves for these mixtures were: (a) criticial micelle concentration (CMC) close to that for LSDA alone; (b) absence of a surface tension minimum or substantial reduction in the minimum, which was often found with LSDA alone; (c) surface tension values above the CMC very close to those found for soap alone above its CMC; and (d) slope below the CMC greater than that for soap alone, more like that for soap with alkali added or lime soap dispersing agent alone. Higher CMC values were confirmed by dye solubilization measurements. The surface tension curves provided further evidence for the mixed micellar nature of soap-LSDA mixtures and suggested that the addition of LSDA to soap increased the surface concentration of surfactant. Presented at the AOCS Meeting, Chicago, September 1976.     

Interfacial properties of cationic and anionic Gemini surfactant mixtures

The possibility and the prospect of cationic/anionic (“catanionic”) surfactant mixtures based on sulfonate Gemini surfactant (SGS) and bisquaternary ammonium salt (BQAS) in the field of enhanced oil recovery was investigated. The critical micelle concentration (CMC) of SGS/BQAS surfactant mixtures was 5.0 × 10⁻⁶ mol/L, 1–2 orders of magnitude lower than neat BQAS or SGS. A solution of either neat SGS or BQAS, could not reach an ultra-low interfacial tension (IFT); but 1:1 mol/mol mixtures of SGS/BQAS reduced the IFT to 1.0 × 10⁻³ mN/m at 100 mg/L. For the studied surfactant concentrations, all mixtures exhibited the lowest IFT when the molar fraction of SGS among the surfactant equaled 0.5, indicating optimal conditions for interfacial activity. The IFT between the 1:1 mol/mol SGS/BQAS mixtures and crude oil decreased and then increased with the NaCl and CaCl₂ concentrations. When the total surfactant concentration was above 50 mg/L, the IFT of SGS/BQAS mixtures was below 0.01 mN/m at the studied NaCl concentrations. Adding inorganic salt reduced the charges of hydrophilic head groups, thereby making the interfacial arrangement more compact. At the NaCl concentration was above 40,000 mg/L, surfactant molecules moved from the liquid–liquid interface to the oil phase, thus resulting in low interfacial activity. In addition, inorganic salts decreased the attractive interactions of the SGS/BQAS micelles that form in water, decreasing the apparent hydrodynamic radius (D_{H, app}) of surfactant aggregates. When the total concentration of surfactants was above 50 mg/L, the IFT between the SGS/BQAS mixtures and crude oil decreased first and then increased with time. At different surfactant concentrations, the IFT of the SGS/BQAS mixtures attained the lowest values at different times. A high surfactant concentration helped surfactant molecules diffuse from the water phase to the interfacial layer, rapidly reducing the IFT. In conclusion, the cationic-anionic Gemini surfactant mixtures exhibit superior interfacial activity, which may promote the application of Gemini surfactant.     

Fluorescence technique for the determination of low critical micelle concentrations

A technique for determining low critical micelle concentrations (CMC) by means of a hydrophobic fluorescence probe has been developed. The amount of the fluorescent probe at the CMC is so small that the effect of the probe on micelle formation is negligible. The fluorescence intensity was measured at fixed dye/surfactant ratios, and it decreased with concentration. A quantity proportional to fluorescent quantum yield was calculated and found to be high for concentrations of surfactant above the CMC and almost zero below the CMC, giving a distinct break in the quantum yield vs. the concentration curve.     

Synthesis and surface-active properties of trimeric-type anionic surfactants derived from tris(2-aminoethyl)amine

Trimeric-type anionic surfactants (3C_ntaAm, where n is a hydrocarbon chain length of 8, 10, or 12) with three hydrocarbon chains and three carboxylate headgroups were synthesized from tris(2-aminoethyl)amine, and their properties were investigated by surface tension, electrical conductivity, dynamic and static light-scattering, fluorescence of pyrene, and emulsification power techniques. The critical micelle concentrations (CMC) of 3C_ntaAm were 0.00092–0.00834 mmol dm⁻³, and the surface tensions at the CMC were 33.3–39.9 mN m⁻¹. The areas per molecule occupied by 3C₁₀taAm and 3C₁₂taAm were extremely small, showing they were highly compact at the air/water interface. In addition, adsorption or micellization behavior of 3C_ntaAm was estimated by parameters such as pC ₂₀ (the efficiency of surface adsorption), CMC/C ₂₀ (the ease of adsorption relative to the ease of micellization), and ΔG _M ^o (Gibbs energy of micellization). Dynamic and static light-scattering mesurements of 3C_ntaAm showed a hydrodynamic radius of 45–61 nm above the CMC and aggregation numbers of 10–82 at the CMC, respectively. The fluorescence intensity ratio of the first to the third band in the emission spectra of pyrene started to lower from far above the CMC for 3C₈taAm and 3C₁₀taAm, and below the CMC for 3C₁₂taAm. This suggests that loose micelles or premicellar aggregates are formed in solutions. Mixtures of aqueous solutions of 3C_ntaAm and toluene formed oil-in-water-type emulsions, and the stabilizing abilities were in the order of 3C₈taAm>3C₁₀taAm>3C₁₂taAm. The degree of emulsification of 3C₈taAm remained at 69% after 24 h of standing. Thus, 3C_ntaAm exhibited unique properties superior to monomeric or dimeric surfactants that were significantly influenced by their hydrocarbon chain lengths.     

Physicochemical characterization of psychosine by 1H nuclear magnetic resonance and electron microscopy

Krabbe's disease is an autosomal recessive disease that affects the lysosomal enzyme galactosylceramidase. The storage of one of its substrates, psychosine (β-galactosylsphingosine), is thought to be responsible for the induction of pathological changes. Psychosine has a free amine group which is necessary for the mediation of its toxic effects. In the present study, the physicochemical properties of psychosine were investigated. Nuclear magnetic resonance (NMR) detected pH titration was used to determine that the amine group had a pKa of 7.18±0.05. Pulsed-field gradient NMR spectroscopy was used to determine that the diffusion coefficient of 2.8 mM psychosine in D₂O at pD 4.46 or 7.04 is 1.16±0.02×10⁻¹⁰ m²/s or 0.77±0.02×10⁻¹⁰ m²/s, respectively. Negative staining electron microscopy (EM) studies of acidic and neutral solutions of psychosine also were performed. At pH 4.5, spherical structures were formed, which were relatively stable between 3, 120, and 216 h following preparation; the diameter ranged from ∼14 nm at the earliest time point to ∼18 nm at the last time point. The critical micelle concentration (CMC) was 1.26 mM at pH 4.0. At pH 7.1, the structures changed from spherical structures with a diameter of 15–23 nm, at the earliest time point, to a heterogeneous population of structures ranging from spherical structures, with a diameter of only a few nm, to irregularly shaped oblong structures that had one or more dimensions exceeding 100 nm. The NMR and EM data indicate that the deprotonation of the amine group causes psychosine to form aggregates that are unstable, which prevents a determination of the CMC at a neutral pH. These data indicate that molecular interactions of psychosine at the acidic pH of the lysosome, where it is normally digested, are more orderly than those at the pH of the cytoplasm or extracellular space where psychosine goes during disease.     

The study of Sunset Yellow anionic dye interaction with gemini and conventional cationic surfactants in aqueous solution

In the present study, the interaction of an anionic azo dye, Sunset Yellow, with two cationic gemini surfactants with different spacer lengths (s = 3, 6 methylene groups) and their monomeric counterpart, dodecyl trimethyl ammonium bromide (DTAB), was investigated by surface tension, UV–Vis spectroscopy, and zeta potential measurements. The critical micelle concentration (CMC) was determined from plots of the surface tension (γ) as a function of the logarithm of total surfactant concentration. Moreover, the values of binding constants (K_b) of dye-surfactant complexes were calculated by UV–Vis spectroscopy. The UV–Vis spectra showed that the dye–surfactant interaction occurred in the solution at concentrations far below the CMC of each surfactant. The gemini surfactant with a shorter spacer showed stronger interaction with dye in comparison to DTAB and the gemini with longer spacer. The effect of surfactant chemical structure on solubilization of dye-surfactant aggregates at surfactant concentration above CMC was investigated by zeta potential.     

Determination of critical micelle concentration of surfactant by ultraviolet absorption spectra

A method was investigated for determining the critical micelle concentration (CMC) by the shift of absorption maxima when an organic compound (I) with ultraviolet absorption was added to an aqueous solution of a surfactant. When I was added to the surfactant solution at higher concentrations (above the CMC), λ_max of I approached the value inn-octane, since I was solubilized in the hydrocarbon atmosphere of the inner part of the surfactant micelle. At lower concentrations (below the CMC), however, I was present in the water phase and λ_max approached the value in water. The curve of λ_max vs. surfactant concentration declined from the high concentration values as the CMC was approached and at the CMC, the curve broke upward sharply. Then, it rose for some time and approached the value in water. N,N′-diethylaniline was used because it exhibited larger shifts of λ_max. The standard amount used was 0.002 ml/3–10 ml of aqueous solution of the surfactant. The CMC values obtained agreed with those obtained by the electric conductivity method, dye adsorption method and light scattering method, for surfactants such as tetradecyldimethylbenzylammonium chloride, sodium dodecyl sulfate and polyoxyethylene cetyl ether.     

表面活性剂对气体水合物生成过程的定量影响

为确定HCFC?141b水合物生成条件下阴离子表面活性剂十二烷基硫酸钠(SDS)和十二烷基苯磺酸钠(SDBS)的临界胶束浓度(CMC),在0~20℃温度下,通过圆环法实验研究了不同浓度表面活性剂溶液体系的表面张力,考察了表面活性剂对溶液体系表面张力的影响机理并通过C3H8水合物的生成过程实验进行了验证,确定了SDS和SDBS的临界胶束浓度. 结果表明,当SDS和SDBS的质量浓度分别低于500?10?6和100?10?6时,表面活性剂降低水表面张力的效果最明显,二者的CMC分别为1950?10?6和400?10?6,表面活性剂能明显缩短水合反应的诱导时间,提高了其平均生成速率.     

对-烷基-苄基聚氧乙烯醚羧酸甜菜碱的合成与表面活性

以脂肪酸、苯、二缩三乙二醇为原料,经酰化反应、黄鸣龙还原反应、氯甲基化反应、威廉逊成醚反应、卤化反应、季铵化反应,合成出了3个对烷基苄基聚氧乙烯醚羧酸甜菜碱两性离子表面活性剂。用IR、1HNMR和ESI-MS对产物进行了结构鉴定。用Wilhelmy-plate法测定了30℃时它们在水溶液中的临界胶束浓度(CMC)和临界胶束浓度下的表面张力(γCMC)。实验表明,纯水溶液中表面活性剂的临界胶束浓度(CMC)为10-4～10-6mol/L,临界胶束浓度下的表面张力(γCMC)为27～30 mN/m;随着苯环上长链烷基碳数(n=8、10、12)的增加,CMC分别为1.12×10-4、1.51×10-5、6.21×10-6 mol/L;γCMC分别为27.9、28.4、29.9 mN/m。结果表明,该类表面活性剂具有比较好的表面活性。     

Properties of aqueous solution of a fluorocarbon surfactant and a nonionic surfactant,and their mixtures

The surface tensions of aqueous solutions of lithium perfluorooctane sulfonate (LiFOS) and hexaethyleneglycoln-dodecylether (6ED), and of their mixtures, were measured. The effect of each surfactant additives on the adsorption and the micelle formation was discussed on the basis of the surface tension values using the Langmuir adsorption equation for the mixture of both surfactants and the modified Szyszkowski equation. From these results, in the range of low concentrations of 6ED or LiFOS, some of the 6ED molecules which had already adsorbed on the solution surface were found to be replaced by LiFOS molecules in an addition of LiFOS surfactant and vice-versa. In the ranges of higher concentration above critical micelle concentration (CMC) of each surfactant, it was concluded that the mixed micelle could be formed in the mixed system of both surfactants as well as in the mixed system of two kinds of ordinary hydrocarbon surfactants.     

Impact of Phosphoethanolamine Reverse Micelles on Lipid Oxidation in Bulk Oils

Phospholipids are important minor components in edible oil that play a role in lipid oxidation. Surface active phospholipids have an intermediate hydrophilic–lipophilic balance value, which allows them to form association colloids such as reverse micelles in bulk oil. These association colloids can influence lipid oxidation since they create lipid–water interfaces where prooxidants and antioxidants can interact with triacylglycerols. In this study, we examined the formation of reverse micelles in a stripped oil system by dioleoyl phosphoethanolamine (DOPE) and the effect of these physical structures on lipid oxidation kinetics. The critical micelle concentration (CMC) of DOPE was approximately 200 µmol/kg oil at 45 °C. Oxidation kinetics studies showed that DOPE was prooxidative when it was above its CMC (400 and 1,000 µM), reducing the lag phase from 14 days (control) to 8 days. The addition of combinations of DOPE and dioleoyl phosphocholine (DOPC) resulted in formation of mixed micelles with a CMC of 80 µmol/kg oil at 45 °C. These mixed micelles were also prooxidative when concentrations (100 and 500 µM) were above the CMC, decreasing the lag phase from 14 to 8 days. These findings provide a better understanding of the role of phospholipids in lipid oxidation of edible oil and could contribute to better antioxidant solutions.     

Observing the Effects of Temperature and Surface Roughness on Cetyltrimethylammonium Bromide Adsorption Using a Quartz-Crystal Microbalance with Dissipation Monitoring

The effects of temperature and surface roughness on the mass and viscoelasticity of an adsorbed surfactant layer were monitored using a quartz crystal microbalance with dissipation monitoring (QCM-D). Adsorption isotherms at 30, 40, 50, and 60 °C and at two different roughnesses on gold were measured for cetyltrimethylammonium bromide (CTAB). All isotherms displayed an increase in mass and dissipation as surfactant concentration was increased to its critical micelle concentration (CMC). Above the CMC, adsorption reached a peak followed by a slight decrease to a plateau at the equilibrium adsorption value. As the temperature was increased, the adsorbed mass above the CMC decreased. The adsorbed mass decreased further by increasing substrate roughness, while the dissipation remained unchanged within experimental uncertainty. Dynamic adsorption experiments were also conducted at various temperatures for select concentrations above and below the CMC, providing evidence for the importance of different adsorption mechanisms as a function of both surfactant concentration and surface roughness.