A Systematic Study of Mixed Surfactant Solutions of a Cationic Ester-Bonded Dimeric Surfactant with Cationic, Anionic and Nonionic Monomeric Surfactants in Aqueous Media

A novel cationic biodegradable dimeric (gemini) surfactant, ethane-1,2-diyl bis(N,N-dimethyl-N-hexadecylammoniumacetoxy) dichloride (16-E2-16), containing an ester-linked spacer was synthesized. Its pure and mixed micellization properties with monomeric surfactants cetyl trimethyl ammonium chloride, cetyl pyridinium chloride, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, cetyl alcohol ethoxylate (20EO) and tert-octylphenol ethoxylate (9.5EO) were investigated by surface tension measurements at 30 °C. The critical micelle concentration (CMC) of 16-E2-16 is well below that of cetyl trimethyl ammonium chloride containing the same number of carbon atoms in the hydrophobic tail per polar head. At different mole fractions of the gemini surfactant, the CMCs of the gemini-conventional binary mixtures were determined and were found to be less than the ideal CMC values in all the cases indicating synergistic interactions. Aggregation number and Stern–Volmer constant, obtained by the fluorescence quenching technique, also support the synergistic behavior of the surfactant systems.     

Interactions Between a Sulfobetaine-Type Zwitterionic Gemini Surfactant and Fatty Acid Alkanolamide in Aqueous Micellar Solution

The critical micelle concentration (CMC) of 1,2-bis[N-methyl-N-(3-sulfopropyl)-alkylammonium]-ethane betaine (GCS12) was measured using a tensiometric method in the presence of inorganic salts. Inorganic salt has a little impact on the surface tension and CMC of zwitterionic gemini surfactant. The CMC value of GCS12 is 0.07 mmol/L in distilled water, while all CMC values are around 0.04–0.05 mmol/L in the presence of 0.5 % NaCl, 2 % NaCl, and 2 % NaCl + 0.05 % CaCl₂. The interactions between GCS12 and non-ionic surfactant lauric acid diethanolamide (CDA) were investigated by measuring the CMC of their mixtures at different molar ratios. CDA and GCS12 form mixed micelles and exhibit synergism when the mole fraction of CDA is higher than 0.25. Both the steric effect of the head group and GCS12 charge affect the formation and stability of the mixed micelles. Small amounts of GCS12 with a lower CMC penetrate into the micelle of nonionic surfactant with a higher CMC and reduce its degree of hydration inducing an attractive interaction between the two surfactants.     

Effect of Head Groups,Temperature, and Polymer Concentration on Surfactant—Polymer Interactions

The micellization behaviour of sodium dodecyl sulphate, sodium dodecylbenzenesulfonate, hexadecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, and cetylpyridinium chloride in water and in aqueous solutions of polyethylene oxide (PEO, molecular weight = 100,000) having concentrations (0.005–0.04 %, w/v) has been studied at different temperatures (288.15–318.15 K) using conductivity, surface tension, and viscosity methods. From conductivity measurements various micellar parameters, like critical micellar concentration (CMC), critical aggregation concentration (CAC), polymer saturation point (PSP), degree of ionization (β), and standard free energy of transfer ( \( \Delta G_{t}^{0} \) ), have been calculated. CAC values have been found to decrease with polymer concentration and increase with temperature. However, the PSP values increase with both polymer concentration and temperature for all surfactants. Similar parameters have also been calculated from surface tension data (CMC^σ, CAC^σ, PSP^σ) along with other parameters such as maximum surface excess concentration at the air/water interface ( \( \Gamma_{\hbox{max} } \) ), minimum area per molecule (A _min), and packing parameter (p). The CMC^σ, CAC^σ, and PSP^σ values are smaller than the corresponding CMC, CAC, and PSP values, but both show similar behaviour with temperature and concentration of polymer. Various parameters indicate that the presence of the aromatic ring in the head group of surfactant decreases its interaction with PEO, whereas the increased hydrophobicity in the tail leads to stronger interactions with PEO. Viscosity studies further supplement the conclusions drawn from the above results.     

An Alternative Approach for Determining Critical Micelle Concentration: Dispersion of Ink in Foam

The present work investigates the critical micelle concentration (CMC) of nonionic surfactant solutions using a new approach by monitoring the dirt dispersion (DD) defined as the amount of dirt absorbed by foam using India ink as a model dirt. DD has so far been studied qualitatively by eye estimation. Our quantification studies show that DD increases with increasing surfactant concentration and reaches a maximum. After this, it decreases and becomes very small. The concentration for which DD is maximum corresponds to the CMC, as determined from surface tension measurements. The CMC of natural surfactants obtained from plants Sapindus mukorossi, Albizia procera, Juglans regia, Zephyranthes carinata, and Acacia concinna was determined. The CMC obtained by DD are in reasonably good agreement with those obtained using the surface tension method. The DD method is easy, rapid, and inexpensive and can become an effective tool for estimating the CMC.     

Determination of Critical Aggregation Concentration in the Poly-(vinylpyrrolidone)–Sodium Dodecyl Sulfate System by Capillary Electrophoresis

We introduce an alternative separation method, i.e., capillary electrophoresis to examine the polymer/surfactant interaction. The migration behavior of the poly-(vinylpyrrolidone)–sodium dodecyl sulfate (PVP–SDS) model system was screened under a high electrical field for seven different PVP initial concentrations. From the electrophoretic mobilities of formed polymer–surfactant species, the critical aggregation concentration (CAC) of SDS for PVP was determined. The CAC value in the present study was very well matched with the CAC values of this system reported by alternative methods. A strong interaction between polymer and SDS under CAC concentration was observed and the independence of CAC on polymer concentration was experimentally demonstrated.     

Effects of the Polypropylene Oxide Number on the Surface Properties of a Type of Extended Surfactant

The surface properties of 5 extended surfactant C_12–14P _mE₂S solutions in pure water and 0.1 M NaCl were investigated through surface tension and electrical conductivity measurements. The surface properties measured include the critical micelle concentration (CMC), critical surface tension (γ_cmc), maximum surface excess concentration (Γ_max), minimum area occupied per surfactant molecule (A_min), and efficiency in surface tension reduction (pC₂₀). The CMC values of the 5 surfactants decreased with increasing polypropylene oxide number (PON) and were higher than those obtained in 0.1 M NaCl. The Γ_max values showed a downward trend whereas the A_min values exhibited an upward trend with increasing PON without NaCl. The Γ_max values were higher and the A_min values were lower than those obtained without 0.1 M NaCl. The CMC values increased at elevated temperatures. The CMC values of C_12–14P₃E₂S, C_12–14P₅E₂S, and C_12–14P₈E₂S were similar but were markedly lower than those of C_12–14E₂S at different temperatures. When PON was less than 12, the log CMC value decreased linearly with increasing PON in the absence of salt, and the relationship between pC₂₀ and PON was linear. But in the presence of 0.1 M NaCl, the log CMC value decreased exponentially with increasing PON.     

Surface and Aggregation Properties of Synthesized Cetyl Alcohol Based Bis-Sulfosuccinate Gemini Surfactants in Aqueous Solution

A series of cetyl alcohol based anionic bis‐sulfosuccinate gemini surfactants (BSGSCA1,4; BSGSCA1,6 and BSGSCA1,8) with different spacer lengths was prepared using dibromoalkanes. The surfactant structure was elucidated using elemental analysis, Fourier transform infrared spectroscopy (FT‐IR) and nuclear magnetic resonance spectroscopy (NMR). Surface tension measurements were used to determine the critical micelle concentration (CMC), the surface tension at the CMC (γ_CMC), surface pressure at the CMC (π_CMC) and efficiency of adsorption (pC20). On the basis of surface studies, the CMC and γ_CMC decreases with increasing length of the spacer group. The micelle aggregation number, determined by fluorescence quenching studies, increases with increasing surfactant concentration above the CMC. The micropolarity in the micelle increases with increasing length of the spacer and decreases with increasing surfactant concentration.     

温度及无机盐对LMEE和SDS混合溶液表面张力的影响

通过表面张力的测定,研究了温度和不同无机盐对月桂酸甲酯乙氧基化物(laurylmethylesterethoxylate,简称LMEE)与十二烷基硫酸钠(SDS)复配物表面张力及临界胶束浓度(CMC)的影响。研究表明:混合体系的CMC在很宽的复配比例内出现最低值,25℃、未加无机盐时可使CMC最低降至3 8×10-5mol/L;温度对复配体系表面张力的影响较小,温度上升复配物的CMC略有降低。3种价态无机盐的加入均可使复配物的CMC有所降低,但与单一表面活性剂相比,温度和无机盐对复配物的CMC影响均不大,说明复配体系的抗温变及抗盐能力均有增强。     

Investigation of Mixing Behavior of both a Conventional Surfactant and Different Inorganic Salts with a Cationic Gemini Surfactant in Aqueous Solution

N,N′-bis [3-(dodecanoylamino)propyl]-N,N,N′,N′-tetramethylhexane-1,6-diaminium dibromide is a cationic Gemini surfactant including quaternary ammonium salt with amide groups. Critical micelle concentration (CMC) and some thermodynamic parameters of the cationic Gemini surfactant were investigated using surface tension and conductivity methods. Mixed micellization of binary mixtures of the cationic Gemini surfactant with a conventional surfactant cetyl trimethylammonium bromide (CTAB) was investigated using the conductometric method at five different temperatures ranging from 303.15 to 323.15 K. CMC, micellar ionization degree (α_m), counterion binding constant (g₁), interaction parameter (β), and activity coefficients ( and ) of mixed systems were found out from data of conductivity at different mole fractions for all studied temperatures. Additionally, the effects of some inorganic salts with different concentrations on the surface properties of cationic Gemini surfactant were examined by surface tension measurements. Some surface properties of the pure cationic Gemini surfactant and mixed salts systems were calculated using the data of surface tension.     

Structural and Physicochemical Properties of a Polymerizable Surfactant Synthesized from <Emphasis Type="Italic">N</Emphasis>-Methylol Acrylamide

A new polymerizable nonionic surfactant with reactive vinyl groups has been synthesized from N‐methylol acrylamide using a two‐step procedure. The structure of the surfactant molecule was characterized by Fourier transform infrared, ¹H nuclear magnetic resonance and mass spectroscopy. The surface active properties alongside its self‐assembly properties were investigated by surface tension, electrical conductivity, and fluorescence spectroscopy measurements. As compared with other nonionic surfactants, this study showed that this polymerizable surfactant possesses slightly a higher critical micelle concentration (CMC) value and the surface tension value at CMC. The obtained CMC values were compatible among measurements, ca. 0.02–0.038 M. The evidence of micelle formation also provided by the zeta potential measurements and the obtained zeta potential values showed that the polymerizable surfactant solutions had limited stability. The hydrolysis stability and solubility of the polymerizable surfactant were also investigated. The solubility results have shown that it was soluble in polar solvents while insoluble in nonpolar solvents both at room temperature and 40 °C. The acidic and basic hydrolysis of the surfactant increased as the temperature increased and the hydrolysis stability was 180 min (basic medium) and 55 min (acidic medium) at 80 °C.     

Surface Chemical Properties and Micellization of Disodium Hexadecyl Diphenyl Ether Disulfonate in Aqueous Solution

The surface tension of disodium hexadecyl diphenyl ether disulfonate (C₁₆‐MADS) was measured at different NaCl concentrations (0.00–0.50 mol L^?1) and temperatures (298.0–318.0 K) using the drop‐volume method. The results show that, with increasing temperature, the critical micelle concentration (CMC) of C₁₆‐MADS increases slightly, but the maximum surface adsorption capacity (Γ_max) at the air–water interface decreases. When the concentration of NaCl was increased from 0.00 to 0.50 mol L^?1, the CMC of C₁₆‐MADS decreased from 1.45 × 10^?4 to 4.10 × 10^?5 mol L^?1, but the surface tension at the CMC (γ_cmc) was not affected. When the concentration of NaCl was increased at 298.0 and 303.0 K, the Γ_max of C₁₆‐MADS increased. When the temperature was increased from 308.0 to 318.0 K, the surface excess concentration (Γ_max) of C₁₆‐MADS abnormally decreased from 2.26 to 1.41 μmol m^?2 with increasing NaCl concentration. The micellization free energy () decreased from ?63.98 to ?76.20 kJ mol^?1 with increase of temperature and NaCl concentration. The micellar aggregation number (N_m) of disodium hexadecyl diphenyl ether disulfonate (C₁₆‐MADS) was determined using the molecule fluorescence probe method with pyrene as probe and benzophenone as quencher. The results show that an appropriate N_m could be measured only at surfactant concentration above the CMC. The N_m increased with an increase in C₁₆‐MADS concentration, but the micropolarity in the micelle nucleus decreased. The temperature had little effect on N_m. Compared with typical single hydrophilic headgroup surfactants, aggregates of C₁₆‐MADS exhibit different properties.     

Surface Activity Properties and Aggregation Behaviors of Partially Fluorinated Gemini Surfactants in Aqueous Solution

The surface activity and aggregation behavior of partially fluorinated gemini surfactant N,N′‐bis(3‐perfluorohexyl‐2‐hydroxypropyl)‐N,N′‐dipropanesulfonylhexylenediamine (N‐6‐Sul) was studied by surface tension, resonance light scattering and fluorescence spectra measurements. The critical micelle concentration (CMC) values obtained by the three methods are in good agreement. The surface activity parameters such as the effectiveness of surface tension reduction (Π_cmc), the maximum surface excess concentration (Γ_max) and the minimum surface area per molecule (A_min) were obtained through surface tension curves. The effects of pH, inorganic salts and temperature on the surface activity were also investigated. The morphology and size of the aggregates of N‐6‐Sul were examined by transmission electron microscopy (TEM). The results show that the partially fluorinated gemini surfactant N‐6‐Sul has many advantages such as high surface activity, low CMC value, great salt tolerance and temperature resistance.     

Salt‐Induced Modulation of the Krafft Temperature and Critical Micelle Concentration of Benzyldimethylhexadecylammonium Chloride

In this work, the effect of some sodium salts on the Krafft temperature (T_K) and critical micelle concentration (CMC) of benzyldimethylhexadecylammonium chloride (C16Cl) in aqueous solution has been studied. It was observed that the T_K can be modulated to lower and higher values and the CMC can be depressed significantly upon the addition of the electrolytes. More chaotropic Br^? and I^? raise the T_K with an increase of the concentration of the ions. On the other hand, less chaotropic NO₃^? initially lowers and then raises the T_K. Kosmotropic F^?, SO₄^2? and CO₃^2? gradually lower the T_K with increasing concentration of the electrolytes. The more chaotropic ions form contact ion pairs with the surfactant and decrease the solubility with a consequent increase in the T_K. On the other hand, kosmotropic ions, being extensively hydrated in the bulk, remain separated from the surfactant by hydrated layers of water molecules. As a result, a significant electrostatic repulsion exists between the charged headgroups of the surfactant, resulting in a decrease in the T_K. The CMC of the surfactant decreases significantly in the presence of these ions. The surface tension at the CMC (γ_CMC) also decreases in the presence of all the salts except for F^?. The electrostatic repulsion between the charged headgroups is significantly reduced because of screening of the surface charge of both micelles and adsorbed monolayers by the associated counterions, resulting in a decrease in both the CMC and γ_CMC.     

Alcohols Effect on Critic Micelle Concentration of Polysorbate 20 and Cetyl Trimethyl Ammonium Bromine Mixed Solutions

In this research, the micellar behavior of a cationic surfactant, cetyl trimethyl ammonium bromide (CTAB) and an nonionic surfactant, polysorbate 20 (Polyoxyethylene (20) sorbitan monolaurate) in different alcohol solutions media was investigated over the temperature range 293.15–313.15 K. The interaction between two surfactants in binary systems can be determined by calculating the values of their β parameters. The critical micelle concentrations (CMC) of the micelles were determined from the surface tension, the conductivity at different temperatures. The CMC behavior of CTAB and polysorbate 20 was analyzed in terms of the effect of temperature and the increase in the alcohol carbon chain. Changes in the critical micelle concentration of mixed surfactant systems of different alcohol solutions were measured. The CMC decreased sharply as the hydrocarbon chain length of the alcohols becomes larger. This shows that the more hydrophobic alcohols are, the more marked a decrease in CMC is observed.     

Influence of sodium dodecyl sulfate on the characteristics of bovine serum albumin solutions and foams

Results from surface tension measurements on mixed solutions of the protein bovine serum alburnin (BSA) and an anionic surfactant (SDS: sodium dodecyl sulfate) suggested that at an air-liquid interface, adsorption was affected by the protein-surfactant interaction and by the relative concentration of each component in solution. Two plateaus corresponding to the critical aggregation concentration (CAC) and the critical micelle concentration (CMC) of SDS, respectively, were observed in the surface tension isotherms of SDS in the presence of BSA. The CAC and CMC depended on the concentration of BSA. Effects of SDS concentration on the conformational changes of BSA were investigated by Fourier transform-Raman spectroscopy. The results showed that the contents of α-helix decreased while the contents of random coil increased. The presence of the anionic surfactant SDS had a negative influence on the way that proteins adsorb at an air-liquid interface, leading to the change of behavior of protein-stabilized film.     

Surface Activity and Performance Properties of Gemini Salts of Linear Alkylbenzene Sulfonate in Aqueous Solution

Gemini salts of linear alkylbenzene sulfonate (LABS) were prepared by neutralization of sulfonic acid with a series of low-molecular-weight diamines in aqueous solution. The equilibrium surface activity of Gemini salts of LABS was determined by measuring the surface tension as a function of surfactant concentration to determine the critical micelle concentration (CMC), surface tension at the CMC (γ_CMC), and the area per molecule at the air-water interface (Ų). Electrical conductivity was measured as a function of surfactant concentration to determine the CMC and counterion binding. Dynamic surface tension was measured using a bubble pressure tensiometer to infer the rate at which the surfactant migrates to the air-water interface. Equilibrium interfacial tension against mineral oil was measured using a spinning drop tensiometer. Dynamic interfacial tension was measured using a drop volume tensiometer. The surface tension, CMC, and interfacial tension of Gemini salts of LABS decreased compared to monovalent organic and inorganic salts. The CMC decreases with increasing molecular weight of the diamine spacer group. Dynamic surface and interfacial tension of Gemini salts of LABS are lower than monovalent salts. The foam volume of Gemini salts of LABS was determined using a high shear blender test. The foam volume of Gemini salts of LABS is lower than monovalent salts and depends on the size of the spacer group. Hard-surface cleaning was measured using artificial soil applied to white Formica tiles. Soil removal was determined by optical reflectance as a function of abrasion cycles. Gemini salts of LABS show reduced hard-surface cleaning performance compared to monovalent salts. Detergency of different types of soils on cotton and polyester/cotton fabric was determined by optical reflectance measurements. Gemini salts of LABS show improved cleaning performance compared to monovalent salts. Cleaning performance increases with increasing molecular weight of the diamine spacer group. In situ neutralization of LABS with organic diamines is a simple and efficient way to prepare anionic Gemini surfactants for industrial scale applications.     

Aggregation and Phase Separation Phenomenon of Amitriptyline Hydrochloride Under the Influence of Pharmaceutical Excipients

The interaction between the amphiphilic drug amitriptyline hydrochloride (AMT) and the nonionic surfactants used in drug delivery has been investigated. Herein, we report the micellization behavior of AMT in presence of ethoxylated alkyl phenols in aqueous medium and the clouding phenomenon in the absence and presence of different nonionic surfactants in buffer solution. The values of critical micelle concentration (CMC) of AMT obtained using the conductivity method, decrease as nonionic surfactant concentration increases. With an increase in temperature, the CMC first increases and then decreases. At 303.15 K, the maximum CMC values were obtained with or without nonionic surfactant. The results obtained indicate attractive interactions (synergism) between the two mixing amphiphiles in solution. The experimentally obtained critical micelle concentration (CMC) values are always lower than ideal CMC values. Micellar mole fraction (X₁) values, calculated by different proposed models, show the contribution of nonionic surfactant concentration. At a fixed drug concentration (50 mmol kg^?1) and pH (=6.7) nonionic surfactants show continuous increase in cloud point (CP). Increase in drug concentration and pH, in the presence of fixed amounts of nonionic surfactant, increases and decreases the CP, respectively.     

Synthesis and some studies on fluorinated cationic surfactants: surface and biocidal activities

Three fluorinated cationic surfactants were prepared by condensing N-(2-bromoethyl)perfluoroalkylamides with stoichiometric amounts of pyridine, triethanolamine, and triethylamine to produce three quaternary ammonium salts. The surface and biocidal properties of these surfactants were investigated to find the relation between the structure of the hydrophilic portion of the compounds and their efficiency as biocides. The properties studied included critical micelle concentration (CMC), effectiveness (II_CMC), surface excess concentration (T_max), and area occupied by a molecule (A_min). Free energies of micellization (ΔG _mic ^o) and adsorption (ΔG _ads ^o) of the surfactants in aqueous solution were calculated. The minimal inhibitory concentrations of the prepared compounds were tested against five strains as representative group of microorganisms.     

Synthesis and Properties of Lipoamino Acid–Fatty Acid Mixtures: Influence of the Amphiphilic Structure

The acylation of amino acids by acid chlorides with from 8 to 12 carbon atoms in alkaline aqueous medium following Schotten–Baumann reaction results in sodium salts of a N ^α-acylamino acid and fatty acid mixture. The latter are present in a proportion from 40 to 60%. These compositions represent mixtures of amphiphilic anionic surfactants. Together they contribute to the properties of the formulation. Measurements of the surface-active properties of these formulations, such as critical micelle concentration (CMC), surface tension at the CMC (ST), foaming capacity (FC) and foaming stability (FS), show that surfactant mixtures with the longest chain have the most desirable properties. They are comparable to commercial petroleum-based surfactants. Thus, the CMC, ST and CM values of the formulation obtained starting from leucine and dodecanoyl chloride (310 mg/l, 30.1 mN/m and 200%, respectively) are similar to, and even better than, sodium dodecylsulfate (290 mg/l, 39.1 mN/m and 230%, respectively).     

Synthesis and Surface Properties of Anionic Gemini Surfactants having N-acylamide and Carboxylate Groups

A straightforward synthetic strategy to an anionic gemini surfactant having both N-acylamide and carboxylate groups in a molecule has been demonstrated. The surface properties of the anionic gemini surfactant, such as CMC (critical micelle concentration), C₂₀ (the concentration required to reduce the surface tension of the solvent by 20 mN/m), γ _CMC (the surface tension at the CMC), ∏ _CMC (the surface pressure at the CMC), Γ _max (the maximum surface excess concentration at the air/aqueous solution interface), A _min (the minimum area per surfactant molecule at the air/water interface), and the CMC/C₂₀ ratio (a measure of the tendency to form micelles relative to adsorbtion at the air/water interface), have been studied. The influence of the different concentrations of NaCl on the surface properties of the gemini surfactant has been discussed. The results have shown that the CMC values decreased with an increase in the concentration of NaCl indicating that the Na⁺ preferentially adsorbs onto the surface of the charged aggregate and facilitates the aggregate growth by suppressing the main impediment of electrostatic repulsion among head groups. Additionally, the values of Γ _max are always higher in salt solutions as compared to those in pure water due to their salting out effect. The larger pC₂₀ value indicates that the surfactant adsorbs more efficiently at the air/water interface and reduces surface tension more efficiently. In addition, the geminis in water show little or no break in their specific conductance versus surfactant molar concentration plots. This is attributable to protonation of the carboxylate group and strong Na⁺ release during micellization.