The Synergism Effect Between Sodium Dodecylbenzene Sulfonate and a Block Copolymer in Aqueous Solution

The synergistic behavior of sodium dodecylbenzene sulfonate (SDBS) with poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) block copolymer was studied using surface tension measurements. The surface tension of single and mixed solutions of SDBS and the block copolymer in this study was measured at different concentrations and at 25 °C. The critical micelle concentration (CMC) of these solutions was determined from the surface tension measurements. The SDBS gives higher CMC values than those of the block copolymer. The results show that the CMC value of SDBS decreases as the molar ratio of SDBS increases in the mixture solution with the block copolymer. The surface parameters of adsorption and micellization for single and mixed solutions were investigated. The results show that the surface and micellization properties of SDBS were improved as a result of mixing with the block copolymer. The mole fractions in the micelles and interaction parameters of the mixed solutions were calculated. The foam stability of single and mixed solutions at 25 °C was determined. The results show that the SDBS has more foam stability than the block copolymer and the foam stability increases as the molar ratio of SDBS increase in mixed solution of it with block copolymer.

Adsorption of Anionic–Cationic Surfactant Mixtures on Metal oxide Surfaces

This research evaluates the adsorption of anionic and cationic surfactant mixtures on charged metal oxide surfaces (i.e., alumina and silica). For an anionic-rich surfactant mixture below the CMC, the adsorption of anionic surfactant was found to substantially increase with the addition of low mole fractions of cationic surfactant. Two anionic surfactants (sodium dodecyl sulfate and sodium dihexyl sulfosuccinate) and two cationic surfactants (dodecyl pyridinium chloride and benzethonium chloride) were studied to evaluate the effect of surfactant tail branching. While cationic surfactants were observed to co-adsorb with anionic surfactants onto positively charged surfaces, the plateau level of anionic surfactant adsorption (i.e., at or above the CMC) did not change significantly for anionic–cationic surfactant mixtures. At the same time, the adsorption of anionic surfactants onto alumina was dramatically reduced when present in cationic-rich micelles and the adsorption of cationic surfactants on silica was substantially reduced in the presence of anionic-rich micelles. This demonstrates that mixed micelle formation can effectively reduce the activity of the highly adsorbing surfactant and thus inhibit the adsorption of the surfactant, especially when the highly adsorbing surfactant is present at a low mole fraction in the mixed surfactant system. Thus surfactant adsorption can be either enhanced or inhibited using mixed anionic–cationic surfactant systems by varying the concentration and composition.

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Micellization of Cetyl Triphenyl Phosphonium Bromide Surfactant in Binary Aqueous Solvents

The effect of the different binary aqueous organic solvents viz. 1,4-dioxane, acetonitrile, dimethylsulfoxide, ethylene glycol, and methanol, on the micelle formation and thermodynamics of a cationic surfactant cetyl triphenyl phosphonium bromide has been studied conductometrically at 298–318 K. From the conductivity data critical micelle concentration, degree of counter ion dissociation (α) and thermodynamic parameters of micellization have been determined. It is observed that micellization tendency of the surfactant decreases in the presence of binary aqueous solvents. The entropies of micellization are all positive, and they compensate the enthalpies of the process.

Synthesis of Ethoxylated Alkyl Sulfosuccinate Surfactants and the Investigation of Mixed Solutions

A series of ethoxylated sodium monoalkyl sulfosuccinate (ESMASS) ester surfactants were prepared by reacting polyethylene glycol (molecular weight 600) with sodium monoalkyl sulfosuccinate (SMASS). The esters were prepared by reacting octyl, lauryl, or cetyl alcohol with sodium sulfosuccinate (SSS) to prepare E(14)SMOSS, E(14)SMLSS, and E(14)SMCSS. The chemical structures of the prepared surfactants were confirmed by Fourier transform infrared (FTIR) and ¹H-NMR spectroscopy. The surface tension of the synthesized surfactants was measured at 25 °C individually or mixing at different molar fractions with sodium dioctyl sulfosuccinate. The surface active properties were calculated and the micellization process of the mixture was investigated. The molar ratio of anionic (SDOSS) and anionic–nonionic surfactant moieties [E(14)SMOSS, E(14)SMLSS, and E(14)SMCSS] in the mixed aggregates were deduced using the regular solution approximation equations. Depending on the critical micelle concentration values measured for each surfactant individually, and as well as the mixed systems, the minimum surface tension was exhibited at a ratio of 0.6 SDOSS:0.4 E(14)SMCSS. The micellar composition of the mixed aggregates were explained and discussed based on the effect of their chemical structures. The activity coefficient (f ₁, f ₂), interaction parameter (β), and ideality of anionic–nonionic mixed aggregates were evaluated.

Synthesis of Unsymmetrical Bolaform Surfactants with a Sulfonate Group and a Carboxyl Group

Three unsymmetrical bolaform surfactants with different aromatic rings and a ω-carboxyalkyl chain were synthesized and their molecular structures were characterized by ESI–MS and ¹H NMR. The percentages of conversion of alkylation were judged by the iodine value measurements and the effect of reaction temperature on sulfonate content of synthesized products has also been discussed.

Synthesis of Cleavable Aryl Sulfonate Anionic Surfactants and a Study of their Surface Activity

A series of cleavable aryl sulfonate anionic surfactants were synthesized from cyanuric chloride, aliphatic amine and H-acid mono sodium salt. Their structures were identified by ¹H NMR, Infrared Spectrum (IR) and Elementary Analysis (EA). Their critical micelle concentrations (CMC) in aqueous solutions at 25 °C were determined by a steady-state fluorescence probe method and a surface-tension method. With the increasing length of the carbon chain, the value of their CMCs and surface tensions under CMC (γ _CMC) initially decreased and then reached a minimum (respectively 2.63 × 10⁻⁵ mol L⁻¹ and 28.29 mN m⁻¹) when the carbon number was 10. The CMC and γ _CMC then increased when the carbon number was increased to 12. The results showed that, compared with sodium dodecyl benzene sulfonate (SDBS), such kinds of surfactants have much lower surface adsorption amounts and greater molecular areas on the aqueous surface.

Pure N-Alkylaminopropionic Acid and N-Alkylaminodipropionic Acid Sodium Salts: Synthesis, Characterization, and Physicochemical Properties

Fourteen pure β-aminopropionic acid amphoteric surfactants were synthesized from methyl acrylate using primary amines. The synthesis was done in two steps. First, Michael addition of a primary amine to methyl acrylate gave two separable addition products. Second, because the resulting esters gave, by the classical saponification procedure, undesired retro-Michael products, they were treated with sodium trimethylsilanolate to give the corresponding pure anhydrous acid salt under mild non-aqueous reaction conditions. Two types of amphoteric surfactants were obtained: the monocarboxylate and the dicarboxylate series. The pure surfactants were characterized by IR, ¹H NMR, and ¹³C NMR spectroscopy. The surfactant critical micelle concentrations were evaluated. From these the Gibbs free energy of micellizations [∆G(–CH₂–)_mic] were calculated. These are related to the methylene units that contribute an average of −1.0 (±0.3) kJ mol⁻¹ for both the monocarboxylate and the dicarboxylate series.

A Rheological Approach to Viscoelastic Worm-Like Micelles of Tunable Properties

The rheological behavior of micellar solutions of cationic surfactant, cetyl trimethyl ammonium bromide in the presence of a salt (KBr) and a co-surfactant (n-octanol) were analyzed. Shear viscosity and shear moduli were measured as a function of concentrations of the co-surfactant and additive. When these concentrations attained a certain critical threshold value, the micellar solution was found to exhibit a nonlinear viscoelastic behavior. It is due to the formation of supramolecular structures, which has been described by the Maxwell model of a viscoelastic fluid typical of worm-like micelles. The rheological behavior was also analyzed using Carreau and Carreau–Gahleitner models which were found to be in good agreement with the experimental results.

Surface and Biological Activity of Some Novel Cationic Surfactants

In this study, steps were taken toward the development of bactericidal and fungicidal synthetic cationic surfactants by reacting decyl, dodecyl or tetradecyl amine with acetic or hydrochloric acid to produce a series of amine salts which consequently converted to copper or cobalt cationic complexes via complexing the first series compounds with copper (II) or cobalt (II) ions. Surface properties such as interfacial tension and emulsifying power of these surfactants were investigated. The surface parameters including critical micelle concentration (CMC), maximum surface excess (Γ_max) and minimum surface area (A _min) were studied. Free energy of micellization (ΔG°_mic) and adsorption (ΔG°_ads) were calculated. The antimicrobial activity was determined via the inhibition zone diameter of the prepared compounds, which measured against five strains of a representative group of microorganisms. FTIR spectra, elemental analysis and H¹ NMR spectrum were performed to confirm compound structure and purity.

Micellization Behavior of Mixtures of Sodium Dioctylsulfosuccinate with Sodium Dodecylsulfate in Water

Mixtures of sodium dioctylsulfosuccinate (AOT) and sodium dodecylsulfate (SDS) that were studied in water at 25 °C by using surface tension, conductance, emf and fluorescence emission methods exhibit synergism in the region where the mole fraction of AOT in the bulk solution (α ₁) is less than 0.7 and ideality in the region where α ₁ ≥ 0.7. The molal conductance versus the concentration behavior of an aqueous solution of AOT is found to be different from that of other ionic surfactants with the exception of bile salts. Composition of the mixed micelle was evaluated and discussed using the Rubingh’s and the Rodenas–Valiente–Villafruela (RVV) treatments. The values of the counter ion binding constant determined from the emf data show that the counter ion binding behavior of the mixed micelle is controlled entirely by AOT. The free energy for mixed micelle formation was calculated using a modified equation. The aggregation number determined by the fluorescence quenching method indicated that in the mixed micelle, as α ₁ increases, the number of molecules of AOT remains constant and that of SDS decreases. Characteristics of the adsorption layer of the mixed surfactant system were also examined using the theoretical treatment of Rosen and Hua.

Environmentally Friendly Vegetable Oil Microemulsions Using Extended Surfactants and Linkers

Microemulsion formation of triglyceride oils at ambient conditions (temperature and pressure) and without the addition of co-oil and/or alcohols is challenging at best. Undesirable phases, such as macroemulsions, liquid crystals and sponge phases, are often encountered when formulating triglyceride microemulsions. The purpose of this study is to investigate the use of extended surfactants, lipophilic linkers, and hydrophilic linkers in enhancing triglyceride solubilization and interfacial tension reduction. We have studied two classes of extended surfactants, linear alkyl polypropoxylated sulfate (LAPS) surfactants and linear alkyl polypropoxylated ethoxylated sulfate (LAPES) surfactants. Linkers evaluated were oleyl alcohol (lipophilic linker), sodium mono and dimethyl naphthalene sulfonate (SMDNS), and polyglucoside (hydrophilic linkers). Oils studied include olive, peanut, soybean, canola and sunflower oils. The effect of electrolyte concentration on microemulsion phase behavior was studied. The microemulsion “fish” diagram was obtained by plotting the total surfactant and linker concentrations versus the electrolyte concentration. We were able to form Winsor Type I, II, III and IV microemulsions at ambient conditions and without co-oil or short and medium chain length alcohol addition. Winsor Type III and IV triglyceride microemulsions are particularly useful in numerous applications such as cosmetics, vegetable oil extraction and soil remediation.

The Characteristic Curvature of Ionic Surfactants

Characterizing the hydrophilic-lipophilic nature of a surfactant molecule has been a challenge for colloid scientists and technologists. The hydrophilic-lipophilic balance (HLB), the packing factor, the phase inversion temperature (PIT) and the natural curvature of the surfactant are all terms that seek to address this issue. In this article we build on the hydrophilic–lipophilic difference concept (HLD) (Salager et al. Langmuir, 16, 5534–5539, 2000) to develop a methodology to determine a characteristic curvature (Cc) for ionic surfactants based on the phase behavior of mixed ionic surfactant microemulsions. In essence, the method consists of evaluating the shift in optimal electrolyte concentration as a function of the mole fraction of the test surfactant in a mixture with a reference surfactant, sodium dihexyl sulfosuccinate (SDHS) and applying the appropriate HLD equation for ionic surfactant mixtures to determine Cc. The values of Cc were determined for a range of surfactants, including sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS), sodium naphthenate, and others. The method was also extrapolated to nonionic additives and hydrophilic linkers. It was observed that the calculated values of Cc were similar to those predicted by group contribution models, however the proposed method can be used even for complex surfactant mixtures. Finally, when Cc values were compared to apparent packing factor and HLB values, it was found that Cc is correlated with the apparent packing factor of ionic surfactants, and that Cc correlates with the HLB value for nonionic amphiphiles. The physical interpretation of Cc, and its potential application in the Net-Average Curvature equation of state for oil-surfactant-water systems is discussed.

Study of Foaming Properties and Effect of the Isomeric Distribution of Some Anionic Surfactants

Using different reaction conditions of photosulfochlorination of n-dodecane, two samples of anionic surfactants of sulfonate type are obtained. Their micellar behavior has been already reported and the relationship between their isomeric distribution and their chemical structures and micellar behaviors have been more thoroughly explored. In this investigation, we screened the foaming properties (foaming power and foam stability) by a standardized method very similar to the Ross–Miles foaming tests to identify which surfactants are suitable for applications requiring high foaming, or, alternatively, low foaming. The results obtained for the synthesized surfactants are compared to those obtained for an industrial sample of secondary alkanesulfonate (Hostapur 60) and to those of a commercial sample of sodium dodecylsulfate used as reference for anionic surfactants. The foam formation and foam stability of aqueous solutions of the two samples of dodecanesulfonate are compared as a function of their isomeric distribution. These compounds show good foaming power characterized in most cases by metastable or dry foams. The highest foaming power is obtained for the sample rich in primary isomers which also produces foam with a relatively high stability. For the sample rich in secondary isomers we observe under fixed conditions a comparable initial foam height but the foam stability turns out to be low. This property is interesting for applications requiring low foaming properties such as dishwashing liquid for machines. The best results are observed near and above the critical micellar concentrations and at 25 °C for both the samples.

Influence of Ionic Surfactants on the Formation of Liquid Crystals in Oleic Acid/Glycol/Water Systems

The influence of surfactant structure on the formation of lamellar liquid crystals with very low surfactant concentration was investigated for systems composed of oleic acid, diethyleneglycol ethyl ether and water. Surfactants belonging to anionic and cationic families were checked: phosphated oleyl ether 3 EO (PO₃EO), triethanolamine oleate (TEAO) and sodium lauryl ether sulphate (SLES) as anionic surfactants and two alkyl trimethylammonium bromide type (C₁₂TAB and C₁₄TAB) as cationic surfactants. For each of the surfactants, the appropriate relationships between surfactant, oleic acid and glycol to furnish lamellar liquid crystals when these basic compositions were further diluted with water were established. The appropriate ranges of dilution allowing the liquid crystal formation were also determined. These liquid crystals presented an attractive appearance because of their transparency and high viscosity, although in the beginning of its formation, a short range of less viscous compositions (so called liquid/gel compositions) appears in some cases. Through water dilution, the initial surfactant percentages are noticeably reduced being possible liquid crystals with 2–5 wt% of surfactant.

Preparation and Application of Fluorinated Cationic Surfactants

Four fluorinated cationic surfactants were prepared by condensing 2,2,3,3, tetrafluoro-1-propyl chloroacetate with stoichiometric amounts of pyridine, 2-hydroxypyridine, 8-hydroxyquinoline and 8-hydroxyquinaldine to produce four quaternary ammonium salts. The surface and biocidal properties of these surfactants were investigated. Surface properties of their solutions including surface tension, critical micelle concentration (CMC), effectiveness (Π_cmc), maximum surface excess (Γ_max) and minimum surface area (A _min) were investigated with respect to different concentrations at 25 °C. Standard free energies of micellization and adsorption of the prepared surfactants in the aqueous solution were studied. The biocidal activity was determined via the inhibition zone diameter of prepared compounds which tested against six strains as a representative group of microorganisms.

Aggregation of Alcohols Ethoxylates in n-Heptane

The solubility and aggregation process of polyethoxylated non-ionic surfactants, of general formula C _i H_2i+1–(O–CH₂–CH₂) _j –OH with i = 6, 8, 10 and j = 3–6 (C _i EO _j ), in heptane were studied. The aggregation of C _i EO _j surfactants in heptane was investigated by using methylene blue (MB) as an absorption probe. In solutions of MB in the presence of these surfactants in heptane, at concentrations larger than the re-dissolution concentration, the UV bands associated to free MB (A ₁) and MB–EO complex (A ₂) were detected. The ratio of these intensities A ₂/A ₁, was used to study the kinetics of the complex formation in pure surfactant. The value of A ₂/A ₁ depends on the surfactant structure and the media wherein MB is dissolved, being larger in the pure surfactant than in heptane solutions. These results are explained in terms of solvent effect and aggregate structures on the complex formation.

Adsorption of Aroma Chemicals on Cotton Fabric in Different Aqueous Environments

Surfactants enhance adsorption of an aroma chemical on cotton fiber. Strong hydrophobic and electrostatic interactions between surfactant and fiber substrate result in higher adsorption of surfactant/aroma chemical aggregates than for the aroma chemical alone, with higher adsorption for cationic systems than for anionic systems. Adsorption is attributed to solution physical entrapment, hydrophobic interaction, dispersion forces, and interaction with surfactant molecules adsorbed on fiber. Log P and water solubility are important factors in aroma chemical adsorption. Hydrophobicity increased selective partitioning of aroma chemicals on the fiber surface particularly in the presence of surfactants. Statistical analyses indicate some evidence of polar–polar interaction between aroma chemicals and cellulose. With no surfactant, more adsorption is often observed in systems with a higher concentration of NaCl. The screening effect of electrolytes increases with the electrolyte reducing the energy of the liquid–solid interface. Lower interfacial energy results in increased adsorption of an aroma chemical on the fiber surfaces. Electrolyte screening affects aroma chemical adsorption most for anionic surfactant systems. Increase in the concentration of the electrolyte increases the screening effect that reduces the repulsive forces between the anionic molecules and weakly electronegative cotton fiber surfaces. In a cationic system, the screening effect of the electrolyte reduces adsorption of aroma chemicals with increased electrolyte concentration, due to the screening-reducing attraction between cationic surfactant molecules and the fiber surface. Chemical functionality shows a significant effect (alkanol ≥ ketone ≥ aldehyde > ester) on adsorption. Adsorption increased with increasing molecule ovality. Statistical analyses indicate that molecular shape within a chemical class of compounds influences adsorption of the aroma chemical.

Effects of Spacers on Surface Activities and Aggregation Properties of Anionic Gemini Surfactants

This present article employs four anionic Gemini surfactants with different spacer groups and investigates their physicochemical and aggregation properties. The critical micelle concentration (CMC), surface tension at CMC (γ_CMC) and C ₂₀ of these surfactants have been investigated using the du Nouy ring method. The aggregation number (N) was determined with intrinsic fluorescence quenching method using pyrene as a fluorescence probe and benzophenone as a quencher. Results show that these anionic Gemini surfactants have lower CMC and C ₂₀ values compared with those conventional ones and show higher surface activity. As expected, the spacer plays an important role in the aggregation properties of Gemini surfactants. Under experimental conditions, Gemini B–D with an alkoxylated group as spacer has a lower CMC and a higher aggregation number than Gemini A with methylene as spacer. For Gemini B–D, the CMC and aggregation number values decrease with the increasing flexible spacer length. The micropolarity also affects the aggregation of the present anionic Gemini surfactants. The micropolarity of micelle becomes low when the concentration of surfactants increases. Aggregation numbers of surfactants increase and fluorescence intensities decrease with the increasing concentration of NaCl. These results will help us to understand the relationship between the architectures of Gemini surfactants and their various properties in aqueous solution. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

Effect of Ionic Strength on the Interfacial and Bulk Properties of Unsymmetrical Bolaamphiphiles

By performing measurements of the equilibrium surface tensions of electrolyte solutions of three unsymmetrical bolaamphiphiles, each of which has an aromatic ring and a ω-carboxyalkyl chain in its molecular structure, we conclude that the carboxyl and sulfonate groups at both ends of the molecule—which enter the solution while the hydrophobic chain extends into the air—can force these surfactants to adopt a looped configuration which looks like the letter “U” upside-down, resulting in regular arrangements at the air/water interface and micelles in bulk solution. Surface tension measurements of these surfactants as a function of added salt reveal the limiting surface tension to be less sensitive to the ionic strength in LiCl solution and significantly sensitive to divalent Ca²⁺ and Mg²⁺ ions in hard water. This result reveals that the looped configuration of the molecule is the dominant factor in determining whether the molecules of this surfactant are sensitive to ionic strength or not. This paper also reports briefly on the effect of the interactions of divalent Ca²⁺ and Mg²⁺ ions with unsymmetrical bolaamphiphiles on the turbidity of hard water. These results suggest that the interactions of divalent Ca²⁺ and Mg²⁺ ions with carboxyl groups are strong, and the two breaks in the surface tension curves disappear. In 200 ppm hard water, the turbidity appears over just a small range of surfactant concentrations, showing that the presence of the Ca²⁺ and Mg²⁺ ions has little effect on the application of these surfactants.

Synthesis and Properties of Novel Antifungal Gemini Compounds Derived from <Emphasis Type="Italic">N</Emphasis>-Acetyl Diethanolamines

A series of new N-acetylated non-ionic and cationic gemini surfactants (3a–f) having dimeric structures derived from primary and tertiary amines with variably long tails (C₈–C₁₂–C₁₈) were synthesized. In addition, N-acetylated monomeric analogues 6a and 6b were prepared and their antifungal potency and surface properties were also determined. Critical micelle concentration (CMC), effectiveness of surface tension reduction (γ_CMC), surface excess concentration (Γ), and area per molecule at the interface (A) were also determined and the resulting values indicate that the cationic series is characterized by good surface-active and self-aggregation properties. For the first time, all surfactants were tested to evaluate their antifungal properties using the method for the broth macrodilution test (M27-A2, NCCLS). Four microbial strains were used to perform the study: Candida parapsilosis (ATCC 22019), C. albicans (ATCC 64548), and a wild-type strain of C. parasilosis and Saccharomyces cerevisiae (ATCC 9763). The antimicrobial activity was measured by yeast growth inhibition expressed as minimum inhibitory concentration (MIC) values. Results were compared to those obtained for their monomeric analogues and for a commercially available reference compound (Fluconazole). Gemini 3b, 3e and 3f were found to be the most potent compounds. The results show S. cerevisiae as the most sensitive strain. In contrast, the wild strain of C. parapsilosis was resistant.