Synthesis, Antimicrobial Activity and Micellization of Gemini Anionic Surfactants in a Pure State as Well as Mixed With a Conventional Nonionic Surfactant

New gemini anionic surfactants were prepared from sodium salts of monoalkyl sulfosuccinate esters of ethylene glycol having variably long tails (C₁₂, C₁₆, C₁₈) and dichloroethane. The chemical structures of the prepared surfactants were confirmed using different spectroscopic techniques. The surfaces tension values of the synthesized surfactants were measured at 25 °C individually or mixing at different molar fractions with ethoxylated alkylphenol. In all cases, mixed micellar aggregates were formed and critical micellar concentrations of binary mixtures containing different mole fractions of the surfactants were measured. The micellization processes of the individual and mixed surfactants were investigated. The effect of different alkyl chains of gemini anionic surfactants on properties of binary systems and molar ratio in the mixed aggregates were deduced. The critical micelle concentration of mixed surfactants shifted to lower values compared to those of the single surfactants. Effectiveness values increased with decreases in the mole fraction of gemini anionic surfactants. The negative values of interaction parameter (β) increased with increases in the chain length of anionic surfactants. The activity coefficient (f ₁, f ₂) and total minimum surface area of mixed solution were calculated. Also, the gemini anionic surfactants prepared have moderate antimicrobial activity towards bacteria and not active towards fungi.     

Precipitation and Micellar Properties of Novel Mixed Anionic Extended Surfactants and a Cationic Surfactant

Surfactant-modified mineral surfaces can provide both a hydrophobic coating for adsorbing organic contaminants and, in the case of ionic surfactants, a charged exterior for adsorbing oppositely charged species. This research evaluates the precipitation phase boundaries and synergistic behavior of the mixtures of carboxylate-based anionic extended surfactants with a pyridinium-based cationic surfactant. One cationic surfactant (cetylpyridinium chloride) and four anionic extended surfactants were studied. The anionic surfactants studied were ethoxy carboxylate extended surfactants with average carbon chain lengths of either 16 and 17 or 16 and 18 with 4 mol of a propylene oxide group and a different number of moles of an ethylene oxide group (2 and 5 mol). Precipitation phase boundaries of mixed anionic extended surfactants and cationic surfactant were evaluated to ensure that the surface tension studies are in regions without precipitate. Surface tension measurements were conducted to evaluate the critical micelle concentration of individual and mixed surfactant systems. Precipitation phase boundaries of these novel mixed surfactant systems showed greatly reduced precipitation areas as compared to a conventional mixed surfactant system which is attributed to the presence of the ethylene oxide and propylene oxide groups and resulting steric hindrances to precipitation. Moreover, it was demonstrated that the CMC of mixed surfactant systems were much lower than that of individual surfactant systems. Synergism was evaluated in the four systems studied by the β parameter which found that all systems studied exhibited synergism. From these results, these novel mixed surfactant systems can greatly increase formulation space (reduce the precipitation region) while maintaining synergism, although slightly reduced from conventional anionic-cationic mixtures reported previously.     

Synergism and Phase Behavior of Alcohol Polyoxyethylene Ether Acetate and Cationic Surfactant-Mixed Systems

Synergism in mixed micelle formation and surface tension reduction efficiency and the ternary phase behavior of anionic surfactant (alcohol polyoxyethylene ether acetate containing 10 ethylene oxide group and a fatty chain of C_16–18) with cationic surfactants (dodecyldimethylbenzyl ammonium chloride and lauryltrimethyl ammonium chloride) were investigated. Surface tension of the systems at different molar ratios was studied in detail and the interaction parameters of each system were calculated. The results show that both systems have lower values of critical micelle concentration (CMC) and γ_cmc than individual surfactants especially at equal ratio between cationic and anionic surfactants. Both systems present synergism in mixed micelle formation and surface tension reduction efficiency. The ternary phase behavior of the two systems was investigated using a polarized microscope. The micellar phase and lamellar phase were observed in both systems and the coexisting phase was only observed in the dodecyldimethylbenzyl ammonium chloride system.     

Mixtures of anionic and cationic surfactants with single and twin head groups: Solubilization and adsolubilization of styrene and ethylcyclohexane

Mixtures of anionic and cationic surfactants with single and twin head groups were used to solubilized styrene and ethylcyclohexane into mixed micelles and adsolubilize them into mixed admicelles on silica and alumina surfaces. Two combinations of anionic and cationic surfactants were studied: (i) a single-head anionic surfactant, sodium dodecyl sulfate (SDS), with a twin-head cationic surfactant, pentamethyl-octadecyl-1,3-propane diammonium dichloride (PODD), and (ii) a twin-head anionic surfactant, sodium hexadecyl-diphenyloxide disulfonate (SHDPDS), with a single-head cationic surfactant, dodecylpyridinium chloride (DPCl). Mixtures of SDS/PODD showed solubilization synergism (increased oil solubilization capacity) when mixed at a molar ratio of 1∶3; however, the SHD-PDS/DPCl mixture at a ratio of 3∶1 did not show solubilization enhancement over SHDPDS alone. Adsolubilization studies of SDS/PODD (enriched in PODD) adsorbed on negatively charged silica and SHDPDS/DPCl adsorbed on positively charged alumina showed that while mixtures of anionic and cationic surfactants had little effect on the adsolubilization of styrene, the adsolubilization of ethylcyclohexane was greater in mixed SHPDS/DPCl systems than for SHDPDS alone. Finally, it was concluded that whereas mixing anionic and cationic surfactants with single and double head groups can improve the solubilization capacity of micelles or admicelles, the magnitude of the solubilization enhancement depends on the molecular structure of the surfactant and the ratio of anionic surfactant to cationic surfactant in the micelle or admicelle.     

Mixtures of anionic and cationic surfactants with single and twin head groups: Adsorption and precipitation studies

This research reports on the adsorption and precipitation of mixtures of anionic and cationic surfactants having single and twin head groups. The surfactant mixtures investigated were: (i) a single-head anionic surfactant, sodium dodecyl sulfate (SDS), in a mixture with the twin-head cationic surfactant pentamethyl-octadecyl-1,3-propane diammonium dichloride (PODD)—adsorption was studied on negatively charged silica; and (ii) a twin-head anionic surfactant, sodium hexadecyl-diphenyloxide disulfonate (SHDPDS), and the single-head cationic surfactant dodecylpyridinium chloride (DPCI)—adsorption was studied on positively charged alumina. Whereas the mixed surfactant system of SHDPDS/DPCI showed adsorption on alumina that was comparable to the of SHDPDS alone, the mixed surfactant system of SDS/PODD showed increased adsorption on silica as compared with PODD alone. The adsorption of the SDS/PODD mixture increased as the anionic and cationic system approached an equimolar ratio. Precipitation diagrams for mixtures of single- and twin-head surfactant systems showed smaller precipitation areas than for single-head-only surfactant mixtures. Thus, the combination of single- and double-head surfactants helps reduce the precipitation region and can increase the adsorption levels, although the magnitude of the effect is a function of the specific surfactants used.     

Adsorption, Desorption and Adsolubilization Properties of Mixed Anionic Extended Surfactants and a Cationic Surfactant

Anionic and cationic surfactant mixtures exhibit desirable synergism, but are limited by their tendency to form precipitates. This research evaluates the adsorption, adsolubilization and desorption of mixtures of carboxylate-based anionic extended surfactants and a pyridinium-based cationic surfactant. The mixture of cetylpyridinium chloride (CPC), selected as the cationic surfactant, with four anionic extended surfactants were studied. The anionic surfactants studied were alkyl propoxylated ethoxylated carboxylate with average number of carbon chain length of 16 and 17 or 16 and 18 with 4?mol of propylene oxide groups and either 2 or 5?mol of ethylene oxide groups. The adsorption of anionic extended and cationic surfactant mixtures onto a negatively charged metal oxide surface (silica dioxide) was evaluated. The adsolubilization of phenylethanol, styrene and ethylcyclohexane were evaluated for these mixed surfactant systems. The desorption potential of individual and mixed surfactant systems was also evaluated by varying the number of washing (desorption) steps. It was found that the plateau adsorption of mixed anionic extended surfactant and cationic surfactant occurred at lower surfactant concentration than that of the CPC alone, although the maximum adsorption capacity of CPC was not enhanced in our mixed surfactant systems. Adsolubilization capacities of these mixed surfactant systems are higher than that of the individual surfactant system. For desorption studies, these mixed surfactant systems showed lower stability than the individual surfactant system.     

Microemulsion phase behavior of anionic-cationic surfactant mixtures: Effect of tail branching

This research evaluated middle-phase microemulsion formation by varying the mole ratio of anionic and cationic surfactants in mixtures with four different oils (trichloroethylene, n-hexane, limonene, and n-hexadecane). Mixtures of a double-tailed anionic surfactant (sodium dihexyl sulfosuccinate, SDHS) and an unbalanced-tail (i.e., doubletailed with tails of different length) cationic surfactant (benzethonium chloride, BCl) were able to form microemulsions without alcohol addition. The amount of NaCl required to form the middle-phase microemulsion decreased dramatically as an equimolar anionic-cationic surfactant mixture was approached. Although the mixture of anionic and cationic surfactants demonstrated a higher critical microemulsion concentration (cμc) compared to the anionic surfactant alone, the Winsor Type IV single-phase microemulsion started at lower surfactant concentrations for the anionic-cationic mixture than for the anionic surfactant alone. Under optimum middlephase microemulsion conditions, mixed anionic-cationic surfactant systems solubilized more oil than the anionic surfactant alone. Pretreatment detergency studies were conducted to test the capacity of these mixed surfactant systems to remove oil form fabrics. It was found that anionic-rich mixed surfactant formulations yielded the largest oil removal, followed by cationic-rich systems.     

Mixed micelles of some metal dodecyl sulfates and triton X-100 in aqueous media

Tensiometric studies on several binary surfactant mixtures containing anionic surfactants, viz., metal (lithium, sodium, potassium, copper, cobalt, and magnesium) dodecyl sulfates and a nonionic surfactant (Triton X-100) in water at different mole fractions (0–1) provide critical micelle concentration (CMC) values. The composition of mixed micelles and the interaction parameter, β, evaluated from the CMC data for different systems using Rubingh's theory, are discussed. Marked interaction is observed with monovalent dodecyl sulfates. The influence of counter-ion valence on the formation of mixed micelles was investigated for anionic-nonionic systems, and results indicated that mixed systems with bivalent counter-ions in metal dodecyl sulfate resembled nonionic-nonionic systems where weak/negligible interaction has been reported. Salt addition revealed the weakening of interaction in the mixed systems, which is attributed to the head group charge neutralization and the dehydration of the ethylene oxide units of the nonionic surfactants. A few cloud point and viscosity data are also reported.     

Formulating middle-phase microemulsions using mixed anionic and cationic surfactant systems

Although mixtures of anionic and cationic surfactants can show great synergism, their potential to precipitate and form liquid crystals has limited their use. Previous studies have shown that alcohol addition can prevent liquid crystal formation, thereby allowing formation of middle-phase microemulsions with mixed anionic-cationic systems. This research investigates the role of surfactant selection in designing alcohol-free anionic-cationic microemulsions. Microemulsion phase behavior was studied for three anionic-cationic surfactant systems and three oils of widely varying hydrophobicity [trichloroethylene (TCE), hexane, and n-hexadecane]. Consistent with our hypothesis, using a branched surfactant and surfactants with varying tail length allowed us to form alcohol-free middle-phase microemulsion using mixed anionic-cationic systems (i.e., liquid crystals did not form). The anionic to cationic molar ratio required to form middle-phase microemulsions approached 1∶1 for univalent surfactants as oil hydrophobicity increased (i.e., TCE to hexane to n-hexadecane); even for these equimolar systems, liquid crystal formation was avoided. To test the use of these anionic-cationic surfactant mixtures in surfactant-enhanced subsurface remediation, we performed soil column studies: Greater than 95% of the oil was extracted in 2.5 pore volumes using an anionic-rich surfactant system. By contrast, cationic-rich systems performed very poorly (<1% oil removal), reflecting significant losses of the cationic-rich surfactant system in the porous media. The results thus suggest that, when properly designed, anionic-rich mixtures of anionic and cationic surfactants can be efficient for environmental remediation. By corollary, other industrial applications and consumer products should also find these mixtures advantageous.     

Synergistic Effect of Mixed Surfactant Systems on Foam Behavior and Surface Tension

Foam and surface tension behaviors of different ionic/nonionic surfactant solutions along with their different combinations have been investigated. Among different surfactants, sodium dodecyl sulfate showed the highest foamability over other surfactants. Mixed surfactant systems were always found to have higher foamability than the individual surfactant. It was also noticeable that nonionic surfactants show good foamability when they combine with anionic and cationic surfactants. In the case of mixed surfactant systems, nonionic/cationic surfactant mixtures showed lower surface tension than nonionic/anionic surfactant mixture due to a synergistic effect.     

Micellar and Interfacial Behavior of Mixed Systems Containing Glycoside‐Based Surfactant and Cationic Didecyldimethylammonium Chloride

The behavior of binary mixtures of glycoside‐based surfactants in combination with didecyldimethylammonium chloride (DDAC) has been studied using surface tension measurements. The three glycoside‐based surfactants are nonionic decyl glycoside (APG), nonionic dodecyl ethoxy glycoside (AEG) and anionic disodium dodecyl ethoxy glycoside citrate (AEG‐EC). Lower critical micelle concentrations (CMC) and minimum molecular area (A_min) values were obtained for all the mixed systems. The pC₂₀ values of APG/DDAC and AEG‐EC/DDAC mixtures are larger than pure surfactants, while the values of AEG/DDAC are between those of AEG and DDAC. Interactions between the monomers have also been investigated by determining the interaction parameters. Negative β_m and β_s values indicate synergistic effects in both the mixed micelle and monolayer formation. For different mixed systems, interaction in the mixed micelle formation becomes stronger in the order: AEG/DDAC < AEG‐EC/DDAC < APG/DDAC. The degree of synergism in the mixed monolayer formation follows the order: AEG/DDAC < APG/DDAC < AEG‐EC/DDAC.     

荧光探针法研究新型Gemini表面活性剂在水溶液中的聚集行为

以芘为荧光探针、二苯酮为猝灭剂,用稳态荧光探针法测定了新型Gemini表面活性剂的临界胶团浓度(CMC)、胶团聚集数(Nagg)及胶团微极性.研究了Gemini表面活性剂结构和氯化钠浓度对CMC、Nagg、胶团微极性的影响.结果表明,新型Gemini表面活性剂的CMC比常规表面活性剂的CMC低1—2个数量级.当疏水基碳原子数增加时,CMC依次降低,Nagg增大,胶团微极性减小.当氯化钠浓度增大时,Nagg增大,胶团微极性减小.     

双子表面活性剂体系的界面活性研究

测定了阳离子型双子表面活性剂烷基 α ,ω 双二甲基烷基溴化铵以及它与普通表面活性剂复配体系的表面张力。结果表明 :双子表面活性剂的表面活性大大高于普通表面活性剂 ,双子表面活性剂溶液的表面活性受其联接基团的影响远大于其烷基链的影响。通过研究阳离子型双子表面活性剂 /阴离子普通表面活性剂复配体系和阴 /阳普通表面活性剂复配体系的协同效应 ,发现双子表面活性剂与普通表面活性剂有很好的复配协同效应 ,这主要是由双子表面活性剂的特殊结构造成的。     

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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Comparison of QSAR and QSPR Based Aquatic Toxicity for Mixed Surfactants

In the present study, quantitative structure-activity relationship (QSAR) equations were derived using the logarithm of the octanol/water partition co-efficient for the prediction of acute aquatic toxicity of mixed surfactant systems. Further mixed surfactant systems of an anionic surfactant (sodium lauryl sulfate) and several nonionic surfactants (alkyl polyglucoside) of different hydrophobic chain lengths were taken together to calculate the parameter pEC50. Quantitative structure-properties relationship (QSPR) equations based on pC20, and A _min were developed from the surface tension data to predict pEC50 values and compared with QSAR derived pEC50 values to understand the probable mechanisms of action of the mixed surfactants blends for aquatic toxicity. The established QSAR and QSPR equations for mixed surfactants indicate that given blends of surfactants act as a polar narcotic.

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.     

Properties of Sodium Methyl Ester Alpha-Sulfo Alkylate/Trimethylammonium Bromide Mixtures

The surface properties of binary mixtures of anionic sodium methyl ester ??-sulfo alkylate (C _m MES) and cationic alkyl trimethylammonium bromide (C _n TAB) of different carbon chain length have been studied in the present work. The critical micelle concentration (CMC) that was obtained from the plots of surface tension (??) versus concentration showed that mixed surfactants have CMC values that were about 10 times lower than their single components. The large negative values for both interaction parameters suggest the existence of strong synergism between the oppositely charged surfactant molecules. The effect of hydrocarbon chain length of either surfactant was also compared and results showed that the effect of cationic surfactant chain length dominated that of the anionic surfactants. It was also discovered that certain mixed surfactant combinations behave differently from the expected trend.     

Solubilization of phospholipid bilayer caused by surfactants

The interaction of surfactants with liposomes eventually leads to the rupture of such structures and the solubilization of the phospholipid components. In this paper, solubilization is regarded as a decrease in light scattering of liposome suspensions. To this end, in accordance with the nomenclature, adopted by Lichtenberg, three parameters were considered as corresponding to the effective surfactant/lipid molar ratios (Re) at which light scattering starts to decrease, Re_sat; reaches 50% of the original value, Re₅₀; and shows no further decrease, Re_sol. These parameters corresponded to the Re at which the surfactant (i) saturated the liposomes, (ii) resulted in a 50% solubilization of vesicles and (iii) led to a total solubilization of liposomes. The surfactants tested were the nonionic surfactant octylphenol ethoxylated with 10 units of ethylene oxide or Triton X-100 (OP-10EO), two anionic surfactants, sodium dodecyl sulfate and sodium dodecyl ether sulfate, and an amphoteric surfactant dodecyl betaine (D-Bet). Unilamellar liposomes formed by egg phosphatidylcholine containing increasing amounts of phosphatidic acid were used. The Re parameters were the lowest for D-Bet, followed by OP-10EO, whereas the anionic surfactants always showed the highest values regardless of the electrical charge of the lipid bilayers. These parameters seem also to be inversely related to the critical micelle concentration (CMC) of the surfactant, except for OP-10EO. Moreover, the CMC values of the surfactant/lipid systems at 0.5 mM lipid concentration corresponded in all cases to the surfactant concentration at which liposomes were saturated by surfactants. As a consequence, this ratio can be regarded as an interesting parameter associated with the mixed micelle formation in liposome solubilization.     

Kinetics of precipitation of surfactants. II. Anionic surfactant mixtures

Precipitation kinetics were measured for calcium-induced precipitation of mixtures of two anionic surfactants. The overall time required for precipitation to occur increased dramatically in specific ranges of compositions for the surfactant mixtures when compared to single components. Adsorption of the nonprecipitating surfactant onto the precipitate surface was shown to be responsible for this remarkable synergism. The higher the supersaturation of surfactant monomers, the more rapidly precipitation occurred. Under conditions where both surfactants were supersaturated, precipitation sometimes occurred in stepwise fashion, where crystals of different composition were formed with different induction times. Image analysis of the crystalline precipitate showed that crystal habit was affected when the two surfactants were mixed, indicating that processes such as adsorption and coprecipitation (most likely by inclusion) were occurring. When the crystals were allowed to age in solution for a period of 1 wk, the crystalline phase from the mixed surfactant solutions was found to separate into two types of crystals, which resembled week-old crystals formed from single surfactant systems.     

Microemulsion polymerization of microlatex in sublimation ink for cotton fabric ink jet printing

A novel microlatex of styrene/2‐ethylhexylacrylate (2‐EHA)/2‐hydroxyethyl methacrylate (2‐HEMA)/N‐(isobutoxy methyl) acrylamide (IBMA) copolymer was synthesized and mixed in sublimation inks to be inkjet printed on the cotton fabric to provide soft hand feel and good color fastness after heat‐press. In the optimized microemulsion composition with highest monomer mixture amount, polymerizable maleate surfactants with moderate EO value attained smaller microemulsion droplet size in mono distribution and lower dosage than conventional POE surfactants in combination with anionic surfactants. With adopted semicontinuous process in microemulsion copolymerization at 65°C, the polymerizable surfactants stabilized the growth of microlatex particle size within 70 nm in 240 min and attained 100% of monomer conversion rate with two initiator systems, 2‐2‐azobis(2‐methlypropionamidine dihydrochloride (AAPH) and tert‐butylhydroperoxide (TBHP)/sodium formaldehyde sulfoxylate (SFS). The microlatex particle size of two surfactant systems increased with higher conversion rate and reaction temperature, which synchronized with initiator concentration. High polymer solid content was contributed mainly by IBMA monomer ratio requiring higher amounts of anionic surfactants and 2‐HEMA as a cosurfactant in particle stabilization. Although the optimum ink containing high IBMA microemulsion exhibited small variation in viscosity, pH value and surface tension, disperse dyes in four colors had different interaction with the microlatex to demonstrate distinct printing durability and color performance. The resulted cotton fabric attained high K/S value for color strength, great AATCC grade for color fastness, and nearly zero color difference for negative dye particle diffusion or migration. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011