Synthesis and Properties of a Cationic Gemini Surfactant with the Hydrophenanthrene Structure

A novel cationic gemini surfactant with the hydrophenanthrene structure has been synthesized from dehydroabietylamine. Its structure was confirmed by IR, ¹H NMR, and elemental analysis. The critical micelle concentration (CMC) of the surfactant and its surface tension at the CMC (γ _CMC) in aqueous solution were about 1.58 × 10^?5 mol L^?1 and 36.6 mN m^?1 at 25 °C, respectively. The emulsion composed of equal amounts of benzene and an aqueous solution with 0.1 % gemini surfactant as emulsifier maintained its stability for 8.5 h. Meanwhile, the antimicrobial activities of the gemini surfactant against Pseudomonas aeruginosa, Escherichia aerogenes, and Staphylococcus epidermidis were much better than those of bromogeramine and ampicillin sodium against the same bacteria, and its minimum inhibitory concentrations (MIC) were 16, 32, and 4 μg mL^?1, respectively.     

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.     

Micellar and Surface Properties of Some Monomeric Surfactants and a Gemini Cationic Surfactant

The physicochemical and interfacial properties of the monomeric surfactants cetyltrimethyl ammonium bromide (CTAB), cetyltriphenyl phosphonium bromide (CTPB), tetradecyl triphenyl phosphonium bromide (TTPB), cetyldiethylethanol ammonium bromide (CDEEAB), cetyltrimethyl ammonium chloride (CTACl), tetradecyltrimethyl ammonium bromide (TTAB), and a gemini surfactant (C₁₆-3-C_16, 2Br⁻) at different pH (3.1, 7.0, and 7.75) have been investigated by conductivity and surface tension measurements at 300 K. The critical micellar concentration (CMC), degree of micellar ionization (α), surface excess concentration (Г_max), minimum surface area per molecule of surfactant (A _min), Gibbs free energy of micellization (∆G _m⁰), surface pressure at the CMC (π _CMC), and the Gibbs energy of adsorption (∆G _ads⁰) of the monomeric surfactants have also been determined. The CMC, α and Г_max, increase with increasing pH whereas A _min decreases.     

Salt Effect on the Solution Properties of Cationic Gemini/Conventional Surfactants in the Presence of the Nonionic Polymer Hydroxypropylmethyl Cellulose

In this article, we report the salt effect on interaction of a water-soluble polymer hydroxypropylmethyl cellulose (HPMC) with the cationic Gemini surfactant (ethane-1, 2-diyl bis(N,N-dimethyl-N-hexadecylammoniumacetoxy) dichloride, 16-E2-16), and also its monomeric counterpart cetyltrimethylammonium chloride (CTAC) using the tensiometric method. Surface tension of the amphiphiles diminished in the presence of the polymer as well as salts; eventually, the polymer gets saturated with the surfactant and there is no further change of surface tension of the solution. Interaction between the polymer and surfactant starts at the critical aggregation concentration (CAC) that is stronger for 16-E2-16 than CTAC. CAC and critical micelle concentration (CMC) values of the surfactant-polymer binary mixtures at various concentrations of the polymer were determined. CAC as well as CMC of 16-E2-16 are considerably lower than CTAC. The inorganic salts (KCl and KBr) have a considerable influence on the polymer–surfactant interaction.     

Interactions of Polyacrylamide with Cationic Surfactants: Thermodynamic and Surface Parameters

The aggregation behaviour of two cationic surfactants, viz. cetyl trimethyl ammonium bromide (CTAB) and N-cetyl pyridinium chloride (CPC), in different concentrations of water-soluble polyacrylamide has been studied in alkaline medium by electrical conductivity and surface tension measurements. A decrease in the critical micelle concentration (CMC) of the surfactant with an increase in polymer content in the mixture was observed. The thermodynamic and surface parameters have been determined and discussed. The results indicate that micellisation becomes more favourable at higher polymer content.     

Thermoresponsive poly-(N-isopropylmethacrylamide) microgels: Tailoring particle size by interfacial tension control

Size control is one of the most important tasks in colloid synthesis. In the present work, the anionic surfactant sodium dodecyl sulfate (SDS) and the cationic surfactant cetyl trimethyl ammonium bromide (CTAB) were used to precisely control the size of poly-N-isopropylmethacrylamide [poly-(NIPMAM)] microgels prepared by precipitation polymerization. For each surfactant the concentration was varied over a broad range below the critical micelle concentration (cmc). The resulting particle size, size distribution, and shape were studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Photon correlation spectroscopy (PCS) was employed to analyze the volume phase transition behavior of the microgels.     

Effect of Low Concentration Salt on Organic Contact Angle in Ionic Surfactant Solutions: Insight from Theory and Experiment

Abstract

A theoretical approach to predict equilibrium organic/solid‐surface contact angles as affected by the addition of electrolytes to an aqueous surfactant solution has been developed. While the effects of electrolytes on surfactant self‐assembly and adsorption are extensively documented, there is a noticable gap in the literature for systems where less than 10 mM of electrolyte is added to the solution. This article presents an improved approach, based on our earlier model, that accounts for the dramatic changes observed for previously published hexadecane droplet contact angles data on gold for very low concentration additions of sodium chloride (NaCl) in separate aqueous solutions of sodium dodecyl sulfate (SDS) and cetyl trimethyl ammonium bromide (CTAB). In addition to providing insight into changes in interfacial phenomena the model demonstrates that both charge and type of salt ions play a significant role in the extent to which droplet contact angles vary from those of salt free solutions.     

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.     

Effect of Ionic Strength on Oil Removal from Stainless Steel in the Presence of Ionic Surfactant

Abstract

Contact angles of oil droplets on solid surfaces provide useful insight into surfactant cleaning behavior. Contact angles of hexadecane and MAR‐TEMP^® 355, an industrial quench oil, on stainless steel were measured for ionic surfactant solutions as a function of ionic strength. The ionic strength of sodium dodecyl sulfate (SDS) and cetyl trimethyl ammonium bromide (CTAB) solutions was modified by the addition of sodium chloride. Increases in the contact angle with additions of 1.0 mM and 2.5 mM NaCl were observed for the two oils in SDS and for hexadecane in CTAB. For the industrial quench oil, detachment occurred in CTAB concentrations above the critical micelle concentration; as a result, the equilibrium contact angle measurements were not measured. The critical concentration of CTAB decreased with increasing NaCl concentration. Oil‐removal studies indicate that increasing ionic strength by as little as 2.5 mM can result in improved cleaning. A theoretical insight previously used to explain contact‐angle behavior for a hexadecane‐gold system is used to describe the results obtained with the current system.     

Effect of Sodium Salicylate on the Properties of Gemini Surfactant Solutions

In this paper, the effect of sodium salicylate on the solution properties of a gemini surfactant, butylidene-α, ω-bis (cetyl dimethyl ammonium bromide), was investigated through absorbance and dynamic light scattering (DLS) measurement, transmission electron microscope (TEM) observation, and rheology measurement. The DLS experiment showed that the average size of aggregates increases with the addition of sodium salicylate. The TEM experiment showed that the addition of sodium salicylate causes the change of the size and shape of aggregate. With the increase of the concentration of sodium salicylate, the viscosity of the gemini surfactant solution reaches a maximum value and the flow pattern of the gemini surfactant solution also undergoes a great change with a transition from a Newtonian fluid to a non-Newtonian fluid.     

Micellization and Interfacial Interaction Behaviors of Gemini Cationic Surfactants–CTAB Mixed Surfactant Systems

The interfacial and micellization behaviors of binary mixtures of two gemini cationic surfactants and conventional the cetyl trimethyl ammonium bromide surfactant were studied at various molar ratios. From the equilibrium surface tension measurements, the critical micelle concentrations (CMC) data were obtained as functions of the composition. Values of the CMC were analyzed according to the regular solution model developed by Rubingh for mixed micelles. Two interaction parameters were obtained for each system, the interaction at the interface, and in the micellar phase. The results showed that micellization and adsorption properties of the studied mixed systems depend on the spacer chain lengths of the gemini surfactants and their ratio in the mixed systems.     

Aggregation and Thermodynamic Properties of Some Cationic Gemini Surfactants

In this study, the gemini surfactants of the alkanediyl-α-ω-bis(alkyl dimethyl ammonium) dibromide type, on the one hand, with different alkyl groups containing m carbon atoms and an ethanediyl spacer, referred to as “m-2-m” (m = 10, 12 and 16) and, on the other hand, with n-C₁₆ alkyl groups and different spacers containing s carbon atoms, referred to as “16-s-16” (s = 2, 6, 10 and Ar (8)) have been synthesized, purified and characterized. The critical micelle concentration (CMC), micelle ionization degree (α) and Gibbs free energy of micellization (∆G _mic) of these surfactants and the monomeric cationic surfactants DTAB and CTAB have been determined by means of electric conductivity measurements. In addition, the temperature dependence of the CMC was determined for the 10-2-10 gemini surfactant. The CMCs of the gemini surfactants are found to be much lower than those of the corresponding monomeric surfactants and the effect of the hydrophobic alkyl chain length is more important than that of the spacer. The CMC of 16-s-16 passes through a maximum of (or around) s = 6 and then decreases for s = 10. The presence of a maximum CMC is explained by the contribution of a change of conformation of the surfactant with increasing spacer chain length. The changes of α with s and m are found qualitatively similar to those found for CMC values. The values of ∆G _mic are more negative for the dimers than for the monomers and also change with an increasing spacer carbon number, as CMC values do. The thermodynamic parameters of micellization indicate that the micellization of 10-2-10 is enthalpy driven.     

Study of the Interaction Between Methyl Orange and Mono and Bis-Quaternary Ammonium Surfactants

The solubilization and interaction of an azo-dye (methyl orange) with dodecyl trimethyl ammonium bromide and cationic gemini surfactants in the series of alkanediyl α,ω-bis[(dimethyl alkyl ammonium)bromide)] referred to as (m-s-m), m = 10, 12, 14 and s = 2, 3, 4 were investigated by means of UV–Vis spectroscopy. Aggregation with the anionic dye was reflected by a hypsochromic shift with a decrease in the intensity of the absorption band. The results also show a bathochromic shift followed by a sharp increase in the intensity of the maximum absorption band λ_max after the critical micellar concentration (CMC). This indicates that the dye solubility increased with increasing surfactant concentration. It was also observed that the aggregation of surfactant and dye takes place at a surfactant concentration far below the CMC of the individual surfactant. The effects of the chain length as well as the spacer length of gemini surfactants on the critical aggregation concentration and CMC were also examined. Moreover, the partition coefficients between the bulk water and surfactant micelles K _S and K _X as well as the Gibbs energies of distribution of dye between the bulk water and surfactant micelles were determined using the pseudo-phase model. The effect of the hydrophobic chain length and spacer of gemini surfactants on the distribution parameters is also reported.     

Interaction Between Ionic Liquids and Gemini Surfactant: A Detailed Investigation into the Role of Ionic Liquids in Modifying Properties of Aqueous Gemini Surfactant

Tuning physicochemical properties of aqueous surfactant solutions comprised of normal or reverse micelles by external additives is of utmost importance due to the enormous application potential of surfactant‐based systems. Unusual and interesting properties of environmentally benign ionic liquids (IL) make them suitable candidates for this purpose. To understand and establish the role of IL in modifying properties of aqueous gemini surfactants, we studied the effect of the IL, 1‐hexyl‐3‐methylimidazolium bromide ([Hmim][Br]) and 1‐octyl‐3‐methylimidazolium bromide ([Omim][Br]) on the properties of the aqueous cationic gemini surfactant 1,6‐hexanediyl‐α,ω‐bis(dimethyltetradecyl)ammonium bromide (14‐6‐14,2Br^?). The behavioral changes were investigated by measuring the critical micelle concentration (CMC) using electrical conductance, surface tension, dye solubilization and fluorescence probe measurements at 298.15 K. It was observed that the CMC of 14‐6‐14,2Br^? gemini surfactant decreases with addition of IL, thus favoring the micellization process. An increase in micellar size was observed at lower IL concentration using dynamic light scattering, with a decrease in aggregation number (N_agg) determined from fluorescence probe quenching measurements. It is noteworthy that the extent of modulation of the micellar properties is different for both the IL due to their structural differences. IL behave like electrolytes at lower concentrations and cosurfactants at higher concentrations and form mixed micelles with the cationic gemini surfactant showing an increase in N_agg.     

高温高盐对阳离子双子表面活性剂表面活性的影响研究

考察了25℃条件下商品化阳离子双子表面活性剂PF-CGS在纯水、饱和NaCl盐水及含1000mg·L-1Ca2+、Mg2+的饱和NaCl盐水溶液中的表面张力行为,并对上述条件下的表面活性剂溶液在130℃下热滚16h后测定表面张力以进行对比研究。研究发现,与在纯水中的表面活性相比,随着无机盐的加入,PF-CGS溶液的CMC、C20和γCMC均降低,表面活性升高;经高温老化后的PF-CGS溶液的(CMC无明显变化,但CMC和C20均比老化前有所下降,表面活性有一定程度提高。上述实验结果表明,高温、高盐不会削弱阳离子双子表面活性剂PF-CGS的表面活性,该类表面活性剂完全可以适用于高温、高盐的油气开采环境。     

Some Surface Properties of Polysorbates and Cetyl Trimethyl Ammonium Bromine Mixed Systems

Mixed surfactant solutions consisting of cationic/nonionic surfactants were prepared in different compositions of the components in aqueous solution in order to determine the surface properties. The critical micelle concentration (CMC) of aqueous solutions of the individual surfactants cetyl trimethyl ammonium bromide (CTAB) and polysorbate nonionics, and their mixtures are determined at different proportions. The results show that there is synergistic behavior in mixtures at higher mole fraction of nonionic surfactant. The effect of the alkyl chain on the CMC is also determined.     

Synthesis and Physicochemical Investigation of Novel Quaternary Ammonium Salt Cationic Gemini Surfactant Derived from Cyanuric Chloride

Three novel quaternary ammonium salt cationic gemini surfactants (QAS C _n ?C2?CC _n where n represents the hydrocarbon chain lengths of aliphatic amine, i.e., 6, 8, 12) were synthesized from 2,4,6?Ctrichloro?C1,3,5?Ctriazine, ethylenediamine, N,N?Cdimethylpropane?C1, 3?Cdiamine and benzyl chloride. ¹H-NMR, ¹³C-NMR, ESI?CMS spectra and elemental analysis were used to confirm the chemical structures of the prepared compounds. Their critical micelle concentrations (CMC) in the aqueous solutions were determined by surface?Ctension, electrical conductivity and steady?Cstate fluorescence methods respectively. With the increasing length of the hydrophobic chain, the values of their CMC decreased. The values of CMC, ?? _CMC, pC ₂₀, ??_max, and A _min were derived from surface tension measurements, while the thermodynamic parameters of micellization (?G _mic ^° and ?G _ads ^° ) were determined by electrical conductivity. These properties are significantly influenced by the hydrophobic chain length.     

Synthesis and Antibacterial Activity of Novel Amido-Amine-Based Cationic Gemini Surfactants

A series of novel cationic gemini surfactants were synthesized from corresponding amido-amines in a single step reaction. The amido-amines were obtained from long chain carboxylic acids and 3-N,N-dimethylamino-1-propyl-amine with excellent isolated yield (up to 95 %). All the synthesized quaternary ammonium compounds (QACs) were further investigated for surface active properties. The critical micelle concentration (CMC) and the effectiveness of surface tension reduction were determined. The surface tension measurements of newly synthesized gemini surfactants showed good water solubility, and low CMC values, had great efficiency in lowering the surface tension and a strong adsorption at the air/water interface than the corresponding monomeric surfactants. Further, the antibacterial activity of the synthesized QACs against both Gram-positive and Gram-negative bacteria was also investigated.     

Effect of Surfactants on Catalytic Activity of Diastase α-Amylase

The enzyme amylase is one of the hydrolyzing enzymes used in detergent formulation in order to remove soil based on polysaccharides. The effectiveness of the enzyme depends on its compatibility with other ingredients of the formulation. Among the studied additives, comprising anionic surfactants sodium dodecyl hydrogen sulfate (SDS) and dioctyl sodium sulfosuccinate, the cationic surfactant cetyl trimethyl ammonium bromide (CTAB), nonionic surfactants polyoxyethylene sorbitan monooleate and polyoxyethylene octyl phenyl ether, carboxy methyl cellulose and sodium sulfate, only the anionic surfactant SDS and cationic surfactant CTAB showed catalytic enhancement of α-amylase. The kinetic parameters, K _m and k _cat, showed an increase in catalytic activity in the micellar pseudophase. The decrease in optimum temperature from 55 to 30 °C and the shift in optimum pH from 5.5 to 7 on the addition of SDS and CTAB for the hydrolysis of starch are very favorable to enhance the washing characteristics.     

Comparison of a Cationic Gemini Surfactant and the Corresponding Monomeric Surfactant for Corrosion Protection of Mild Steel in Hydrochloric Acid

A cationic gemini surfactant, N,N′-didodecyl-N,N,N′,N′-tetramethyl-1,4-butanediammonium dibromide (12-4-12) and the corresponding monomeric surfactant dodecyltrimethylammonium bromide were compared with respect to corrosion inhibition efficiency in 1 M hydrochloric acid solution. Polarization and electrochemical impedance spectroscopy were used to evaluate corrosion inhibition. The 12-4-12 surfactant showed an extremely high corrosion inhibition efficiency at very low concentration. Surface tension measurements performed under the strongly acidic conditions revealed that the gemini surfactant is remarkably electrolyte tolerant, which is beneficial for adsorption at the steel surface.