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.     

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.     

A Comparative Study on the Aggregation and Thermodynamic Properties of Anionic Sodium Dodecylsulphate and Cationic Cetyltrimethylammonium Bromide in Aqueous Medium: Effect of the Co-solvent N-Methylacetamide

The effect of co‐solvent N‐methylacetamide (NMA) (0.035, 0.046, 0.127, and 0.258 mol kg^?1) on the micellization behaviour of anionic surfactant sodium dodecylsulphate (SDS) (3.21–10.35 mmol kg^?1) and cationic surfactant cetyltrimethylammonium bromide (CTAB) (0.19–3.72 mmol kg^?1) in aqueous solution was explored by employing conductivity measurements at different temperatures (298.15–313.15 K). The critical micelle concentration (CMC) values for SDS and CTAB in aqueous solutions of NMA were determined from the conductivity versus surfactant concentration plots. The variations in the CMC values of SDS with NMA concentration are in striking contrast to those observed in the case of CTAB. The various relevant thermodynamic parameters of micellization, viz. standard enthalpy change, ΔH_m^o, standard entropy change, ΔS_m^o, and standard Gibbs free energy change, ΔG_m^o, were determined using the temperature variation of the CMC values and counterion binding. The results not only relate these thermodynamic parameters to the consequences of intermolecular interactions but are also able to differentiate between SDS–water–NMA and CTAB–water–NMA systems in terms of contributions from head groups as well as alkyl chains of surfactants.     

Polymerization of vinyl acetate in microemulsions stabilized with dodecyltrimethylammonium bromide and cetyltrimethylammonium bromide

The polymerization of vinyl acetate in microemulsions stabilized with dodecyltrimethylammonium bromide (DTAB), cetyltrimethylammonium bromide (CTAB) or mixture of these surfactants is examined. The polymerization rate diminishes as the surfactant mixture becomes richer in DTAB. Also, particles grow with conversion and become increasingly larger as the DTAB content in the mixture increases. Our results indicate that chain transfer reactions to monomer are more important than chain transfer reactions to polymer even at high conversions with CTAB. However, as the content of DTAB increases, bimolecular termination induced by coagulation, terminal double bond polymerization and chain transfer reactions to polymer become increasingly more important.     

Interaction of cetyltrimethylammonium bromide with drug in aqueous/ electrolyte solution: A combined conductometric and molecular dynamics method study

Interaction between beta-lactum antibiotic drug ciprofloxacin hydrochloride(CFH)and cationic surfactant cetyltrimethylammonium bromide(CTAB)was performed conductometrically in aqueous as well as in the occurrence of different salts(NaCl,KCl as well as NH_4Cl)over the temperature range of 298.15–323.15 K at the regular interval of 5 K.CFH drug has been suggested for the treatment of bacterial infections such as urinary tract infections and acute sinusitis.A clear critical micelle concentration(CMC)was obtained for pure CTAB as well as(CFH+CTAB)mixed systems.The decrease in CMC values of CTAB caused by the addition of CFH reveals the existence of the interaction between the components and therefore it is the indication of micelle formation at lower concentration of CTAB and their CMC values further decrease in attendance of salts.A nonlinear behavior in the CMC versus T plot was observed in all the cases.The ΔG_m~0 values are found to be negative in present study systems demonstrated the stability of the solution.The values of ΔH_m~0 and ΔS_m~0 reveal the existence of hydrophobic and electrostatic interactions between CFH and CTAB.The thermodynamic properties of transfer for the micellization were also evaluated and discussed in detail.Molecular dynamic simulation disclosed that environment of water and salts have impact on the hydrophobic interaction between CFH and CTAB.In water and salts,CTAB adopts spherical micelle in which charged hydrophilic groups are interacted with waters whereas hydrophobic tails form the core of the micelle.This hydrophobic core region is highly conserved and protected.In addition,micelle formation is more favorable in aqueous Na Cl solution than other solutions.     

Salt Effect on Mixed Micelle and Interfacial Properties of Conventional Cationic Surfactants and the Ionic Liquid Surfactant 1-Tetradecyl-3-methylimidazolium Bromide ([C14mim]Br)

The surface properties and mixed micellization behavior of binary combinations of an ionic liquid surfactant, namely, 1-tetradecyl-3-methylimidazolium bromide ([C₁₄mim]Br) with common cationic surfactants viz. tetradecyltrimethylammonium bromide and tetradecylpyridinium bromide in the presence of sodium bromide (NaBr) were investigated by surface tension and conductivity measurements. The critical micelle concentration (CMC) and interfacial parameters, such as the maximum surface excess (Γ_max), minimum area per molecule (A_min) and surface pressure at the CMC (π_CMC) were determined from the surface tension data. The CMC and Γ_max values were found to decrease with increasing salt concentrations. The $ \Updelta G_{\text{ad}}^{ \circ } $ and $ \Updelta G_{\text{m}}^{ \circ } $ values are negative indicating the spontaneity of micelle formation.     

Synthesis,Characterization, and Micellization Behavior of Cationic Surfactants: n-Alkyl-3-Methylpyridinium Bromides and Their Drug Interaction Study by UV–Visible Spectroscopy and Conductometry

The synthesis of new cationic surfactants i.e., n-hexyl-3-methylpyridium bromide ( a ) and n-octyl-3-methylpyridium bromide ( b ), and their characterization using multinuclear nuclear magnetic resonance spectroscopy (NMR) (¹H, ¹³C) and Fourier-transform infrared spectroscopy (FT-IR) spectroscopic techniques were reported. The micellization behavior of the synthesized surfactants was studied using conductometry and ultraviolet–Visible spectroscopy. The critical micelle concentration (CMC) of compounds a and b was found to be 0.41 and 0.35 m mol L⁻¹, respectively. The effect of temperature on the CMC of these compounds was examined in the range of 298–318 K and thermodynamic parameters (ΔG, ΔH, and ΔS) of the micellization process were calculated. The antibacterial study of the synthesized surfactants revealed their strong activity against different bacterial strains. Moreover, the interaction of drugs i.e., flurbiprofen and ketoprofen, with the synthesized surfactants was investigated for gaining insights into the role of micelles as drug-delivery devices. Drug–surfactant interactions were also confirmed via a conductometric method.     

Synthesis and surface activity of poly(maleic diester) surfactants

A series of maleic diester monomers have been prepared by esterification of maleic anhydride with a series of n-alkanols and poly(ethylene glycol) with different molecular weights. These monomers were polymerized in acetic anhydride solution in the presence of cumene hydroperoxide as initiator. The synthesized polymers have been characterized by IR and ¹H NMR spectroscopy, and their surface and thermodynamic properties as non-ionic surfactants is investigated. The surface tension as a function of concentration of the surfactant in aqueous solutions was measured at 298, 308, 318 and 328 K. The surface parameters are calculated. The data reveal that the CMC value of the polymeric surfactant is lower than that of the monomeric surfactant. It is also found that the CMC value decreases with increasing temperature and the number of ethylene oxide units in the surfactant molecule. The thermodynamic parameters of micellization and adsorption are also determined. The structural effectiveness of surface tension is discussed in terms of these parameters. © 1999 Society of Chemical Industry     

Surface Activity of Monomeric and Polymeric (3-alkyloxy aniline) Surfactants

ABSTRACT

The adsorption and micellization processes of 3-alkyloxy aniline namely [3-decyloxy aniline (C10M), 3-dodecyloxy aniline (C12M) and 3-cetyloxy aniline (C16M)] and their polymers [C10P, C12P and C16P] have been investigated using surface tension (γ) measurements at different temperatures. The synthesized monomers and polymers have been characterized by IR and elemental analysis. The surface and thermodynamic parameters of these monomeric and polymeric surfactants are investigated. The results show that the critical micelle concentration (CMC) of the polymeric surfactants is lower than that of monomers. The CMC values decreases as the hydrophobic chain lengthens for both monomeric and polymeric surfactants. The surface parameters show the ability of monomeric and polymeric surfactants to adsorb at the air/water interface and decrease the surface tension. The thermodynamic parameters reveal that the micellization process is spontaneous for all investigated surfactants. The specific conductance measurements show that the specific conductance increases with increasing chain length of the substituted alkyl groups, the synthesized polymeric surfactants have higher values of specific conductance than the corresponding monomers and the specific conductance increases with rising solution temperature.     

Conductometric Probe Analysis of the Effect of Benzyldimethylhexadecylammonium Chloride on the Micellization Behavior of Dodecyltrimethylammonium Bromide in Aqueous/Urea Solution: Investigation of Concentration and Temperature Effect

Surfactant mixtures are used in many different industrial formulations. In this study, the mixed micelle formation behavior of 2 different cationic surfactants, namely dodecyltrimethylammonium bromide (DTAB) and benzyldimethylhexadecylammonium chloride (BDHAC), in the absence and presence of urea at various temperatures (298.15–318.15 K) was studied using the conductometric method. The attractive interaction between DTAB and BDHAC was estimated from the values of critical micelle concentration (CMC) and the CMC for ideal mixing (CMC^id). Urea increases the CMC value as a result of the enrichment in the surface charge of the micelles/mixed micelles. The values of micellar mole fraction (X₁^Rub [Rubingh], X₁^M [Motomura], X₁^Rod [Rodenas]) and ideal micellar (X₁^id) of surfactant BDHAC were obtained by different models and are shown to exhibit the high contribution or effective involvement of BDHAC in mixed micelles and increase with increasing BDHAC mole fraction (α₁). Activity coefficients (f₁ and f₂) were also evaluated from the relevant formula given in the literature. The negative values of the interaction parameters (β) show the attractive interaction among the studied components. Excess Gibbs free energy (?G_ex) of micellization revealed that the stability of mixed micelles is higher in aqueous solution than in urea solution. The thermodynamic parameters, namely the Gibbs free energy change, enthalpy change, and entropy change (?G^o_m, ΔH^o_m, and ?S^o_m, respectively), were also calculated from the conventional standard equations.     

Surface Parameters and Biological Activity of <Emphasis Type="Italic">N</Emphasis>-(3-(Dimethyl Benzyl Ammonio) Propyl) Alkanamide Chloride Cationic Surfactants

Three cationic surfactants containing amide groups were prepared by quaternization of dimethylaminopropylamine with benzyl chloride. FTIR and ¹H-NMR spectroscopy were used to confirm the chemical structure of the prepared cationic surfactants. The surface parameters were estimated using surface tension measurements at three different temperatures. The prepared cationic surfactant showed a lower CMC than conventional cationic surfactants. Thermodynamic parameters of adsorption and micellization depend mainly of alkyl chain length and temperature. The adsorption process is more favorable than micellization. The biological activity of the three surfactants was estimated using inhibition zone showing that amidoamine cationic surfactants have good activity and the surfactants C12Bn is the most effective one.     

Spectroscopic Investigation of the Interaction of BSA with Cationic Surfactants

The interactions between dodecyltrimethylammonium bromide (DTAB), tetradecyltrimethylammonium bromide (TTAB), cetyltrimethylammonium bromide (CTAB), and hexadecylpyridinium chloride (HDPC) with bovine serum albumin (BSA) in an aqueous solution (pH = 7.0, 0.001 M HEPES buffer) were studied by fluorescence and circular dichroism (CD) measurements. These categories of surfactants were used to elucidate the effect of hydrophilic group and length of hydrophobic chain surfactant on the mechanism of binding to BSA. The result revealed that for all surfactants, at low concentrations, the Stern‐Volmer plots have an upward curvature and in high concentrations, the quenching efficiency was decreased with increase in surfactant concentration. The activation energy of the interaction between cationic surfactants and BSA was measured. The results of CD show that the conformation of BSA has been changed in the presence of cationic surfactants.     

Physicochemical Studies on the Interfacial and Micellization Behavior of CTAB in Aqueous Polyethylene Glycol Media

Interfacial and micellization behavior of cetyltrimethylammonium bromide (CTAB) have been studied in aqueous polyethylene glycol (PEG) mixed solvent systems of varying concentrations and molar mass. Interfacial behavior of CTAB was investigated by the equilibrium surface tension method. Conductance studies of surfactant solutions under different condition helped in determining the critical micelle concentration (CMC) and degree of dissociation of CTAB micelles. In addition, the limiting molar conductivity of surfactant and micellar species were evaluated from the differential plots. The CMC of CTAB was found to increase with increasing PEG concentration as well as its molar mass, although, the process of interfacial adsorption and micellization was found to be spontaneous, as evidenced by negative free energy change. The viscosity of CTAB micelles in aqueous-PEG mixtures was found to increase with the increase in PEG concentration and molar mass. Dynamic light scattering measurements revealed a size enhancement effect contributed by the PEG oligomers. An increase in the CMC of CTAB and the subsequent presence of a higher number of ionic species in their dissociated form was further established by an overall increase in the zeta potential value in the presence of PEG oligomers. It is proposed that the PEG could wrap around the micelles through their conformational changes. Results also suggest that PEG oligomers could give solvophobic effect which enhances the CMC of CTAB compared to that in pure water.     

利用荧光素异硫氰酸酯检测季铵盐阳离子表面活性剂的方法

使用荧光素异硫氰酸酯（FITC）实现了对季铵盐阳离子表面活性剂（QAS）在水溶液中临界胶束浓度（CMC）的准确测量及其在CMC以下的浓度定量。用该法测得十二烷基三甲基溴化铵（DTAB）和十六烷基三甲基溴化铵（CTAB）在水中的CMC分别为12～13 mmol·L^-1和0.70～096 mmol·L^-1,与电导率法、表面张力法和芘荧光法的检测值相近。对DTAB和CTAB的检测下限分别是011 mmol·L^-1和1.7 μmol·L^-1,定量范围分别为0.11～9.73 mmol·L^-1（0.034～3.0 g·L^-1）和1.7 μmol·L^-1～0.27 mmol·L^-1（6.2×10^-4～0.1 g·L^-1）。结果表明,使用FITC荧光探针检测QAS具有安全、简便、灵敏度和准确度高的优点。     

Interfacial Dynamic Properties and Dilational Rheology of Sulfonate Gemini Surfactant and its Mixtures with Quaternary Ammonium Bromides at the Air–Water Interface

The dynamic interfacial properties and dilational rheology of gemini sulfonate surfactant (SGS) and its mixtures with quaternary ammonium bromides (DTAB, CTAB) at the air–water interface were investigated using drop shape analysis. Results suggest that the adsorption process of these surfactants is diffusion-controlled at dilute concentrations, whereas the adsorption mechanism gradually shifts to a mixed kinetic-diffusion control with increasing surfactant concentration. The mixed surfactant system possesses the best surface activity when the molar ratios of SGS/DTAB and SGS/CTAB mixtures are 9:10. The formation of catanionic complexes shields the electrostatic repulsion between surfactant molecules and lowers the electrostatic adsorption barrier. Therefore, SGS/DTAB and SGS/CTAB mixtures exhibit higher adsorption rates than either component alone. The effects of oscillating frequency and surfactant concentration on the surface dilational properties of SGS, DTAB, CTAB, SGS/DTAB, and SGS/CTAB mixtures were also determined. As the oscillating frequency increases, the dilational elasticity of these surfactants gradually increases. The dilational elasticity peaks at a certain concentration, which is less than the critical micelle concentration (CMC). Results show that the dilational elasticity of SGS/DTAB and SGS/CTAB mixtures is higher than that of either component, resulting from the formation of a denser monomolecular adsorption layer at the air–water interface. Our study provides a basis for understanding the interaction mechanism of catanionic surfactant mixtures containing Gemini surfactant at the air–water interface.     

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.     

The Effect of NaCl on the Krafft Temperature and Related Behavior of Cetyltrimethylammonium Bromide in Aqueous Solution

This paper presents the effect of NaCl on the Krafft temperature (T _K), surface adsorption and bulk micellization of cetyltrimethylammonium bromide (CTAB) in aqueous solution. The critical micelle concentration (CMC) of CTAB in the presence of NaCl increased and then decreased with increasing temperature. Thus, the CMC–temperature data can be represented by a bell-shaped curve. The micellar dissociation (fraction of counterion binding) and energetic parameters (free energy, enthalpy and entropy changes) of both adsorption and micellization were calculated. The processes were found to be both enthalpy and entropy controlled and appeared to be more and more enthalpy driven with increasing temperature. An enthalpy–entropy compensation rule was observed for both adsorption and micelle formation. The T _K of the surfactant decreased significantly in the presence of NaCl, which is a sharp contrast to the usual behavior of the effect of electrolytes on the T _K of classical ionic surfactants. The surface excess concentrations decreased with increasing temperature. However, the values were much higher in the presence of NaCl compared to the corresponding values in pure water. The solubilization behavior of a water-insoluble dye, Sudan red B (SRB), in the micellar system was studied by the UV–visible spectrophotometric technique. The molar solubilization ratio in the presence of NaCl was found to be about three times higher than that in pure water, indicating that the solubilization of SRB in the CTAB micelles significantly increases in the presence of NaCl.     

Surface Activity,Thermodynamics of Micellization and Adsorption Properties of Quaternary Salts Based on Ethanolamines and Decyl Bromide

The surface-active properties of ionic-liquid type salts synthesized by the interaction of ethanolamines and decyl bromide have been studied. Surface tension as a function of concentration of the surfactant in aqueous solution was measured at 10, 20, 30 and 40 °C using a drop volume stalagmometer. From these measurements, the maximum surface excess concentration and the minimum area per molecule at the aqueous solution/air interface, the critical micelle concentration (CMC), the surface pressure at the CMC, and the standard thermodynamic parameters of adsorption and micellization were calculated. The structural effects on adsorption, micellization, and the effectiveness of surface tension reduction are discussed in terms of these parameters.     

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.     

Effect of Self-Assemblies on the Dynamics of the Briggs–Rauscher Reaction

The study involves the dynamic evolution of the Briggs–Rauscher (BR) reaction in the presence of various surfactants—SDS (sodium dodecyl sulphate) as anionic, CTAB (cetyl trimethylammonium bromide) as cationic and TritonX‐100 [4‐(1,1,3,3‐(tetramethylbutyl) phenyl polyethylene glycol] as a neutral one in single as well as mixed mode conditions (SDS + TX‐100 and CTAB + TX‐100). The reaction has been monitored potentiometrically at 30 °C under CSTR conditions. These surfactants affect the reaction dynamics to an extent which depends on the nature and concentration of the surfactant and the formation of their self‐assemblies. The experimental findings indicate that the oscillatory behavior of the BR reaction in the presence of surfactants is due to the efficacy of organized surfactant assemblies to selectively distribute the key species involved in the reaction, and their interaction with the counter ions in cases of ionic micelles. The study reveals that the evolution of oscillatory behavior is a characteristic feature of the surfactant.