Implicit solvent models for micellization of ionic surfactants

We propose a method for parametrization of implicit solvent models for the simulation of the self-assembly of ionic surfactants into micelles. The parametrization is carried out in two steps. The first step involves atomistic molecular dynamics simulations of headgroups and counterions with explicit solvent to determine structural properties. An implicit solvent model of the headgroup/counterion system is obtained by matching structural quantities between explicit solvent and implicit solvent systems. In the second step, we identify the solvophobic attractions between the tail beads. We determine the solvophobic parameters using grand canonical Monte Carlo simulations with histogram reweighting techniques. The matching objective for the identification of solvophobic attractions is the critical micelle concentration (cmc). We choose sodium dodecyl sulfate as the reference system. On the basis of hydrophobic parameters obtained from this particular model, we study specific ion effects (lithium and potassium instead of sodium) as well as the effect of cationic headgroups (dodecyltrimethylammonium bromide/chloride). Furthermore, the chain length dependence of micellization properties is investigated for sodium alkyl sulfate, with alkyl lengths between 6 and 14. All cases considered give results in broad agreement with experimental data, confirming the transferability of parameters and the generality of the approach.     

Thermodynamics of micellization of multiheaded single-chain cationic surfactants

The energetics of micelle formation of three single-chain cationic surfactants bearing single (h = 1), double (h = 2), and triple (h = 3) trimethylammonium [(+)N(CH(3))(3)] headgroups have been investigated by microcalorimetry. The results were compared with the microcalorimetric data obtained from well-known cationic surfactant, cetyl trimethylammonium bromide (CTAB), bearing a single chain and single headgroup. The critical micellar concentrations (cmc's) and the degrees of counterion dissociation (alpha) of micelles of these surfactants were also determined by conductometry. The cmc and the alpha values increased with the increase in the number of headgroups of the surfactant. The relationship between the cmc of the surfactant in solution and its free energy of micellization (DeltaG(m)) was derived for each surfactant. Exothermic enthalpies of micellization (DeltaH(m)) and positive entropies of micellization (DeltaS(m)) were observed for all the surfactants. Negative DeltaH(m) values increased from CTAB to h = 1 to h = 2 and decreased for h = 3 whereas DeltaS(m) values decreased with increase in the number of headgroups. The DeltaG(m) values progressively became less negative with the increase in the number of headgroups. This implies that micelle formation becomes progressively less favorable as more headgroups are incorporated in the surfactant. From the steady-state fluorescence measurements using pyrene as a probe, the micropolarities sensed by the probe inside various micelles were determined. These studies suggest that the micelles are more hydrated with multiheaded surfactants and the micropolarity of micelles increases with the increase in the number of headgroups.     

Thermodynamics of micellization of alkylimidazolium surfactants in aqueous solution

Alkylimidazolium salts are a very important class of compounds. So far, calorimetry has hardly been used to characterize their solution behaviour. The enthalpies obtained from indirect methods have an intrinsic large uncertainty, and nowadays it is clear that calorimetry is the most sensitive technique for directly measuring the thermodynamic properties of aggregation.In this work, isothermal titration calorimetry (ITC) was used along with conductivity to determine the thermodynamics of aggregation of 1-alkyl-3-methylimidazolium chlorides ([C_nmim]Cl, n = 8, 10, 12, and 14) in aqueous solution. The critical micelle concentrations, cmc, were obtained from conductivity and calorimetry, and the enthalpies of micelle formation, ΔH_mic, were derived from the calorimetric titrations. From conductivity, we could also derive the values for the degree of ionisation of the micelles (α), the molar conductivity (Λ^M) of the [C_nmim]Cl micellar species and the molar conductivity at infinite dilution (Λ^∞) for the [C_nmim]⁺ cations.Values are therefore reported for the enthalpy (ΔH_mic), the Gibbs free energy (ΔG_mic) and entropy (ΔS_mic) changes for micelle formation. Further, the aggregate sizes and aggregation numbers were obtained by light scattering (LS) measurements.The observed variation of the thermodynamic properties with the alkyl chain length is discussed in detail and compared with the traditional cationic surfactants 1-alkyl-trimethylammonium chlorides, [C_nTA]Cl. The difference in the values of the thermodynamic parameters for both types of surfactants is here related to the structure of their head groups.     

Adsorption and micellization behavior of novel gluconamide-type gemini surfactants

The adsorption and micellization behavior of novel sugar-based gemini surfactants (N,N(')-dialkyl-N,N(')-digluconamide ethylenediamine, Glu(n)-2-Glu(n), where n is the hydrocarbon chain length of 8, 10 and 12) has been studied on the basis of static/dynamic surface tension, fluorescence, dynamic light scattering (DLS) and cryogenic transmission electron microscope (cryo-TEM) data. The static surface tension of the aqueous Glu(n)-2-Glu(n) solutions measured at the critical micelle concentration (cmc) is observed to be significantly lower than that of the corresponding monomeric surfactants. This suggests that the gemini surfactants, newly synthesized in the current study, are able to form a closely packed monolayer film at the air/aqueous solution interface. The greater ability in the molecular association is supported by the remarkably (approximately 100-200 times) lower cmc of the gemini surfactants compared with the corresponding monomeric ones. With a combination of the fluorescence and DLS data, a structural transformation of the Glu(n)-2-Glu(n) micelles is suggested to occur with an increase in the concentration. The cryo-TEM measurements clearly confirm the formation of worm-like micelles of Glu(12)-2-Glu(12) at the concentration well above the cmc.     

Mixed micellization and surface properties of non-ionic/cationic surfactants

We investigate the surface properties of aqueous binary mixtures of our cationic surfactant O-dodecyl-N,N′-diisopropylisourea hydrochloride (ISO-DIC C₁₂) with commercially available nonionic surfactant polyoxyethylene p-(1,1,3,3-tetramethylbutyl)phenyl ether (TritonX-100) at different temperatures (288 to 303?K). The micellization behavior of the binary systems is studied by determining the surface tension and other important physicochemical parameters, such as the critical micelle concentration (CMC), surface tension at the CMC(γ_cmc), Krafft Temperature (T_K), maximum excess concentration (Γ_max), minimum surface area per molecule (A_min), surface pressure at the CMC (П_cmc), and the adsorption efficiency (pC20) at the air/water interface. The study has additionally covered the calculation of thermodynamic parameters of micellization, including the standard Gibbs free energy, the standard enthalpy, the standard entropy, the free energy, and the Gibbs free energy of adsorption at air/water interface. The CMC values of the binary systems determined by experimental data are used to evaluate the micellar composition in the mixed micelle, the interaction parameter β and the activity coefficients f₁(ISO-DIC C₁₂) and f₂ (polyoxyethylene p-(1,1,3,3-tetramethylbutyl)phenyl ether) using the theoretical treatment proposed by Clint and Rubingh. Our results reveal that the proposed binary systems possess enhanced surface activity compared to those of the individual surfactants.     

Effect of aminoacids on the critical micellization concentration of different surfactants

The effect of aminoacids (DL-glycine, DL-alanine, DL-serine, L-leucine, L-lysine, DL-phenylalanine, DL-tyrosine, and L-aspartic acid) on the critical micellization concentration (CMC) of nonionic, anionic, and cationic surfactants is investigated. It is established that, as the hydrophobicity of aminoacids rises, the CMC values of ionic and nonionic surfactants increase and decrease, respectively. An exception is aspartic acid, which reduces CMC values irrespective of the nature of surfactants.     

Thermodynamics of micellization for partially fluorinated cationic gemini surfactants and related single-chain surfactants in aqueous solution

A series of partially fluorinated cationic gemini surfactants and their corresponding monomeric surfactants have been studied by isothermal titration microcalorimetry. The critical micelle concentration (CMC) and enthalpy of micellization (DeltaH(mic)) were obtained from calorimetric curves. The CMCs of the gemini surfactants are much lower than those of the corresponding monomeric surfactants and decrease with an increase in the number of fluorine atoms on the hydrophobic chain. The micellization of partially fluorinated cationic gemini surfactants is much more exothermic than that of the corresponding monomeric surfactants. Because of the incompatibility of hydrocarbon spacer and partially fluorinated chain, DeltaH(mic) values of the surfactants with a C6 spacer are more negative than those of the surfactants with a C12 spacer. The variations in the architecture of the fluorocarbon chain segments may be the reason of the irregularities in the change of DeltaH(mic) for the gemini surfactants. Moreover, the contribution of the enthalpy generally increases with an increase in the number of fluorine atoms.     

Energetics in correlation with structural features: the case of micellization

Understanding micellization processes at the molecular level has direct relevance for biological self-assembly, folding, and association processes. As such, it requires complete characterization of the micellization thermodynamics, including its correlation with the corresponding structural features. In this context, micellization of a series of model non-ionic surfactants (poly(ethylene glycol) monooctyl ethers, C(8)E(gamma)) was studied by isothermal titration calorimetry (ITC) and differential scanning calorimetry (DSC). The corresponding structural properties of C(8)E(gamma) micelles were investigated by small-angle X-ray scattering (SAXS). The C(8)E(gamma) micellization, characterized independently from ITC, DSC, and structural data, reveals that deltaH(M)(o) > 0, deltaS(M)(o) > 0, and deltaC(P)(M)(o) < 0, while the dissection of its energetics shows that it is primarily governed by the transfer of 20-30 C(8) alkyl chains from aqueous solution into the nonpolar core (r approximately 1.3 nm) of the spherical micelle. Moreover, thermodynamic parameters of micellization, estimated from the structural features related to the changes in solvent-accessible surface areas upon micellization, are in a good agreement with the corresponding parameters obtained from the analysis of ITC and DSC data. We have shown that the contributions to deltaS(M)(o) other than from hydration (deltaS(M)(other)(o)), estimated from experimental data, appear to be small (deltaS(M)(other)(o) < 0.1 deltaS(M)(other)(o)) and agree well with the theoretical estimates expressed as a sum of the corresponding translational, conformational, and size contributions. These deltaS(M)(other)(o) contributions are much less unfavorable than those estimated for a rigid-body association, which indicates the dynamic nature of the C(8)E(gamma) micellar aggregates. the dynamic nature of the C8EY micellar aggregates.     

Physicochemistry of mixed micellization: Binary and ternary mixtures of cationic surfactants in aqueous medium

The importance of studying mixed micellization lies in tuning the performance of an amphiphile to bend through variation of stoichiometry of the blend. In this study, the binary and ternary mixed systems of cetylpyridinium chloride (CPC), tetradecyltrimethylammonium bromide, and dodecylpyridinium chloride (DPC) have been studied at 30°C using tensiometry and conductometry. In most cases, the cmc observed from either method is in close proximity whereas in CPC/DPC mixtures, tensometric cmc precedes conductometric cmc which may arise from a lowering in degree of counterion binding on micellar interface in the mixed system with lower stoichiometric mole fraction of CPC. Various existing theories have been used and the results were compared with the experimental observations.     

Monte carlo simulations of micellization in model ionic surfactants: application to sodium dodecyl sulfate

A lattice model for ionic surfactants with explicit counterions is proposed for which the micellization behavior can be accurately determined from grand canonical Monte Carlo simulations. The model is characterized by a few parameters that can be adjusted to represent various linear surfactants with ionic headgroups. The model parameters have a clear physical interpretation and can be obtained from experimental data unrelated to micellization, namely, geometric information and solubilities of tail segments. As a specific example, parameter values for sodium dodecyl sulfate were obtained by optimizing for the solubility of hydrocarbons in water and the structural properties of dodecane. The critical micelle concentration (cmc), average aggregation number, degree of counterion binding, and their dependence on temperature were determined from histogram reweighting grand canonical Monte Carlo simulations and were compared to experimental results. The model gives the correct trend and order of magnitude for all quantities but underpredicts the cmc and aggregation number. We suggest ways to modify the model that may improve agreement with experimental values.     

Molecular-thermodynamic theory of micellization of multicomponent surfactant mixtures: 1. Conventional (pH-Insensitive) surfactants

A molecular-thermodynamic (MT) theory was developed to model the micellization of mixtures containing an arbitrary number of conventional (pH-insensitive) surfactants. The theory was validated by comparing predicted and experimental cmc's of ternary surfactant mixtures, yielding results that were comparable to, and sometimes better than, the cmc's determined using regular solution theory. The theory was also used to model a commercial nonionic surfactant (Genapol UD-079), which was modeled as a mixture of 16 surfactant components. The predicted cmc agreed well with the experimental cmc, and the monomer concentration was predicted to increase significantly above the cmc. In addition, the monomer and the micelle compositions were predicted to vary significantly with surfactant concentration. These composition variations were rationalized in terms of competing steric and entropic effects and a micelle shape transition near the cmc. To understand the packing constraints imposed on ternary surfactant mixtures better, the maximum micelle radius was also examined theoretically. The MT theory presented here represents the first molecular-based theory of the micellization behavior of mixtures of three or more conventional surfactants. In article 2 of this series, the MT theory will be extended to model the micellization of mixtures of conventional and pH-sensitive surfactants.     

The temperature dependence of the heat capacity change for micellization of nonionic surfactants

The thermodynamic parameters that govern micelle formation by four different nonionic surfactants were investigated by ITC and DSC. These included n-dodecyldimethylphosphine oxide (APO12), Triton X-100 (TX-100), n-octyltetraoxyethylene (C8E4), and N,N-dimethyloctylamine-N-oxide (DAO8). All of these surfactants had been previously investigated by solution calorimetry over smaller temperature ranges with conflicting conclusions as to the temperature dependence of the heat capacity change, DeltaCp, for the process. The temperature coefficient of the heat capacity change, B (cal/mol K2), was derived from the enthalpy data that were obtained at small intervals over a broad temperature range. The values obtained for each of the surfactants at 298.2 K for DeltaCp and B were -155+/-2 and 0.50+/-0.36 (APO12), -97+/-3 and -0.24+/-0.18 (TX-100), -105+/-2 and 1.0+/-0.3 (C8E4), and -82+/-1 and 0.36+/-0.04 (DAO8), cal/mol K and cal/mol K2, respectively. The resulting B-values did not correlate with the cmc, aggregation number, or structure of the monomer in an obvious way, but they were found to reflect the relative changes in hydration of the polar and nonpolar portions of the surfactant molecule as the micelles are formed. An analysis of the data obtained from DSC scans was used to describe the temperature dependence of the critical micelle concentration, cmc. An abrupt increase in heat capacity was observed for TX-100 and C8E4 solutions of 36.5+/-0.5 and 21+/-5 cal/mol K, respectively, as the temperature of the scan passed through the cloud point. This change in heat capacity may reflect the increased monomer concentration of the solutions that accompanies phase separation, although other interpretations of this jump are possible.     

Gemini阳离子表面活性剂在水溶液中胶团化行为的温度效 应与焓、熵补偿

测定了Cemini阳离子表面活性剂C~m-----s-----C~m·2Br(m=8,10,12,;s=2,6及m=12;s=3,4)水溶液的电导,从电导(k)～表面活性剂浓度(c)曲线的转折点可求得临界胶团浓度cmc.实验发现,Gemini阳离子表面活性剂的胶团化倾向明显强于其“单体分子”)即单离子头基单烷烃链表面活性剂)。根据质量作用模型计算了胶经过程的吉布氏能、焓和熵的改变。结果表明Gemini表面活性剂聚集机理和其对应的“单体分子”类似,主要来自熵驱动。所有的焓/熵补偿图均呈现良好的线性关系,补偿直线在γ轴的截距随s减小而变小,这意味着具有较小s的Gemini表面活性剂倾向于生成稳定的胶团。     

Synthesis,micellization properties,and cytotoxicity trends of N-hydroxyethyl-3-alkyloxypyridinium surfactants

N-hydroxyethyl-3-alkyloxypyridinium amphiphiles have been synthesized and characterized by various spectroscopic techniques. Self-assembling properties of these amphiphiles have been studied by surface tension, conductivity, and fluorescence measurements. Basic micellization parameters like critical micelle concentration (cmc), surface tension at the cmc (γ _cmc), adsorption efficiency (pC₂₀), effectiveness of surface tension reduction (Π _cmc), maximum surface excess concentration (Γ _max) and minimum surface area/molecule (A _min), and Gibbs free energy of the micellization (ΔG⁰ _mic) have also been determined. The micellization of these 3-alkyloxypyridinium halides in aqueous phase have been found to be exothermic and entropy-driven as assessed by conductivity measurements at different temperatures. Thermal degradation of these surfactants has also been assessed by thermal gravimetric analysis under nitrogen atmosphere. Further, 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay of these surfactants on C6 glioma cells show them to be less toxic than conventional cationic surfactants.     

Head-group-influenced mixed micellization of sodium deoxycholate with conventional hydrocarbon surfactants of identical hydrocarbon tails

Conductivity, viscosity, turbidity, and NMR measurements were performed over most of the mole fraction range for sodium deoxycholate (SDC) with hexadecyltrimethylammonium bromide (HTAB), hexadecylpyridinium bromide (HPyBr), and hexadecylpyridinium chloride (HPyCl). All studies demonstrate that the mixed-micelle formation is more favorable in SDC plus HTAB rather than SDC plus HPyBr or SDC plus HPyCl mixtures. The results showed that the bulky pyridinium head groups of HPyBr or HPyCl create steric incompatibility with rigid SDC monomers in the mixed state.     

Mixed micellization of anionic–nonionic surfactants in aqueous media: a physicochemical study with theoretical consideration

Mixed micellization of binary and ternary mixtures of anionic and nonionic surfactants, such as lithium dodecyl sulfate, polyoxyethylene(23)laurylether, and polyoxyethylene-tert-octylphenylether, is studied in aqueous solution using tensiometric, conductometric, and spectrophotometric methods. Although tensiometry and conductometry complement each other closely, the spectroscopic critical micellar concentration (cmc) is far from agreement with tensiometric study. Several parameters, e.g., cmc, degree of counterion binding, free energies of micellization, and interfacial adsorption, have been evaluated. Established theories of Clint, Rosen, Rubingh, Motomura, Georgiev, Maeda, and Blankschtein were applied to evaluate the mole fraction of different components in the self-aggregated phase, the interaction parameter, free energy contributions, and expected cmc.