Showing papers on "Aggregation number published in 2014"

Molecular dynamics simulations of sodium dodecyl sulfate micelles in water-the effect of the force field.

Abstract: Molecular dynamic (MD) simulations of preassembled sodium dodecyl sulfate (SDS) micelles are carried out using three versions of GROMOS, as well as CHARMM36, OPLS-AA, and OPLS-UA force fields at different aggregation numbers and box sizes. The differences among force fields have little effect on the overall micelle structure of small aggregates of size 60 or 100, but for micelles of an aggregation number of 300 or higher, bicelle structures with ordered tails, rather than the more realistic rodlike or cylindrical micelles with disordered tails, occur when using versions of GROMOS45A3 or the OPLS-AA force fields that are adapted to model the sulfate head group atoms using methods given in the literature. We find that the Lennard-Jones (L-J) parameters for the sodium ions and the ionic oxygens of the SDS head group, as well as the water model, control the transition to bicelles, regardless of other L-J parameters. A closer binding of the sodium ions to the head group ionic oxygens screens the electrostatic ...

Influence of temperature and organic solvents (isopropanol and 1,4-dioxane) on the micellization of cationic gemini surfactant (14-4-14).

Abstract: The micellar properties of gemini surfactant, tetramethylene-1,4-bis(dimethyltetradecylammonium bromide) (14-4-14) in binary aqueous mixtures of isopropanol (IP) and 1,4-dioxane (DO) were investigated by tensiometric, conductometric and microcalorimetric methods in the temperature range of 298 to 323 K. The values of both critical micelle concentration (cmc) and degree of dissociation increase with increasing temperature and concentration of cosolvent. The energetics of micellization was determined from the temperature dependence of critical micelle concentration values. The standard Gibbs free energy of micellization (ΔG) was found to be negative and the negative value decreases with both temperature and concentration of cosolvent. The Gibbs free energy of micellization (ΔG) is mainly controlled by tail transfer free energy. The enthalpy of micellization obtained from direct calorimetry, Gibbs-Helmholtz equation and van't Hoff methods are presented and compared. Entropic contribution is found to be larger than the enthalpy and for all the systems, an enthalpy-entropy compensation phenomenon was obtained. Some interfacial parameters, e.g., Gibbs surface excess (Γmax), minimum area per surfactant molecule (Amin), surface pressure (Πcmc) were been calculated. The fluorimetric technique was used to understand the microenvironment of the solution under the influence of cosolvent. The micellar aggregation number of 14-4-14 in a binary mixed solvent was also determined from fluorimetry using pyrene as a probe. Two fluorophores, fluorescein and curcumin delivered the information of the peripheral region of the micellar interface and palisade region. The self-diffusion coefficients of the micellar media were evaluated using the cyclic voltammetry (CV) method. Such multi-technique investigation provides a new look into the role of solvation in micellization.

Effect of cationic head group on micellization behavior of new amide-functionalized surface active ionic liquids

Abstract: Amide-functionalized surface active ionic liquids (SAILs), 1-methyl-1-dodecyl piperidinium chloride, [C12APip][Cl]; 1-methyl-1-dodecyl pyrrolidinium chloride, [C12APyrr][Cl]; 1-methyl-3-dodecyl imidazolium chloride, [C12Amim][Cl], and 1-methyl-1-dodecyl morpholinium chloride, [C12AMorph][Cl], have been synthesized, characterized and investigated for thermal stability, and micellization behavior in aqueous medium. The introduction of an amide moiety in the alkyl chain decreased the thermal stability of the functionalized SAILs compared to non-functionalized SAILs bearing a simple alkyl chain. A variety of state of the art techniques, viz. tensiometry, conductometry, steady-state fluorescence, isothermal titration calorimetry (ITC), dynamic light scattering (DLS) and atomic force microscopy (AFM), have been employed to investigate the micellization behavior. Amide-functionalized SAILs have shown much lower critical micelle concentration, cmc, and better surface active properties as compared to homologous non-functionalized SAILs. Steady-state fluorescence has provided information about cmc, aggregation number (Nagg) and polarity of the cybotactic region of the micelles, whereas ITC has provided insights into the thermodynamics of micellization. Furthermore, the size and shape of the micelles have been investigated using DLS and AFM techniques.

Micellization and Thermodynamic Study of 1-Alkyl-3-methylimidazolium Tetrafluoroborate Ionic Liquids in Aqueous Solution

Abstract: Three surfactant-like ionic liquids, 1-dodecyl-3-methylimidazolium tetrafluoroborate (C12mimBF4), 1-tetradecyl-3-methylimidazolium tetrafluoroborate (C14mimBF4), and 1-hexadecyl-3-methylimidazolium tetrafluoroborate (C16mimBF4) had been systematically studied by conductivity measurement, surface tension, steady-state fluorescence measurement and ultraviolet (UV) absorption spectra at 298.15 K. Micellization of the three ILs were certified by the above methods and aggregation number of micelles (Nagg) were determined by pyrene fluorescence quenching method. A comparison of CnmimBF4 with different alkyl chain lengths shows that that the critical micelle concentration (cmc) decreased remarkably with the increase of alkyl chain length, but the surface tensions at cmc (γcmc) were approximately the same, except for that of C16mimBF4. The effects of temperature, inorganic salt, and organic alcohols on the cmc of CnmimBF4 (n = 12, 14, 16) aqueous solution were also investigated. The results showed that the cmc va...

Effect of amide bonds on the self-assembly of gemini surfactants

Abstract: This study provides an insight into the micellar aggregation properties in aqueous solutions of various gemini surfactants bearing one or more amide groups at the side chains and/or in the spacer by conductivity and small angle neutron scattering (SANS) studies. The amide functionality was found to enhance the surfactant aggregation properties as compared to the surfactants having no amide bond. Furthermore, the aggregation properties of the gemini surfactants bearing amide groups were found to strongly depend on the position and number of amide bonds. With the increase in the number of amide bonds, the aggregation number (N) and the size of the micelles increased. Additionally, the size and shape of the micelles were also found to depend both on the hydrocarbon chain length and the spacer chain length. It was also found that the aggregation number and the size of the micelles increased with an increase in concentration and decreased with an increase in temperature. The critical micellar concentration (CMC) values of the gemini surfactants obtained by a conductometric method were found to vary greatly with variation in the hydrocarbon chain.

Cluster of Asphaltene Nanoaggregates by DC Conductivity and Centrifugation

Abstract: A model of the dominant molecular and stable colloidal structures of asphaltenes has been proposed, the Yen–Mullins model. The formation of clusters of asphaltene nanoaggregates in toluene was reported elsewhere to occur at a concentration of a few grams per liter with a cluster aggregation number of approximately 8 (Mullins, O. C. Energy Fuels 2010, 24, 2179−2207). Here, we measure the DC-conductivity signal of toluene as a function of asphaltene concentration obtaining support for the critical clustering concentration (CCC) of a roughly 1.7 g/L in toluene. In addition, the small change in the Stokes drag at the CCC indicates that the cluster aggregation number is small, less than 10. The temperature variation of the CCC is measured to be small and within error, suggesting that cluster formation is entropically driven. Centrifugation experiments were also performed on asphaltene–toluene solutions at different concentrations. These experiments confirmed that a significant change in asphaltene aggregation ...

Chaotropic‐Anion‐Induced Supramolecular Self‐Assembly of Ionic Polymeric Micelles

Abstract: Traditional micelle self-assembly is driven by the association of hydrophobic segments of amphiphilic molecules forming distinctive core–shell nanostructures in water. Here we report a surprising chaotropic-anion-induced micellization of cationic ammonium-containing block copolymers. The resulting micelle nanoparticle consists of a large number of ion pairs (≈60 000) in each hydrophobic core. Unlike chaotropic anions (e.g. ClO4−), kosmotropic anions (e.g. SO42−) were not able to induce micelle formation. A positive cooperativity was observed during micellization, for which only a three-fold increase in ClO4− concentration was necessary for micelle formation, similar to our previously reported ultra-pH-responsive behavior. This unique ion-pair-containing micelle provides a useful model system to study the complex interplay of noncovalent interactions (e.g. electrostatic, van der Waals, and hydrophobic forces) during micelle self-assembly.

Micellar drug nanocarriers and biomembranes: how do they interact?

Abstract: Pluronic based formulations are among the most successful nanomedicines and block-copolymer micelles including drugs that are undergoing phase I/II studies as anticancer agents. Using coarse-grained models, molecular dynamics simulations of large-scale systems, modeling Pluronic micelles interacting with DPPC lipid bilayers, on the μs timescale have been performed. Simulations show, in agreement with experiments, the release of Pluronic chains from the micelle to the bilayer. This release changes the size of the micelle. Moreover, the presence of drug molecules inside the core of the micelle has a strong influence on this process. The picture emerging from the simulations is that the micelle stability is a result of an interplay of drug–micelle core and block-copolymer–bilayer interactions. The equilibrium size of the drug vector shows a strong dependency on the hydrophobicity of the drug molecules embedded in the core of the micelle. In particular, the radius of the micelle shows an abrupt increase in a very narrow range of drug molecule hydrophobicity.

Influence of N-Alkylpyridinium Halide Based Ionic Liquids on Micellization of P123 in Aqueous Solutions: A SANS, DLS, and NMR Study

Abstract: The isotropic micellar state of Pluronic P123 in the presence and absence of N-alkylpyridinium halide ionic liquids (ILs) is investigated using SANS, DLS, and 1H NMR studies. The micellar structural parameters are obtained as a function of variation in alkyl chain length, anions, and concentrations of ILs by fitting the SANS scattering data with a model composed of core–shell form factor and a hard sphere structure factor of interaction. Addition of ILs decreases the micellar core, aggregation number, and hard sphere radius of P123 micelles. From quantitative analysis, we determined the amount of solvent (D2O + IL) present inside the core and the core–shell interface along with cationic head groups. This is further supported by monitoring interaction between ILs and polymer micelle using 1H NMR spectroscopy. The results are discussed and explained as a function of concentration of C8PyCl, alkyl chain length, and anions of N-alkylpyridinium halides.

Surfactant or block copolymer micelles? Structural properties of a series of well-defined n-alkyl–PEO micelles in water studied by SANS

Abstract: Here we present an extensive small-angle neutron scattering (SANS) structural characterization of micelles formed by poly(ethylene oxide)-mono-n-alkyl ethers (Cn–PEOx) in dilute aqueous solution. Chemically, Cn–PEOx can be considered as a hybrid between a low-molecular weight surfactant and an amphiphilic block copolymer. The present system, prepared through anionic polymerization techniques, is better defined than other commercially available polymers and allows a very precise and systematic testing of the theoretical predictions from thermodynamical models. The equilibrium micellar properties were elaborated by systematically varying the n-alkyl chain length (n) at constant PEO molecular weight or increasing the soluble block size (x), respectively. The structure was reminiscent of typical spherical star-like micelles i.e. a constant core density profile, ∼r0, and a diffuse corona density profile, ∼r−4/3. Through a careful quantitative analysis of the scattering data, it is found that the aggregation number, Nagg initially rapidly decreases with increasing PEO length until it becomes independent at higher PEO molecular weight as expected for star-like micelles. On the other hand, the dependency on the n-alkyl length is significantly stronger than that expected from the theories for star-like block copolymer micelles, Nagg ∼ n2 similar to what is expected for surfactant micelles. Hence the observed aggregation behavior suggests that the Cn–PEOx micelles exhibit a behavior that can be considered as a hybrid between low-molecular weight surfactant micelles and diblock copolymer micelles.

Cyclodextrins and surfactants in aqueous solution above the critical micelle concentration: where are the cyclodextrins located?

Abstract: Cyclodextrins (CDs) are known to bind surfactant molecules below the surfactant critical micelle concentration (CMC); however, interactions of CDs with surfactant micelles (above the CMC) are not well understood. In particular, direct structural evidence of the location of CDs in the different subphases found in micellar solutions is lacking. We have utilized small-angle neutron scattering (SANS) with contrast matching to probe the localization of α-cyclodextrin (α-CD) and 2-hydroxypropyl-β-cyclodextrin (HPβ-CD) in sodium dodecyl sulfate (SDS) micelles in aqueous (D2O) solutions. SANS data from solutions containing either hydrogenated or deuterated surfactants were analyzed by considering three different scenarios pertaining to the localization of cyclodextrin, either all in solution or some in the micelle shell or some in the micelle core, and were simultaneously fitted using the core-shell prolate ellipsoid form factor and the Hansen-Hayter-based structure factor. The scenario that considered a fraction of CD to localize in the micelle core well described the SANS data from both hydrogenated and deuterated SDS-CD-D2O solutions, while the other two scenarios did not. Among the various structural and interaction parameters obtained from this analysis, it emerged that the micelle core consisted of up to ∼10% HPβ-CD or ∼16% α-CD with respect to the total number of molecules (surfactants and CDs) present in the micelle at 25 mM SDS, and up to 14% HPβ-CD or 28% α-CD at 50 mM SDS. This is the first study that provides direct evidence on the location of cyclodextrin in the core of surfactant micelles. An improved understanding of CD interactions with surfactants and lipids would enable better strategies for drug encapsulation and delivery with CDs.

The Mass-Action-Law Theory of Micellization Revisited

Abstract: Among numerous definitions of the critical micelle concentration (CMC), there is one related to the constant K of the mass action law as CMC = K1–n (n is the aggregation number). In this paper, the generalization of this definition for multicomponent micelles and the development of the mass-action-law theory of micellization based on this definition and the analysis of a multiple-equilibrium polydisperse micellar system have been presented. This variant of the theory of micellization looks more consistent than the earlier one. In addition, two thermodynamic findings are reported: the stability conditions for micellar systems and the dependence of aggregation numbers on the surfactant concentrations. The growth of the monomer concentration with the total surfactant concentration is shown to be a thermodynamic rule only in the case of a single sort of aggregative particles or at adding a single surfactant to a mixture. The stability condition takes more complex form when adding a mixture of aggregative part...