Micelle-forming Surfactants Research Articles

Volume and Expansivity Changes of Micelle Formation Measured by Pressure Perturbation Calorimetry

We present the application of pressure perturbation calorimetry (PPC) as a new method for the volumetric characterization of the micelle formation of surfactants. The evaluation is realized by a global fit of PPC curves at different surfactant concentration ranging, if possible, from below to far above the CMC. It is based on the knowledge of the temperature dependence of the CMC, which can for example be characterized by isothermal titration calorimetry. We demonstrate the new approach for decyl-β-maltopyranoside (DM). It shows a strong volume increase upon micelle formation of 16 ± 2.5 mL/mol (+4%) at 25 °C, and changes with temperature by -0.1 mL/(mol K). The apparent molar expansivity (E(S)) decreases upon micelle formation from 0.44 to 0.31 mL/(mol K) at 25 °C. Surprisingly, the temperature dependence of the expansivity of DM in solution (as compared with that of maltose) does not agree with the principal behavior described for polar (E(S)(T) decreasing) and hydrophobic (E(S)(T) increasing) solutes or moieties before. The results are discussed in terms of changes in hydration of the molecules and internal packing of the micelles and compared with the volumetric effects of transitions of proteins, DNA, lipids, and polymers.

Control of spontaneous spiral formation in a zwitterionic micellar medium

The transition from planar fronts, trigger waves or solitary pulses to spirals in excitable media, has attracted increasing interest in the past few decades, mainly because of its relevance for biological and medical applications. In this paper we describe a new and convenient method for spiral generation starting from symmetric wavefronts. By using the micelle-forming zwitterionic surfactant N-tetradecyl-N,N-dimethylamine oxide in a Belousov–Zhabotinsky solution, it is possible to control to a large extent the domains where spirals can be spontaneously generated. The mechanism responsible for the wavefront break up lies in the interaction of the propagating waves with the unexcitable regions formed by the interaction of the surfactant with some of the Belousov–Zhabotinsky key intermediates.

Mechanism of the Mixed Surfactant Micelle Formation

This article provides a full description of the mixed micelle formation process at a molecular level. The mechanism of mixed micelle formation in binary surfactant aqueous solution systems, ionic/nonionic mixed systems (12-2-12/TX-100, 14-2-14/TX-100, and SDS/TX-100), and ionic/ionic mixed systems (12-2-12/TTAB, 14-2-14/TTAB, and SDS/CTAB), in heavy water solutions was studied by (1)H NMR spectroscopy. The critical micellization concentrations of each individual component in the mixed surfactant solutions were gained by analyzing changes in chemical shift and intensities of resonance peaks. The chemical shift changes indicated that in the 12-2-12/TX-100 and SDS/TX-100 systems, micelles of TX-100 formed first, and then 12-2-12 or SDS molecules were fused in the micelles, respectively, which has been proved by 2D NOESY experiments. In contrast, 14-2-14 was the first component to form the micelles in the 14-2-14/TX-100 system. Although 12-2-12 and 14-2-14 are analogs and differ only in the length of the hydrophobic chain by two methylene groups, they showed different behaviors in the micellization processes in the mixture with TX-100. The observation suggests that in the binary surfactant system under current study, the component with lower cmc in the mixed solution aggregates first; then, the other one fuses, resulting in the mixed micelles as the total concentration increases. The same results were obtained for the ionic/ionic solutions, 12-2-12/TTAB, 14-2-14/TTAB, and SDS/CTAB. The above results suggest that the two mixed surfactants do not aggregate synchronously. It obviously demonstrates that the so-called "cmc of the mixed surfactant solution" needs reconsideration.

The Role of Bromide Ions in Seeding Growth of Au Nanorods

We report our findings on the important role of bromide ions in the seeding growth process of Au nanorods. The seed-mediated process constitutes a well-developed method for synthesizing gold nanorods in high yield, which is facilitated by a micelle-forming surfactant, cetyltrimethylammonium bromide (CTA-Br). Despite the tremendous work in recent years, the growth mechanism of Au nanorods has not been fully understood. Contrary to the widely accepted mechanism of CTA(+) micelle-templated growth of Au nanorods, we have identified the critical role of bromide ions in the seeding growth of Au nanorods. We found that even when the micelle-forming agent (CTA(+)) concentration is below its critical micelle concentration (cmc), bromide ions added in the form of NaBr can successfully effect the growth of Au nanorods in good yield. By controlling the concentration of externally added bromide ions, the rod shape and dimensions of the resulting Au nanoparticles can be readily controlled in the presence of only a minimum amount of CTABr (as a steric stabilizer for nanorods). High-resolution TEM studies show that the as-formed nanorods are perfectly single crystalline, instead of penta-twinned ones, and are bound by {111} and {100} facets with a [110] direction as the elongation direction. A mechanism is proposed to account for the seeding growth of single crystalline Au nanorods. Overall, this work explicitly demonstrates that Br(-) indeed serves as an important shape-directing agent for gold nanorod formation in the seed-mediated process.

Self-assembly of ionogenic surfactants during their interaction with poly(propylenimine) dendrimers

The structure of complexes formed by poly(propylenimine) dendrimers of five generations and anionic micelle-forming surfactants is studied by X-ray diffraction. It is shown that, in complexes of lower generation dendrimers, the lamellar packing of surfactants is dominant. In complexes formed by dendrimers of the fourth and fifth generations, packing typical of compact dendrimer molecules prevails. This packing can be attributed to the distorted dense packing of ball-like complex species. Structural models of complexes that allow for penetration of surfactants into the dendrimer molecule and the size ratio of the aliphatic radical of a surfactant and a dendrimer are advanced.

Studies of Triton X-165–β-cyclodextrin interactions using both extrinsic and intrinsic fluorescence

The interaction of β-cyclodextrin with the non-ionic micelle-forming surfactant Triton X-165 (TX-165) has been studied using steady state fluorescence and fluorescence anisotropy techniques. Both extrinsic and intrinsic fluorescence have been exploited for the purpose. Phenosafranin (PSF), a cationic phenazinium dye, has been used as the extrinsic probe while fluorescence of TX-165 has served as the intrinsic one. PSF shows discernible interactions with both TX-165 and β-CD. The experimental results reveal that the extent of interaction of PSF with TX-165 is greater than with β-CD. However, addition of β-CD to a micellar solution of TX-165 containing PSF leads to a disruption of the micelles whereby the fluorophore is released from the micellar environment to the bulk aqueous phase. It has been substantiated that an inclusion complex is formed between the non-ionic surfactant and the cyclodextrin. A 1:1 stoichiometry of the TX-165–β-CD inclusion complex has been proposed. Such a complexation between TX-165 and β-CD results in an inhibition in the micellization process of TX-165 leading to an enhancement in the apparent CMC value. The inferences are drawn from a series of experiments, viz., binding studies, determination of micropolarity, heavy-ion quenching studies and steady state fluorescence anisotropy experiments monitoring both extrinsic and intrinsic fluorescences.

Thermodynamic analysis of the interaction between trivalent metal ions and sodium dodecyl sulfate: An electrical conductance study

The interaction between the trivalent cations chromium(III), lanthanum(III) and gadolinium(III) and the anionic surfactant sodium dodecyl sulfate (SDS) has been studied in aqueous solutions using electrical conductivity. This data, together with previous results for aluminium(III) and SDS, are considered in terms of interaction of the metal ions and dodecyl sulfate at a critical aggregation concentration ( cac) considerably below the surfactant cmc. The aggregates have a stoichiometry somewhat greater than that expected from simple charge neutralization, possibly due to formation of lamellar structures. Aggregates redissolve upon increasing SDS concentration, and at higher surfactant concentrations formation of surfactant micelles is observed. From detailed thermodynamic analysis of this process considerations are given on the major factors responsible for differences in behavior between the four trivalent cations.

Influence of a singly-charged electrolyte on the efficiency of solubilization compositions for the template synthesis of silica nanoadsorbents

Silica mesoporous materials of the MSM-41 type were obtained by bitemplate (solubilization) synthesis in an aqueous electrolyte solution (sodium chloride) using sodium metasilicate as the source of silica, alkylpyridinium halogenides as the micelle-forming surfactants, and monoethanoamides of n-aliphatic acids or trialkylphosphine oxides as the solubilizers. The influence of a singly-charged electrolyte and a solution of bitemplate composition on the X-ray structure and structure adsorption characteristics of the synthesized materials was analyzed. It was shown that mesoporous silica with better spatial structure and high specific surface values (Ssp = 1170–1200 m2/g, ΣV = 0.80–1.10 cm3/g, Dmeso = 3.5–4.1 nm) are formed under the investigated conditions of synthesis when alkylpyridinium halogenides with a length of a hydrocarbon radical consisting of 10, 12, or 14 carbon atoms are used.

Thermothickening in Solutions of Telechelic Associating Polymers and Cyclodextrins

Telechelic associating polymers (hydrophilic ethoxylated backbone, hydrophobic n-alkyl end-groups) form viscous solutions in water due to associations between the hydrophobes. The addition of alpha-, beta-, or gamma-cyclodextrin (CD) substantially reduces the solution viscosity because the CD molecules envelop and sequester the hydrophobes in their hydrophobic cavities. The present paper explores the variation in polymer-CD solution viscosity with temperature. We find that, in the case of alpha-CD alone, the solutions show "thermothickening", i.e., the viscosity increases from 25 to ca. 60 degrees C whereupon it reaches a peak value and then drops. In contrast, solutions with beta- and gamma-CD show monotonic drops in viscosity upon heating. At a fixed polymer content, the thermothickening is higher for higher alpha-CD concentrations. We have also studied how surfactants and lipids impact the thermothickening. Addition of single-tailed micelle-forming surfactants causes the viscosity to revert to the more typical decreasing trend with temperature. However, addition of double-tailed lipids to a polymer/alpha-CD solution accentuates the thermothickening behavior. The thermothickening is explained by the propensity of alpha-CDs to unbind from the hydrophobes and form inclusion complexes with the polymer backbone as the temperature is raised.

Enantiomeric separation by MEKC using dodecyl thioglycoside surfactants: Importance of an equatorially oriented hydroxy group at C‐2 position in separation of dansylated amino acids

To investigate the influence of stereogenic centers of sugar-based surfactants for enantiomeric separation, four n-dodecyl thioglycoside sulfates (CMC 1.5-3.6 mM) were chosen as micelle-forming surfactants and five dansylated hydrophobic amino acids were used as test analytes. The analytes were mutually separated by these micelles exhibiting almost similar migration times independent of the used surfactant. Baseline separations of all enantiomers were achieved using both beta-D-glucose and beta-D-galactose derivates that have an equatorially oriented hydroxy group at C-2 position. In contrast, the ability of enantioseparation was markedly decreased in the case of beta-D-mannose and 2-deoxy-beta-D-glucose derivatives. These results suggested that the structure of C-2 position of the sugar unit, namely presence of an equatorially oriented hydroxy group, is highly important for the enantiomeric separation of the chosen hydrophobic dansylated amino acids.

Enantioseparation by MEKC using a ligand exchange‐based chiral pseudostationary phase

In this paper, a new ligand-exchange -MEKC mode, based on the design of a unique lipohilic species (4'-octadecylneamine derivative), which served both as micelle-forming surfactant (by its hydrophobic part) and central ion-complexing ligand (by its hydrophilic part) is described. The CMC of the used lipophilic neamine derivative was first determined by surface tension measurements. Subsequent NMR experiments were performed in order to investigate the Cu(II) binding properties of the neamine micellar phase. The enantioseparation properties of both the octadecylneamine derivative-Cu(II) MEKC and the native neamine-Cu(II) CE systems were evaluated and compared using the tryptophan racemate as a probe analyte. The effects of several different electrophoretic conditions on the enantiomer migration behavior in the ligand-exchange-MEKC mode were examined. The developed methodology was also applied to the enantioseparation of other analytes such as 1-methyl-tryptophan, 3,5-diiodo-tyrosine and 1-naphtyl-alanine.

Bitemplate Synthesis of Mesoporous Silicas with Thiourea Groups

Mesoporous silicas with the thiourea functional group ≡Si(CH2)3NHC(S)NHC2H5 have been synthesized by monotemplate and bitemplate route (bitemplate is cetylpyridinium chloride as micelle-forming surfactant and monoethanolamide of saturated n-aliphatic acid as non-micelle-forming surfactant). The infl uence of a number of factors on mesoporous silicas structure has been studied: alkoxysilanes and surfactants concentration, and as well as the nature of medium in hydrothermal treatment of mesophases. The optimum conditions under which functionalized mesoporous silicas have possessing highly ordered hexagonal structure have been found. The surface area of mesoporous silicas synthesized using optimum bitemplate solubilization composition reaches 1055-1350 m2/g and sorption volume and pore diameter are 0.75-0.95 cm3/g and 2.5-2.9 nm respectively.

Formation and transformations of polyelectrolyte gel-ampholyte dendrimer-surfactant ternary complexes

The reactions of complex gels formed via the sorption of a poly(propylenimine) ampholyte dendrimer of the fourth generation by oppositely charged lightly cross-linked polyelectrolyte hydrogels with ionogenic micelle-forming surfactants have been studied. The sorption of surfactant ions likely charged relative to the complexed ampholyte dendrimer by complex gels is associated with two parallel chemical reactions controlled by the concentration of the surfactant and pH which give rise to the formation of network-dendrimer-surfactant tertiary complexes. The reactions of complex gels with surfactant ions likely charged relative to the network polyelectrolyte make it possible at different solution pHs to prepare both negatively and positively charged hydrogels reinforced by disperse particles of the dendrimer-surfactant complex.

Physicochemical and toxicological properties of novel amino acid-based amphiphiles and their spontaneously formed catanionic vesicles

The design of efficient liposomal systems for drug delivery is of considerable biomedical interest. In this context, vesicles prepared from cationic/anionic surfactants may offer several advantages, mainly due to their spontaneity in formation and long-term stability. There is also an impending need to produce less toxic, more biocompatible amphiphiles, while maintaining the desirable aggregation properties. In this work, we present data for acute toxicity to Daphnia magna (IC 50), and potential ocular irritation (HC 50) for some newly prepared ionic surfactants with dodecyl chains, derived from the amino acids tyrosine (Tyr), serine (Ser), hydroxyproline (Hyp) and lysine (Lys). The micellization behavior of the compounds, evaluated from surface tension measurements, is presented and compared to more conventional ionic amphiphiles. Two types of spontaneouly formed catanionic vesicles, composed either by a dodecyltrimethylammonium bromide (DTAB)/Lys-derivative and or Ser-/Lys-derivative mixture, have also been tested for their ecotoxicity and hemolytic potential. All the micelle-forming surfactants as well as the vesicle-containing mixtures are found to have lower ecotoxicity than the reference surfactant DTAB. Moreover, the results from hemolysis and hemoglobin denaturation tests show that the Tyr- and Lys-derivatives are moderately irritant, whereas the Hyp- and Ser- ones are just slightly irritant. Even more significantly, the vesicle-containing mixtures exhibit lower hemolytic activity than the neat surfactants, a positive result for their potential use in liposomal formulations.

Phenanthrene partitioning in sediment–surfactant–fresh/saline water systems

The objective of this study was to investigate the influence of salinity on the effectiveness of surfactants in the remediation of sediments contaminated with phenanthrene (PHE). This is an example of a more general application of surfactants in removing hydrophobic organic compounds (HOCs) from contaminated soil/sediment in saline environments via in-situ enhanced sorption or ex-situ soil washing. Salinity effects on surfactant micelle formation and PHE partitioning into solution surfactant micelles and sorbed surfactant were investigated. The critical micelle concentration of surfactants decreased, and PHE partition between surfactant micelles and water increased with increasing salinity. Carbon-normalized partition coefficients ( K ss) of PHE onto the sorbed cationic surfactant increased significantly with increasing salinity, which illustrates a more pronounced immobilization of PHE by cationic surfactant in a saline system. Reduction of PHE sorption by anionic surfactant was more pronounced in the saline system, indicating that the anionic surfactant has a higher soil washing effectiveness in saline systems.

Imperfect Dissolution in Nonionic Block Copolymer and Surfactant Mixtures

Self-assembled copolymer micelles have been widely explored for numerous applications including cosmetic formulations and detergency, drug delivery, and agriculture. In many of these technologies at least trace amounts of surfactants and detergents are present, yet little is known regarding their effect on the copolymer micelle structure. In this paper we examine the influence of a nonionic micelle-forming surfactant, Triton X-100, on spherical, nonionic polymeric micelles composed of poly(butadiene)-co-poly(polyethylene oxide). Using cryo-TEM we find that relatively small surfactant concentrations (less than 1:1 molar ratio) are sufficient to disrupt the copolymer assemblies, and to yield, via dimerization, mixed polymer-surfactant micelles with characteristic diameters. Saturation of the polymeric micelles is reached with approximately 3 mM surfactant (1:8 mol ratio). Upon saturation, and in high surfactant excess, coexistence of two homogeneous micellar populations is found: saturated polymer-surfactant micelles, and much smaller micelles of pure surfactant. The lack of complete demicellization of the polymeric micelles is explained by packing constraints of the polymer hydrophobic chains by the added surfactant. This behavior is found to be characteristic of polymeric molecules with hydrophobic-to-hydrophilic molecular weight ratio close to, or exceeding, 0.75. We further found that structural transitions in polymer-surfactant mixtures are fast, and the systems reach equilibrium at time scales characteristic to the small molecule, in contrast with the slow equilibration in polymer-polymer mixtures.

Mechanism of Surfactant Micelle Formation

The mechanism of micelle formation of surfactants sodium dodecyl sulfate (SDS), n-hexyldecyltrimethylammonium bromide (CTAB) and Triton X-100 (TX-100) in heavy water solutions was studied by 1H NMR (chemical shift and line shape) and NMR self-diffusion experiments. 1H NMR and self-diffusion experiments of these three surfactants show that their chemical shifts (delta) begin to change and resonance peaks begins to broaden with the increase in concentration significantly below their critical micelle concentrations (cmc's). At the same time, self-diffusion coefficients ( D) of the surfactant molecules decrease simultaneously as their concentrations increase. These indicate that when the concentrations are near and lower than their cmc's, there are oligomers (premicelles) formed in these three surfactant systems. Carefully examining the dependence of chemical shift and self-diffusion coefficient on concentration in the region just slightly above their cmc's, one finds that the pseudophase transition model is not applicable to the variation of physical properties (chemical shift and self-diffusion coefficient) with concentration of these systems. This indicates that premicelles still exist in this concentration region along with the formation of micelles. The curved dependence of chemical shift and self-diffusion coefficient on the increase in concentration suggests that the premicelles grow as the concentration increases until a definite value when the size of the premicelle reaches that of the micelle, i.e., the system is likely dominated by the monomers and micelles. Additionally, the approximate values of premicelle coming forth concentration (pmc) and cmc were obtained by again fitting chemical shifts to reciprocals of concentrations at a different perspective, and are in good accordant with experimental results and literature values and prove the former conclusion.

Prevention of MDR development in leukemia cells by micelle-forming polymeric surfactant

Doxorubicin (Dox) incorporated in nanosized polymeric micelles, SP1049C, has shown promise as monotherapy in patients with advanced esophageal carcinoma. The formulation contains amphiphilic block copolymers, Pluronics, that exhibit the unique ability to chemosensitize multidrug resistant (MDR) tumors by inhibiting P-glycoprotein (Pgp) drug efflux system and enhancing pro-apoptotic signaling in cancer cells. This work evaluates whether a representative block copolymer, Pluronic P85 (P85) can also prevent development of Dox-induced MDR in leukemia cells. For in vitro studies murine lymphocytic leukemia cells (P388) were exposed to increasing concentrations of Dox with/without P85. For in vivo studies, BDF1 mice bearing P388 ascite were treated with Dox or Dox/P85. The selected P388 cell sublines and ascitic tumor-derived cells were characterized for Pgp expression and functional activity (RT-PCR, Western Blot, rhodamine 123 accumulation) as well as Dox resistance (3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay). The global gene expression was determined by oligonucleotide gene microarrays. We demonstrated that P85 prevented development of MDR1 phenotype in leukemia cells in vitro and in vivo as determined by Pgp expression and functional assays of the selected cells. Cells selected with Dox in the presence of P85 in vitro and in vivo exhibited some increases in IC 50 values compared to parental cells, but these values were much less than IC 50 in respective cells selected with the drug alone. In addition to mdr1, P85 abolished alterations of genes implicated in apoptosis, drug metabolism, stress response, molecular transport and tumorigenesis. In conclusion, Pluronic formulation can prevent development of MDR in leukemia cells in vitro and in vivo.

Analysis of fluorescence spectra of PRODAN in protic solvents as the superposition of two Gaussian functions

The steady-state fluorescence emission spectra of 6-propionyl-2-dimethylaminonaphthalene (PRODAN) in aqueous solutions of methanol, ethanol and 1-propanol were studied in a wide range of concentrations. The flourescence of PRODAN was also studied in aqueous solutions (from 3 × 10−3 to 21 × 10−3 mole L−1) of dodecyltrimethylammonium bromide (DTAB), a micelle-forming ionic surfactant. In all cases, experimental data, as a function of wavelength, are very well fitted by the sum of two Gaussian functions. In alcohol solutions, the maximum of lower wavelength depends linearly both on concentration and polarizability. In DTAB solutions, the maximum of higher wavelength varies smoothly with concentration, but the lower wavelength maximum changes abruptly at the Critical Micellar Concentration. Results are explained by assuming that the fluorescence emission of PRODAN is originated in transitions from two excited states which are close in energy but have dissimilar interactions with the probe environment.

Thermotropic phase behavior in aqueous mixtures of dioctadecyldimethylammonium bromide and alkyltrimethylammonium bromide surfactant series studied by differential scanning calorimetry

The effect of the micelle-forming surfactant series alkyltrimethylammonium bromide (C n TAB, n = 12, 14, 16 and 18) on the thermotropic phase behavior of dioctadecyldimethylammonium bromide (DODAB) vesicles in water was investigated by differential scanning calorimetry at constant 5.0 mM total surfactant concentration and varying individual surfactant concentrations. The pre-, post- and main transition temperatures ( T s, T p and T m), melting enthalpy (Δ H) and peak width of the main transition (Δ T 1/2) are reported as a function of the surfactant molar fraction. No clear dependence of these parameters on the C n TAB chain length was found. At 5 mM, neat DODAB in water exhibits two transition temperatures, T s = 32.1 and T m = 42.7 °C, as obtained from the DSC upscans, but not a clear T p. For every n, except n = 12, T s vanishes as C n TAB concentration increases and approaches CMC. T m behaves differently for different n, the longer C 14TAB and C 16TAB decrease, while C 18TAB increases T m with increasing concentration. The data indicate that changes in T m, T s, T p and Δ H of the transition are related not only to the extent of C n TAB affinity to DODAB but also to the surfactant chain length. Accordingly, C 18TAB yields a more compact bilayer, thus increasing T m, while C 14TAB and C 16TAB yield a less organized bilayer and reduce T m. C 12TAB does not much affect T s and T m, although it yields T p ≈ 51.6 °C.