Mixing of partially fluorinated carboxylic acids with their hydrocarbon analogs at the air-water interface

Rheological behavior of surfactant-stabilized colloidal dispersions of silica particles under extreme conditions (low pH, high ionic strength) has been investigated in relation to interparticle forces and stability of the dispersion. The surfactant used as the dispersing agent was C(12)TAB, a cationic surfactant. Stability analysis through turbidity measurements indicated that there is a sharp increase in the stability of the dispersion when the surfactant concentration is in the range of 8 to 10 mM in the system. The state of the dispersion changes from an unstable regime to a stable regime above a critical concentration of C(12)TAB in the system. In the case of interaction forces measured between the silica substrate and AFM tip, no repulsive force was observed up to a surfactant concentration of 8 mM and a transition from no repulsive forces to steric repulsive forces occurred between 8 and 10 mM. Rheological measurements as a function of C(12)TAB concentration indicated a significant decrease in the viscosity and linear viscoelastic functions of the dispersion over the same range of surfactant concentration (8 to 10 mM C(12)TAB), showing a strong correlation between the viscosity behavior, interparticle forces, and structure development in the dispersion.     

Co-adsorption of carboxymethyl-cellulose and cationic surfactants at the air-water interface

We investigated the interaction between an anionic polyelectrolyte (carboxymethylcellulose) and cationic surfactants (DTAB, TTAB, and CTAB) at the air/water interface, using surface tension, ellipsometry, and Brewster angle microscopy techniques. At low surfactant concentration, a synergistic phenomenon is observed due to the co-adsorption of polyelectrolyte/surfactant complexes at the interface, which decreases the surface tension. When the surfactant critical aggregation concentration (cac) is reached, the adsorption saturates and the thickness of the adsorbed monolayer remains constant until another characteristic surfactant concentration, C0, is reached, at which all the polymer charges are bound to surfactant in bulk. Above C0, the absorbed monolayer becomes much thicker, suggesting adsorption of bulk aggregates, which have become more hydrophobic due to charge neutralization.     

Mixed adsorption of fluorinated and hydrogenated surfactants

The adsorption isotherms of sodium perfluorooctanoate and sodium decyl sulfate and their 1:1 mixture on gamma-alumina are recorded by depletion-type experiments with (1)H and (19)F NMR spectroscopy as the detection tool. The isotherms of the different surfactant species, obtained with and without added salt, closely resemble each other. Salt addition changes the isotherms from stepwise to the familiar S-shaped. After having reached saturation, a further increase of surfactant concentration in the mixed system leads to decyl sulfate desorption and increased perfluorooctanoate adsorption. The (19)F chemical shift of adsorbed perfluorooctanoate suggests that, for saturated surfaces, the two sorts of adsorbed surfactants form molecularly mixed surface aggregates.     

Mixed micelles of fluorinated and hydrogenated surfactants

The model mixed surfactant system of sodium perfluorooctanoate and sodium decyl sulfate was carefully reexamined by a combination of nuclear magnetic resonance methods. Over a wide range of sample compositions, detailed (19)F and (1)H chemical shift data in combination with self-diffusion coefficients for the perfluorooctanoate and decyl sulfate ions are collected. All data are analyzed together in a framework that uses a minimal number of initial assumptions to extract the monomer concentrations of both surfactants and the micellar chemical shifts of (19)F and (1)H as a function of relative concentration. The main conclusion drawn from this analysis is that there exists neither complete demixing nor complete mixing on molecular or micellar levels. Instead, the experimental data favor a single type of micelles within which fluorinated surfactants are preferentially coordinated by fluorinated ones and hydrogenated surfactants by hydrogenated ones. The data are quantitatively interpreted in the framework of the first approximation of the regular solution theory (also called the quasi-chemical treatment) leading to an energy of mixing of omega = W/kT = 0.98 between the constituting surfactant types. These findings may help to resolve a long controversy about micellar mixing-demixing in this particular mixture and in its relatives.     

Adsorption of ionic surfactants at an expanding air-water interface

A quantitative model for the kinetics of adsorption of ionic surfactants to an expanding liquid surface is presented for surfactant concentrations below and above the critical micelle concentration (cmc). For surfactant concentrations below the cmc, the electrostatic double layer is accounted for explicitly in the adsorption isotherm. An overflowing cylinder (OFC) was used to create nonequilibrium liquid surfaces under steady-state conditions. Experimental measurements of the surface excess for solutions of cationic surfactants CH3(CH2)n-1N+(CH3)3 Br- (CnTAB, n = 12, 14, 16) and the anionic fluorocarbon surfactant sodium bis(1H,1H-nonafluoropentyl)-2-sulfosuccinate (di-CF4) in the OFC are in excellent agreement with the theoretical predictions for diffusion-controlled adsorption for all concentrations studied below the cmc. For surfactant concentrations above cmc, the diffusion ofmicelles and monomers are handled separately under the assumption of fast micellar breakdown. This simplified model gives excellent agreement for the system C14TAB + 0.1 M NaBr above the cmc. Agreement between theory and experiment for C16TAB + 0.1 M NaBr is less good. A plausible explanation for the discrepancy is that micellar breakdown is no longer fast on the time scale of the OFC (ca. 0.1 s).     

Dynamic surface tension and adsorption mechanisms of surfactants at the air-water interface

Recent advances in understanding dynamic surface tensions (DSTs) of surfactant solutions are discussed. For pre-CMC solutions of non-ionic surfactants, theoretical models and experimental evidence for a mixed diffusion-kinetic adsorption mechanism are covered. For micellar solutions of non-ionics, up to approximately 100 x CMC, the DST behaviour can also be accounted for using a mixed mechanism model. Finally, the first reported measurements of the dynamic surface excess Gamma(t), using the overflowing cylinder in conjunction with neutron reflection, are described.     

Dependence of phase behavior of some non-ionic surfactants at the air-water interface on micellization in the bulk

The temperature-dependent surface phase behavior of two sparingly soluble surfactants, namely, ethylene glycol n-dodecyl ether (EGDE) and ethylene glycol n-tetradecyl ether (EGTE), at the air-water interface was investigated by film balance and Brewster angle microscopy (BAM). A cusp point followed by a pronounced plateau region in the surface pressure-time (pi-t) adsorption isotherms of the amphiphiles measured by film balance indicates the first-order phase transition. Bright two-dimensional condensed phase domains in a dark background are observed by BAM just after the phase transition. In both cases the critical surface pressure necessary for the phase transition increases with increasing temperature. The domains are found to be circular up to 5 and 27 degrees C for EGDE and EGTE, respectively, above which they show a fingering pattern. Condensed domains are observed up to 23 and 37 degrees C for EGDE and EGTE, respectively. The surface properties of the amphiphiles are found to be markedly affected by their tendency to aggregate in the bulk as micelles. The CMC values of both the amphiphiles show a maximum at a definite temperature, T(max), that corresponds well to their respective maximum temperatures of domain formation. An increase in temperature beyond T(max) results in an increasing trend for the formation of micelles. Consequently the system suffers from a shortage of two-dimensional surface concentration of the molecules to attain the surface pressure necessary for phase transition. With increasing temperature, the enthalpy, DeltaH(m) degrees , and entropy, DeltaS(m) degrees , of micellization change from negative to positive in both cases. An enthalpy-entropy compensation effect is found to hold for both the amphiphiles over the entire temperature range. The thermodynamic quantities reveal that the increase in temperature is favorable for micellization when the temperature exceeds the corresponding T(max) of the amphiphiles.     

Interactions of a fluoroaryl surfactant with hydrogenated, partially fluorinated, and perfluorinated surfactants at the air/water interface

A novel surfactant containing pentafluorophenyl moiety attached at the terminal position of undecanol (11,11-difluoro-11-(pentafluorophenyl)undecan-1-ol, abbr. PBD) was synthesized and employed for the Langmuir monolayer characterization and miscibility studies with a semifluorinated alkane (perfluorodecyleicosane, abbr. F10H20) and four alcohols differing in the degree of fluorination in their hydrophobic chains: octadecanol (C18OH), perfluorooctyldecanol (F8H10OH), perfluoroisononyldecanol (iF9H10OH) and 1H,1H-perfluorooctadecanol (F18OH). Pure monolayers of all of the investigated surfactants as well as their mixtures were investigated with surface pressure-area isotherms complemented by Brewster angle microscopy (BAM) images. PBD was found to form stable Langmuir monolayers of liquid-expanded character. Characteristic dendritic structures were formed at the very early stage of compression and remained up to the vicinity of collapse, where 3D crystallites appeared. 2D miscibility studies revealed that PBD forms mixed monolayers with the investigated semifluorinated alkane (F10H20) as well as with perfluorinated alcohol (F18OH) within the whole composition range, do not mix with octadecanol to the fully hydrogenated alcohol, whereas it is partially miscible (up to a certain surface pressure value) with the studied semifluorinated alcohols. The analysis of the miscibility derived from the surface pressure-area isotherms (collapse pressure vs composition dependencies) agrees well with BAM images. Molecular interactions in the investigated systems have been quantified with interaction parameter, alpha.     

Mixtures of hydrogenated and fluorinated lactobionamide surfactants with cationic surfactants: study of hydrogenated and fluorinated chains miscibility through potentiometric techniques

The work reported herein deals with the aqueous behavior of hydrocarbon and/or fluorocarbon ionic and nonionic surfactants mixtures. These mixtures were studied using potentiometric techniques in NaBr (0.1 mol L-1) aqueous solution as well as in pure water. Mixed micelles were formed from a cationic surfactant (dodecyl or tetradecyltrimethylammonium bromide respectively called DTABr or TTABr) and neutral lactobionamide surfactants bearing a hydrogenated dodecyl chain (H12Lac) or a fluorinated chain (CF3-(CF2)5-(CH2)2- or CF3-(CF2)7-(CH2)2-). We showed that concentrations of ionic and nonionic surfactants in the monomeric form as well as the composition of the mixed micelles can be specified thanks to a potentiometric technique. The complete characterization does not request any model of micellization a priori. The activities of the micellar phase constituents, as well as the free enthalpies of mixing, were calculated. The subsequent interpretation only relies on the experimental characterization. Comparison of the behaviors of the various systems with a model derived from the regular solution theory reveals the predominant part of electrostatic interactions in the micellization phenomenon. It also appears that the energy of interaction between hydrogenated and fluorinated chains is unfavorable to mixing and is of much lower magnitude than the electric charges interactions.     

Protein-surfactant interaction: differences between fluorinated and hydrogenated surfactants

The interactions of proteins with fluorinated/hydrogenated surfactants were investigated by circular dichroism and turbidity measurement. Pairs of fluorinated and hydrogenated surfactants with similar critical micelle concentrations (cmc), including sodium perfluorooctanoate/sodium decylsulfate and lithium perfluorononanoate/sodium dodecylsulfate were compared in view of their interactions with proteins including BSA, lysozyme, β-lactoglobulin and ubiquitin. It was found that fluorinated surfactants exhibited stronger interactions with proteins than hydrogenated ones, which, however, depended on the structures of both proteins and surfactant molecules. If the proteins are very stable, or the surfactant–protein interactions are very strong, such differences between the two kinds of surfactants might be indistinguishable.     

Area per surfactant molecule values of gemini surfactants at the liquid-hydrophobic solid interface

Areas per surfactant molecule at the liquid/hydrophobic solid (A(LS)) and the liquid/air (A(LA)) interface as a function of the spacer length are reported for cationic gemini surfactants having (CH2)n spacer s. A(LA) increases with increasing spacer length up to 6-8 CH2 groups in the spacer and then levels off. A(LS) values indicate a more closely packed arrangement of the surfactant molecules than that at the liquid/air interface. Comparison of A(LA) and A(LS) values indicates that the surfactant molecules at the liquid/hydrophobic solid interface are almost three times as closely packed as those at the liquid/air interface. A comparison of the experimental values of the area per surfactant molecule at both interfaces was made with those calculated from dimensions of the surfactant molecule in vacuo.     

Aggregation behaviors of gemini nucleotide at the air-water interface and in solutions induced by adenine-uracil interaction

Cationic gemini surfactants having nucleotides as counterions (called nucleo-gemini hereafter) were synthesized and their aggregation behavior at air-water surfaces as well as in bulk solutions were studied. Fluid solutions of these nucleo-gemini surfactants show transitions to hydrogels upon addition of complementary nucleoside bases or other nucleo-gemini surfactants having complementary bases as counterions. The FTIR-ATR measurements show that the carboxylate groups of uridine form hydrogen bonds with the amine groups of adenosine. The aggregation behavior was also confirmed at the air-water interface by Brewster angle microscopy as well as surface pressure measurements; the monolayer of a gemini nucleotide was observed to undergo a transition to multilayers when nucleosides with complementary bases were added into the subphase. Isotherm curves of surface pressure monitored in parallel show a decrease in molecular area upon addition of such nucleosides.     

Molecular aggregates of partially fluorinated quaternary ammonium salt gemini surfactants

The size and shape of novel partially fluorinated gemini surfactant 1,2-bis[dimethyl-(3-perfluoroalkyl-2-hydroxypropyl)ammonium]ethane bromide (CnFC3-2-C3CnF, where n=4, 6, and 8) were investigated in aqueous solution by means of light scattering and transmission electron microscopy (TEM). The sizes of these molecular aggregates changed with increasing carbon number of the alkyl chain and concentration. For example, the apparent hydrodynamic radius by dynamic light scattering was 18 nm at a concentration of cmcx5 for n=4, 115 nm at the cmcx15 for n=6, and 62 nm at the cmcx30 for n=8, at 298.2 K. The shapes of CnFC3-2-C3CnF aggregates drastically changed with the alkyl chain length; the aggregates were mainly in the form of large or irregular small aggregates (n=4), string-like aggregates (n=6), and vesicles (n=8). The bromide-ion activity was measured using a bromide-ion-selective electrode to determine the degree of counterion binding to the aggregates. The degree of counterion binding to aggregate was very small compared with that in the typical hydrogenated gemini surfactants. These results indicated that the small curvature of large aggregates was not influenced by an electrostatic repulsion between the cationic head groups in the case of the bulky molecular volume of fluorinated gemini surfactants.     

Temperature-dependent aggregation behavior of symmetric long-chain bolaamphiphiles at the air-water interface

The behavior of the symmetric long-chain bolaamphiphiles dotriacontane-1,32-diyl bis[2-(trimethylammonio)ethyl phosphate] (PC-C32-PC), and dotriacontane-1,32-diyl bis[2-(dimethylammonio)ethyl phosphate] (Me(2)PE-C32-Me(2)PE) at the air-water interface was investigated by means of temperature-dependent film-balance measurements and Brewster angle microscopy. Upon compression of the monolayer the isotherms show a strong surface pressure increase. We assume that at high pressure the monolayer consists of molecules in a reversed U-shaped conformation. At an area of 0.9-1.1 nm(2) per molecule a plateau is reached for both bolaamphiphiles, which marks the beginning of an aggregate formation on the water surface. The plateau pressure increases with increasing temperature. For PC-C32-PC at 6.7 degrees C curved shorter fibrous domains with a diameter of 20-30 mum are seen on the water surface, whereas at 29.2 degrees C stripelike domains with a thickness of 200-500 mum are observed. Isotherms recorded within this temperature range show a characteristic break within the steep slope marking a region where a mixture or a hybrid form of both structures exists. Me(2)PE-C32-Me(2)PE in its zwitterionic state at low pH forms microcrystals on the water surface, whose formation is kinetically retarded. Depending on the temperature, the aqueous subphase is more or less homogeneously covered with a crystalline-like film. In contrast, no aggregates are observed at pH 10 when the bolaamphiphile is negatively charged.     

Disruption of viscoelastic beta-lactoglobulin surface layers at the air-water interface by nonionic polymeric surfactants

Nonequilibrium interfacial layers formed by competitive adsorption of beta-lactoglobulin and the nonionic triblock copolymer PEO99-PPO65-PEO99 (F127) to the air-water interface were investigated in order to explain the influence of polymeric surfactants on protein film surface rheology and foam stability. Surface dilatational and shear rheological methods, surface tension measurements, dynamic thin-film measurements, diffusion measurements (from fluorescence recovery after photo bleaching), and determinations of foam stability were used as methods. The high surface viscoelasticity, both the shear and dilatational, of the protein films was significantly reduced by coadsorption of polymeric surfactant. The drainage rate of single thin films, in the presence of beta-lactoglobulin, increased with the amount of added F127, but equilibrium F127 films were found to be thicker than beta-lactoglobulin films, even at low concentration of the polymeric surfactant. It is concluded that the effect of the nonionic triblock copolymer on the interfacial rheology of beta-lactoglobulin layers is similar to that of low molecular weight surfactants. They differ however in that F127 increases the thickness of thin liquid films. In addition, the significant destabilizing effect of low molecular weight surfactants on protein foams is not found in the investigated system. This is explained as due to long-range steric forces starting to stabilize the foam films at low concentrations of F127.     

Surface properties and aggregate morphology of partially fluorinated carboxylate-type anionic gemini surfactants

Three anionic homologues of a novel partially fluorinated carboxylate-type anionic gemini surfactant, N,N′-di(3-perfluoroalkyl-2-hydroxypropyl)-N,N′-diacetic acid ethylenediamine (2 edda, where n represents the number of carbon atoms in the fluorocarbon chain (4, 6, and 8)) were synthesized. In these present gemini surfactants, the relatively small carboxylic acid moieties form hydrophilic head groups. The surface properties or structures of the aggregates of these surfactants are strongly influenced by the nonflexible fluorocarbons and small head groups; this is because these surfactants have a closely packed molecular structure. The equilibrium surface tension properties of these surfactants were measured at 298.2 K for various fluorocarbon chain lengths. The plot of the logarithm of the critical micelle concentration (cmc) against the fluorocarbon chain lengths for 2 edda (n = 4, 6, and 8) showed a minimum for n = 6. Furthermore, the lowest surface tension of 2 edda at the cmc was 16.4 mN m⁻¹. Such unique behavior has not been observed even in the other fluorinated surfactants. Changes in the shapes and sizes of these surfactant aggregate with concentration were investigated by dynamic light scattering and transmission electron microscopy (TEM). The TEM micrographs showed that in an aqueous alkali solution, 2 edda mainly formed aggregates with stringlike (n = 4), cagelike (n = 6), and distorted bilayer structures (n = 8). The morphological changes in the aggregates were affected by the molecular structure composed of nonflexible fluorocarbon chains and flexible hydrocarbon chains.     

Studies of the aggregation behavior of cyclic gemini surfactants

The specific conductance, surface tension, mean aggregation number, and apparent molar volume properties of aqueous solutions of a novel series of N,N'-bis(cyclododecyldimethyl)-alpha,omega-alkanediammonium dibromide (c12-s-c12) surfactants, where s is the spacer chain length, are reported. Surfactants with s = 3, 4, and 6 have been prepared and characterized in terms of their Krafft temperature (T(Kr)), critical micelle concentration (cmc), surfactant head group area (a) at the air-water interface, mean aggregation number (N(agg)), and the volume change upon micelle formation (deltaV(phi,M)). The c12-3-c12 shows little evidence of aggregate formation, while the results obtained for the c12-4-c12 and c12-6-c12 homologues suggest the formation of small, poorly defined micellar aggregates in aqueous solution.     

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.     

Segregation phenomena in micelles from mixtures of fluorinated and hydrogenated surfactants

Mixtures of hydrogenated and fluorinated surfactants are known to form either mixed or segregated micelles: the conclusions are much dependant on the precision of the experimental measurements and on the model used for interpretation. Recently, mixed surfactant solutions were probed at the micellar or molecular level by SANS, fluorescence or NMR. It leads to an intermediate structure for the mixed micelles with an intramicellar segregation of the fluorinated and hydrogenated surfactant.This intramicellar segregation was also observed in a variety of more complex systems which are rapidly surveyed in the second part.