Lyotropic Lamellar Structures of a Long-Chain Imidazolium and Their Application as Nanoreactors for X-ray-Initiated Polymerization.

The lyotropic behavior of the ternary system formed by 1-tetradecyl-3-methylimidazolium chloride, 1-decanol, and water is investigated. A lamellar mesophase is formed for a wide range of compositions and is characterized by polarized optical microscopy, low-temperature scanning electron microscopy, small- and wide-angle X-ray scattering with synchrotron radiation, and differential scanning calorimetry. This phase presents onionlike structures. Two lamellar structures are formed: an Lα mesophase between 25 and 50 °C, with an isobaric thermal expansivity of the bilayer thickness of -3.2 × 10-3 K-1, and a lamellar gel phase, when the temperature decreases below 25 °C. This new medium is employed to perform in situ X-ray-initiated polymerization of N-isopropylacrylamide. When the monomer is incorporated in the lamellar structure, it is distributed between the water layer and bilayer interface and its polymerization can be followed by variations in the diffractograms with time.

In situ X-ray polymerization: from swollen lamellae to polymer-surfactant complexes.

The influence of the monomer diallyldimethylammonium chloride (D) on the lamellar liquid crystal formed by the anionic surfactant aerosol OT (AOT) and water is investigated, determining the lamellar spacings by SAXS and the quadrupolar splittings by deuterium NMR, as a function of the D or AOT concentrations. The cationic monomer D induces a destabilization of the AOT lamellar structure such that, at a critical concentration higher than 5 wt %, macroscopic phase separation takes place. When the monomer, which is dissolved in the AOT lamellae, is polymerized in situ by X-ray initiation, a new collapsed lamellar phase appears, corresponding to the complexation of the surfactant with the resulting polymer. A theoretical model is employed to analyze the variation of the interactions between the AOT bilayers and the stability of the lamellar structure.

Copolymer-surfactant complexes obtained in a lamellar lyotropic medium.

Polymer-surfactant complexes formed between charged copolymers and oppositely charged surfactants are analyzed as a function of the charge density in the macromolecule. Copolymers of ionizable diallyldimethylammonium chloride (DADMAC) and neutral acrylamide are obtained at different comonomer ratios. When mixed with the lamellar medium formed by the anionic surfactant 1,4-bis(2-ethylhexyl)sodium sulfosuccinate (AOT) in water, they give rise to highly condensed lamellar phases in equilibrium with another lyotropic phase. The structure of these phases is studied by SAXS and optical microscopy revealing the formation of copolymer-surfactant complexes which present a lamellar structure. The composition of the phases is inaccessible to direct determination, because they do not separate macroscopically (in most of the samples). Thus, the stoichiometry is determined using a model which considers the charge density of the copolymers. This model allows, from the experimental data provided by SAXS, to calculate the composition and volume ratio of the phases. The results indicate that these complexes are nonstoichiometric, containing a lesser amount of DADMAC than surfactant units. The neutral sequences of acrylamide can be considered as bridges along the water domains remaining anchored to the AOT bilayers by the cationic DADMAC units. When the charge density diminishes, the bridges become longer, rendering structures with higher water content.

Fluorescence study on the structure of ionic liquid aggregates in aqueous solutions.

Although ionic liquids are a relatively novel class of materials, it is well documented that they form micelles through aggregation of cation aliphatic tails. However, anion self-assembly has not yet been reported. In this study, we analyzed the intrinsic fluorescence of p-toluenesulfonate groups (tosylate) as part of the ionic liquid 1-ethyl-3-methylimidazolium tosylate ([emim][TOS]) and p-toluenesulfonic acid (pTSA), in aqueous solution. pTSA was found to have overlapping monomer and excimer emissions for chromophore concentrations from 10(-3) to 1 M, whereas [emim][TOS], in the same conditions, showed monomer emission slightly broadened by much weaker excimer emission. These different photophysical behaviors of the same chromophore in the two compounds are explained by the formation of ion pairs by [emim][TOS], which can also be inferred from the loss of vibrational structure of the absorption spectra with respect to pTSA. Despite this different behavior regarding ion pairing, anion aggregation was observed in the excitation spectra of both pTSA and [emim][TOS]. While the absorption spectra corresponded to single chromophores, the excitation spectra changed from those characteristic of a single chromophore (below 10(-3) M) to red-shifted narrow bands (above 0.1 M) typical of J aggregates. Between those concentrations, the excitation spectra split into blue- and red-shifted bands with relative intensities that changed with concentration as the chromophores rearranged in their clusters from head-to-head to head-to-tail aggregates. Differences between the absorption and excitation spectra were ascribed to aggregation-induced fluorescence enhancement.

Polyelectrolyte-surfactant complexes with long range order.

Mixtures of carboxymethyl cellulose (CMC) or hydrophobically modified CMC with an oppositely charged surfactant (benzyldimethyltetradecylammonium chloride) in water were prepared. When the global polymer concentration is 0.18% by weight and the surfactant content is high enough, a precipitate with hexagonal order is formed. The precipitate composition shows practically constancy in its water content and a slight diminution in polymer concentration when the global surfactant content is varied between 0.9 and 23 wt%. The lattice parameter in this phase decreases when the polymer/surfactant ratio in the phase increases; this variation is faster with CMC than with the hydrophobically modified CMC. In this way electrostatic and hydrophobic interactions are far from being additive. From the extrapolation to infinite dilution, the global interaction seems to depend on the substitution degree in the polymer. Additionally, the comparison between the radius at the polar-apolar interface in the cylinders and the lattice parameter as a function of polymer/surfactant ratio in the hexagonal phase is compatible with some of the alkyl chains belonging to the hydrophobically modified CMC being present in the aqueous zone.

Incorporation of substituted acrylamides to the lamellar mesophase of Aerosol OT.

The structure and stability of the lamellar liquid crystal formed by the surfactant sodium bis-2ethylhexyl sulfosuccinate (AOT) in water is perturbed by small amounts of the substituted acrylamides N-isopropyl, N,N-diethyl, N-acryloylmorpholine, and N,N-dimethyl methacrylamide, as revealed by small angle X-ray scattering (SAXS), deuterium NMR, and microscopy. These molecules are water soluble and stay mostly in the water layers between lamellae, but a small fraction of them (5-19%) are incorporated into the AOT bilayers, thereby producing dramatic changes. Both, the degree of anisotropy in the water molecules hydrating AOT (quadrupolar splitting in (2)H NMR) and the long period spacing between lamellae (SAXS), decrease with addition of this molecules at low concentrations, which is attributed to the lower average headgroup density at the AOT/water interface when the acrylamide is incorporated. The strength of these perturbations depends on the acrylamide, and goes in parallel with the hydrophobic character of the alkyl side groups in its molecule, which suggests that the acrylamides incorporated to the bilayer enter into contact with the lipophilic tails of the AOT molecule. An interaction with the hydrated heads of AOT is also suggested in the particular case of N-isopropylacrylamide. On increasing the molecule concentration an incipient melting of the lamellar phase towards an isotropic solution takes place, first at the microscopic level, then macroscopic. Near this phase transition, the ordered domains lose the random orientation prevailing at lower acrylamide concentrations, and adopt a preferred orientation, perpendicular to the magnetic field.

Fragmentation of the lamellae and fractionation of polymer coils upon mixing poly(dimethylacrylamide) with the lamellar phase of aerosol OT in water.

The lamellar mesophase formed by surfactant 1,4-bis(2-ethylhexyl) sodium sulfosuccinate (AOT) in deuterated water is mixed with poly(dimethylacrylamide) (PDMAA) polymers of low molecular weight (Mn= (2-20) x 10(3)). The mixtures separate into microphases (lamellar plus isotropic polymer solution). Their microstructures are studied by microscopy, small-angle X-ray scattering (SAXS), and deuterium NMR (2H NMR). According to SAXS, the lamellar phase fractionates the molecular weight distribution of the polymer, by dissolving only chains with coil sizes smaller than the thickness of the water layers between lamellae, and keeping larger chains segregated from the lamellar phase. The fraction of polymer that is segregated from the lamellar phase grows with Mn of the polymer. In 2H NMR, there are two signals, a quadrupolar doublet (water molecules hydrating the anisotropic lamellar phase contribute to this doublet) and a singlet (water molecules in the isotropic polymer solution contribute to this singlet). These two signals are deconvoluted to analyze the phases. Mixing with the polymer produces the partial dispersion of the lamellar phase into small fragments (microcrystallites). The structure of these microcrystallites is such that they conserve the regular long period spacing of the macrophase, and are thus identified in SAXS, but they are smaller than the minimum size required to produce quadrupolar splitting (about 4 microm), and therefore, in 2H NMR, they contribute to the singlet. 2H NMR can thus not distinguish between small microcrystallites and an isotropic polymer solution segregated from the lamellar phase; instead small microcrystallites are detected as an apparent increase of the isotropic solution. The degree of dispersion produced by the polymer in the lamellar phase is correlated with the degree of segregation that the polymer suffers. Thus, much greater dispersion into microcrystallites is produced by the higher Mn polymers than by the lower Mn polymers (in the range covered by the present samples, although with a much higher molecular weight sample (3 x 10(6)) that is totally segregated no such microcrystallites were detected).