Ewelina Kalwarczyk

Incorporation of carbon nanotubes into a lyotropic liquid crystal by phase separation in the presence of a hydrophilic polymer.

Single-walled carbon nanotubes (SWNTs) were incorporated into a lyotropic liquid crystal (LLC) matrix formed by n-dodecyl octaoxyethene monoether (C(12)E(6)) at room temperature through spontaneous phase separation induced by nonionic hydrophilic polymer poly(ethylene glycol) (PEG). The quality of SWNTs/LLC composite was evaluated by polarized microscopy observations and small-angle X-ray scattering (SAXS) measurements. The results obtained clearly indicated that SWNTs have been successfully incorporated into the LLC matrix up to a considerable high content without destroying the LLC matrix, although interesting changes of the LLC matrix were also induced by SWNTs incorporation. By varying the ratio of PEG to C(12)E(6), the type of LLC matrix can be controlled from hexagonal phase to lamellar phase. Temperature was found to have a significant influence on the quality of SWNTs/LLC composite, and tube aggregation can be induced at higher temperature. When SWNTs were changed to multiwalled carbon nanotubes (MWNTs), they became difficult to be incorporated into LLC matrix because of an increase in the average tube diameter.

Reverse Vesicles from a Salt-Free Catanionic Surfactant System: A Confocal Fluorescence Microscopy Study

We give a detailed confocal fluorescence microscopy study on reverse vesicles from a salt-free catanionic surfactant system. When tetradecyltrimethylammonium laurate (TTAL) and lauric acid (LA) are mixed in cyclohexane at the presence of a small amount of water, stable reverse vesicular phases form spontaneously. The reverse vesicular phases can be easily labeled with dyes of varying molecular size and hydrophobicity while the dyes are nearly insoluble in cyclohexane without reverse vesicles. This indicates the reverse vesicular phases can be good candidates to host guest molecules. With the help of a fluorescence microscope combined a confocal method, the features of these interesting reverse supramolecular self-assemblies were revealed for the first time. Because of the absence of electrostatic repulsions and hydration forces between adjacent vesicles, the reverse vesicles have a strong propensity to aggregate with each other and form three-dimensional clusters. The size distributions of both individual reverse vesicles and clusters are polydisperse. Huge multilamellar reverse vesicles with closely stacked thick walls (giant reverse onions) were observed. Besides the spherical reverse vesicles and onions, other supramolecular structures such as tubes have also been detected and structural evolutions between different structures were noticed. These interesting supramolecular self-assemblies form in a nonpolar organic solvent may serve as ideal micro- or nanoreaction centers for biological reactions and synthesis of inorganic nanomaterials.

Single-walled carbon nanotube/lyotropic liquid crystal hybrid materials fabricated by a phase separation method in the presence of polyelectrolyte.

We present a detailed study on the incorporation of single-walled carbon nanotubes (SWNTs) into lyotropic liquid crystals (LLC) by phase separation in the presence of polyelectrolytes. Two cases were studied in this work: (i) incorporation of SWNTs into the LLC phase formed by an anionic surfactant sodium dodecyl sulfate (SDS) in the presence of an anionic polyelectrolyte poly(sodium styrenesulfonate) (PSS); (ii) incorporation of SWNTs into the LLC phase formed by a cationic surfactant cetyltrimethylammonium bromide (CTAB) in the presence of a cationic polyelectrolyte poly(diallydimethylammonium chloride) (PDADMAC). The SWNTs/LLC composites were characterized by polarized optical microscopy (POM) observations and small-angle X-ray scattering (SAXS) measurements. In both systems, the surfactant phase was condensed into a hexagonal lattice by the polyelectrolyte within the investigated concentration range. Several factors that can influence the property of SWNTs/LLC composite were examined, including concentration of surfactants and polyelectrolytes and temperature. Aggregated SWNTs were not observed, indicating that SWNTs were well dispersed in the LLC phases. SAXS measurements showed the lattice parameter of the host LLC phase changed upon varying the mixing ratio of polyelectrolyte to ionic surfactant. The SWNTs/LLC hybrids showed considerable stability against temperature rise in both systems, and desorption of surfactant from SWNTs was not observed at higher temperature.

Formation and structure of PEI/DNA complexes: quantitative analysis

Controlled formation of gene delivery complexes (DNA and a vector, usually a cationic polymer) is one of the key challenges in developing efficient gene delivery systems. The researchers focused their procedures on the ratio of vector to DNA, neglecting the influence of concentration on the complex formation process. In this study we show, by studying the association of polyethylenimine (PEI) and 66-base pair (bp) DNA fragments, that the concentration of the gene delivery system greatly influences the formation of PEI/DNA complexes even at a fixed PEI/DNA ratio. We find that the charge and the size of PEI/DNA complexes are increasing functions of their concentration even in a highly dilute regime of concentrations. The number of PEI/DNA molecules in a complex was calculated from the measured charge and electrophoretic mobility. We established a model, on the basis of Smoluchowski theory, to explain the relation between the concentration and the size of PEI/DNA complexes. We analyzed the structure of the complexes and found out that a large proportion of space in the PEI/DNA complexes is occupied by the solvent. This study indicates that the influence of concentration should be seriously considered in gene delivery studies, since large PEI/DNA complexes can be prepared by scaling up their concentration simultaneously without increasing the dosage of PEI.

Polymer-induced ordering and phase separation in ionic surfactants

We present a new method to induce phase separation in solutions of ionic surfactants. In this method, the phase separation is obtained either by addition of polyelectrolytes or nonionic polymers along with inorganic salt. As a result, the system separates into polyelectrolyte-rich (or nonionic polymer-rich) and surfactant-rich phase. Four types of the mixtures were investigated: (i) anionic surfactants and anionic polyelectrolytes, (ii) cationic surfactants and cationic polyelectrolytes, (iii) cationic surfactants and nonionic polymers, and (iv) anionic surfactants and nonionic polymers. We found that the addition of polyelectrolyte with the charge of the same sign as that of surfactant can induce the phase separation in a wide range of surfactant concentrations. The addition of nonionic polymers induces the phase separation only in solutions of cationic surfactants. Moreover, the addition of nonionic polymers induces the phase separation only for relatively high total content of polymer and surfactant in the mixture. We found however that the addition of inorganic salt to the mixture of cationic surfactant and nonionic polymer triggers the phase separation even for a small concentrations of surfactant. In our experiments, water as well as mixtures of water and polar solvents were employed as solvents. Based on the optical microscopy studies we found that the surfactant-rich phase represents hexagonal ordering.

New One-Pot Technique to Introduce Charged Nanoparticles into a Lyotropic Liquid Crystal Matrix

We present a new method to incorporate hydrophilic charged nanoparticles into the lyotropic liquid crystal (LLC) template. This method is based on the effect of the polymer-induced phase separation (PIPS) and consists of two steps. In the first step, the nanoparticles are mixed with a surfactant micellar solution. In the second step, upon addition of polymer, phase separation is induced and the LLC phase doped with the nanoparticles is formed. Columnar hexagonal and lamellar LLC templates are obtained with the PIPS method. The ordering of the LLC phase can be controlled by the amount of polymer added to induce phase separation. The method works both for the system of nonionic surfactants and polymers and ionic surfactants and polyelectrolytes. We demonstrate that the PIPS method enables the fabrication of the LLC templates doped with positively or negatively charged nanoparticles as well as with a mixture of oppositely charged nanoparticles in arbitrary proportions.