MWNTs or PEG as Stability Enhancers for DNA-Cationic Surfactant Gel Particles.

Cationic surfactants interact with DNA (Deoxyribonucleic acid), forming surfactant-DNA complexes that offer particularly efficient control for encapsulation and release of DNA from DNA gel particles. In the present work, DNA-based particles were prepared using CTAB (Cetyltrimethylammonium bromide) as the cationic surfactant and modified using two different additives: (Multi-Walled Carbon Nanotubes) MWNT or PEG (Poly Ethylene Glycol). The use of both additives to form composites increased the stability of the gel particles. The stability was monitored by the release of DNA and CTAB in different pH solutions. However, not much is known about the influence of pH on DNA-surfactant interaction and the release of DNA and surfactant from gel particles. It was observed that the solubilization of DNA occurs only in very acid media, while that of CTAB does not depend on pH and gets to a plateau after about 8 h. Within 2 h in contact with a pH = 2 solution, about 1% DNA and CTAB was released. Complete destruction for the gel particles was observed in pH = 2 solution after 17 days for PEG and 20 days for MWNT. The composite particles show a considerably enlarged sustained release span compared to the unmodified ones. The dehydration-rehydration studies show that the structure of the composite gel particles, as determined from SAXS (Small-Angle-X-Ray-Scattering) experiments, is similar to that of the unmodified ones. These studies will allow a better knowledge of these particles' formation and evolution in view of possible applications in drug delivery and release.

Effects of ionic strength on the surface tension and nonequilibrium interfacial characteristics of poly(sodium styrenesulfonate)/dodecyltrimethylammonium bromide mixtures.

We rationalize the surface tension behavior and nonequilibrium interfacial characteristics of high molecular weight poly(sodium styrenesulfonate)/dodecyltrimethylammonium bromide (NaPSS/DTAB) mixtures with respect to the ionic strength. Excellent agreement is achieved between experimental data and our recent empirical model [Langmuir 2013, 29, 11554], which is based on the lack of colloidal stability of bulk aggregates in the phase separation region and has no free fitting parameters. We show that the size of a surface tension peak positioned at the edge of the phase separation region can be suppressed by the addition of inert electrolyte, which lowers the critical micelle concentration in relation to the phase separation region. Such manipulation of the peak is possible for the 100 ppm NaPSS/DTAB system because there is a high free surfactant concentration in the phase separation region. The close agreement of our model with the experimental data of samples in the phase separation region with respect to the ionic strength indicates that the surface tension behavior can be rationalized in terms of comprehensive precipitation regardless of whether there is a peak or not. The time scale of precipitation for the investigated system is on the order of one month, which emphasizes the need to understand the dynamic changes in the state of bulk aggregation in order to rationalize the surface properties of strongly interacting mixtures; steady state surface properties measured in the interim period will represent samples far from equilibrium. We show also that the surface properties of samples of low ionic strength outside the equilibrium phase separation region can be extreme opposites depending on the sample history, which is attributed to the generation of trapped nonequilibrium states. This work highlights the need to validate the underlying nature of oppositely charged polyelectrolyte/surfactant systems prior to the interpretation of experimental data within an equilibrium framework.

Self assembly of pH-sensitive cationic lysine based surfactants.

Three cationic surfactants of the type N(ε)-acyl lysine methyl ester hydrochloride have been studied with respect to solution behavior and adsorption on the air/water interface, as well as the thermolyotropic behavior. The self-assembly of these surfactants, which have the cationic charge on amine protonated groups, was assessed by different physicochemical methods. Depending on the pH value, these surfactants can dissociate in aqueous solutions, losing the cationic charge. Therefore, knowledge of the pK(a) of these compounds is essential to explain their behavior in aqueous solutions. The bulk techniques, conductivity, and nuclear magnetic resonance diffusion (NMR) obtained similar critical micellar concentration (CMC) values, which were well above those obtained from surface tension. Surface tension measurements were strongly dependent on the technique used, namely, Wilhelmy plate and pendant drop. The phase behavior at medium to high concentrations has been studied by optical polarizing microscopy and small angle x-ray scattering (SAXS). The X-ray studies showed that the lysine-based surfactants at low hydration have rich thermotropic liquid crystalline behavior. The results are discussed in terms of the structure of the compounds and the cationic charge of the molecule. We will show how apparently small changes in molecule structure have a large influence on phase behavior.

Nonequilibrium features of the association between poly(vinylamine) and sodium dodecyl sulfate: the validity of the colloid dispersion concept.

The effect of different mixing protocols on the bulk and surface properties of the aqueous mixtures of linear poly(vinylamine) (PVAm) and sodium dodecyl sulfate (SDS) has been investigated using pH, electrophoretic mobility, dynamic light scattering, coagulation kinetics, and surface tension measurements. For the preparation of the solutions, two kinds of mixing protocols were applied. The so-called "stop flow mixing" enables a very rapid mixing whereas in the case of "gentle mixing" the mixing of the components is less efficient. At high surfactant concentrations a kinetically stable colloid dispersion of the PVAm/SDS particles is formed via the application of the stop flow mixing method. The mixing protocols have a significant effect on the bulk properties of the PVAm/SDS system, in particular, at the low pH range and at large PVAm concentrations. The effect of mixing can be qualitatively understood in terms of the enhanced local rate of coagulation of the PVAm/SDS complexes as well as of the appearance of polyelectrolyte/surfactant aggregates via the application of a less efficient mixing. The study also reveals that the applied methods of solution preparation do not have a major impact on the bound amount of the surfactant as well as on the surface tension isotherms of the system. This latter finding is attributed to the hindered adsorption of the large polyelectrolyte/surfactant aggregates at the air/water interface.

Novel nanocomplexes of hyperbranched poly(ethyleneimine), and dodecyl maltoside.

The aqueous complexes of poly(ethyleneimine) (PEI), sodium dodecyl sulfate (SDS) and dodecyl maltoside (C12G2) have been studied under dilute conditions using dynamic light scattering, electrophoretic mobility, surface tension and pH measurements. According to the surface tension data the complexation between PEI and C12G2 can be neglected while a strong interaction was detected between PEI and SDS. The charged nature and size of the PEI-SDS-C12G2 complexes vary in a similar manner with SDS concentration as for the PEI-SDS systems. At large excess of SDS a kinetically stable colloid dispersion of the compact PEI-SDS-C12G2 particles forms. The electrophoretic mobility measurements indicate that the charge reversal of the PEI molecules occurs at lower SDS concentrations in the presence than in the absence of dodecyl maltoside. The enhanced charge inversion of PEI affords a significant extension of the concentration range with kinetically stable dispersion of the polyelectrolyte-surfactant nanoparticles compared with the PEI-SDS system. The pH of the PEI-SDS-C12G2 mixtures also reveals a peculiar dependence on the surfactant concentration. These latter findings are explained by the synergistic binding of the ionic and non-ionic surfactants to both the uncharged and charged amine groups of the PEI. It can be concluded that the addition of sugar surfactants is an efficient way to increase the kinetic stability and manipulate the pH of the mixtures of oppositely charged weak polyelectrolytes and surfactants.

Release of DNA and surfactant from gel particles: the receptor solution effect and the dehydration-hydration aspects.

DNA and cetyltrimethylammonium bromide (CTAB) have been used to prepare gel particles for controlled release studies. This article reports on the release of DNA and CTAB in four different solutions: in sodium bromide, in strong acid, pH 2 and pH 9 solutions for salmon testes DNA-CTAB gel particles. Also, compares results at extreme acid media and 10 mM NaBr solution with higher molecular weight DNA gel particles. The direct surfactant release was followed for the first time and shows the need of using biocompatible surfactants for the preparation of these gel particles. The release behavior depends on the receptor solution pH and the molecular weight of DNA. The first stage of the release corresponds to the so-called normal release profile and after this period, the release changed to a slow release profile. Also, the effect of dehydration and rehydration on the gel particles structure has been studied for the first time. The last process was observed visually and by SAXS measurements as a function of time. This process maintains the particle membrane integrity, structure and barrier function. The rehydration of dry gel particle in water occurs in only a few hours.

The nanostructure of surfactant-DNA complexes with different arrangements.

The nanostructure of DNA with different cationic surfactant has been studied in order to elucidate the detailed arrangement concerning the position of DNA and surfactant domains in the complexes. Also, the orientation of the DNA cylinders in the thin films of the complexes was investigated. Attention was directed on the preparation methods of the complexes and to how the different surfactant structure affects the compaction of the DNA. The cationic surfactant-DNA complexes were investigated by X-ray scattering, polarized light microscopy and elemental microanalysis. It was observed that the molecular organization of the complexes between DNA and cationic surfactant corresponds to a hexagonal structure with different packing arrangements. The nanostructure of the complexes depends on the hydrophobic/hydrophilic balance of the cationic surfactant. In particular the use of arginine derived surfactants, with a large polar head group able to interact not only by electrostatics but also by hydrogen bonding, allows for the formation of more compact structures. The results suggest that the smaller the lattice parameter the more compact and stable is the complex implying slower DNA release.

The impact of electrolyte on the aggregation of the complexes of hyperbranched poly(ethyleneimine) and sodium dodecyl sulfate.

The aggregation of the negatively charged complexes of hyperbranched poly(ethylenimine) (PEI) and sodium dodecyl sulfate (SDS) has been investigated at different sodium chloride (NaCl) concentrations using coagulation kinetics, electrophoretic mobility and dynamic light scattering measurements. The observed variation of the initial rate of coagulation with NaCl concentration indicates the formation of kinetically stable colloid dispersions in the investigated composition and pH range. These dispersions are electrostatically stabilized due to the adsorption of excess dodecyl sulfate ions on the surface of the polyelectrolyte/surfactant particles. Because of the enhanced adsorption of the anionic surfactant, the kinetic stability of the PEI/SDS dispersions increases with increasing SDS concentration and decreasing pH. Finally, we rationalize the effect of salt on the phase behavior and surface properties of polyelectrolyte/surfactant mixtures in terms of the salt-induced aggregation features of polyelectrolyte/surfactant particles.

Effect of mixing on the formation of complexes of hyperbranched cationic polyelectrolytes and anionic surfactants.

The effect of different mixing protocols on the charged nature and size distribution of the aqueous complexes of hyperbranched poly(ethylene imine) (PEI) and sodium dodecyl sulfate (SDS) was investigated by electrophoretic mobility and dynamic light scattering measurements at different pH values, polyelectrolyte concentrations, and ionic strengths. It was found that at large excess of the surfactant a colloidal dispersion of individual PEI/SDS nanoparticles forms via an extremely rapid mixing of the components by means of a stop-flow apparatus. However, the application of a less efficient mixing method under the same experimental conditions might result in large clusters of the individual PEI/SDS particles as well as in a more extended precipitation regime compared with the results of stop-flow mixing protocol. The study revealed that the larger the charge density and concentration of the PEI, the more pronounced the effect of mixing becomes. It can be concluded that an efficient way to avoid precipitation in the solutions of oppositely charged polyelectrolytes and surfactants might be provided by extending the range of kinetically stable colloidal dispersion of polyelectrolyte/surfactant nanoparticles via the application of appropriate mixing protocols.

Novel method for the estimation of the binding isotherms of ionic surfactants on oppositely charged polyelectrolytes.

One of the most important characteristics of the polyelectrolyte/surfactant interaction is the binding isotherm of the surfactant because it provides basic thermodynamic information about the binding mechanism. However, the amount of the surfactant bound to the polymer may crucially affect the surface properties of these systems via changing the thermodynamic activity of the components. Therefore, a knowledge of the binding isotherms can also be useful in tuning the efficiency of commercial products. However, the determination of these isotherms is still subject to significant experimental difficulties. In this letter, we offer a novel method for the estimation of binding isotherms based on electrokinetic measurements. The technique provides a simple and quick way to estimate the bound amount of surfactant that might be useful in both fundamental and industrial research. In principle, the proposed method could also be extended to the determination of the binding isotherms of small ligands on biomacromolecules.