Coexistence of Two Kinds of Fluorinated Hydrogenated Micelles as Building Blocks for the Design of Bimodal Mesoporous Silica with Two Ordered Mesopore Networks

A simple and effective route has been developed for the synthesis of bimodal (3.6 and 9.4 nm) mesoporous silica materials that have two ordered interconnected pore networks. Mesostructures have been prepared through the self assembly mechanism by using a mixture of polyoxyethylene fluoroalkyl ether and triblock copolymer as building block. The investigation of the RF8(EO)9/P123/water phase diagram evidences that in the considered surfactant range of concentrations, the system is micellar (L1). DLS measurements indicate that this micellar phase is composed of two types of micelles, the size of the first one at around 7.6 nm corresponds unambiguously to the pure fluorinated micelles. The second type of micelles at higher diameter consists of fluorinated micelles which have accommodated a weak fraction of P123 molecules. Thus, in this study the bimodal mesoporous silica are really templated by two kinds of micelles.

Preparació i caracterització de materials mesoporosos en sistemes tensioactius

Estudi elaborat a partir d’una estada a la Universitat Nacional de Yokohama des de maig fins a mitjans de juny del 2006. S'ha estudiat el comportament fàssic i la preparació de sílica mesoporosa pels nous tensioactius fluorats d'estructura C8F17SO2(C3H7)N(C2H4O)nH (abreujat C8F17(EO)n. El tensioactiu C8F17(EO)n forma micel•les allargades i cristalls líquids en aigua, i per tant pot ser adequat per a la preparació de materials mesoporosos. Sílica mesoestructurada es va preparar pel mètode de precipitació per autoagregació cooperativa. Un estudi sistemàtic es va realitzar, investigant la influència de les concentracions de tensioactiu i precursor (TEOS), l’efecte del pH i de la longitud de cadena de poliòxid d’etilè. Els materials es van caracteritzar per raigs X a angle petit (SAXS), sorció de nitrògen i TEM. Els materials obtinguts presenten diàmetres de por petits i parets de por gruixudes. A més, aquests materials posseeixen altes superfícies específiques, que s’han obtingut emprant concentracions de tensioactiu petites, produint parets de por robustes sense microporositat significativa. La superfície específica es manté durant el procés de calcinació, malgrat un petit encongiment degut a l’entrecreuament de la sílica. Els materials de sílica obtinguts han mostrat ser significativament més robustos que altres materials similars descrits a la bibliografia, com la sílica MCM-41.

Experimental and computational study on the synthesis and characterization of self-assembling meso/macroporous materials in highly concentrated emulsions

Report for the scientific sojourn carried out at Massachusetts General Hospital Cancer Center-Harvard Medical School, Estats Units, from 2010 to 2011. The project aims to study the aggregation behavior of amphiphilic molecules in the continuous phase of highly concentrated emulsions, which can be used as templates for the synthesis of meso/macroporous materials. At this stage of the project, we have investigated the self-assembly of diblock and triblock surfactants under the effect of a confined geometry being surrounded by the droplets of the dispersed phase. These droplets limit the growth of the aggregates, deeply modify their orientation and hence alter their spatial arrangement as compared to the self-assembly taking place far enough from any boundary surface, that is in the bulk. By performing Monte Carlo simulations, we have showed that the interface between the dispersed and continuous phases as well as its shape has a significant impact on the structural order of the resulting aggregates and hence on the potential applications of highly concentrated emulsions as reaction media, drug delivery systems, or templates for meso/macroporous materials. Due to the combined effect of symmetry breaking and morphological frustration, very intriguing structures, such as square columnar liquid crystals, twisted X-shaped aggregates, and helical phases of cylindrical aggregates, never observed in the bulk for the same model surfactant, have been found. The presence of other more conventional structures, such as micelles and cubic and hexagonal liquid crystals, formed at low and high amphiphilic concentrations, respectively, further enhance the interest on this already rich aggregation behavior.

Counter-ion effect on surfactant-DNA gel particles as controlled DNA delivery systems

The ability to entrap drugs within vehicles and subsequently release them has led to new treatments for a number of diseases. Based on an associative phase separation and interfacial diffusion approach, we developed a way to prepare DNA gel particles without adding any kind of cross-linker or organic solvent. Among the various agents studied, cationic surfactants offered particularly efficient control for encapsulation and DNA release from these DNA gel particles. The driving force for this strong association is the electrostatic interaction between the two components, as induced by the entropic increase due to the release of the respective counter-ions. However, little is known about the influence of the respective counter-ions on this surfactant-DNA interaction. Here we examined the effect of different counter-ions on the formation and properties of the DNA gel particles by mixing DNA (either single- (ssDNA) or double-stranded (dsDNA)) with the single chain surfactant dodecyltrimethylammonium (DTA). In particular, we used as counter-ions of this surfactant the hydrogen sulfate and trifluoromethane sulfonate anions and the two halides, chloride and bromide. Effects on the morphology of the particles obtained, the encapsulation of DNA and its release, as well as the haemocompatibility of these particles, are presented, using the counter-ion structure and the DNA conformation as controlling parameters. Analysis of the data indicates that the degree of counter-ion dissociation from the surfactant micelles and the polar/hydrophobic character of the counter-ion are important parameters in the final properties of the particles. The stronger interaction with amphiphiles for ssDNA than for dsDNA suggests the important role of hydrophobic interactions in DNA.

Shear thinning and thixotropy of HMHEC and HEC water solutions

Steady state viscosity and thixotropy of hydrophobically modified hydroxyethyl cellulose HMHEC and nonassociative cellulose water solutions are studied. Although all the samples are shear thinning, only the HMHEC is thixotropic, since the migration of hydrophobes to micelles is controlled by diffusion. The Cross model fits steady state curves. The Mewis model, a phenomenological model that proposes that the rate of change of viscosity when the shear rate is suddenly changed is related to the difference between the steady state and current values of viscosity raised to an exponent, fits structure construction experiments when the exponent, n, is estimated to be around 2. The Newtonian assumption used by Mewis cannot be used here, however. This seems to be related to the fact that the thickening is due to bridged micelle formation, which is a slow process, and also to topological constraints and entanglements, which are rapid processes. The kinetic parameter was redefined to kn in order to make it independent of initial conditions. So, kn depends only on how the shear affects the structure. kn reaches a plateau at shear rates too low to produce structure destruction and decreases at higher shear rates.

Tailored Jeffamine molecular tools for ordering mesoporous Silica

Herein, we report the formation of organized mesoporous silica materials prepared from a novel nonionic gemini surfactant, myristoyl-end capped Jeffamine, synthesized from a polyoxyalkyleneamine (ED900). The behavior of the modified Jeffamine in water was first investigated. A direct micellar phase (L1) and a hexagonal (H1) liquid crystal were found. The structure of the micelles was investigated from the SAXS and the analysis by Generalized Indirect Fourier Transformation (GIFT), which show that the particles are globular of coreshell type. The myristoyl chains, located at the ends of the amphiphile molecule are assembled to form the core of the micelles and, as a consequence, the molecules are folded over on themselves. Mesoporous materials were then synthesized from the self-assembly mechanism. The recovered materials were characterized by SAXS measurements, nitrogen adsorptiondesorption analysis, transmission and scanning electron microscopy. The results clearly evidence that by modifying the synthesis parameters, such as the surfactant/silica precursor molar ratio and the hydrothermal conditions, one can control the size and the nanostructuring of the resulting material. It was observed that, the lower the temperature of the hydrothermal treatment, the better the mesopore ordering.