Thermal stability of PMMA-LDH nanocomposites: decoupling the physical barrier, radical trapping, and charring contributions using XAS/WAXS/Raman time-resolved experiments.

In-depth understanding of the thermal stability of polymer-clay nanocomposites requires the use of advanced time-resolved techniques combined with multivariate data analysis, as well as the preparation of layered nanofillers with well-defined composition. The layered double hydroxide (LDH) compounds Zn2Al(OH)6·nH2O, Zn2Al0.75Fe0.25(OH)6·nH2O, ZnCuAl(OH)6·nH2O, and ZnCuAl0.5Fe0.5(OH)6·nH2O were prepared, each designed to specifically identify the physical barrier, radical trapping, and char formation contributions to the thermal stability of the PMMA-LDH nanocomposites. The unique combination of conventional methods (TG, DSC, and Raman spectroscopy) and synchrotron radiation techniques (XAS and WAXS), applied during PMMA-LDH heating, revealed the synergetic (of iron) and antagonist (of copper) effects of the LDH layers transformations on the three main endothermic steps of mass loss of the polymer. The diffusion barrier effect was proved by the downshift of the PMMA thermal decomposition temperature caused by the decrease of the LDH edifice thermostability when divalent cations were substituted in the LDH (passing from PMMA-Zn2Al(OH)6·nH2O to PMMA-ZnCuAl(OH)6·nH2O). For PMMA-Zn2Al0.75Fe0.25(OH)6·nH2O, a cooperative contribution of iron reduction, stabilisation of layered edifice, and radical trapping effects was observed for the thermal stability of the nanocomposite. LDH also acted as a diffusion barrier to the efflux and evaporation of depolymerized species, favouring the charring which exerts an additional contribution to thermal stability of the PMMA-LDH nanocomposites.

Ureasil-polyether hybrid film-forming materials.

The objectives of this work were to study the suitability and highlight the advantages of the use of cross-linked ureasil-polyether hybrid matrices as film-forming systems. The results revealed that ureasil-polyethers are excellent film-forming systems due to specific properties, such as their biocompatibility, their cosmetic attractiveness for being able to form thin and transparent films, their short drying time to form films and their excellent bioadhesion compared to the commercial products known as strong adhesives. Rheological measurements have demonstrated the ability of these hybrid matrices to form a film in only a few seconds and Water Vapor Transmitting Rate (WVTR) showed adequate semi-occlusive properties suggesting that these films could be used as skin and wound protectors. Both the high skin bioadhesion and non-cytotoxic character seems to be improved by the presence of multiple amine groups in the hybrid molecules.

Stimuli-responsive controlled growth of mono- and bidimensional particles from basic zirconium sulfate hydrosols.

A thermostimulated sol-gel transition in a system prepared by mixing a ZrOCl(2) acidified solution to a hot H(2)SO(4) aqueous solution was studied by dynamic rheological measurements and quasi-elastic light scattering. The effect of temperature and of molar ratio R(S) = [Zr]/[SO(4)] on the gelation kinetics was analyzed using the mass fractal aggregate growth model. This study shows that the linear growth of aggregates occurs at the early period of transformation, while bidimensional growth occurs at the advanced stage. The bidimensional growth can be shifted toward monodimensional growth by decreasing the aggregation rate by controlling the temperature and/or molar ratio R(S). EXAFS and Raman results gave evidence that the linear chain growth is supported by covalent sulfate bonding between primary building blocks. At the advanced stage of aggregation, the assembly of linear chains through hydrogen bonding gave rise to the growth of bidimensional particles.

Structural changes of biocompatible neutral microemulsions stabilized by mixed surfactant containing soya phosphatidylcholine and their relationship with doxorubicin release.

Depending on the composition, the mixture of surfactant, oil and water, may form supramolecular aggregates with different structures which can significantly influence the drug release. In this work several microemulsion (ME) systems containing soya phosphatidylcholine (SPC) and eumulgin HRE40 (EU) as surfactant, cholesterol (O) as oil phase, and ultra-pure water as an aqueous phase were studied. MEs with and without the antitumoral drug doxorubicin (DOX) were prepared. The microstructures of the systems were characterized by photon correlation spectroscopy, rheological behavior, polarized light microscopy, small-angle X-ray scattering (SAXS) and X-ray diffraction (XRD). The results reveal that the diameter of the oil droplets was dependent on the surfactant (S) amount added to formulations. The apparent viscosity was dependent on the O/S ratio. High O/S ratio leads to the crystallization of cholesterol polymorphs phases which restricts the mobility of the DOX molecules into the ME structure. Droplets with short-range spatial correlation were formed from the ME with the low O/S ratio. The increase of the cholesterol fraction in the O/S mixture leads to the formation of ordered structures with lamellar arrangements. These different structural organizations directly influenced the drug release profiles. The in vitro release assay showed that the increase of the O/S ratio in the formulations inhibited the constant rate of DOX release. Since the DOX release ratio was directly dependent on the ratio of O/S following an exponential decay profile, this feature can be used to control the DOX release from the ME formulations.

Relationship between structural features and in vitro release of doxorubicin from biocompatible anionic microemulsion.

In this work structural features of anionic microemulsions, containing the pharmaceutical biocompatible components soya phosphatidylcholine (SPC), eumulgin HRE 40 (EU) and sodium oleate (SO) as surfactant, cholesterol (CHO) as oil phase and aqueous buffer were studied. Microemulsions were formulated with and without the antitumor drug doxorubicin (DOX). The various microstructures characterized in the pseudo-ternary phase diagram were analyzed by polarized light microscopy, small-angle X-ray scattering (SAXS) and X-ray diffraction (XRD) as well as by their ability to incorporate and release DOX. The experimental results demonstrated a correlation between the composition, the structural features and drug delivery. It was found that at higher cholesterol contents, the crystallization of CHO polymorph phases changed the mobility of DOX molecules. Droplets were formed with short-range spatial correlation from a microemulsion (ME) with a low surfactant:oil ratio. More ordered structures with lamellar arrangements formed by the increasing of the CHO proportions in the formulation may be due to CHO crystallization. The in vitro release of DOX showed that the presence of a high content of crystalline CHO prolongs the release of DOX from ME. The retention of DOX in the internal oil phase of the ME may modulate the drug release for a prolonged time. These results clearly demonstrate the potential of ME as a drug-delivery system.

Doxorubicin biocompatible O/W microemulsion stabilized by mixed surfactant containing soya phosphatidylcholine.

Microemulsions (ME) containing soya phosphatidylcholine (SPC)/polyoxyethylenglycerol trihydroxystearate 40 (EU)/sodium oleate (SO) as surfactant cholesterol (CHO) as oil phase and aqueous buffer were studied. Pseudo-ternary phase diagrams of the investigated systems were obtained at constant SPC/EU/SO weight ratio 3.5:3.5:3.0 by titration, in order to characterize the proportions between the components to form clear systems. The dynamic light scattering results showed that the size of the oil droplets decreases significantly with the ratio of surfactant/oil phase added to system. Depending on the composition ME system could exhibit a thixotropic behavior. The apparent viscosity increased 25- and 13-folds with cholesterol concentration for drug-free and drug-load ME, respectively. It was also verified that the octanol/aqueous buffer partition coefficient (KO/B) of doxorubicin (DOX) was pH dependent increasing abruptly above pH 6.0. It was possible to incorporate 2.24 mg/ml of DOX into ME. The incorporation of DOX in the ME systems increased the droplets size for all surfactant concentrations used in the system. The results suggest that DOX interacts with the microstructure of the ME at the studied pH increasing significantly the drug solubility. It was possible to conclude that the investigated ME can be a very promising vehicle as drug-carrier for administration of doxorubicin.

Local structure and near-infrared emission features of neodymium-based amine functionalized organic/inorganic hybrids.

Nd(3+)-based organic/inorganic hybrids have potential application in the field of integrated optics. Attractive sol-gel derived di-urea and di-urethane cross-linked poly(oxyethylene) (POE)/siloxane hybrids (di-ureasils and di-urethanesils, respectively) doped with neodymium triflate (Nd(CF(3)SO(3))(3)) were examined by Fourier transform mid-infrared (FT-IR), Raman (FT-Raman), (29)Si magic-angle spinning (MAS) nuclear magnetic resonance (NMR) and photoluminescence spectroscopies, and small-angle X-ray scattering (SAXS). The goals of this work were to determine which cation coordinating site of the host matrix (ether oxygen atoms or carbonyl oxygen atoms) is active in each of the materials analyzed, its influence on the nanostructure of the samples and its relation with the photoluminescence properties. The main conclusion derived from this study is that the hydrogen-bonded associations formed throughout the materials play a major role in the hybrids nanostructure and photoluminescence properties.

Studies on the encapsulation of diclofenac in small unilamellar liposomes of soya phosphatidylcholine.

The encapsulation of acid (AD) and sodium diclofenac (SD) in small unilamellar liposomes (SUV) as well as the interactions of the drug with the bilayer was studied. SUV was prepared by sonication from multilamellar liposomes containing soya phosphatidylcholine and diclofenac at various proportions. The size distribution obtained from dynamic light scattering showed that the incorporation of SD decreases significantly the size of the liposomes suggesting that the drug interacts with the bilayer of the liposomes. This size decrease is related with the phase transition of liposomes to mixed micelar solution. The encapsulation of the hydrophilic dye indocyanine green in the aqueous compartment of liposomes showed that the rate of captured dye decreases with SD concentration suggesting the transition of liposomes to mixed micelles. The (31)P NMR analysis indicates that SD interacts with the phosphate of phosphatidylcholine head groups. A schematic model for interaction of SD with phosphatidylcholine of the liposomes in which the diclofenac anion interacts with the ammonium group of the phospholipid and the dichlorophenyl ring occupies a more internal site of bilayer near phosphate group was proposed.