Effect of type of polymerization on different properties of dental composites.

The aim of this study is to assess the influence of plasma lamps on the properties of the composites compared to the influence of conventional polymerization. Vickers hardness tests, three-point bending tests, and measurement of the shrinkage marginal gap by scanning electron microscopy were carried out on three resin composites (Tetric Ceram, Z-100 and Inten-S) irradiated with to lamps (Flipo) plasma and Astralis 7 halogen lamps). With a 3-second exposure, the results of Vickers hardness and resistance to flexion (excepting values for Z-100) were lower for the composites cured by the Flipo plasma lamp, than after 40-second curing by the conventional halogen lamp (Astralis 7), notably at a depth of 3 mm. With a 5-second exposure the results of Vickers hardness and resistance to flexion obtained using the plasma lamp approached those obtained by using the halogen lamp. Whatever the polymerization protocol used, the measurements of the gap between the tooth and the filling are very similar except for Z-100/Astralis 7, for which shrinkage results are more important. For any one resin composite and lamp used, the shrinkage values obtained at a depth of 4 mm are twice higher than those obtained at the surface. In conclusion, for a 3-second exposure the level of polymerization obtained by plasma curing is lower than the one obtained by halogen curing, particularly in depth. On the other hand, 5-second plasma curing results recommends the use of this kind of lamp.

Physicochemical behaviour of chitin gels.

Syneresis of chitin gels formed in the course of N-acetylation of chitosan in hydroalcoholic media has been studied. A critical cross-linking density related to a critical acetylation degree for which the gel undergoes weak syneresis and swells in water was shown (degree of acetylation (DA) 88%). Above this value, the weight loss during syneresis increases with DA. Conversely, syneresis decreases on increasing the polymer concentration, but disappears at a macroscopic level for a polymer concentration close to the critical concentration of entanglement in the initial solution. An increase in temperature favours the formation of hydrophobic interactions and new inter- and intramolecular hydrogen bondings. Due to the weak polyelectrolyte character of chitin, the weight of the gel depends on the pH and ionic strength of the media. Swelling-deswelling experiments show that the swelling of the gel is not fully reversible in relation with the formation of new cross-links during the depletion of the network. Our results reveals that the balance between segment-segment and segment-solvent interactions as well as the molecular mobility play the major role.

Synthesis and characterization of polyurethane and poly(ether urethane) nanocapsules using a new technique of interfacial polycondensation combined to spontaneous emulsification.

Polyurethane polymers and poly(ether urethane) copolymers were chosen as drug carriers for alpha-tocopherol. This active ingredient is widely used as a strong antioxidant in many medical and cosmetic applications, but is rapidly degraded, because of its light, heat and oxygen sensitivity. Polyurethane and poly(ether urethane)-based nanocapsules were synthesized by interfacial reaction between two monomers. Interfacial polycondensation combined with spontaneous emulsification is a new technique for nanoparticles formation. Nanocapsules were characterized by studying particle size (150-500 nm), pH, yield of encapsulation and morphologies. Polyurethanes (PUR) were obtained from the condensation of diisocyanate (isophorone diisocyanate: IPDI) and polyol: 1,2-ethanediol (EG), 1,4-butanediol (BD), 1,6-hexanediol (HD). Poly(ether urethane) copolymers were obtained by replacing diols by polyethylene glycol oligomers (PEG) M(w) 200, 300, 400 and 600. Molecular weights of di- and polyols have a considerable influence on nanocapsules characteristics cited above. The increase of molecular weight of polyols tends to increase the mean size of nanocapsules from (232+/-3)nm using EG to (615+/-39)nm using PEG 600, and led to the apparition of a population of agglomerate particles. We also noted that the yield of encapsulation increases with the increase of polyol length (from 85.6 to 92.2% w/w). Microscopic observations confirmed particle size analysis, but cannot predict the membrane structure owing the small size of the particles.

Sorption and desorption studies on chitin gels.

The aim of this work was to study various transport phenomena in chitin gels obtained by N-acetylation of chitosan in a water-alcohol mixture. Three kinds of transport were investigated: the sorption of solutes interacting with chitin, the desorption of solutes without significant interaction with the polymer, and osmosis phenomena. In the case of interactive sorption, dyes having different chemical structures such as C.I. Acid Blue 74, C.I. Reactive Violet 5 or C.I. Direct Red 28 were tested. Sorptions of C.I. Acid Blue 74 and C.I. Reactive Violet 5 depend on the charge density of the polymer network and, as a consequence, on DA, pH and the dielectric constant of the media. This result reveals the importance of electrostatic interactions. On the other hand, the sorption of C.I. Direct Red 28 is mainly due to hydrophobic interactions and H-bonding, it is limited to the extreme surface of the gel. Concerning the non-interactive desorption, solutes of different steric hindrance such as PP vitamin, B1 vitamin and caffeine exhibit similar diffusion coefficients located within 3.7-5.6x10(-6) cm(2) s(-1). Finally, the osmotic behaviour of the gel immersed in a concentrated solution of gelatin allows us to multiply by 25 the concentration of chitin in the gel without any penetration of gelatin.

Effects of process parameters on the properties of biocompatible ibuprofen-loaded microcapsules.

The objective of this study was to obtain an optimum formulation for microencapsulating Ibuprofen. This was achieved by investigating various factors which influenced the microcapsule size. Considering Ibuprofen as a lipophilic model drug, biocompatible Ibuprofen-loaded microcapsules in the size range of 20-60microm were prepared by the water in oil emulsion-solvent evaporation method. An aqueous surfactant phase was used as the continuous external phase (W), a biocompatible organic solvent dissolving Ibuprofen was used as oil phase (O), in addition with a low boiling solvent. The biocompatible polymeric microcapsule membrane was composed of Eudragit RSPO or Ethylcellulose. The influence of various process parameters, such as the volatile organic solvent, the oily core, the stirring rate, on the characteristics of microcapsules was investigated. The encapsulation yield of Ibuprofen close to 100%, whatever the polymer type, was determined by UV-vis experiments, in accordance with the results obtained by (13)C NMR spectroscopy. An innovative technique, DSC-based thermoporosimetry, was used for the estimation of the loading rate of Ibuprofen. The results indicated that this developed analytical method had to be improved since DSC-transitions accounted to free and enclosed Ibuprofen were observed and altered the accuracy of the results.

Microencapsulation of dehydroepiandrosterone (DHEA) with poly(ortho ester) polymers by interfacial polycondensation.

An original encapsulation process of DHEA was developed, based on the formation of poly(ortho ester) membrane from interfacial polycondensation in an oil-in-oil emulsion. First, the formation of poly(ortho ester) (POE) in solution under anhydrous conditions between a polyol, a lactide diol and a diketene acetal (3,9-diethylidene-2,4,8,10-tetraoxaspiro-[5.5]-undecane) was studied in order to determine the structural and thermal characteristics of the POE polymer. The optimization of the formation of a fine and stable emulsion with the required size distribution was performed in relation with the type of the internal and external phases, the type and the concentration of the surfactant and the stirring rate and duration. The diffusion of monomers and DHEA was evaluated by GC-MS analysis in order to determine the mechanisms of the membrane formation. Finally the synthesis of poly(ortho ester) DHEA-loaded microcapsules was performed under anhydrous conditions required by the particular synthesis of POE. Stable poly(ortho ester) microcapsules containing DHEA were obtained with particle sizes; 1 micro m.

Mode of action of chitin deacetylase from Mucor rouxii on N-acetylchitooligosaccharides.

The mode of action of chitin deacetylase from the fungus Mucor rouxii on N-acetylchitooligosaccharides with a degree of polymerization 1-7 has been elucidated. Identification of the sequence of chitin oligomers following enzymatic deacetylation was verified by the alternative use of two specific exo-glycosidases in conjunction with HPLC. The results were further verified by 1H-NMR spectroscopy. It was observed that the length of the oligomer is important for enzyme action. The enzyme cannot effectively deacetylate chitin oligomers with a degree of polymerization lower than three. Tetra-N-acetylchitotetraose and penta-N-acetylchitopentaose are fully deacetylated by the enzyme, while in the case of tri-N-acetylchitotriose, hexa-N-acetylchitohexaose and hepta-N-acetylchitoheptaose the reducing-end residue always remains intact. Furthermore, the enzyme initially removes an acetyl group from the nonreducing-end residue of all chitin oligomers with a degree of polymerization higher than 2, and further catalyses the hydrolysis of the following acetamido groups in a processive fashion. The results are in agreement with the mode of action that the same enzyme exhibits on partially deacetylated water soluble chitosan polymers.