Irina M. Pelin

Phosphorylated curdlan microgels. Preparation, characterization, and in vitro drug release studies.

Curdlan derivative with anionic phosphate groups was used for the first time to obtain hydrogel microspheres. The chemical cross-linking of the phosphorylated curdlan was performed with epichlorohydrin using the water-in-oil inverse emulsion technique. The optical and scanning electron microscopies were used to analyze the morphology of the microgels, whereas the FTIR spectroscopy was used to investigate their chemical structure. The main characteristics such as the swelling degree, the exchange capacity, and the thermal resistance were also studied. These new anionic microgels could be used as potential carriers for controlled release of opposite charged drugs retained through electrostatic forces. Diphenhydramine, a cationic model drug, was used to investigate the loading and the release processes in various pH media simulating physiological fluids. Several mathematical models were applied to evaluate the drug transport processes and to calculate the drug diffusion coefficients. The synthesized microspheres presented an excellent biocompatibility.

Cationic curdlan: Synthesis, characterization and application of quaternary ammonium salts of curdlan.

Water-soluble curdlan derivatives containing quaternary ammonium groups with a degree of substitution up to 0.15 were synthesized using different cationic agents in alkaline medium. The chemical structure of curdlan derivatives was confirmed by FTIR, (13)C and (1)H NMR spectroscopy. The influence of some reaction conditions (temperature, time, and molar ratio) on the degree of substitution and the viscosimetic behaviour were studied. The degree of substitution increased with the amount of the cationization agent per anhydroglucose unit and was higher when the glycidyl reagents were used, compared with the case when the reagents contained chloro-hydroxypropyl groups. The viscosity behaviour of these new derivatives of curdlan in aqueous solutions and the values of intrinsic viscosities calculated using different semi-empirical equations denote a high hydrodynamic dimension of the macromolecular coils. The interaction of these cationic curdlan derivatives with an anionic curdlan (monobasic curdlan phosphate) was studied in situ by turbidimetric measurements and after 24h by optical density and dynamic light scattering. The formation of polyelectrolyte complexes was influenced by the degree of substitution, the nature of the quaternary substituent, and by the ionic strength of the aqueous solution. The morphology of the polyelectrolyte complexes particles in dry state was examined by atomic force microscopy.

Influence of the Comonomer on the Dissociation of Some Alternating Maleic Acid Copolymers

Five alternating copolymers of maleic acid with N-vinylpyrrolidone, vinyl acetate, styrene, 2-vinylnaphthalene, and vinyl cyclohexane were used in order to study the influence of the comonomer on the polyelectrolyte behavior. The dissociation of the maleic acid copolymers was investigated by electrochemical methods in pure water and in the presence of supporting electrolytes. The conformational modifications during the dissociation were directly investigated by viscosimetry and fluorescence probing. The shape of the potentiometric and conductometric titration curves was influenced by the comonomer structure. In salt-free solution, only the first dissociation step was observed. The addition of univalent counterions permitted the evidencing of the second ionization step only for the copolymers with hydrophilic comonomers, but the addition of divalent counterions permitted the evidencing of the second ionization step for all five copolymers. The apparent dissociation constants increase with the increase of the comonomer hydrophobicity. A conformational transition was evidenced especially in the case of the maleic acid-2-vinylnaphthalene copolymer.

A new fluorinated urethane dimethacrylate with carboxylic groups for use in dental adhesive compositions

A urethane macromer containing hexafluoroisopropylidene, poly(ethylene oxide) and carboxylic moieties (UF-DMA) was synthesized and used in proportions varying between 15 and 35 wt.% (F1-F3) in dental adhesive formulations besides BisGMA, triethylene glycol dimethacrylate and 2-hydroxyethyl methacrylate. The FTIR and (1)H ((13)C) NMR spectra confirmed the chemical structure of the UF-DMA. The experimental adhesives were characterized with regard to the degree of conversion, water sorption/solubility, contact angle, diffusion coefficient, Vickers hardness, and morphology of the crosslinked networks and compared with the specimens containing 10 wt.% hydroxyapatite (HAP) or calcium phosphate (CaP). The conversion degree (after 180 s of irradiation with visible light) ranged from 59.5% (F1) to 74.8% (F3), whereas the water sorption was between 23.15 μg mm(-3) (F1) and 40.52 μg mm(-3) (F3). Upon the addition of HAP or CaP this parameter attained values of 37.82-49.14 μg mm(-3) (F1-F3-HAP) and 34.58-45.56 μg mm(-3), respectively. Also, the formation of resin tags through the infiltration of a dental composition (F3) was visualized by SEM analysis. The results suggest that UF-DMA taken as co-monomer in dental adhesives of acrylic type may provide improved properties in the moist environment of the mouth.

A Novel Light-Cured Dental Material Based on Maleic Copolymer Functionalized With Urethane Derivative for Dental Applications

The purpose of this work was to obtain a polymeric material aimed at being easily applied in a thin film on an organic substrate for dental applications. A maleic anhydride copolymer functionalized with a urethane derivative bearing methacrylate groups was synthesized, and by its mixing with commercial dental monomers, two light-curing formulations were prepared and investigated. The surface morphology and physicochemical properties of the obtained materials are affected by their composition. An increase of the diffusion coefficient from 0.38 at 3.58 µm2/s (estimated by fluorescence recovery after photobleaching) could ensure minimal moisture of an organic injectable paste situated under this polymer film. GRAPHICAL ABSTRACT

Dual-responsive hydrogels based on maleilated curdlan-graft-poly(N-isopropylacrylamide)

ABSTRACT The esterification reaction between curdlan and maleic anhydride was performed to provide polymerizable double bonds and pH-sensitive carboxylic groups for the curdlan chains. The new derivative was used as macromolecular cross-linker in the polymerization of N-isopropylacrylamide, when thermo and pH-sensitive networks were obtained in the form of microparticles. The loading and releasing profiles of a model macromolecular drug, lysozyme, were evaluated. The protein release rate was influenced by the pH and temperature. The pulsatile release of the lysozyme was also observed, the pulse being the swelling of the microparticles due to the decrease of the temperature under the volume phase transition temperature. GRAPHICAL ABSTRACT

Investigation of Interpolymer Complexation Between Poly(Vinylcaprolactam) and Poly(Maleic Acid-Alt-Styrene)

ABSTRACT The interactions between two synthetic polymers used in biomedical applications, maleic acid-styrene copolymer (MAc-St) and poly(vinylcaprolactam) (PVCL), were investigated in dilute aqueous solution considering the influence of the pH, the added salt and the ratio between the components in the mixture. Hydrogen-bonding interactions between the COOH groups of MAc-St and the C═O groups of PVCL, together with hydrophobic interactions are involved in the formation of the interpolymer complex. The complex is insoluble below pH = 2.85 in aqueous solution, but the addition of NaCl enlarged the pH domain where the precipitation of the complex occurred. When the ratio between the polymers was varied, two maxima of the optical density were obtained: at a 1:1 ratio between the COOH and caprolactam groups, and also at a lower ratio (1:3). Other investigations, like the measurements of the turbidity in situ during mixing, and fluorescence, viscometric and potentiometric measurements were performed in order to understand these interactions. The phase separation of the thermosensitive poly(vinylcaprolactam) in the presence of MAc-St was also studied. The cloud point and the phase transition profile were found to be influenced by the amount of polyacid, as well as by the pH.