Amphiphilic polymers bearing gluconolactone moieties: synthesis and long side-chain crystalline behavior.

The synthesis and characterization of amphiphilic polymers bearing gluconolactone moieties has been described. In a first step, an unprotected glycomonomer 2-[({[4-(d-gluconamid-N-yl)butyl]amino}carbonyl)oxy]ethyl acrylate, HEAG, has been synthesized. Posterior, this glycomonomer has been copolymerized with methyl methacrylate at different compositions and the kinetic behavior has been also studied calculating the monomer reactivity ratios by Kelen-Tüdös extended equation. In addition, the long side-chain crystalline behavior of these carbohydrate-based copolymers with high composition of glycomonomer has been examined by using conventional and modulated differential scanning calorimetry and X-ray diffraction measurements. At the same time, the phase separation behavior of carbohydrate-based copolymers with lower HEAG content has been determined by their glass transition temperature measurements. Finally, the thermal stability of all these amphiphilic copolymers has been evaluated by thermogravimetric analysis.

Fabrication of honeycomb-structured porous surfaces decorated with glycopolymers.

We prepared breath figure patterns on functional surfaces by the surface segregation of a statistical glycopolymer, (styrene-co-2-(D-glucopyranosyl) aminocarbonyloxy ethyl acrylate (S-HEAGl). The synthesis of the statistical glycopolymer is prepared in a straightforward approach by conventional free radical copolymerization of styrene and the unprotected glycomonomer. Blends of this copolymer and high-molecular-weight polystyrene were spin coated from THF solutions, leading to the formation of surfaces with both controlled functionality and topography. AFM studies revealed that both the composition of the blend and the relative humidity play key roles in the size and distribution of the pores at the interface. Thus, the topographical features obtained on the polymer surfaces during film preparation by the breath figure methodology varied from 200 to 700 nm. Moreover, this approach leads to porous films in which the hydrophilic glycomonomer units are oriented toward the pore interface because upon soft annealing in water the holes are partially swelled. The self-organization of the glycopolymer within the pores was additionally confirmed by the reaction of carbohydrate hydroxyl groups with rhodamine isocyanate. Equally, we demonstrate the bioactivity of the anchored glycopolymers by means of the lectin binding test using concanavalin A (Con A).