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Polysaccharide-based biomaterials are an emerging class in several biomedical fields such as tissue regeneration, particularly for cartilage, drug delivery devices and gel-entrapment systems for the immobilization of cells. Important properties of the polysaccharides include controllable biological activity, biodegradability, and their ability to form hydrogels. Most of the polysaccharides used derive from natural sources; particularly, alginate and chitin, two polysaccharides which have an extensive history of use in medicine, pharmacy and basic sciences, and can be easily extracted from marine plants (algae kelp) and crab shells, respectively. The recent rediscovery of poly-saccharide-based materials is also attributable to new synthetic routes for their chemical modification, with the aim of promoting new biological activities and/or to modify the final properties of the biomaterials for specific purposes. These synthetic strategies also involve the combination of polysaccharides with other polymers. A review of the more recent research in the field of chemical modification of alginate, chitin and its derivative chitosan is presented. Moreover, we report as case studies the results of our recent work concerning various different approaches and applications of polysaccharide-based biomaterials, such as the realization of novel composites based on calcium sulphate blended with alginate and with a chemically modified chitosan, the synthesis of novel alginate-poly(ethylene glycol) copolymers and the development of a family of materials based on alginate and acrylic polymers of potential interest as drug delivery systems.

In this work, a coating of chitosan onto alginate hydrogels was realized using the water-soluble hydrochloride form of chitosan (CH-Cl), with the dual purpose of imparting antibacterial activity and delaying the release of hydrophilic molecules from the alginate matrix. Alginate hydrogels with different calcium contents were prepared by the internal setting method and coated by immersion in a CH-Cl solution. Structural analysis by cryo-scanning electron microscopy was carried out to highlight morphological alterations due to the coating layer. Tests in vitro with human mesenchymal stromal cells (MSC) were assessed to check the absence of toxicity of CH-Cl. Swelling, stability in physiological solution and release characteristics using rhodamine B as the hydrophilic model drug were compared to those of relative uncoated hydrogels. Finally, antibacterial activity against Escherichia coli was tested. Results show that alginate hydrogels coated with chitosan hydrochloride described here can be proposed as a novel medicated dressing by associating intrinsic antimicrobial activity with improved sustained release characteristics.

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The use of a modified poly(ε-caprolactone) (gPCL) to enhance polymer miscibility in films based on thermoplastic starch (S) and poly(ε-caprolactone) is reported. PCL was functionalized by grafting with maleic anyhdride (MA) and/or glycidyl methacrylate (GMA) by reactive blending in a batch mixer. gPCL based materials were analysed in terms of their grafting degree, structural and thermal properties. Blends based on starch and PCL (wt. ratio 80:20) with including gPCL (0, 2.5 and 5wt.%), as a compatibilizer, were obtained by extrusion and compression moulding, and their structural, thermal, mechanical and barrier properties were investigated. Blends containing gPCL evidenced better interfacial adhesion between starch and PCL domains, as deduced from both structural (XRD, FTIR, SEM) and bulk properties (DSC, TGA). Moreover, grafted PCL-based compatibilizers greatly improved functional properties of S-PCL blend films, as pointed out from mechanical performance and higher barrier properties, valuable to meet the food packaging requirements.

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