The main aim of this work is the synthesis and characterization of cross-linked chitosan systems. Chitosan hydrogels can be prepared by physical or chemical cross-linking of polymer chains. Chemical cross-linking, leading to the creation of hydrogel networks possessing improved mechanical properties and chemical stability, can be achieved using either synthetic agents or naturalbased agents. In this work, the cross-linker Genipin, a naturally derived compound, was selected because of the lower acute toxicity compared to many other commonly used synthetic cross-linking reagents. In particular, the chemical stabilization of chitosan through genipin cross-linking molecules was performed and characterized by calorimetric analyses (differential scanning calorimetry), swelling measurements in different pHs, and ionic strength. The reaction kinetics was carried out by means of rheological measurements, and both the activation energy (E a ) and the reaction order (m) were calculated. The hydrogel analyses were carried out at different concentrations of genipin (GN1 and GN2). The results were used to evaluate the possibility to use the chemical cross-linked chitosangenipin hydrogel for biomedical applications.

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Physical foaming combined with microwave-induced curing was used in this study to develop an innovative device for bone tissue regeneration. In the first step of the process, a stable physical foaming was induced using a surfactant (i.e. pluronic) as blowing agent of a homogeneous blend of Sodium salt of carboxymethylcellulose (CMCNa) and polyethylene glycol diacrylate (PEGDA700) solution. In the second step, the porous structure of the scaffold was chemically stabilized by radical polymerization induced by a homogeneous rapid heating of the sample in a microwave reactor. In this step 2,2-Azobis[2-(2-imidazolin-2 yl)propane]Dihydrochloride was used as thermoinitiator (TI). CMCNa and PEGDA were mixed with different blends to correlate the properties of final product with the composition. The chemical properties of each sample were evaluated by spectroscopy analysis ATR-IR (before and after curing) in order to maximize reaction yield, and optimize kinetic parameters (i.e. time curing, microwave power). The stability of the materials was evaluated in vitro by degradation test in Phosphate Buffered Saline. Biological analyses were performed to evaluate the effect of scaffold materials on cellular behavior in terms of proliferation and early osteogenic differentiation of human Mesenchymal Stem Cells. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 726-733, 2016.

Abstract:The Mark-Houwink-Sakurada (MHS) equation allows for estimation of rheological properties, if the molecular weight is known along with good understanding of the polymer conformation. The intrinsic viscosity of a polymer solution is related to the polymer molecular weight according to the MHS equation, where the value of the constants is related to the specific solvent and its concentration. However, MHS constants do not account for other characteristics of the polymeric solutions, i.e., Deacetilation Degree (DD) when the solute is chitosan. In this paper, the degradation of chitosan in different acidic environments by thermal treatment is addressed. In particular, two different solutions are investigated (used as solvent acetic or hydrochloric acid) with different concentrations used for the preparation of chitosan solutions. The samples were treated at different temperatures (4, 30, and 80˝C) and time points (3, 6 and 24 h). Rheological, Gel Permeation Chromatography (GPC), Fourier Transform Infrared Spectroscopy (FT-IR), Differential Scanning Calorimetry (DSC) and Thermal Gravimetric Analyses (TGA) were performed in order to assess the degradation rate of the polymer backbones. Measured values of molecular weight have been integrated in the simulation of the batch degradation of chitosan solutions for evaluating MHS coefficients to be compared with their corresponding experimental values. Evaluating the relationship between the different parameters used in the preparation of chitosan solutions (e.g., temperature, time, acid type and concentration), and their contribution to the degradation of chitosan backbone, it is important to have a mathematical frame that could account for phenomena involved in polymer degradation that go beyond the solvent-solute combination. Therefore, the goal of the present work is to propose an integration of MHS coefficients for chitosan solutions that contemplate a deacetylation degree for chitosan systems or a more general substitution degree for polymers in which viscosity depends not only on molecular weight and solvent combinations.