Preparation, Characterization and Study of the Dissociation of Naproxen from Its Chitosan Salt.

Salts of naproxen (NAP) with chitosan (CTS) and reticulated chitosan (CEP) were prepared under optimized conditions to maximize the yield of reaction. The objective was to evaluate the dissociation in water, which can guide studies of release of the drug from biopolymeric salts in pharmaceutical applications. Higher salification was found after 24 h of reaction at 60 °C in a molar ratio 1:1.05 (CTS:NAP, mol/mol), resulting in a degree of substitution (DS) of 17% according to 13C NMR, after neutralization of the -NH2 group of the biopolymer by the carboxylic group of the drug. The presence of NAP salt is evidenced by FTIR bands related to the -NH3+ group at 856 cm-1, a decrease in crystallinity index in XRD diffractograms as well as changes in mass loss ratios (TG/DTG/DTA) and increased thermal stability of the salt regarding CTS itself. The CEPN crosslinked salt presented a DS = 3.6%, probably due to the shielding of the -NH2 groups. Dissociation studies revealed that at pH 2.00, dissociation occurred faster when compared to at pH 7.00 in the non-reticulated salt, while the opposite was observed for the reticulated one.

A new look towards the thermal decomposition of chitins and chitosans with different degrees of deacetylation by coupled TG-FTIR.

Chitins and Chitosans with different degrees of deacetylation (DD¯) were analyzed for the first time by thermogravimetry coupled to infrared spectroscopy TG-FTIR in order to evaluate the effect of DD¯ on the thermal decomposition process. DD¯ values of chitins and chitosans were determined by 1H-NMR and structural difference were investigated by FTIR, SEM and XRD. Thermal stability of chitosan with 98, 87, 71% DD¯, chitins with 47 and 27% DD¯ and commercial α-chitin were evaluated. Thermal decomposition of chitosans occurs in two steps, while for chitins occurs predominantly in first stage under air atmosphere. Commercial chitin thermally decomposed at lower temperatures than highly deacetylated chitosan. A faster thermal degradation process was found for chitins, except for commercial sample. TG-FTIR of evolved gas evidenced a complex gaseous mixture mainly composed by ammonia, acetic acid, acetamide, water, monoxide and carbon dioxide in proportions that are deeply dependent on the DD¯.