Studies on physicochemical characteristics of chitosan derivatives with dicarboxylic acids

Abstract

Chitosan (N-deacetylated derivative of chitin) was solubilised in different aqueous dicarboxylic acid solutions, including oxalic acid, malonic acid, adipic acid, azelaic acid and also in monocarboxylic acetic acid. These dicarboxylic acid solutions were used with the objective that they not only act as solvents but also enhance material properties of chitosan gel films through chemical cross-linking. The properties including conformational changes of chitosan, chemical interaction, and mechanical, morphological and thermal characteristics of selected chitosan samples studied in this work. The circular dichroism study indicated that the intensity of the broad negative transition of chitosan helical structure in the wavelength region of 190–230 nm decreased with decreasing the chain length of the dicarboxylic acids. The infrared spectra revealed the formation of amide linkage between chitosan and carboxylic acids in solid state. The cross-sections of the films produced from malonic acid and acetic acid solutions of chitosan exhibited granular morphologies with different granule sizes and hill-valley-structures under atomic force microscope. The chitosan/malonic acid film showed improved water resistance and decreased tensile properties compared with the chitosan/acetic acid and chitosan/adipic acid films. These physical characteristics of chitosan/malonic acid film are attributed to the dual effects of malonic acid, which acts as a chemical cross-linker and also as a plasticizer. A strong glass transition (Tg) peak at 166 °C in differential scanning calorimetric analysis was observed, indicating the possible plasticizing effect with malonic acid.