Chitosan is a biopolymer used in biomedical applications which has the ability to form lyotropic mesophases (chiral nematic) in several solvents. Currently, chitosan liquid crystalline phase is only observed at high polymer concentrations where the system has already transitioned to a gel-like state. Due to the non-homogenous mechanical behavior of a gel, it would be preferable to obtain a liquid crystalline phase while at solution state. Therefore, the formation of chitosan liquid-crystalline at solution state was investigated. Malic and hydrochloric aqueous solutions with different concentrations of chitosan were prepared and the gel formation was followed by rheological measurements. The concentration, C Gel , at which the gel is formed, was found to be dependent on the acid used, the malic aqueous solutions presenting higher C Gel . For the chitosan/malic acid system the chiral nematic mesophase appeared in solution and was preserved in the gel (for C>C Gel ) while for the chitosan/hydrochloric acid system, mesophase was only observed in gel. Using Polarized Optical Microscopy (POM) Swirl-like fingerprint textures typical of cholesteric mesophases were observed and the helical pitch was determined. The existence of mesophases in the gel, in both chitosan aqueous solutions, was also confirmed by rheometry.Keywords: Morphology; Rheology; Cholesteric; Liquid-crystals; Gels
IntroductionChitin and chitosan are glycosaminoglycans with the rare property of bioactivity. These polysaccharides are in fact copolymers of β-(1→4)-linked 2-acetamido-2-deoxy-Dglucopyranose and 2-amino-2-deoxy-D-glucopyranose. The difference between the two is determined by the DA, the degree of acetylation, corresponding to the molar fraction of acetyl units constituting the polymer chains. It is considered that chitosan refers to polymers with DAs below 50 % (more commonly 10-30 %) [1]. Chitin is considered the second most abundant polymer in nature but due to its low solubility has limited applications and therefore is mostly used in the deacetylated form, as chitosan. Chitosan is the product of the alkali hydrolysis of chitin and is soluble in dilute acidic solutions [2]. The reason why chitosan presents a higher solubility than chitin is the presence of protonated free amine groups below pH 6.2 [3] and this polycation material has several applications in different fields, from agriculture, waste and water treatment, food and beverages, cosmetic and toiletries, biopharmaceuticals to biomedical applications [4,5]. In biomedical and pharmaceutical applications chitosan is used to produce hydrogels, due to its gelation properties. Several reports on literature can be found concerning the production of chemical [6,7] and physical [8,9] hydrogels from chitosan. Hamdine [10,11] reported an extensive work regarding chitosan gelation in different acids and concluded that chitosan has different behaviours when dissolved in acid malic and in hydrochloric acid. In the first case, due to the considerable volume of the acid molecule, that ...