Chitosan-Based Thermosensitive Materials

Thermosensitive polymers are materials capable of undergoing a reversible phase transition in aqueous media in response to a variation of the temperature. They have attracted high scientific interest for advanced applications in diverse areas, such as biotechnology, biomedical, environmental, food industry and other fields. At the same time, chitosan is a promising marine polysaccharide that has long been used in applications such as drug, peptide or gene delivery systems. Being the most abundant marine polysaccharide, chitin and chitosan do not exhibit thermoresponsive properties, but some of their derivatives do. In the present chapter, the efforts to produce chitosan-based thermosensitive materials are reviewed. Particularly, the properties and applications of chitosan-glycerophosphate thermogelling system are examined; the methods of synthesis of chitosan copolymers grafted with poly(N-isopropylacrylamide) or poly(N-vinylcaprolactam), their physicochemical properties and most of their prominent applications are discussed as well

Síntesis y caracterización de redes poliméricas interpenetradas de quitosana-poli(ácido acrílico-coacrilamida)

Se prepararon redes poliméricas interpenetradas de quitosana (QUI) con poli(ácido acrílico) (PAAc) y poliacrilamida (PAAm) mediante la polimerización radicálica de la acrilamida (AAm) y el ácido acrílico (AAc) en presencia de la quitosana, utilizando como sistema iniciador persulfato de amonio, [(NH4)2S2O8, a 1,2 · 10-3 mol/L] con N,N,N’,N’- tetrametilendiamina como activador, en relación 1 : 1 mol/L con el persulfato a 50 ºC . Se utilizó como entrecruzante la N,N’-metilenbisacrilamida a 3,3 ·10-3 mol/L . Los materiales obtenidos se caracterizaron por microscopia electrónica de barrido y la composición relativa de los polímeros en los sistemas fue confirmada por espectroscopia FTIR. Se utilizaron la relaciones de absorbancias a 1 670, 1 662 y 1 082 cm–1, A1662/A1082 y A 1670/A1082, como indicativas de la composición relativa de AAm y el AAc en estos materiales. La capacidad de hinchamiento en equilibrio de los terpolímeros (QUI/PAAc/PAAm) resultó altamente dependiente de la composición. Al ser sometidos a un tratamiento con NaOH(ac) 1 mol/L las características del sistema variaron apreciablemente. Se incrementó el hinchamiento y la sensibilidad al pH del medio en comparación con los sistemas QUI/PAAc/PAAm antes del tratamiento con NaOH(ac). Estos resultados fueron discutidos en términos de los cambios químicos y estructurales que tienen lugar durante el tratamiento con NaOH(ac). Los geles son denominados “sistemas inteligentes” por ser sensibles a la temperatura y la fuerza iónica del medio

Acemannan Gels and Aerogels

The procedures to obtain two types of acemannan (AC) physical gels and their respective aerogels are reported. The gelation was induced by the diffusion of an alkali or a non-solvent, then supercritical CO2 drying technology was used to remove the solvent out and generate the AC aerogels. Fourier-transform infrared spectroscopic analysis indicated that alkali diffusion produced extensive AC deacetylation. Conversely, the non-solvent treatment did not affect the chemical structure of AC. Both types of gels showed syneresis and the drying process induced further volume reduction. Both aerogels were mesoporous nanostructured materials with pore sizes up to 6.4 nm and specific surface areas over 370 m2/g. The AC physical gels and aerogels enable numerous possibilities of applications, joining the unique features of these materials with the functional and bioactive properties of the AC

Chitosan Derivatives: Introducing New Functionalities with a Controlled Molecular Architecture for Innovative Materials

The functionalization of polymeric substances is of great interest for the development of innovative materials for advanced applications. For many decades, the functionalization of chitosan has been a convenient way to improve its properties with the aim of preparing new materials with specialized characteristics. In the present review, we summarize the latest methods for the modification and derivatization of chitin and chitosan under experimental conditions, which allow a control over the macromolecular architecture. This is because an understanding of the interdependence between chemical structure and properties is an important condition for proposing innovative materials. New advances in methods and strategies of functionalization such as the click chemistry approach, grafting onto copolymerization, coupling with cyclodextrins, and reactions in ionic liquids are discussed

Chitosan Hydrogels Based on the Diels–Alder Click Reaction: Rheological and Kinetic Study

The Diels–Alder reaction is recognized to generate highly selective and regiospecific cycloadducts. In this study, we carried out a rheological and kinetic study of N-furfuryl chitosan hydrogels based on the Diels–Alder click reaction with different poly(ethylene)glycol-maleimide derivatives in dilute aqueous acidic solutions. It was possible to prepare clear and transparent hydrogels with excellent mechanical properties. Applying the Winter and Chambon criterion the gel times were estimated at different temperatures, and the activation energy was calculated. The higher the temperature of gelation, the higher the reaction rate. The crosslinking density and the elastic properties seem to be controlled by the diffusion of the polymer segments, rather than by the kinetics of the reaction. An increase in the concentration of any of the two functional groups is accompanied by a higher crosslinking density regardless maleimide:furan molar ratio. The hydrogel showed an improvement in their mechanical properties as the temperature increases up to 70 °C. Above that, there is a drop in G’ values indicating that there is a process opposing to the Diels–Alder reaction, most likely the retro-Diels–Alder

Aerogels from Chitosan Solutions in Ionic Liquids

Chitosan aerogels conjugates the characteristics of nanostructured porous materials, i.e., extended specific surface area and nano scale porosity, with the remarkable functional properties of chitosan. Aerogels were obtained from solutions of chitosan in ionic liquids (ILs), 1-butyl-3-methylimidazolium acetate (BMIMAc), and 1-ethyl-3-methyl-imidazolium acetate (EMIMAc), in order to observe the effect of the solvent in the structural characteristics of this type of materials. The process of elaboration of aerogels comprised the formation of physical gels through anti-solvent vapor diffusion, liquid phase exchange, and supercritical CO2 drying. The aerogels maintained the chemical identity of chitosan according to Fourier transform infrared spectrophotometer (FT-IR) spectroscopy, indicating the presence of their characteristic functional groups. The internal structure of the obtained aerogels appears as porous aggregated networks in microscopy images. The obtained materials have specific surface areas over 350 m2/g and can be considered mesoporous. According to swelling experiments, the chitosan aerogels could absorb between three and six times their weight of water. However, the swelling and diffusion coefficient decreased at higher temperatures. The structural characteristics of chitosan aerogels that are obtained from ionic liquids are distinctive and could be related to solvation dynamic at the initial state

Characterization and Antiproliferative Activity of Nobiletin-Loaded Chitosan Nanoparticles

Nobiletin is a polymethoxyflavonoid with a remarkable antiproliferative effect. In order to overcome its low aqueous solubility and chemical instability, the use of nanoparticles as carriers has been proposed. This study explores the possibility of binding nobiletin to chitosan nanoparticles, as well as to evaluate their antiproliferative activity. The association and loading efficiencies are 69.1% and 7.0%, respectively. The formation of an imine bond between chitosan amine groups and the carbonyl group of nobiletin, via Schiff-base, is proposed. Nobiletin-loaded chitosan nanoparticles exhibit considerable inhibition (IC50=8 μg/mL) of cancerous cells, revealing their great potential for applications in cancer chemotherapy

Enhanced Antifungal Effect of Chitosan/Pepper Tree (Schinus molle) Essential Oil Bionanocomposites on the Viability of Aspergillus parasiticus Spores

Chitosan nanoparticles (CS) and chitosan/pepper tree (Schinus molle) essential oil (CS-EO) bionanocomposites were synthesized by nanoprecipitation method and the in vitro antifungal activity against Aspergillus parasiticus spores was evaluated. The shape and size were evaluated by scanning electron microscopy (SEM) and dynamic light scattering (DLS). The surface charge was determined by assessing the zeta potential and the inclusion of essential oil in bionanocomposites using Fourier transform infrared spectroscopy (FT-IR). The effect on cell viability of the fungus was evaluated using the XTT technique and morphometric analysis by image processing. SEM and DLS analysis indicated that spherical particles with larger diameters for CS-EO biocomposites were observed. Zeta potential values were higher (+11.1 ± 1.60 mV) for CS nanoparticles. Results suggest a chemical interaction between chitosan and pepper tree essential oil. The highest concentration of CS-EO complex caused a larger (40–50%) decrease in A. parasiticus viability. The inclusion of pepper tree oil in CS nanoparticles is a feasible alternative to obtain antifungal biocomposites, where the activity that each compound presents individually is strengthened