Kinetics of base deacetylation of chitin and chitosan as influenced by their crystallinity

Structural properties of the initial and reprecipitated chitin and chitosan samples in dry and wet states were studied. Original Russian Text E.N. Chebotok, V.Yu. Novikov, I.N. Konovalova, 2007, published in Zhurnal Prikladnoi Khimii, 2007, Vol. 80, No. 10, pp. 1724–1729.     

Kinetics of enzymatic deacetylation of chitosan

The current paper reports on an investigation of the kinetics of chitosan deacetylation by chitin deacetylase isolated from Absidia orchidis vel coerulea. The reaction rate was correlated with the concentration of GlcNHAc units of the polymer. It is shown that the process follows the Michaelis–Menten mechanism. Modification of the Michaelis–Menten equation by introducing the activity of the enzyme instead of its concentration was tested and found to give a better approximation to the experimental data than the original Michaelis–Menten model. Parameters for both the original and the modified Michaelis–Menten equations are also proposed.     

Influence of the degree of deacetylation on the rate of acid degradation of chitin and chitosan and on the yield of D(+)-glucosamine hydrochloride

The dependence of the rate of acid degradation of chitin and chitosan on the degree of deacetylation was examined.     

甲壳素和壳聚糖在电化学分析中的应用进展

甲壳素和壳聚糖特有的吸附、螯合作用的性质使其在电化学分析领域中应用广泛,本文对此进行了综述,着重介绍了甲壳素和壳聚糖修饰电极的制备、特点及其在痕量物质的测定、生物传感器等方面的应用,并对其研究前景进行了展望。     

The crystal structure of chitin and chitosan

Roentgenographic studies are performed to investigate the structural changes in chitin under pressure and shear during its solid-state processing using a twin-screw extruder and Bridgman anvils. The structure of chitosan synthesized by the solid-phase method is studied. Deformation under the conditions of dry extrusion grinding at room temperature reduces the crystallinity of the original chitin. Addition of water restores the crystallinity of the material up to the value characteristic of the original chitin. Extrusion processing of chitin at room temperature with addition of water virtually preserves the crystallinity and degree of ordering of the chitin crystal lattice, the same as ordinary dry grinding at an elevated (180°C) temperature. The maximum degree of amorphization of chitin is attained by its processing on Bridgman anvils. Solid-state synthesis of chitosan from chitin leads to a product with a more amorphous structure in comparison with chitosan produced by the suspension method.     

Influence of the deacetylation degree on chitosan emulsification properties

The emulsification of sunflower oil by chitosan solutions with deacetylation degrees (DD) between 73 and 95% was studied using different techniques. The droplet size distributions, conductivity, ageing behavior and viscosity of emulsions were studied as functions of the chitosan DD. All DD gave stable polydisperse water-in-oil-in-water emulsions with different viscosities. Two optimum DD values were found, 81 and 88%, giving complete emulsification without residual oil or sedimentation. Chitosans with intermediate DD were less effective emulsifiers. Chitosans with higher DD gave poor emulsification. Received: 11 January 1999 Accepted in revised form: 31 May 1999     

Fluorocarbon modified chitin and chitosan I. Synthesis and characterization of perfluorocarbonyl chitin

The esterification reaction of chitin with perflurocarboxylic acid was studied in methanic acid or perfluorocarboxylic acid as solvent. A series of substituted derivatives of trifluoroacyl. perfluorobutyric and perfluorooctanoyl chitin were synthesized. The properties of these chitin derivatives were investigated.     

Production of the low-molecular-weight chitin and chitosan forms in electron-beam plasma

The degradation of chitin and chitosans of different molecular weights stimulated by electronbeam plasmas of different gases has been experimentally studied. Biologically active water-soluble lowmolecular-weight chitooligosaccharides are formed as a result of plasma-beam treatment. It has been found that the degradation is a controlled process and products with a necessary molecular weight can be obtained by appropriately choosing plasma-beam treatment parameters (chemical composition of the plasma gas and treatment time and temperature).     

Advancement of chitin and chitosan as promising biomaterials

Biopolymers like cellulose, polysaccharides, chitosan, starch, chitin, and alginates have sparked an increasing curiosity in creating natural replacements for synthetic polymers during the last several decades. Chitin is a major part of fungi’s cell walls, the crustaceans’ exoskeletons, like lobsters, crabs, and shrimps, cephalopod beaks, the radulae of mollusks, and fish and lissamphibians scales. Since the late 1970 s, biopolymer chitosan has gathered interest in basic science and applied research due to its incredible macromolecular framework, physicochemical properties, and biological activities, which differ from those of synthetic polymers. Chitin and derivatives thereof have practical usages in chemistry, the agriculture sector, medicine, cosmetics, as well as textile and paper industries. Chitosan has also received a lot of recent interest in the fields of dentistry, ophthalmology, veterinary science, biomedicine, the drink industry, hygiene and personal care, catalysis, chromatography, sewage treatment, and biotechnology. Numerous fundamental investigations have been conducted on chitin and chitosan. This article presents a short compact summary of research over the last two decades in an attempt to highlight the works on chitin and chitosan applications.     

Elastic modulus of the crystalline regions of chitin and chitosan

The elastic moduli E_l of the crystalline regions of α‐chitin and chitosan in the direction parallel to the chain axis were measured by X‐ray diffraction. The E_l values were 41 GPa for α‐chitin, and 65 GPa for chitosan, respectively, at 20°C. The contracted skeletons of α‐chitin and chitosan are the key factor for the low E_l values compared with that (138 GPa) of cellulose I. The E_l value of α‐chitin was constant at 41 GPa both at −190°C and 150°C, which indicates that the molecular chain of α‐chitin is stable against heat within the temperature and stress range studied. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1191–1196, 1999     

Water sorption on and water diffusion in chitin and chitosan

The kinetics of the sorption of water vapor on powders of crab-shell chitin and chitosan are studied via the methods of static sorption, thermography, and X-ray structural analysis. Sorption isotherms are obtained in the range of humidity from 10 to 95%. S-Shaped water-sorption isotherms observed for all chitin and chitosan samples are approximated via superpositioning of Langmuir and Flory-Huggins isotherms. The water-polysaccharide interaction parameters and the maximum sorption capacities of water located in chitin and chitosan are determined. The cluster integral is calculated, and the moisture values corresponding to water-cluster formation are determined. The water-diffusion coefficients are determined, and the effective activation energies of water diffusion are estimated: 70 kJ/mol in chitosan and 60 kJ/mol in chitin. The data on the concentration dependences of the coefficients of diffusion of water in the powdered chitin and chitosan are summarized.     

Radiation resistance of chitin and chitosan applied in the chromatography of radioactive solutions

Chitin and chitosan were irradiated in acidic solutions containing a decontaminating soap. It has been shown that these powders suspended in aqueous media do not undergo radiolysis, as their I.R. spectra are not altered, and there is no radiolysis product in the solution, except for the case of nitric acid at lowpH where some chitosan is present in dissolved form. These polymers therefore exhibit very good radiation resistance, in spite of the fact that the monomers undergo very rapid radiolysis.⁶⁰Co radiations up to 50 000 krad were used. Under these conditions, chitosan does not lose its collection capacity for most of the metal ions of interest in the nuclear field, including cobalt, that can be collected from decontaminating soap solutions with a volume reduction of 10.     

Hydrogenation catalytic behaviors of palladium complexes of chitin and chitosan

Palladium complexes of chitin and chitosan have been shown to have catalytic activities for hydrogenation at room temperature and under atmospheric pressure. They could catalyze not only reduction of olefines but also aromatic nitro-compounds and acrylic acid. And they are very active, stable and selective. They also show different catalytic behaviors in different pH solutions. It is noteworthy that the catalytic activities of the two polymer-supported metal complexes in the cycle of pH 11 → pH 2 → pH 11 are reversible.     

Mechanically initiated gelation in solutions of chitosan with low degree of deacetylation

Mechanical activation of solutions of chitosan with low degree of deacetylation under the conditions of combined action of ultrasound and high shear stresses in a rotary pulse apparatus leads to the formation of physical hydrogels. Films capable to retain at repeated swelling up to 5000% water without dissolution were prepared by drying of the hydrogels.     

Preparation and properties of chitin and chitosan from a hydroid polyp

The chemical composition of Obelia longissima hydroid polyp from mariculture system fouling community was examined. Conditions for chitin recovery and chitosan preparation thereof were developed. The initial raw material, chitin, and chitosan were characterized by electron microscopy, infrared spectroscopy, and X-ray diffraction analysis. Also, certain qualitative characteristics of these materials were determined.     

Determination of the degree of acetylation of chitin and chitosan by thermal analysis

Several methods for the rapid determination of the degree of acetylation of chitin and related polymers have been evaluated, including the use of the infrared and the mass spectra. Chitin and chitosan have characteristic degradation temperatures and it is possible to determine the acetylation degree by the use of empirical correlations based on the weight losses associated with the main decomposition peaks.     

Thermomechanical properties of composite films of polyacrylonitrile with chitin and chitosan

Composite films were prepared from polyacrylonitrile synthesized by anionic and radical polymerization and combined with chitin or chitisan. The thermomechanical properties of the films were examined. The compatibility of polyacrylonitrile synthesized by radical polymerization with chitosan was studied by DSC over a wide temperature range 140–280°C.