Highly deacetylated chitosan and its properties

A preparative method has been established for obtaining chitosan products which have a desired degree of deacetylation of up to virtually 100%. Effective deacetylation was attained by intermitently washing the intermediate product in water two or more times during the alkali treatment. The weight average molecular weight (M?_w) of the product, which was measured by gel permeation liquid chromatography, was about 5 × 10⁵ at the highest deacetylation of nearly 100%, and the degradation of the molecular chain was not so significant. Tensile strength of the wet film increased markedly with increasing degree of deacetylation, while the dry film did not show a corresponding significant increase of the tensile strength. In the infrared spectra of chitosan film new sharp bands appeared especially at the high degree of deacetylation. This was attributed to increased “crystallization” brought about by high deacetylation.     

Evaluation of molar weight and deacetylation degree of chitosan during chitin deacetylation reaction: Used to produce biofilm

Chitosan is a polysaccharide derived from chitin, mainly of crustacean shells and shrimp wastes. The utilization of chitosan is related to the molar weight and deacetylation degree of the biopolymer. The aim of this work is to study the chitin deacetylation reaction, by the viscosity average molar weight and deacetylation degree of chitosan as a function of reaction time. Deacetylation was carried out in concentrated alkaline solution, 421 g L⁻¹, at 130 °C and the reaction occurred during 4 h. Chitosan paste obtained after 20, 90 and 240 min was used to produce biofilms, which were characterized according water vapor permeability and mechanical properties (tensile strength and percentage tensile elongation at break). During the reaction time deacetylation degree reached 93%, and a 50% reduction in the viscosity average molar weight value in relation to the value of the first 20 min of reaction was found Both reactions presented a kinetic behavior of the pseudo-first order. Biofilm produced from the paste of chitosan with high deacetylation degree showed higher water vapor permeability (WVP), tensile strength (TS) and elongation (E) when compared to films with a low deacetylation.     

Chitosan and N‐carboxymethylchitosan: I. The role of N‐carboxymethylation of chitosan in the thermal stability and dynamic mechanical properties of its films

Chitosan (degree of deacetylation of 90.2%) and N‐carboxymethylchitosan (N‐CMCh) (degree of substitution of 18.5%) were analyzed using thermogravimetric analysis in order to determine their thermal stability. Also, their films were evaluated using scanning electron microscopy (SEM) and mechanical and dynamic mechanical analysis (DMA). Both polymers showed a thermal degradation peak at T_m ～ 250 °C, with T_onset and weight loss of 175 °C and 62% and 190 °C and 35% for chitosan and N‐CMCh, respectively. N‐CMCh showed a second thermal degradation peak at T_m = 600 °C, with an additional weight loss of 25%. Kinetic thermal analysis showed a slower process of degradation at 100 °C for N‐CMCh compared with chitosan, and an activation energy 13 times higher for the former, confirming the higher stability of N‐CMCh. Analysis of chitosan and N‐CMCh films showed that the latter support a high tension, with lower elasticity, and, as revealed by DMA, N‐CMCh has a more compact film structure, with a crossing arrangement of N‐CMCh fibers, as compared with the chitosan films which were determined from SEM analysis to have fibers in one direction only. Copyright © 2006 Society of Chemical Industry     

Effect of sonolysis on kinetics and physicochemical properties of treated chitosan

Low molecular weight chitosan with weight‐average molecular weight from 161 to 22,000Da were obtained by sonolysis. Optimal conditions for sonolysis were described. The influence of sonolysis condition and the molecular parameters of initial chitosan on the degradation rate and degradation rate constant were investigated in detail. Weight‐average molecular weight (M_w) and molecular weight dispersion (M_w/M_n) of samples were measured by gel permeation chromatography. The structure of degraded chitosan were characterized by Fourier transform infrared, X‐ray diffraction, and electrospray ionization mass spectrometry. For a given sonolysis time, the decrease in molecular weight has been found to be greatest at lowest reaction temperature and lowest chitosan concentration. Molecular weight of samples decreased exponentially with increasing sonication time at early stages. The action mode of ultrasound on the splitting of molecular chain of chitosan has been discussed. The degree of deacetylation of the main hydrolysis products almost unchanged compared with the initial chitosan. The decrease of molecular weight led to transformation of crystal structure but the chemical structures of residues were not modified. Ultrasonic treatment on chitosan is an alternative, safe method to prepare chitosan having different molecular weights, which are more suitable for biomedical and food applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of immobilized neutral protease on the preparation and physicochemical properties of low molecular weight chitosan and chito‐oligomers

Neutral protease was immobilized on glutaraldehyde‐pretreated N‐succinyl chitosan hydrogel beads and the biocatalyst obtained was used for the preparation of low molecular weight chitosan and chito‐oligomers with molecular weight of 1.9–23.5 kDa from commercial chitosan. Factors affecting the chitinolytic hydrolysis were described. The degradation was monitored by gel permeation chromatography. The structure of degraded chitosan was characterized by Fourier transform infrared, X‐ray diffraction and liquid chromatography‐mass spectrometry. Immobilized neutral protease showed optimal depolymerization at pH 5.7 and 50°C. The degree of deacetylation of the hydrolysates did not change compared to that of the initial chitosan. The decrease of molecular weight led to transformation of crystal structure but the chemical structures of residues were not modified. The degree of polymerization of chito‐oligomers was mainly from 3 to 8. The method allows cyclic procedures of immobilized enzyme and N‐succinyl chitosan support utilization, and is suitable for a large‐scale production of the low molecular weight chitosan and chito‐oligomers free of protein admixtures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4185–4193, 2006     

壳聚糖降解探索

本文着重讨论了壳聚糖的主要降解方法及使用氧化降解法制备低聚壳聚糖的方法,采用正交设计,探讨降解条件对产物脱乙酰度、特性粘度等的影响。     

Liquid‐crystalline behavior of chitosan in malic acid

This report describes how the degree of deacetylation and molecular weight of chitosan and the concentrations of sodium chloride and malic acid affect the formation of lyotropic chitosan liquid crystals. Chitosan samples of various degrees of deacetylation were prepared from β‐chitin that was isolated from squid pens. They were degraded by ultrasonic irradiation to various molecular weights. The critical concentrations forming chitosan liquid crystals were determined with a polarized microscope. A chitosan sample with a degree of deacetylation of 67.2–83.6% formed cholesteric lyotropic liquid crystals when it was dissolved in 0.37–2.59M malic acid. The critical concentrations increased with increasing degrees of deacetylation of chitosan. They decreased with increasing molecular weights or increasing concentrations of sodium chloride and malic acid. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Evaluation of wool nanoparticles incorporation in chitosan/gelatin composite films

The aim of this work was to develop chitosan/gelatin composite films embedded with various amounts of wool nanoparticles, which were produced by an environmental friendly process. Films loaded with wool nanoparticles were subjected to physiochemical, biological, and mechanical characterization. The obtained results showed that incorporation of wool nanoparticles into chitosan/gelatin composite led to a reduction in swelling, moisture content and dissolution degree of the films. In vitro degradation test revealed that the nanoparticles‐embedded composites had a lower degradation rate than that of chitosan/gelatin composite. Besides, composite films containing wool nanoparticles showed an improvement in the stability in phosphate buffered saline. On the other hand, tensile strength and elongation at break decreased upon loading the films with wool nanoparticles. The biocompatibility of the produced composites was also confirmed by MTT test. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40294.     

Improvement of the mechanical properties of chitosan films by the addition of poly(ethylene oxide)

The mechanical properties of films prepared from mixed acetic acid aqueous solutions of chitosan (M_w = 400,000; M_w/M_n = 3.8) and poly(ethylene oxide) (PEO) (viscosity average molecular weight of 200,000 or 600,000) were determined. A chitosan:PEO weight ratio of 10:2 improved the mechanical properties compared with pure chitosan films. The improvement of the mechanical properties correlated with a small reduction of the correlation length measured by small‐angle neutron scattering (SANS).     

Preparation and characterization of poly(ethylene glycol) crosslinked chitosan films

Poly(ethylene glycol) (PEG) crosslinked chitosan films with various PEG to chitosan ratio and PEG molecular weight were successfully prepared via the epoxy‐amine reaction between chitosan and PEG‐epoxy. The thermal and mechanical properties and swelling behavior were studied for the PEG crosslinked chitosan films. The mechanical strength of chitosan films were greatly enforced by the introduction of PEG‐epoxy, achieving an elongation of about 80%. It was found that the crosslinked chitosan films form hydrogel in water, achieving a swelling ratio higher than 20 times of original weight. The swelling behavior of chitosan films relied greatly on the molecular weight of the crosslinker PEG‐epoxy and the weight percent of PEG‐epoxy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Preparation of oligochitosan via In situ enzymatic hydrolysis of chitosan by amylase in [Gly]BF4 ionic liquid/water homogeneous system

The preparation of oligochitosan with excellent performance via in situ enzymatic hydrolysis of chitosan by amylase in ionic liquid system is reported. It has been found that [Gly]BF₄ ionic liquid leads to the good solubility and assistant degradation for chitosan, as well as good biocompatibility for amylase. In the homogeneous system that contained 1.0 g chitosan (degree of deacetylation = 88.5%) and 99.0 g 2 wt % [Gly]BF₄ aqueous solution, oligochitosan with 2200 viscosity‐average molecular weight has been obtained after 0.12 g amylase being used for 3 h at 50°C and pH 5.0. This result is superior to that conducted in acetic acid system. Moreover, [Gly]BF₄ can be easily separated from the product and reused with only slight performance loss (oligochitosan product with 2700 viscosity‐average molecular weight has been obtained after [Gly]BF₄ being reused for five times). In addition, the mechanism for enzymatic hydrolysis of chitosan in [Gly]BF₄ ionic liquid has been described. The research on the moisture‐absorption, ‐retention, and antibacterial activity of oligochitosan product shows that the smaller molecular weight would bring the better moisture‐absorption and antibacterial properties. The oligochitosan product with 2200 viscosity‐average molecular weight exhibits preferable antibacterial properties to S. aureus and E. coli. At the same time, the moisture‐absorption and ‐retention capacity of the above product can reach 32% (relative humidity (RH) = 43%), 62% (RH = 81%), and 150% (RH = 43%), 35% (dry silica gel) respectively. The enzymatic preparation of oligochitosan through [Gly]BF₄ ionic liquid/water homogeneous system can be an efficient and environment‐friendly method for academics and industry. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41152.     

Chitosan from Muga silkworms (Antheraea assamensis) and its influence on thermal degradation behavior of poly(lactic acid) based biocomposite films

The research work is focused on extraction of chitin from Muga silkworms (MS) and its conversion into chitosan by chemical treatment process. The extracted amount of chitin and chitosan from MS were obtained ～8 wt % and ～7 wt %, respectively. Potentiometric titrations, conductometric titrations, elemental analysis, ¹H‐NMR and FTIR analyses were employed to calculate the degree of deacetylation of chitosan (extracted at 80 ºC after 10 h) and found as 77% ± 2, 81% ± 1.8, 82% ± 2.4, 97.77% ± 0.3, and 82% ± 1.8, respectively. The deacetylation process of chitin showed pseudo‐first order reaction kinetics and activation energy was estimated as ～15.5 kJ/mole. The extracted chitosan (at 80 ºC after 10 h) showed higher crystallinity and improved thermal stability with respect to chitosan extracted from other marine sources. Subsequently, poly(lactic acid) (PLA) and extracted chitosan dispersed biocomposite films were prepared by solution casting method. Significant dispersion of chitosan (extracted at 80 ºC after 10 h) micro‐particles were observed in biocomposite films using FESEM analysis. Due to chitosan interaction with PLA, significant reduction in thermal degradation and activation energy was observed during nonisothermal degradation scan of such films using Flynn‐Wall‐Ozawa and Kissinger‐Akahira‐Sunose models. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43710.     

Poly(ethylene glycol)‐modulated cellular biocompatibility of polyhydroxyalkanoate films

Polyhydroxybutyrate (PHB) and its copolymer with hydroxyvalerate, P(HB‐co‐HV), are widely used biomaterials. In this study, improvements of their biological properties of degradability and compatibility were achieved by blending with low‐molecular‐weight poly(ethylene glycol) (PEG106) approved for medical use. Surface morphology and chemistry are known to support cell attachment. Attachment and proliferation of neural olfactory ensheathing cells increased by 17.0 and 32.2% for PHB and P(HB‐co‐HV) composite films. Cell attachment was facilitated by increases in surface hydrophilicity, water contact angles decreased by 26 ± 2° and water uptake increased by 23.3% depending upon biopolymer and PEG loading. Cells maintained high viability (>95%) on the composite films with no evidence of cytotoxic effects. Assays of mitochondrial function and cell leakage showed improved cell health as a consequence of PEG loading. The PEG component was readily solubilised from composite films, allowing control of degradation profiles in the cell growth medium. Promotion of biopolymer compatibility and degradability was not at the expense of material properties, with the extension to break of the composites increasing by 5.83 ± 1.06%. Similarly, crystallinity decreased by 36%. The results show that blending of common polyhydroxyalkanoate biomaterials with low‐molecular‐weight PEG can be used to promote biocompatibility and manipulate physiochemical and material properties as well as degradation.© 2013 Society of Chemical Industry     

Effect of degree of deacetylation of chitosan on the kinetics of ultrasonic degradation of chitosan

The objective of the study was to explore the effect of the degree of deacetylation (DD) of the chitosan used on the degradation rate and rate constant during ultrasonic degradation. Chitin was extracted from red shrimp process waste. Four different DD chitosans were prepared from chitin by alkali deacetylation. Those chitosans were degraded by ultrasonic radiation to different molecular weights. Changes of the molecular weight were determined by light scattering, and data of molecular weight changes were used to calculate the degradation rate and rate constant. The results were as follows: The molecular weight of chitosans decreased with an increasing ultrasonication time. The curves of the molecular weight versus the ultrasonication time were broken at 1‐h treatment. The degradation rate and rate constant of sonolysis decreased with an increasing ultrasonication time. This may be because the chances of being attacked by the cavitation energy increased with an increasing molecular weight species and may be because smaller molecular weight species have shorter relaxation times and, thus, can alleviate the sonication stress easier. However, the degradation rate and rate constant of sonolysis increased with an increasing DD of the chitosan used. This may be because the flexibilitier molecules of higher DD chitosans are more susceptible to the shear force of elongation flow generated by the cavitation field or due to the bond energy difference of acetamido and β‐1,4‐glucoside linkage or hydrogen bonds. Breakage of the β‐1,4‐glucoside linkage will result in lower molecular weight and an increasing reaction rate and rate constant. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3526–3531, 2003     

Influence of chitosan characteristics on coagulation and flocculation of organic suspensions

Several samples of chitosan with different degrees of deacetylation and of different molecular weights were tested for the coagulation–flocculation of organic suspensions. Organic suspensions were prepared by mixing mushroom powder with tap water. Experiments were carried out at pH 5, pH 7, and pH 9. Because decreasing the pH reduced the amount of chitosan required to reach the required turbidity, at pH 9, a high concentration of chitosan was required to achieve the required treatment levels, whereas the difference was less significant between pH 7 and pH 5 (the required concentration of chitosan was halved). Though viscosity, correlated to the molecular weight of chitosan, affected treatment performance, its influence on the efficiency of coagulation–flocculation could be substantially reduced by slightly increasing the concentration of the polymer. This is of importance in the processing of industrial effluents: the aging of a chitosan solution, which may cause partial depolymerization, and loss of viscosity, will have a limited impact on process efficiency. The degree of deacetylation also has a limited effect on treatment performance, especially when the degree of deacetylation exceeds 90%. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2070–2079, 2005     

A new approach for the preparation of chitosan from γ‐irradiation of prawn shell: effects of radiation on the characteristics of chitosan

Chitosan is a biodegradable polymer composed of randomly distributed β‐(1,4)‐linked D ‐glucosamine (deacetylated unit) and N‐acetyl‐D ‐glucosamine (acetylated unit). It is produced commercially by deacetylation of chitin, which is the structural element in the exoskeleton of crustaceans (such as crabs and shrimps) and the cell walls of fungi. In the work reported, we developed a facile technique for the preparation of chitosan by irradiating prawn shell at various intensities from 2 to 50 kGy. It was observed that γ‐irradiation of prawn shell increased the degree of deacetylation (DD) of chitin at a relatively low alkali concentration during the deacetylation process. Among the various irradiation doses applied to prawn shell, a dose of 50 kGy and 4 h heating in 50% NaOH solution yielded 84.56% DD while the chitosan obtained from non‐irradiated prawn shell with the same reaction conditions had only 74.70% DD. In order to evaluate the effect of γ‐irradiation on the various physicochemical, thermomechanical and morphological properties, the chitosan samples were again irradiated (2–100 kGy) with γ‐radiation. Molecular weight, DD, thermal properties with differential scanning calorimetry and thermogravimetric analysis, particle morphology by scanning electron microscopy, water binding capacity (WBC), fat binding capacity (FBC) and antimicrobial activity were determined and the effects of various γ‐radiation doses were assessed. The DD, WBC, FBC and antimicrobial activity of the chitosan were found to improve on irradiation. It was obvious that irradiation caused a decrease of molecular weight from 187 128 to 64 972 g mol^?1 after applying a radiation dose of 100 kGy which occurred due to the chain scission of chitosan molecules at glycosidic linkages. The decrease of molecular weight increased the water solubility of the chitosan, the extent of which was explored for biomedical applications. Copyright © 2012 Society of Chemical Industry     

Improved mechanical properties of chitosan fibers

A highly deacetylated chitosan from shrimp with a degree of deacetylation of 95 ± 3% was prepared and spun into a monofilament fiber using a solution of 5% by weight chitosan in 5% by volume aqueous acetic acid. Samples of the spun fibers were immersed in separate solutions containing phosphate ions and phthalate ions, and subsequently washed and dried. The various solutions ranged in pH from 4.12 to 7.75. The highest dry mechanical properties resulted from solutions containing phthalate ions between 4.5–5.5 pH, and from solutions containing phosphate ions at pH 5.4. Immersion time was varied between 1 and 60 min at 25.8°C, and temperature was varied between 25.8 and 70.0°C, in the phosphate ion solutions at a pH of 5.8. Dry mechanical properties were highest at 25.8°C and after 1 h of treatment. Chitosan films were subjected to similar treatments in phosphate and phthalate ion solutions. Fourier transform infrared data (FTIR) on the films suggest that some interaction is occurring between the phosphate ions and the amine group on the chitosan backbone. An additional experiment was performed whereby the same chitosan was used to prepare a dope of 4% by weight chitosan in 4% by volume aqueous acetic acid with 30% by volume methanol. This solution was spun into fibers, but was subjected to a “final draw” by increasing the speed of the winder. With increasing the final draw, denier and elongation‐at‐break decreased, while the other mechanical properties showed a marked increase. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1721–1732, 1999     

Chitosan and modified chitosan membranes I. Preparation and characterisation

Chitosan has been prepared from prawn shell and crab shell chitin. The molecular weight of the material derived from prawn shells is higher than that obtained from crab shell. The molecular weight, tensile strength, elongation at the break, and hydrophilic properties of chitosan are extremely dependent on the degree of deacetylation achieved when chitin is hydrolyzed to chitosan. Graft copolymers have been prepared with chitosan and a series of vinyl monomers using both heterogeneous and homogeneous reaction conditions. The hydrophilic properties of chitosan can be modified by blending with poly(vinyl alcohol).     

Physical properties of water‐borne polyurethane blended with chitosan

Water‐borne polyurethanes based on 4,4‐diphenylmethane diisocyanate, poly(butylene adipate), and chain extender N‐methyldiethanolamine (MDEA) that provided tertiary amine groups were synthesized. The polyurethane–chitosan (PU/CS) blends can be dissolved in the acetic acid and cast into films. The mechanical properties including tensile strength and elongation, as well as the water absorption and thermal properties of the PU/CS films were evaluated. The tensile strength increased with the increased amount of chitosan, but the elongation decreased accordingly. The chitosan in the blends promoted the water absorption. Chitosan was more thermally‐stable than PU, as shown in the thermal gravity analysis. Chitosan also had higher crystallinity, as demonstrated by differential scanning calorimetry. The blends were partial compatible mixtures, based on the data obtained from a dynamic mechanical analysis. Biocompatibility test was conducted utilizing immortalized rat chondrocytes (IRC). After IRC were seeded onto the PU/CS films for 1.5 and 120 h, the number of cells was counted and the morphology of cells was observed by light microscopy and scanning electron microscopy. Blends containing 30% chitosan had more cells attached initially. However, the blends containing more than 70% chitosan appeared to promote the cell proliferation. IRC were round on PU/CS films with more PU, but spread when the chitosan content in blends was higher. Overall, PU/CS films with more chitosan had better mechanical properties as well as biocompatibility. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2683–2689, 2007     

Effect of molecular weight and degree of deacetylation of chitosan on urea adsorption properties of copper chitosan

Copper chitosan complexes prepared by different specifications of chitosan and copper sulfate were used as urea sorbents. Experimental results showed that the adsorption capacity for urea of copper chitosan increased with an increasing degree of deacetylation and decreasing molecular weight of chitosan. The urea adsorption capacity of copper chitosan was 120.0 mg/g, when 1.0 g of copper chitosan was admitted to 100 mL of a 1300 mg/mL (pH 6.0) urea solution, with chitosan degree of deacetylation of 84.3% and viscosity molecular weight of 6.5 × 10⁵, at 37°C for 8 h. No elution of the copper from the copper chitosan could be detected under the optimal conditions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1520–1523, 2003