This review describes the most common methods for recovery of chitin from marine organisms. In depth, both enzymatic and chemical treatments for the step of deproteinization are compared, as well as ...different conditions for demineralization. The conditions of chitosan preparation are also discussed, since they significantly impact the synthesis of chitosan with varying degree of acetylation (DA) and molecular weight (MW). In addition, the main characterization techniques applied for chitin and chitosan are recalled, pointing out the role of their solubility in relation with the chemical structure (mainly the acetyl group distribution along the backbone). Biological activities are also presented, such as: antibacterial, antifungal, antitumor and antioxidant. Interestingly, the relationship between chemical structure and biological activity is demonstrated for chitosan molecules with different DA and MW and homogeneous distribution of acetyl groups for the first time. In the end, several selected pharmaceutical and biomedical applications are presented, in which chitin and chitosan are recognized as new biomaterials taking advantage of their biocompatibility and biodegradability.
Chitin is the second most important natural polymer in the world. The main sources exploited are two marine crustaceans, shrimp and crabs. Our objective is to appraise the state of the art concerning ...this polysaccharide: its morphology in the native solid state, methods of identification and characterization and chemical modifications, as well as the difficulties in utilizing and processing it for selected applications. We note the important work of P. Austin, S. Tokura and S. Hirano, who have contributed to the applications development of chitin, especially in fiber form. Then, we discuss chitosan, the most important derivative of chitin, outlining the best techniques to characterize it and the main problems encountered in its utilization. Chitosan, which is soluble in acidic aqueous media, is used in many applications (food, cosmetics, biomedical and pharmaceutical applications). We briefly describe the chemical modifications of chitosan—an area in which a variety of syntheses have been proposed tentatively, but are not yet developed on an industrial scale. This review emphasizes recent papers on the high value-added applications of these materials in medicine and cosmetics.
The results given in the literature are conflicting when considering the relationship between antimicrobial activity and chitosan characteristics. To be able to clarify, we prepared fifteen ...homogeneous chitosans with different acetylation degrees (DA) and molecular weights (MW) by reacetylation of a fully deacetylated chitin under homogeneous conditions. They were tested at different pH values for their antimicrobial activities against four Gram-negative bacteria (Escherichia coli, Pseudomonas aeruginosa, Klebsiella pneumoniae and Salmonella typhi), four Gram-positive bacteria (Staphylococcus aureus, Bacillus cereus, Enterococcus faecalis and Micrococcus luteus) and three fungi (Aspergillus niger, Fusarium oxysporum and Alternaria solani). Chitosans markedly inhibited growth of most bacteria and fungi tested, although the inhibitory effect depends on the type of microorganism and on the chitosan characteristics (DA and MW) with minimum inhibitory concentrations in the range of 0.001 to 0.1w%.
Considering chitosan efficiency on bacteria, our series of data clearly show that the lower DA and the lower pH give the larger efficiency. Antibacterial activity was further enhanced for Gram-negative bacteria with decreasing MW, whereas, opposite effect was observed with the Gram-positive. Concerning the antifungal activity, the influence of chitosan characteristics was dependent on the particular type of fungus. Fungal growth decreased with increasing MW for F. oxysporum and decreasing DA for A. solani, but no MW or DA dependences were observed with A. niger.
•The role of DA and MW on antimicrobial activity of chitosan was studied independently.•Chitosans markedly inhibited growth of most bacteria and fungi tested.•Inhibitory effect depends on the microorganism, characteristics of chitosan and pH.•Chitosan showed stronger bactericidal effects against Gram-negative bacteria.•MIC of chitosans ranged from 0.001 to up to 0.1w%.
Electrospinning was employed to obtain chitosan nanofibers from blends of chitosans (CS) and poly(ethylene oxide) (PEO). Blends of chitosan (
(weight-average molecular weight) = 102 kg/mol) and PEO ...(M (molecular weight) = 1000 kg/mol) were selected to optimize the electrospinning process parameters. The PEO powder was solubilized into chitosan solution at different weight ratios in 0.5 M acetic acid. The physicochemical changes of the nanofibers were determined by scanning electron microscopy (SEM), swelling capacity, and nuclear magnetic resonance (NMR) spectroscopy. For stabilization, the produced nanofibers were neutralized with K₂CO₃ in water or 70% ethanol/30% water as solvent. Subsequently, repeated washings with pure water were performed to extract PEO, potassium acetate and carbonate salts formed in the course of chitosan nanofiber purification. The increase of PEO content in the blend from 20 to 40 w% exhibited bead-free fibers with average diameters 85 ± 19 and 147 ± 28 nm, respectively. Their NMR analysis proved that PEO and the salts were nearly completely removed from the nanostructure of chitosan, demonstrating that the adopted strategy is successful for producing pure chitosan nanofibers. In addition, the nanofibers obtained after neutralization in ethanol-aqueous solution has better structural stability, at least for six months in aqueous solutions (phosphate buffer (PBS) or water).
Like most of the materials used by humans, polymeric materials are proposed in
the literature and occasionally exploited clinically, as such, as devices or as
part of devices, by surgeons, dentists, ...and pharmacists to treat traumata and
diseases. Applications have in common the fact that polymers function in contact
with animal and human cells, tissues, and/or organs. More recently, people have
realized that polymers that are used as plastics in packaging, as colloidal
suspension in paints, and under many other forms in the environment, are also in
contact with living systems and raise problems related to sustainability,
delivery of chemicals or pollutants, and elimination of wastes. These problems
are basically comparable to those found in therapy. Last but not least,
biotechnology and renewable resources are regarded as attractive sources of
polymers. In all cases, water, ions, biopolymers, cells, and tissues are
involved. Polymer scientists, therapists, biologists, and ecologists should thus
use the same terminology to reflect similar properties, phenomena, and
mechanisms. Of particular interest is the domain of the so-called “degradable or
biodegradable polymers” that are aimed at providing materials with specific
time-limited applications in medicine and in the environment where the respect
of living systems, the elimination, and/or the bio-recycling are mandatory, at
least ideally.
Chitin was recovered through enzymatic deproteinization of the shrimp processing by-products. Different microbial and fish viscera proteases were tested for their deproteinization efficiency. High ...levels of protein removal of about 77±3% and 78±2% were recorded using Bacillus mojavensis A21 and Balistes capriscus proteases, respectively, after 3h of hydrolysis at 45°C using an enzyme/substrate ratio of 20U/mg. Therefore, these two crude proteases were used separately for chitin extraction and then chitosan preparation by N-deacetylation.
Chitin and chitosan samples were then characterized by 13 Cross polarization magic angle spinning nuclear magnetic resonance (CP/MAS)-NMR spectroscopy and compared to samples prepared through chemical deproteinization. All chitins and chitosans showed identical spectra. Chitosans prepared through enzymatic deproteinization have practically the same acetylation degree but higher molecular weights compared to that obtained through chemical process. Antimicobial, antioxidant and antitumoral activitities of chitosan-M obtained by treatment with A21 proteases and chitosan-C obtained by alkaline treatment were investigated. Results showed that both chitosans inhibited the growth of most Gram-negative, Gram-positive bacteria and fungi tested. Furthermore, both chitosans exhibited antioxidant and antitumor activities which was dependent on the molecular weight.
Three marine sources of chitin from Tunisia were investigated. Structural differences between α-chitin from shrimp (Penaeus kerathurus) waste, crab (Carcinus mediterraneus) shells, and β-chitin from ...cuttlefish (Sepia officinalis) bones were studied by the 13C NMR, FTIR, and XRD diffractograms. The 13C NMR analysis showed a splitting of the C3 and C5 carbon signals for α-chitin, while that of β-chitin was merged into a single resonance. The bands contour of deconvoluted and curve-fit FTIR spectra showed a more detailed structure of α-chitin in the region of OH, NH and CO stretching regions. IR and 13C NMR were used to determine the chitin degree of acetylation (DA). XRD analysis indicated that α-chitins were more crystalline polymorph than β-chitin. Shrimp chitin was obtained with a good yield (20% on raw material dry weight) and no residual protein and salts. Chitosans, with a DA lower than 20% and relatively low molecular masses were prepared from the wet chitins in the same experimental conditions. They were perfectly soluble in acidic medium. Nevertheless, chitin and chitosan characteristics were depending upon the chitin source.
In this paper, the behavior of oxidized methylcelluloses is compared with that of the initial methylcellulose, an amphiphilic cellulose derivative. Methylcelluloses are important for many ...applications in the cosmetic and food industries. The mechanism of thermo-gelation of methylcellulose is briefly explained as well as the method of oxidation of polysaccharides. Then, our experiments involve the preparation of oxidized methylcelluloses: three degrees of oxidation are prepared and the new polymers are characterized by NMR, IR, SEC and rheology. Oxidation with periodate theoretically allows introduction of two aldehydic groups on C2–C3 glycol positions of anhydroglucose units. This reaction not only enhances the flexibility of the cellulosic backbone, but also causes a decrease in the molecular weight. In particular, the rheological behavior of methylcellulose and oxidized methylcellulose as a function of temperature is examined. The oxidized methylcelluloses prepared, being rich in aldehyde functions, become interesting intermediaries to prepare new cellulose derivatives. In this paper, three examples of reductive amination based on the reaction of modified methylcelluloses and −NH2 groups of different molecules are described: β-alanine produces a polyelectrolyte; chitosan and hyaluronan-ADH (derivative obtained with adipic dihydrazide allowing introduction of −NH2 functions on HA backbone) are crosslinked and give new biocompatible hydrogels.
This review covers the preparation, characterization, properties, and applications of methylcelluloses (MC). In particular, the influence of different chemical modifications of cellulose (under both ...heterogeneous and homogeneous conditions) is discussed in relation to the physical properties (solubility, gelation) of the methylcelluloses. The molecular weight (MW) obtained from the viscosity is presented together with the nuclear magnetic resonance (NMR) analysis required for the determination of the degree of methylation. The influence of the molecular weight on the main physical properties of methylcellulose in aqueous solution is analyzed. The interfacial properties are examined together with thermogelation. The surface tension and adsorption at interfaces are described: surface tension in aqueous solution is independent of molecular weight but the adsorption at the solid interface depends on the MW, the higher the MW the thicker the polymeric layer adsorbed. The two-step mechanism of gelation is confirmed and it is shown that the elastic moduli of high temperature gels are not dependent on the molecular weight but only on polymer concentration. Finally, the main applications of MC are listed showing the broad range of applications of these water soluble cellulose derivatives.
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