Hiroyuki Saimoto

Chitin, Chitosan, and Its Derivatives for Wound Healing: Old and New Materials

Chitin (β-(1-4)-poly-N-acetyl-d-glucosamine) is widely distributed in nature and is the second most abundant polysaccharide after cellulose. It is often converted to its more deacetylated derivative, chitosan. Previously, many reports have indicated the accelerating effects of chitin, chitosan, and its derivatives on wound healing. More recently, chemically modified or nano-fibrous chitin and chitosan have been developed, and their effects on wound healing have been evaluated. In this review, the studies on the wound-healing effects of chitin, chitosan, and its derivatives are summarized. Moreover, the development of adhesive-based chitin and chitosan are also described. The evidence indicates that chitin, chitosan, and its derivatives are beneficial for the wound healing process. More recently, it is also indicate that some nano-based materials from chitin and chitosan are beneficial than chitin and chitosan for wound healing. Clinical applications of nano-based chitin and chitosan are also expected.

Facile preparation of silver nanoparticles immobilized on chitin nanofiber surfaces to endow antifungal activities.

Silver nanoparticles were prepared on chitin nanofiber surfaces by UV light reduction of silver ions. The chitin nanofibers could be efficient substrates to immobilize silver nanoparticles with stable dispersion states. The dispersion and the nanocomposite film with acrylic resin showed characteristic absorption property in the visible light region due to the effect of the silver nanoparticles. Silver nanoparticles endowed strong antifungal activity to chitin nanofibers.

Biological adhesive based on carboxymethyl chitin derivatives and chitin nanofibers

Novel biological adhesives made from chitin derivatives were prepared and evaluated for their adhesive properties and biocompatibility. Chitin derivatives with acrylic groups, such as 2-hydroxy-3-methacryloyloxypropylated carboxymethyl chitin (HMA-CM-chitin), were synthesized and cured by the addition of an aqueous hydrogen peroxide solution as a radical initiator. The adhesive strength of HMA-CM-chitin increased when it was blended with chitin nanofibers (CNFs) or surface-deacetylated chitin nanofibers (S-DACNFs). HMA-CM-chitin/CNFs or HMA-CM-chitin/S-DACNFs have almost equal adhesive strength compared to that of a commercial cyanoacrylate adhesive. Moreover, quick adhesion and induction of inflammatory cells migration were observed in HMA-CM-chitin/CNF and HMA-CM-chitin/S-DACNF. These findings indicate that the composites prepared in this study are promising materials as new biological adhesives.

Facile preparation of surface N-halamine chitin nanofiber to endow antibacterial and antifungal activities.

N-halamine chitin nanofiber (NF) film was prepared by the reaction of chitin NF film with sodium hypochlorite solution to endow the film with antibacterial and antifungal activities. The amount of active chlorine content loaded on the chitin NF film depended on the sodium hypochlorite concentration and reaction time. FT-IR, UV-vis, XRD, and TG analyses showed that the N-H bond was substituted to the N-Cl bond and that the reaction took place at the chitin NF surface. After chlorination, the characteristic nanochitin morphology was maintained. Although the active chlorine content of the film gradually decreased by disassociation of the N-Cl bond, chlorine was rechargeable into chitin NF by another sodium hypochlorite solution treatment. The chlorinated chitin NF film showed strong efficacies against Gram-negative and -positive bacteria of Escherichia coli and Staphylococcus aureus, respectively. Moreover, the films showed 100% and 80% inhibition of spore germination when faced against Alternaria alternata and Penicillium digitatum fungi, respectively.

Simple preparation of chitosan nanofibers from dry chitosan powder by the Star Burst system.

Chitosan nanofibers were easily prepared from dry chitosan powder using the Star Burst system, which employs a high-pressure water jet system. Although the chitosan nanofibers became thinner as the number of Star Burst passes increased, the fiber thickness did not change significantly above 10 passes. Crystallinity and the chitosan nanofiber length decreased after extensive treatment due to the strong collision forces breaking the fibers. The mechanical properties and thermal expansion of the chitosan nanofiber sheets were improved by increasing the number of passes up to 10, but further treatment resulted in a deterioration of these properties.

Depolymerization of sulfated polysaccharides under hydrothermal conditions

Fucoidan and chondroitin sulfate, which are well known sulfated polysaccharides, were depolymerized under hydrothermal conditions (120-180°C, 5-60min) as a method for the preparation of sulfated polysaccharides with controlled molecular weights. Fucoidan was easily depolymerized, and the change of the molecular weight values depended on the reaction temperature and time. The degree of sulfation and IR spectra of the depolymerized fucoidan did not change compared with those of untreated fucoidan at reaction temperatures below 140°C. However, fucoidan was partially degraded during depolymerization above 160°C. Nearly the same depolymerization was observed for chondroitin sulfate. These results indicate that hydrothermal treatment is applicable for the depolymerization of sulfated polysaccharides, and that low molecular weight products without desulfation and deformation of the initial glycan structures can be obtained under mild hydrothermal conditions.

Control of mechanical properties of chitin nanofiber film using glycerol without losing its characteristics

Surface-deacetylated chitin nanofiber films plasticized with glycerol were prepared to control mechanical properties. Nanofiber networks were able to retain excessive glycerol content up to 70% to obtain self-standing film. All films were flexible and highly transparent independent of glycerol content. Glycerol significantly decreased the Youngs moduli and tensile strengths, and increased the fracture strain due to its plasticizing effect. At the same time, glycerol did not change the high transparency or the low thermal expansion of the nanofiber film.

Effects of Surface-Deacetylated Chitin Nanofibers in an Experimental Model of Hypercholesterolemia

This study evaluated the effects of oral administration of surface-deacetylated chitin nanofibers (SDACNFs) on hypercholesterolemia using an experimental model. All rats were fed a high cholesterol diet with 1% w/w cholesterol and 0.5% w/w cholic acid for 28 days. Rats were divided equally into four groups: the control group was administered 0.05% acetic acid dissolved in tap water, and the SDACNF, chitosan (CS), and cellulose nanofiber (CLNF) groups were administered 0.1% CNF, CS, or CLNF dissolved in the tap water, respectively, during the experimental period. Changes in body weight, intake of food and water, and organ weight were measured. Serum blood chemistry and histopathological examination of the liver were performed. Administration of SDACNF did not affect body weight change, food and water intake, or organ weights. Administration of SDACNF and CS decreased the diet-induced increase in serum total cholesterol, chylomicron, very-low-density lipoprotein, and phospholipid levels on day 14. Moreover, oral administration of SDACNFs suppressed the increase of alanine transaminase levels on day 29 and suppressed vacuolar degeneration and accumulation of lipid droplets in liver tissue. These data indicate that SDACNF has potential as a functional food for patients with hypercholesterolemia.

Facile preparation of aramid nanofibers from Twaron fibers by a downsizing process

We introduce a simple preparation procedure for aramid nanofibers from Twaron fibers by using a downsizing process. Alkaline hydrolysis pretreatment brings ionic charges on the fiber surface, allowing facile disintegration of Twaron into nanofibers by virtue of the electrostatic repulsive force. Since the nanofibers can be dispersed homogeneously in water, the processability and formability of the polymer were improved. The resulting aramid nanofibers, having a high degree of physical performance, a uniform nanosized morphology, and a high surface-to-volume ratio, will expand the range of novel applications of aramid fibers.

Preparation of a protein–chitin nanofiber complex from crab shells and its application as a reinforcement filler or substrate for biomineralization

A protein–chitin nanofiber complex was successfully prepared from crab shells by a mechanical treatment after the removal of CaCO3. One step in the conventional series of treatments—i.e., the removal of proteins—was omitted to bring down the production cost of the nanofibers. The obtained protein–chitin nanofibers had uniform width of approximately 20 nm and a high aspect ratio. These characteristics were similar to conventional chitin nanofibers. The optically transparent protein–chitin nanofiber composite was fabricated with acrylic resin. The nanofibers reinforced the acrylic resin film and thereby increased its mechanical properties. Proteins on the chitin nanofiber surface affected the biomineralization of CaCO3 in the crab shell. Mineralization of CaCO3 on the protein–chitin nanofiber was carried out by the gas-diffusion method. Protein molecules on the chitin NFs increased the chances for biomineralization to occur. The protein molecules stabilized the formation of vaterite and inhibited the transformation of vaterite to calcite.