Manufacture and properties[edit]
Commercial chitosan is derived from the shells of shrimp and other sea crustaceans, including Pandalus borealis, pictured here.[1]
Chitosan is produced commercially by deacetylation of chitin, which is the structural element in the exoskeleton of crustaceans (such as crabs and shrimp) and cell walls of fungi. The degree of deacetylation (%DD) can be determined by NMR spectroscopy, and the %DD in commercial chitosans ranges from 60 to 100%. On average, the molecular weight of commercially produced chitosan is between 3800 and 20,000 Daltons. A common method for the synthesis of chitosan is the deacetylation of chitin using sodium hydroxide in excess as a reagent and water as a solvent. This reaction pathway, when allowed to go to completion (complete deacetylation) yields up to 98% product.[2][dead link]
The amino group in chitosan has a pKa value of ~6.5, which leads to a protonation in acidic to neutral solution with a charge density dependent on pH and the %DA-value. This makes chitosan water soluble and a bioadhesive which readily binds to negatively charged surfaces such as mucosal membranes. Chitosan enhances the transport of polar drugs across epithelial surfaces, and is biocompatible and biodegradable. It is not approved by FDA for drug delivery though. Purified quantities of chitosans are available for biomedical applications.
Chitosan and its derivatives, such as trimethylchitosan (where the amino group has been trimethylated), have been used in nonviral gene delivery. Trimethylchitosan, or quaternised chitosan, has been shown to transfect breast cancer cells, with increased degree of trimethylation increasing the cytotoxicity; at approximately 50% trimethylation, the derivative is the most efficient at gene delivery. Oligomeric derivatives (3-6 kDa) are relatively nontoxic and have good gene delivery properties.[3]
Usage[edit]
Agricultural and horticultural use[edit]
The agricultural and horticultural uses for chitosan, primarily for plant defense and yield increase, are based on how this glucosamine polymer influences the biochemistry and molecular biology of the plant cell. The cellular targets are the plasma membrane and nuclear chromatin. Subsequent changes occur in cell membranes, chromatin, DNA, calcium, MAP Kinase, oxidative burst, reactive oxygen species, callose pathogenesis-related (PR) genes and phytoalexins.[4]
Natural biocontrol and elicitor[edit]
In agriculture, chitosan is used primarily as a natural seed treatment and plant growth enhancer, and as an ecologically friendly biopesticide substance that boosts the innate ability of plants to defend themselves against fungal infections.[5] The natural biocontrol active ingredients, chitin/chitosan, are found in the shells of crustaceans, such as lobsters, crabs, and shrimp, and many other organisms, including insects and fungi. It is one of the most abundant biodegradable materials in the world.
Degraded molecules of chitin/chitosan exist in soil and water. Chitosan applications for plants and crops are regulated by the EPA, and the USDA National Organic Program regulates its use on organic certified farms and crops.[6] EPA-approved, biodegradable chitosan products are allowed for use outdoors and indoors on plants and crops grown commercially and by consumers.[7]
The natural biocontrol ability of chitosan should not be confused with the effects of fertilizers or pesticides upon plants or the environment. Chitosan active biopesticides represent a new tier of cost-effective biological control of crops for agriculture and horticulture.[8] The biocontrol mode of action of chitosan elicits natural innate defense responses within plant to resist insects, pathogens, and soil-borne diseases when applied to foliage or the soil.[9] Chitosan increases photosynthesis, promotes and enhances plant growth, stimulates nutrient uptake, increases germination and sprouting, and boosts plant vigor. When used as seed treatment or seed coating on cotton, corn, seed potatoes, soybeans, sugar beets, tomatoes, wheat and many other seeds, it elicits an innate immunity response in developing roots which destroys parasitic cyst nematodes without harming beneficial nematodes and organisms.[10][11]
Agricultural applications of chitosan can reduce environmental stress due to drought and soil deficiencies, strengthen seed vitality, improve stand quality, increase yields, and reduce fruit decay of vegetables, fruits and citrus crops (see photo right).[12] Horticultural application of chitosan increases blooms and extends the life of cut flowers and Christmas trees.[13] The US Forest Service has conducted research on chitosan to control pathogens in pine trees[14][15] and increase resin pitch outflow which resists pine beetle infestation.[16]
NASA life support GAP technology with untreated beans (left tube) and ODC chitosan biocontrol-treated beans (right tube) returned from the Mir space station aboard the space shuttle – September 1997
Chitosan has a rich history of being researched for applications in agriculture and horticulture dating back to the 1980s.[17] By 1989, chitosan salt solutions were applied to crops for improved freeze protection or to crop seed for seed priming.[18] Shortly thereafter, chitosan salt received the first ever biopesticide label from the EPA, then followed by other intellectual property applications.
Chitosan has been used to protect plants in space, as well, exemplified by NASA's experiment to protect adzuki beans grown aboard the space shuttle and Mir space station in 1997 (see photo left).[19] NASA results revealed chitosan induces increased growth (biomass) and pathogen resistance due to elevated levels of beta 1-3 glucanase enzymes within plant cells. NASA confirmed chitosan elicits the same effect in plants on earth.[20]
Nontoxic, low molecular weight chitosan polymer solutions appear to be safe enough for broad-spectrum agricultural and horticultural uses.[21][22] In 2008, the EPA approved natural broad-spectrum elicitor status for an ultralow molecular active ingredient of 0.25% chitosan.[23]
A natural chitosan elicitor solution for agriculture and horticultural uses was granted an amended label for foliar and irrigation applications by the EPA in 2009.[12] Given its low potential for toxicity and abundance in the natural environment, chitosan does not harm people, pets, wildlife, or the environment when used according to label directions.[24][25][26] The US Forest Service tested chitosan as an ecofriendly biopesticide to prearm pine trees to defend themselves against mountain pine beetles.
Water filtration[edit]
Chitosan can also be used in water processing engineering as a part of a filtration process. Chitosan causes the fine sediment particles to bind together, and is subsequently removed with the sediment during sand filtration. It also removes phosphorus, heavy minerals, and oils from the water. Chitosan is an important additive in the filtration process. Sand filtration apparently can remove up to 50% of the turbidity alone, while the chitosan with sand filtration removes up to 99% turbidity.[27] Chitosan has been used to precipitate caseins from bovine milk and cheese making.[28][29]
Chitosan is also useful in other filtration situations, where one may need to remove suspended particles from a liquid. In combination with bentonite, gelatin, silica gel, isinglass, or other fining agents, it is used to clarify wine, mead, and beer. Added late in the brewing process, chitosan improves flocculation, and removes yeast cells, fruit particles, and other detritus that cause hazy wine. Chitosan combined with colloidal silica is becoming a popular fining agent for white wines, because chitosan does not require acidic tannins (found primarily in red wines) with which to flocculate.[30]
Manufacture[edit]
Large three-dimensional functional objects made from chitosan.[31]
Bioinspired materials, a manufacturing concept inspired by natural nacre, shrimp carapace or insect cuticles,[32][33][34] has led to development of methods to manufacture large scale consumer objects using chitosan.[35][36] This method is based on replicating the molecular arrangement of chitosan from natural materials into fabrication methods, such as injection molding or mold casting.[37] Once discarded, chitosan-constructed objects are biodegradable and non-toxic.[38] The method is being explored to engineer human organs or tissues using three-dimensional bioprinting.[39][40]
Pigmented chitosan objects can be recycled,[41] with the option of reintroducing or discarding the dye at each recycling step, enabling reuse of the polymer independently of colorants.[42][43] Unlike other plant-based bioplastics (e.g. cellulose, starch), the main natural sources of chitosan are from marine environments and do not compete for land or other human resources.[44][31]
The fabrication of large objects with chitosan applies concepts from Shrilk, a chitosan material that replicates insect cuticle and a fibroin protein from silk for uses in bioengineering.[45][46]
Winemaking and fungal source chitosan[edit]
Chitosan has a long history for use as a fining agent in winemaking.[47][48] Fungal source chitosan has shown an increase in settling activity, reduction of oxidized polyphenolics in juice and wine, chelation and removal of copper (post-racking) and control of the spoilage yeast Brettanomyces. These products and uses are approved for European use by the EU and OIV standards.[49]
Potential industrial uses[edit]
Scientists have developed a polyurethane coating that heals its own scratches when exposed to sunlight.[50][51] The self-healing coating uses chitosan incorporated into traditional polymer materials, such as those used in coatings on cars to protect paint. When a scratch damages the chemical structure, the chitosan responds to sunshine by forming chemical chains that bond with other materials in the substance, eventually sm