It is possible to isolate chitosan directly from the cell walls of certain fungi, but commercially
available chitosans are usually prepared from chitin in a heterogeneous deacetylation process.
Chitosans will in this paper be defined as proposed by Roberts [36], i.e., according to their solubility at
acidic pH-values. This distinguishes clearly between chitins and chitosans, although some controversy
may exist when discussing chitin oligomers (N-acetyl-CHOS) and chitosan oligomers (CHOS). To
avoid this problem, we restrict the terms chitin and chitosan to polymers with more than
100 sugar units.
Chitosans can be prepared from chitin by two fundamentally different methods, i.e., homogeneous
[37] and heterogeneous deacetylation. In the homogeneous deacetylation process, the chitin is
dissolved in an alkali solution during the deacetylation process (at low temperature and using
excessive stirring). In the heterogeneous deacetylation process, the chitin is kept insoluble in a hot
alkali solution, meaning that this is a two-phase process. Chitosans with FA varying from 0 to about
65% can be prepared by homogeneous deacetylation of chitin [37]. There is little controversy
regarding the distribution (PA) of the two monomers in these chitosans, which have been found to have
a random distribution of the GlcNAc and GlcN units, i.e., according to Bernoullian distribution
[38–40]. There is, however, more controversy about the distribution of sugar units in chitosan prepared
by heterogeneous deacetylation procedures. Weinhold et al. [41] studied the N-acetylation patterns of
32 different chitosans of various FA, using a previously described NMR-method [39], most of them
prepared by heterogenous deacetylation, and found a close to random distributions for all samples.
Although this recent study indicates that the PA in chitosans prepared by heterogenous deacetylation is
more random than previously assumed, it should be kept in mind that the NMR-method is only capable
of determining an average distribution, meaning that certain block patterns may in fact exist.
The annual production of chitin in nature has been estimated to approximately 1010
–10
11 tons per
year [42]. The amounts of chitin, chitosan and their derivatives that are used/produced in industrial processes [43] have been estimated to be about 30 000 metric tons for chitin and about 10,000 metric
tons for chitosan in 2007 [44]. Most of the chitin is used as raw material for the production of the
monosaccharide GlcN, which is the number one dietary supplement in the USA, used for pain relief of
osteoarthritis [43].