The crystal structures of chitosan acid salts were studied by X-ray diffrac
tion measurements on a fiber diagram and a new procedure to obtain an anhyd
rous polymorph of chitosan was found. The salts prepared by immersing a chi
tosan into a mixture of acid solution and isopropanol were classified into
two types (Types I and II) depending on their conformation. Molecular confo
rmation of the Type I salt retains the extended 2-fold helical structure of
the original chitosan, but that of Type II salt is a twisted 2-fold helix.
All the Type II salts changed to the anhydrous "Annealed" polymorph of chi
tosan when soaking in 75% aqueous isopropanol, but when the Type I salts we
re immersed in the solution, they returned to the hydrated "Tendon" polymor
ph which is that of the original chitosan. The strange transformation obser
ved in Type II salt may be related to the stability of the molecular confor
mation of chitosan in the salt.