Crystalline aggregates are widely present in various
organisms.
Regulation of nanostructures is of vital importance to the revelation
of life secrets as well as material fabrication. As a representative,
chitosan displays polymorphic structures. In tendon chitosan, four
polymer chains are packed into an orthorhombic cell, where the antiparallel
neighboring chains are linked by two sets of N2···O6 hydrogen bonds, and water molecules are connected with N2, O3, and O5 as well as O6 atoms via hydrogen bonds to stabilize the hydrated structure. The
transition from hydrated to anhydrous allomorphs, however, usually
involved high-temperature annealing or multistep concentrated acid
hydrolysis, which weakened the sustainability of chitosan. To address
these issues, we proposed a more convenient strategy to achieve the
polymorphic transitions under mild conditions. By subjecting chitosan
microgels (CSM) to normal freezing treatment, the hydrated aggregates
could be transferred into the anhydrous form. The X-ray diffraction
(XRD) results clearly demonstrated that both the (020) and (200) diffraction
peaks centered at 2θ = 10 and 19.8° gradually disappeared,
while the (110) peak at 2θ = 14.8° indicated the occurrence
of anhydrous crystals. Upon freezing, the water molecules that were
inserted into the hydrated crystals were removed. Meanwhile, under
the effects of N2···O6 intermolecular
hydrogen bonding and hydrophobic association, the adjacent polymer
chains reorganized into new microcrystalline domains. Moreover, the
CSM particles exhibited a strong tendency for self-association during
this process. By introducing CSM into the oil/water mixture system
to form a Pickering emulsion, the resultant macroporous materials
could be used as the oil absorbent through subsequent lyophilization.
This work provides a different way to facilely regulate the microcrystalline
structure of chitosan in a controllable manner, facilitating the construction
of more functional materials.