Chitosan–citric biomembranes Ch-CA-Gx
(x = 0–3) were prepared
by a simple cross-linking. The dependence of mechanical property,
water-resisting capacity, microstructural characteristic, oxygen barrier
ability, and thermal properties of membranes on the content of glycerin
was investigated. The results revealed that vacuum drying at 80 °C
can lead to low-yield amidation and the Maillard reaction, thus affecting
the thermal stability and water resistance of biomembranes. Owing
to the ionic cross-linking and amidation, the chitosan–citrate
complex showed weaker compatibility when the glycerin content increased,
thereby leading to discontinuity of microstructure in the Ch-CA-Gx
(x = 1–3) membranes, which
was in line with the weaker mechanical properties and water-resisting
abilities of membranes, compared to Ch-CA-G0. Chitosan
membranes showed interestingly high oxygen barrier capabilities under
40 and 80% relative humidity (RH) conditions, probably attributed
to the increased diffusion length arising from the hydrogen-bonding,
ionic, and covalent cross-linking. The oxygen transmission rates of Ch-CA-Gx
were below 0.1 cm3 m–2 day–1 at 40% RH. The Ch-CA-Gx
membranes showed a good elasticity assigned to
the reversibly cross-linked structure. The membranes presented strong
antibacterial activities against Staphylococcus aureus and Escherichia coli bacteria, probably
owing to the citric acids. The results demonstrated that these materials
have potential applications as membranes or protecting coatings for
food packaging and successful cross-linking by means of amidation,
and the Maillard reaction under the condition of vacuum drying can
be probably applied as a green and alternative method for the fabrication
of mechanically tough and antibacterial membranes, fibers, and gels.