Chitin and chitosan were hybridized in various weight percentages by genipin crosslinkage under various prefreezing temperatures to form tissue-engineering scaffolds via lyophilization. In addition, deposition of hydroxyapatite (HA) on the surface of the porous scaffolds was performed by precipitation method to achieve modified chemical compositions for chondrocyte attachments and growths. The experimental results revealed that a lower prefreezing temperature or a higher weight percentage of chitin in the chitin-chitosan scaffolds would yield a smaller pore diameter, a greater porosity, a larger specific surface area, a higher Young's modulus, and a lower extensibility. Moreover, a higher chitin percentage could also result in a higher content of amine groups after crosslink and a lower onset temperature for the phase transition after thermal treatment. A decrease in the prefreezing temperature from -4 degrees C to -80 degrees C, an increase in the chitin percentage from 20% to 50%, and an increase in the cycle number of alternate immersion for HA deposition from 1 to 5 generated positive effects on the cell number, the content of glycosaminoglycans, and the collagen level over 28-day cultivation of bovine knee chondrocytes.
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