Poly(L-lactic acid) (PLLA) has been extensively used in tissue engineering, in which its surface hydrophilicity plays an important role. In this work, an efficient and green strategy has been developed to tailor surface hydrophilicity via alkali hydrolysis. On one hand, the ester bond in PLLA has been cleaved and generates carboxyl and hydroxyl groups, both of which are beneficial to the improvement of hydrophilicity. On the other hand, the degradation of PLLA increases the roughness on the film surface. The resultant surface wettability of PLLA exhibits crucial dependence on its crystallinity. In the specimen with high crystallinity, the local enrichment of terminal carboxyl and hydroxyl groups in amorphous regions accelerates the degradation of ester group, producing more hydrophilic groups and slit valleys on film surface. The enhanced contact between PLLA and water in aqueous solution (i.e., the Wenzel state) contributes to the synergistic effect between generated hydrophilic groups and surface roughness, facilitating further degradation. Consequently, the hydrophilicity has been improved significantly in the high crystalline case. On the contrary, the competition effect between them leads to the failure of this strategy in the case of low crystallinity.
Keywords: PLLA; alkali hydrolysis; crystallinity; hydrophilicity.