Surface functionalization of polymer scaffolds is a method used to improve interactions of materials with cells. A frequently used method for polyesters is aminolysis reaction, which introduces free amine groups on the surface. In this study, nanofibrous scaffolds and films of three different polyesters–polycaprolactone (PCL), poly(lactide-co
-caprolactone) (PLCL), and poly(l
-lactide) (PLLA) were subjected to this type of surface modification under the same conditions. Efficiency of aminolysis was evaluated on the basis of ninhydrin tests and ATR–FTIR spectroscopy. Also, impact of this treatment on the mechanical properties, crystallinity, and wettability of polyesters was compared and discussed from the perspective of aminolysis efficiency. It was shown that aminolysis is less efficient in the case of nanofibers, particularly for PCL nanofibers. Our hypothesis based on the fundamentals of classical high speed spinning process is that the lower efficiency of aminolysis in the case of nanofibers is associated with the radial distribution of crystallinity of electrospun fiber with more crystalline skin, strongly inhibiting the reaction. Moreover, the water contact angle results demonstrate that the effect of free amino groups on wettability is very different depending on the type and the form of polymer. The results of this study can help to understand fundamentals of aminolysis-based surface modification.
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