Surface
erosion has been recognized as a valuable design tool for
resorbable biomaterials within the context of drug delivery devices,
surface coatings, and when precise control of strength retention is
critical. Here we report on high tensile strength, aromatic–aliphatic
polycarbonates based on natural phenols, tyrosol (Ty) and homovanillyl
alcohol (Hva), that exhibit enzymatic surface erosion by lipase. The
Young’s moduli of the polymers for dry and fully hydrated samples
are 1.0 to 1.2 GPa and 0.8 to 1.2 GPa, respectively. Typical characteristics
of enzymatic surface erosion were confirmed for poly(tyrosol carbonate)
films with concomitant mass-loss and thickness-loss at linear rates
of 0.14 ± 0.01 mg cm–2 d–1 and 3.0 ± 0.8 μm d–1, respectively.
The molecular weight and the mechanical properties of the residual
films remained constant. Changing the ratio of Ty and Hva provided
control over the glass transition temperature (Tg) and the enzymatic surface erosion: increasing the Hva content
in the polymers resulted in higher Tg and
lower enzymatic erosion rate. Polymers with more than 50 mol % Hva
were stable at 37 °C in enzyme solution. Analysis on thin films
using quartz crystal microbalance with dissipation (QCM-D) demonstrated
that the onset temperature of the enzymatic erosion was approximately
20 °C lower than the wet Tg for all
tested polymers. This new finding demonstrates that relatively high
tensile strength polycarbonates can undergo enzymatic surface erosion.
Moreover, it also sheds light on the connection between Tg and enzymatic degradation and explains why few of the
high strength polymers follow an enzyme-meditated degradation pathway.