A poly(ethylene oxide)-b-poly(epsilon-caprolactone) (PEO-b-PCL) diblock copolymer was micronized into small micelle-like particles (approximately 80 nm) via dialysis-induced microphase inversion. The enzymatic biodegradation of the PCL portion of these particles in water was in situ investigated inside a recently developed novel differential refractometer. Using this refractometry method, we were able to monitor the real-time biodegradation via the refractive index change (Deltan) of the dispersion because Deltan is directly proportional to the particle mass concentration. We found that the degradation rate is proportional to either the polymer or enzyme concentration. Our results directly support previous speculation on the basis of the light-scattering data that the biodegradation follows the first-order kinetics for a given enzyme concentration. This study not only leads to a better understanding of the enzymatic biodegradation of PCL, but also demonstrates a novel, rapid, noninvasive, and convenient way to test the degradability of polymers.
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