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Quantum dots (QDs), have great potential for fabricating optical sensing devices andimaging biomaterial degradation in vivo. In the present study, 2-mercaptoethylamine- (MEA-)and mercaptopropionic acid- (MPA-) capped CdTe-QDs were physically incorporated in silk films that containeda high content (>30%) of crystalline beta-sheet structure. The beta-sheets were induced by theaddition of glycerol, water annealing, glycerol/annealing, or treatment with methanol. Incorporation of QDs didnot influence the formation of beta-sheets. When the films were extracted with water, most QDs remainedassociated with the silk, based on the retention of photoluminescence in the silk films and negligiblephotoluminescence in the extracts. Compared to the solution state, photoluminescence intensity significantly decreasedfor MEA-QDs but not for MPA-QDs in the silk films, while the emission maximum blue shifted (≈4 nm)slightly for both. Further film digestion using protease XIV, alpha-chymotrypsin, and the combination of the two proteasessuggested that QDs may be bound to the silk beta-sheet regions but not the amorphous regions. QDs photoluminescence in silk films was quenched when the concentration of hydrogen peroxide(H2O2) was above 0.2-0.3 mM, indicating the QDs-incorporatedsilk films can be used to report oxidation potential in solution

Binding Quantum Dots to Silk Biomaterials for Optical Sensing