Graphene quantum dot-decorated luminescent porous silicon dressing for theranostics of diabetic wounds

Diabetic wound healing is highly desirable but remains a great challenge owing to the continuous damage of excess reactive oxygen species (ROS) and degradation of therapeutic peptide drugs by over-expressed matrix metalloproteinase (MMP). Herein, we developed a stimuli-responsive smart dressing for theranostics of diabetic wounds using graphene quantum dots-decorated luminescent porous silicon (GQDs@PSi), which was further loaded with peptide and embedded in chitosan (CS) film. The confinement of GQDs in nanochannels of PSi endowed GQDs@PSi with efficient fluorescence resonance energy transfer (FRET) effect, leading to initial red fluorescence of PSi with complete quench of GQD's blue fluorescence. Furthermore, the decoration of GQDs on PSi surface significantly enhanced the loading capacity for peptide drugs including epidermal growth factor (EGF) and insulin (Ins) which can promote diabetic wounds healing. The peptides coloaded in GQDs@PSi exhibited sustained release behavior and could be protected in presence of MMP owing to size exclusion of PSi's nanochannels. As H₂O₂-triggered oxidation of PSi lead to weakened FRET effect and degradation of PSi, GQDs@PSi demonstrated H₂O₂-responsive ratiometric fluorescence change (from red PSi to blue GQDs) and drug release behavior. In combination with CS's degradation in the acidic and oxidation microenvironment, the smart dressing also showed stimuli-responsive drug release toward slightly acid and highly oxidative conditions in diabetic wounds. In vitro and in vivo results demonstrated the smart dressing enhanced the proliferation and migration of cells as well as significantly healed diabetic wounds. Real-time indicating of the exacerbation or healing of diabetic wounds was also realized using the rate of fluorescent discoloration of the dressing. STATEMENT OF SIGNIFICANCE: In this work, a dual luminescent nanomaterial was created by hosting graphene quantum dots (GQDs) in the nanochannel of porous silicon (PSi), which was further applied for theranostics of diabetic wound. The synergistic effect of the host-guest nanohybrid is significant. The GQDs can significantly improve the capacity for peptide drug loading and form a stimuli-response visual ratiometric sensor with luminescent PSi, which can also protect and sustain release of peptide drugs for effective diabetic wounds treatment. After embedded in a chitosan film, the smart dressing displayed H₂O₂-responsive visual ratiometric fluorescence change and drug release behavior. In vitro and in vivo results demonstrated the smart dressing enhanced the proliferation and migration of cells as well as significantly healed diabetic wounds.