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Carbene-based macromolecules are an emerging new stimuli-sensitive class of biomaterials that avoid the impediments of free radical polymerization but maintain a rapid liquid-to-biorubber transition. Activation of diazirine-grafted polycaprolactone polyol (CaproGlu) is limited to UVA wavelengths that have tissue exposure constraints and limited light intensities. For the first time, UVA is circumvented with visible light-emitting diodes at 445 nm (blue) to rapidly activate diazirine-to-carbene covalent cross-linking. Iridium photocatalysts serve to initiate diazirine, despite having little to no absorption at 445 nm. CaproGlu's liquid organic matrix dissolves the photocatalyst with no solvents required, creating a light transparent matrix. Considerable differences in cross-linking chemistry are observed in UVA vs visible/photocatalyst formulations. Empirical analysis and theoretical calculations reveal a more efficient conversion of diazirine directly to carbene with no diazoalkane intermediate detected. Photorheometry results demonstrate a correlation between shear moduli, joules light dose, and the lower limits of photocatalyst concentration required for the liquid-to-biorubber transition. Adhesion strength on ex vivo hydrated tissues exceeds that of cyanoacrylates, with a fixation strength of up to 20 kg·f·cm 2 . Preliminary toxicity assessment on leachates and materials directly in contact with mammalian fibroblast cells displays no signs of fibroblast cytotoxicity.

Bright and stable CuInS2/ZnS@SiO2 nanoparticles with near-infrared (NIR) emission were competently prepared by incorporating the as-prepared hydrophobic CuInS2/ZnS quantum dots (QDs) directly into lipophilic silane micelles and subsequently an exterior silica shell was formed. The obtained CuInS2/ZnS@SiO2 nanoparticles homogeneously comprised both single-core and multicore remarkable CuInS2/ZnS QDs, while the silica shell thickness could be controlled to within 5-10 nm and their overall size was 17-25 nm. Also, the functionalized CuInS2/ZnS QDs encapsulated in the silica spheres, expedited their bioconjugation with holo-Transferrin (Tf) for further cancer cell imaging. The CuInS2/ZnS@SiO2 nanoparticles not only showed a dominant NIR band-edge luminescence at 650-720 nm with a quantum yield (QY) between 30 and 50%, without a recognized photoluminescence (PL) red shift, but also exhibited excellent PL and colloidal stability in aqueous media. Impressively, the cytotoxicity studies revealed minor suppression on cell viability under both CuInS2/ZnS@SiO2 and CuInS2/ZnS@SiO2@Tf concentrations up to 1 mg/mL. The application in live-cell imaging revealed that the potential of CuInS2/ZnS QDs as biocompatible, robust, cadmium-free, and brilliant NIR emitters is considered promising for fluorescent labels.