Creating polymers that combine various functions within a single system expands the potential applications of such polymeric materials. However, achieving polymer materials that possess simultaneously elevated strength, toughness, and self-healing capabilities, along with special properties, remains a significant challenge. The present study demonstrates the preparation of S and Mo codoped graphitic carbon nitride (g-C3N4) (Mo@S-CN) nanohybrid and the fabrication of self-healing waterborne polyurethane (SHWPU)/Mo@S-CN (SHWPU/NS) nanocomposites for advanced applications. Mo@S-CN is an intriguing combination of g-C3N4 nanosheets and molybdenum oxide (MoOx) nanorods, forming a complex lamellar structure. This unique arrangement significantly improves the inborn properties of SHWPU to an impressive degree, especially mechanical strength (28.37-34.11 MPa), fracture toughness (73.65-140.98 MJ m-2), and thermal stability (340.17-348.01 °C), and introduces fluorescence activity into the matrix. Interestingly, a representative SHWPU/NS0.5 film is so tough that a dumbbell of 15 kg, which is 53,003 times heavier than the weight of the film, can be successfully lifted without any significant crack. Remarkably, fluorescence activity is developed because of electronic excitations occurring within the repeating polymeric tris-triazine units of the Mo@S-CN nanohybrid. This fascinating feature was effectively harnessed by assessing the usability of aqueous dispersions of the Mo@S-CN nanohybrid and photoluminescent SHWPU/NS nanocomposites as sustainable stains for bioimaging of human dermal fibroblast cells and anticounterfeiting materials, respectively. The in vitro fluorescence tagging test showed blue emission from 365 nm excitation, green emission from 470 nm excitation, and red emission from 545 nm excitation. Most importantly, in vitro hemocompatibility assessment, in vitro cytocompatibility, cell proliferation assessment, and cellular morphology assessment supported the biocompatibility nature of the Mo@S-CN nanohybrid and SHWPU/NS nanocomposites. Thus, these materials can be used for advanced applications including bioimaging.
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