Polyrotaxanated covalent organic frameworks based on β-cyclodextrin towards high-efficiency synergistic inactivation of bacterial pathogens

Abstract

As an emerging artificial porous material, covalent organic frameworks (COFs) with customizable structure and function, have always been the focus of polymer science. Controllable fabrication of COFs with brand-new structure is the top priority for its development. Here, the ‘supramolecular binding’ strategy is developed as a simple but efficient method to prepare COFs with novel structures and functions. By this means, polymeric rotaxanes threaded COFs, denoted as Por-CD-COF, was facilely prepared via the combination of dynamic covalent imine-bond formation with supramolecular self-assembly, in which the polyrotaxane formed via inclusion of aromatic linker with bactericidal active β-cyclodextrin macrocycle (CD) was condensed with the photosensitive porphyrin via the combination of mechanical grinding and solvothermal synthesis. The formation of polyrotaxane could change the distance between layers, avoiding the quench of photoactivity caused by the severe aggregation of layered structure. Under the same molar amount of reaction monomers, the weight of the Por-CD-COF is approaching five times of the CD-free COF, which could greatly reduce the use of photoactive ingredients. Further experiments demonstrated the introduction of CDs could also significantly improve the biocompatibility. Impressively, this special porphyrin-involved CD-COF, displays excellent photo activity, which could act as an efficient broad spectrum antibacterial agents realizing the combinational action of cyclodextrin enhanced photothermal and photodynamic antimicrobial at an extremely low quality of the effective photosensitizer (Porphyrin). Meanwhile, even at the same dose of fungicide, the bactericidal effect of Por-CD-COF is far exceeding the CD-free therapeutic agent. This novel synthetic strategy allows the incorporation of mechanically interlocked CDs (MIMs) into the porous polymeric materials, providing an easy access to low-cost preparation of COFs for the specific applications.