Metallophthalocyanines: versatile probes for microbial photoinactivation and for pollutant degradation as photocatalysts, both molecular or supported form

Abstract

This thesis investigates the synthesie of metallophthalocyanines for potential use as photosensitizers in two applications: photodynamic antimicrobial chemotherapy and the photodegradation of organic pollutants. To achieve this, phthalocyanines with morpholine (substituted at alpha and beta position, to imine), ethyl and propyl pyrrolidine Schiff bases, asymmetrical mercaptobenzothiazole and morpholine substituents were synthesized for the first time. All nitrogen containing phthalocyanines were methylated to form cationic derivatives. Asymmetrical mercaptobenzothiazole were covalently linked to spherical and pyramidal zinc oxide nanoparticles, while the asymmetrical morpholine were conjugated to polyacrylonitrile (PAN) nanofibers, chitosan modified PAN and glass wool, while carboxylic acid containing phthalocyanines were also linked to glass wool. Various characterization techniques, including electronic spectroscopy, mass spectroscopy, nuclear magnetic resonance (NMR), Fourier-transform infrared (FT-IR), elemental analysis, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscope (SEM), and time-resolved fluorescence measurements were employed to characterize all the phthalocyanine composites. The research aimed to establish general trends in fluorescence quantum yields, triplet and singlet oxygen generation, photodegradation rates, and fluorescence and triplet state lifetimes of the complexes. Notably, the presence of zinc oxide nanoparticles increased the triplet quantum yield of phthalocyanines, however, the singlet oxygen quantum yield decreased. The study also examined the photodynamic inactivation of various planktonic cells and biofilms using all photosensitizers. The photodynamic antimicrobial chemotherapy activities were dose-dependent, and all cationic photosensitizers were highly effective in completely inactivating the microbes in both forms, as opposed to non-charged photosensitizers. For the supports, the chitosan modified PAN showed high efficacy due to improved hydrophilicity. Furthermore, the research was conducted on the photodegradation of 4-chlorophenol, methyl orange and methylene blue using Pc-anchored PAN and glass wool supports. The immobilized photosensitizers demonstrated a strong capacity for generating singlet oxygen in aqueous media, with the cationic Pc-PAN removing methylene blue more efficiently due to its adsorption and photodegradation abilities. All supports were recoverable, showing potential application for future use in the removal of microbes and organic pollutants.