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These electron-affinic, reductively bioactivated nitroheterocyclics undergo initial oxygen-reversible, enzymatic one-electron reductions that lead to the formation of molecular adducts that impair vital molecular processes. The discovery of 2-nitroimidazole (azomycin) heralded the development of many drugs, including effective radiosensitizers of hypoxic cells. Nitroimidazoles, for example, capitalize on oxygen-sensitive reductive activation to achieve hypoxia-selective localization for theranostic consequence. The reduced curability of hypoxic tumours by radiotherapy is one of consequent challenges, but their hypoxia also offers unique, exploitable properties. In cancer cells, hypoxia-induced pathophysiological changes give rise to genetic changes that lead to treatment-resistant, aggressive phenotypes. Oxygen supply-demand imbalances can render proliferating cells acutely or chronically hypoxic. Main group metal – nitroimidazole complexes 4. Lanthanide metal – nitroimidazole complexes.Technetium ligands containing PEG linked nitroimidazoles Technetium 2,2’,2”-nitrilotris(ethanethiol) and isocyanide (4+1) nitroimidazoles Technetium dithiolate and cysteine-based nitroimidazoles Technetium nitroimidazole diethylenetriamines (DETA) Technetium nitroimidazole iminodiacetic acids (IDA) Technetium nitroimidazole hydroxyiminoamides Boronic acid adducts of technetium dioximes (BATO) Copper bis(thiosemicarbazone) nitroimidazoles
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Nitroimidazole-based transition metal coordination complexes Hypoxia-selective bifunctional organometallic coordination complexes 1. Reductively bioactivated, oxygen mimetic, hypoxia-targeted radiosensitizers and theranostics.