Singlet molecular oxygen: generation, reactivity, identification and biological effects

RESUMO

Electronically excited singlet molecular oxygen ((1)O2)) is of great importance in chemical and biological systems due to its high reactivity and involvement in physiological and pathological processes. It is a simple and useful reagent in organic synthesis of peroxides, endoperoxides, hydroperoxides, and dioxetanes. In biological systems, (1)O2 has been implicated in i) Defense mechanisms of living organisms such as phagocytosis; ii) degradative oxidation of endogenous hallucinogens; iii) hormonal activity of prostaglandins; iv) photochemotherapy utilizing the photodynamic action of synthetic dyes; v) photosensitivity to drugs like chlorpromazine and vi) inborn errors of metabolism exemplified by erythropoietic porphyria. The high reactivity of (1)O2 with unsaturated compounds, sulfides and amines arises from its high electrophilicity and relatively long lifetime (2-4 ms in H2O and ~700 ms in CCI4). Thus, biological targets for (1)O2 having the above functional groups include unsaturated fatty acids, proteins, and DNA. Extensively conjugated biomolecules such as carotenoids act as chemical and physical quenchers of (1)O2 and hence provide protective mechanisms against the deleterious effects of this excited state of molecular oxygen. However, due to the difficulties involved in obtaining (1)O2 free from other reactive contaminants, there is a paucity of detailed studies on the mentioned aspects of (1)O2 biochemistry. Chemical and dye-sensitized photophysical methods are available to prepare (1)O2. The aim of this work is to give a general view on (1)O2 with regard to its chemical generation, reactivity with biologically important compounds, detection and its role in biological systems.