One of the paradoxes of life on this planet is that the molecule that sustains aerobic life, oxygen, is not only fundamentally essential for energy metabolism and respiration, but it has been implicated in many diseases and degenerative conditions (Marx, 1985). A common element in such diverse human disorders as ageing, arthritis, cancer, Lou Gehrig's disease and many others is the involvement of partially reduced forms of oxygen. Our realisation of the significance of oxygen in disorders and stress-induced dysfunctions in cultivated plants is recent due in no small part to the difficulty in detecting and tracing oxygen molecules, to the multitude of forms and intermediates that oxygen can assume, and to the extreme reactivity and rate of the chemical reactions involved. As a consequence we often in our experiments can only look for the "footprints" of oxygen reactions in our attempts to determine cause-effect relationships in stress responses. The following chapter describes our current understanding of the general principles of activated oxygen.
Atmospheric oxygen in its ground-state is distinctive among the gaseous elements because it is a biradical, or in other words it has two unpaired electrons. This feature makes oxygen paramagnetic; it also makes oxygen very unlikely to participate in reactions with organic molecules unless it is "activated". The requirement for activation occurs because the two unpaired electrons in oxygen have parallel spins. According to Pauli's exclusion principle, this precludes reactions with a divalent reductant, unless this reductant also has two unpaired electrons with parallel spin opposite to that of the oxygen, which is a very rare occurrence. Hence, oxygen is usually non-reactive to organic molecules which have paired electrons with opposite spins. This spin restriction means that the most common mechanisms of oxygen reduction in biochemical reactions are those involving transfer of only a single electron (monovalent reduction).
Activation of oxygen may occur by two different mechanisms: absorption of sufficient energy to reverse the spin on one of the unpaired electrons, or monovalent reduction. The biradical form of oxygen is in a triplet ground state because the electrons have parallel spins. If triplet oxygen absorbs sufficient energy to reverse the spin of one of its unpaired electrons, it will form the singlet state, in which the two electrons have opposite spins (Fig. 1). This activation overcomes the spin restriction and singlet oxygen can consequently participate in reactions involving the simultaneous transfer of two electrons (divalent reduction). Since paired electrons are common in organic molecules, singlet oxygen is much more reactive towards organic molecules than its triplet counterpart.
One of the paradoxes of life on this planet is that the molecule that sustains aerobic life, oxygen, is not only fundamentally essential for energy metabolism and respiration, but it has been implicated in many diseases and degenerative conditions (Marx, 1985). A common element in such diverse human disorders as ageing, arthritis, cancer, Lou Gehrig's disease and many others is the involvement of partially reduced forms of oxygen. Our realisation of the significance of oxygen in disorders and stress-induced dysfunctions in cultivated plants is recent due in no small part to the difficulty in detecting and tracing oxygen molecules, to the multitude of forms and intermediates that oxygen can assume, and to the extreme reactivity and rate of the chemical reactions involved. As a consequence we often in our experiments can only look for the "footprints" of oxygen reactions in our attempts to determine cause-effect relationships in stress responses. The following chapter describes our current understanding of the general principles of activated oxygen.
Atmospheric oxygen in its ground-state is distinctive among the gaseous elements because it is a biradical, or in other words it has two unpaired electrons. This feature makes oxygen paramagnetic; it also makes oxygen very unlikely to participate in reactions with organic molecules unless it is "activated". The requirement for activation occurs because the two unpaired electrons in oxygen have parallel spins. According to Pauli's exclusion principle, this precludes reactions with a divalent reductant, unless this reductant also has two unpaired electrons with parallel spin opposite to that of the oxygen, which is a very rare occurrence. Hence, oxygen is usually non-reactive to organic molecules which have paired electrons with opposite spins. This spin restriction means that the most common mechanisms of oxygen reduction in biochemical reactions are those involving transfer of only a single electron (monovalent reduction).
Activation of oxygen may occur by two different mechanisms: absorption of sufficient energy to reverse the spin on one of the unpaired electrons, or monovalent reduction. The biradical form of oxygen is in a triplet ground state because the electrons have parallel spins. If triplet oxygen absorbs sufficient energy to reverse the spin of one of its unpaired electrons, it will form the singlet state, in which the two electrons have opposite spins (Fig. 1). This activation overcomes the spin restriction and singlet oxygen can consequently participate in reactions involving the simultaneous transfer of two electrons (divalent reduction). Since paired electrons are common in organic molecules, singlet oxygen is much more reactive towards organic molecules than its triplet counterpart.
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