Spectral and biological changes induced in nicotinic acid and related compounds by ultraviolet light

Abstract

Irraidation of nicotinic acid, nicotinamide, nicotinamide N-oxide, N[image]-methyl-4-pyridone-3-carboxamide, reduced nicotinamide-adenine dinucleotide and pyridine with ultraviolet light at 253.7 m[mu] leads to striking spectral changes. Nicotinic acid and nicotinamide are broken down to photosensitive intermediates which in turn undergo photodecomposition. A major photoproduct of [7-14c] nicotinic acid is radioactive and absorbs ultraviolet light, but is inactive as a growth factor for Candida pseudo-tropicalis. Irradiation of nicotinamide gives rise to small quantities of a biologically acitive photoproduct having the same RF as nicotinic acid. A second photoproduct is also formed, but its identity has not yet been established. Irradiation of nicotinamide N-oxide leads to the formation of several photoproducts, one of which has the same RF as nicotinamide, absorbs ultraviolet light, and is biologically active. Evidence is presented that irradiation of ethanolic solutions of N[image]-methyl-4-pyridone-3-carboxamide gives rise to acetaldehyde. Irradiation of reduced nicotinamide-adenine dinucleotide in the presence of acetaldehyde leads to the formation of oxidized nicotinamide-adenine dinucleotide, which in turn can break down to nucleotide and/or nucleoside (depending on the conditions of the reaction). The quantum yields of photolysis and the molar photosensitivities have been determined for N[image]-methyl-4-pyridone-3-carboxamide and nicotinamide N-oxide. The possible biological significance of these photoreactions is discussed in relation to photosynthesis, visual-pigment metabolism and ultraviolet-light-induced cell damage. A four-step theory is presented for the biochemical evolution of oxidation-reduction systems, involving photoactivated transformations of pyridine derivatives.