EMISSION SPECTRA FROM SYNTHETIC POLYNUCLEOTIDES AND DEOXYRIBONUCLEIC ACID IN AQUEOUS SOLUTIONS†

A study has been made of the emission spectra at 77°K from poly A, poly U, poly C, their complexes, and from native and heat-denatured DNA in buffered aqueous solutions containing 0·25 per cent glucose: no emission was observed from these polynucleotides at room temperature. The spectra differed from those obtained in the polyalcoholic glasses used by other workers. The principal differences between the emission spectra of poly A and adenosine at pH 7 in a water-glucose mixture were: (a) a decrease in both P/F and the overall intensity in poly A; (b) absence of the structure normally found in adenosine phosphorescence; and (c) appearance of a new short-lived component in the phosphorescence decay. Further changes in the emission characteristics (e.g. the increase of P/F, the proportional increase of the short-lived component in the phosphorescence decay) from poly A were observed at pH 5. These can not be explained solely by protonization of adenosine residues, but rather appear to depend upon exciton interactions of the most intense π–π* transition in double-stranded poly A. and perturbation of the lowest-lying emitting band. When poly A or poly C is complexed with poly U or poly I the luminescence intensity decreases in two-strand complexes and is completely quenched in poly (A + 2U), poly (A+2I) and poly (C⁺+I); no emission was observed from either, single-strand poly I or poly U. Identical emission patterns were obtained from native and heat-denatured samples of DNA. The comparison of polynucleotide emission spectra in the water-glucose medium with those obtained from polyalcoholic glasses leads to the conclusion that the emission spectra depend most critically upon the relative proportions of base-solvent and base-base interactions in each environment: the possible importance of proton tunneling and/or triplet-triplet transfer mechanisms is briefly discussed.