Effects of ultrasound on nucleic acid bases.

To understand the effects of ultrasound in biological systems at the molecular level, sonolysis of nucleic acid bases at sonic intensities less than or equal to 5 W/cm2 was studied. These sonoreactions were followed by UV-spectral decrease and by sonoproduct analysis. The order of reactivity was found to be thymine greater than uracil greater than cytosine greater than guanine greater than adenine. The extent of sonoreactions depends on the exposure time and the rate of the intensity. Aeration was necessary for maintenance of a reasonable reaction rate. "Threshold" intensities for uracil and thymine were observed at approximately 0.5 W/cm2. The effectiveness of the dissolved gases in producing sonoreactions was Ar greater than 02 greater than air greater than N2 greater than He greater than N2O, suggestive of free radicals mediating these reactions since N2O is an effective radical scavenger. Studies of the effects of substituents have shown that electronic rather than steric effects may have a greater influence. Preliminary identification indicates that cis- and trans-uracil glycols are the major products of uracil. Thus, a stepwise mechanism of pyrimidine sonolysis is proposed. Sonolysis of a dilute aqueous solution of uracil yielded pseudo-first-order kinetics in terms of [Ura] with a rate constant of 3.9 X 10(-2) min-1, implying that the rate-limiting step is the reaction of HO- with the base.