Acid-base reactions double helix disruption

Acid-Base Reactions Can Disrupt the Double Helix... 

The pKa for the proton on N -1 of guanine is typically 9.7. When the pH approaches this value, the proton on N-1 is lost (see Figure 1.16). Because this proton participates in an important hydrogen bond, its loss substantially destabilizes the DNA double helix. The DNA double helix is also destabilized by low pH. Below pH 5, some of the hydrogen bond acceptors that participate in base-pairing become protonated. In their protonated forms, these bases can no longer form hydrogen bonds and the double helix separates. Thus, acid—base reactions that remove or donate protons at specific positions on the DNA bases can disrupt the double helix. 

An unusual photochemical reaction of 2-pyridones, 2-aminopyridinium salts and pyran-2-ones is photodimerization to give the so-called butterfly dimers. These transformations are outlined in equations (13) and (14). Photodimerization by [2+2] cyclization is also a common and important reaction with these compounds. It has been the subject of particular study in pyrimidines, especially thymine, as irradiation of nucleic acids at ca. 260 nm effects photodimerization (e.g. equation 15) this in turn changes the regular hydrogen bonding pattern between bases on two chains and hence part of the double helix structure is disrupted. The dimerization is reversed if the DNA binds to an enzyme and this enzyme-DNA complex is irradiated at 300-500 nm. Many other examples of [2+2] photodimerization are known and it has recently been shown that 1,4-dithiin behaves similarly (equation 16) (82TL2651). 

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