Tuesday, July 17, 2007
Tautomers of Adenine, Cytosine, Guanine, and Thymine
The four bases of DNA can exist in at least two tautomeric forms as shown below. Adenine and cytosine (which are cyclic amidines) can exist in either
amino or imino forms, and guanine, thymine, and uracil (which are cyclic amides) can exist in either lactam (keto) or lactim (enol) forms. The tautomeric forms of each base exist in equilibrium but the amino and lactam tautomers are more stable and therefore predominate under the conditions found inside most cells. The rings remain unsaturated and planar in each tautomer.
Fifty years ago it wasn't clear whether the amino or imino forms of the purines were stable under physiological conditions. (Or the lactam lactim forms.) As we will see, this uncertainty played a significant role in events leading up to the discovery of the structure of DNA.
We now know that all of the bases in the common nucleotides can participate in hydrogen bonding. The amino groups of adenine and cytosine are hydrogen donors, and the ring nitrogen atoms (N-1 in adenine and N-3 in cytosine) are hydrogen acceptors (see below). Cytosine also has a hydrogen acceptor group at C-2. Guanine, cytosine, and thymine can form three hydrogen bonds. In guanine, the group at C-6 is a hydrogen acceptor, and N-1 and the amino group at C-2 are hydrogen donors. In thymine, the groups at C-4 and C-2 are hydrogen acceptors, and N-3 is a hydrogen donor. (Only two of these sites, C-4 and N–3, are used to form base pairs in DNA.) The hydrogen-bonding patterns of bases have important consequences for the three-dimensional structure of nucleic acids.
©Laurence A. Moran and Pearson/Prentice Hall 2007