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PKa of cytosine on the third strand of triplex DNA: Preliminary Poisson–Boltzmann calculations

✍ Scribed by George R. Pack; Linda Wong; Gene Lamm


Publisher
John Wiley and Sons
Year
1998
Tongue
English
Weight
346 KB
Volume
70
Category
Article
ISSN
0020-7608

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✦ Synopsis


The energetics of formation of a triple-helical structure in homopurine᎐homopyrimidine mixtures has been modeled using Poisson᎐Boltzmann Ž . Ž . calculations. Oligomers with the sequence d TC and d AG form hydrogen-bonded n n Ž . Ž . Ž q . triple-helical structures of the form d TC и d AG и d TC . The third base, a n n n pyrimidine in this case, forms Hoogsteen-type hydrogen bonds with the purine, requiring that the cytosine residues of the third strand protonate at N3. The p K of cytosine, 4.3 in a the isolated solvated molecule, is raised by the strong electrostatic field in the triple helix.

We have done calculations of the effective p K of this cytosine and compared the results a with experimental studies of triple-helix formation as a function of pH. This provides a test of various models of the dielectric constant for triplex DNA and its local environment.