title: Use of pK(a) differences to enhance the formation of base triplets involving C-G and G-C base pairs.
abstract: Two C-nucleosides are employed for the recognition of dC-dG base pairs. Both derivatives are related to dC but lack the O2-carbonyl. The absence of the carbonyl should eliminate any unfavorable steric interactions at this site. One of the derivatives contains a 2-aminopyridine heterocycle (d2APy) while the second contains a 2-aminopyrimidine heterocycle (d2APm). The former with a pK(a) of 6. 8 functions better for the recognition of dG-dC base pairs than it does in the binding to dC-dG base pairs. The d2APm derivative with a pK(a) of 3.3 functions better to form base triplets with dC-dG base pairs than with dG-dC targets. Triplex T(m)'s in both cases are compared with the sequence containing the native dC residue. The dC analogues appear to make two hydrogen bonds to a target dG base residue, one of which requires protonation of the ring nitrogen. Recognition of a target dC residue appears to require the formation of a single hydrogen bond to the C-nucleoside and having that nitrogen largely in the unprotonated state facilitates its formation.
authors.affiliation: Department of Chemistry, Merkert Chemistry Center, 2609 Beacon Street, Boston College, Chestnut Hill, Massachusetts 02467, USA.
authors.forename: D L
authors.initials: DL
authors.lastname: Chen
authors.forename: L W
authors.initials: LW
authors.lastname: McLaughlin
mesh_terms: D020029:Base Pairing; D002855:Chromatography, Thin Layer; D006863:Hydrogen-Ion Concentration; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D009841:Oligonucleotides / Q000138:chemical synthesis; D011741:Pyrimidine Nucleosides / Q000138:chemical synthesis* / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet
chemical_list: D007202:Indicators and Reagents; D009841:Oligonucleotides; D011741:Pyrimidine Nucleosides