A New Model for the K+-Induced Macromolecular Structure of Guanosine 5‘-Monophosphate in Solution

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Abstract
The 31P NMR spectra of (TMA)2(5‘-GMP), where TMA is [(CH3)4N]+ and 5‘-GMP is guanosine 5‘-monophosphate, and K2(5‘-GMP), containing various amounts of KCl or TMACl, have been obtained at 2 °C. Variable-temperature spectra have also been obtained for K2(5‘-GMP). The TMA+ ion serves to neutralize the charge on the dianionic 5‘-GMP and permits the added K+ to bond preferentially in structure-forming sites. 1H NMR spectra (one- and two-dimensional) have been obtained for K2(5‘-GMP) and used to assign the proton resonances in the self-associated structures and determine that all residues have the anti glycosidic conformation. The 31P and 1H NMR spectra are very complex and indicate the presence of a large number of molecular environments and a structural variation dependent upon the mole ratio of 5‘-GMP to K+. A new model for the solution structure is proposed in which the 5‘-GMP forms a pseudo-four-stranded helix with guanine−guanine hydrogen bonding forming a continuous helical strand, rather than the usual planar G-tetrad structure. The guanine−guanine hydrogen bonding sites are the same as that found in a G-tetrad. The K+ ions would be located in the center of the helix and bonding to the carbonyl oxygens. They are interacting with the phosphates as well. Integration data from the largest sized species give an estimate of 14.3 ± 1.1 residues in a helical structure.

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