A solid-state deuterium NMR investigation of conformation and order in magnetically oriented [d(CGCGAATTCGCG)]2.

Solid-state deuterium NMR has been used to investigate the oriented liquid crystal phase of the hydrated oligonucleotide [d(CGCGAATTCGCG)]2. Previous investigations have shown that the helix axis is aligned perpendicular to the magnetic field, while at reduced temperatures motion about the helix axis is eliminated. Synthetic oligonucleotide samples incorporating different labeled nucleosides, [2"-2H]-2'-deoxyadenosine, [methyl-2H]thymidine, [8-2H]-2'-deoxyguanosine, and [8-2H]-2'-deoxyadenosine, permitted investigation of both the base and sugar conformation and ordering in the aligned phase. From line-shape analysis of the purine-labeled samples the orientation of the base C8 C-D bond with respect to the helix axis was determined to be theta = 90 degrees with a distribution of sigma total = 20 degrees, which is comparable to the orientation of theta = 90 degrees, sigma total = 15 degrees, with an oriented fraction P = 0.7 found for the C3 symmetry axis of the methyl-labeled dodecamer. The orientation of the sugar 2" C-D bond with respect to the helix axis is theta = 22 degrees with a distribution of sigma total = 15 degrees in agreement with the expected C2'-endo sugar conformation. The fraction of C3'-endo was also investigated and from analysis of line shape cannot exceed 20%. These results, though preliminary in nature, illustrate the application of this aligned phase for structural investigations.