Double helices, oligomers

Copper(I) tends towards a tetrahedral coordination geometry in complexes. With 2,2 -bipyr-idine as a chelate ligand a distorted tetrahedral coordination with almost orthogonal ligands results. 2,2 -Bipyridine oligomers with flexible 6,6 -links therefore form double helices with two 2,2 -bipyridine units per copper(I) ion (J. M. Lehn, 1987,1988). J. M. Lehn (1990 U. Koert, 1990) has also prepared such helicates with nucleosides, e.g., thymidine, covalently attached to suitable spacers to obtain water-soluble double helix complexes, so-called inverted DNA , with internal positive charges and external nucleic bases. Cooperative effects lead preferentially to two identical strands in these helicates when copper(I) ions are added to a mixture of two different homooligomers. 

During the 1980s several laboratories prepared and investigated double-stranded helical complexes, systems containing either pyirolic ligands [75, 76] and derivatives [77-79] (with Zn2+, Ag+, Cu+) or oligomers of 2,2 -bipyridine [80, 81]. Helicates [80-84] may consist of up to five copper centers and these systems are reminiscent of the DNA double helix. 

Internal Loops in RNA Oligomer Crystals. The first crystal structure of an RNA internal loop was solved in 1991(8). The dodecamer rGGACUUCGGUCC (internal loop underlined) forms a duplex in the crystal with an internal loop of consecutive U-G, U-C, C-U and G-U mismatches as shown in Figure 2. The chains of the double helix show two-fold symmetry in the crystal, thus the U-G and U-C pairs are identical to the C-U and G-U pairs. As can be seen, the internal loop generally continues the double helices which surround it by formation of non-Watson-Crick base pairs. The major groove of the A-form helix is opened with respect to a canonical RNA helix. 

---