ABSTRACT
In this work, we for the first time conducted a detailed study on the structure, dynamics, and hybridization properties of N-benzimidazole group-bearing phosphoramide benzoazole oligonucleotides (PABAOs) that we developed recently. By circular dichroism we established that the introduction of the modifications does not disrupt the B conformation of the DNA double helix. The formation of complexes is approximated by a two-state model. Complexes of PABAOs with native oligodeoxriboynucleotides form efficiently, and the introduction of such modifications reduces thermal stability of short duplexes (8-10 bp) by â¼5°Ð¡ per modification. Using UV-spectroscopy analysis, a neutral charge of the phosphate residue modified by the N-benzimidazole moiety in the pH range of 3-9.5 was found. The results confirm possible usefulness of PABAOs for both basic research and biomedical applications.
Subject(s)
Oligonucleotides , Phosphoramides , Oligonucleotides/chemistry , Nucleic Acid Denaturation , DNA/chemistry , Nucleic Acid Hybridization , Nucleic Acid Conformation , Thermodynamics , Circular DichroismABSTRACT
The triple molybdates K3-xNa1+xM4(MoO4)6 (M = Ni, Mg, Co) and K3+xLi1-xMg4(MoO4)6 were found upon studying the corresponding ternary molybdate systems, and their structures, thermal stability and electrical conductiviplusmnty were investigated. The compounds crystallize in the space group R3c and are isostructural with the sodium-ion conductor II-Na3Fe2(AsO4)3 and yurmarinite, Na7(Fe3+, Mg, Cu)4(AsO4)6; their basic structural units are flat polyhedral clusters of the central M1O6 octahedron sharing edges with three surrounding M2O6 octahedra, which combine with single NaO6 octahedra and bridging MoO4 tetrahedra to form open three-dimensional (3D) frameworks where the cavities are partially occupied by disordered potassium (sodium) ions. The split alkali-ion positions in K3-xNa1+xM4(MoO4)6 (M = Ni, Mg, Co) give their structural formulae as [(K,Na)0.5â¡0.5)]6(Na)[M1][M2]3(MoO4)6, whereas the lithium-containing compound (K0.5â¡0.5)6(Mg0.89K0.11)(Li0.89Mg0.11)Mg3(MoO4)6 shows an unexpected (Mg, K) isomorphism, which is similar to (Mn, K) and (Co, K) substitutions in isostructural K3+xLi1-xM4(MoO4)6 (M = Mn, Co). The crystal chemistry of the title compounds and related arsenates, phosphates and molybdates was considered, and the connections of the cationic distributions with potential 3D ionic conductivity were shown by means of calculating the bond valence sum (BVS) maps for the Na+, Li+ and K+ ions. Electrical conductivity measurements gave relatively low values for the triple molybdates [σ = 4.8 × 10-6â Sâ cm-1 at 390°C for K3NaCo4(MoO4)6 and 5 × 10-7â Sâ cm-1 at 400°C for K3LiMg4(MoO4)6] compared with II-Na3Fe2(AsO4)3 (σ = 8.3 × 10-4â Sâ cm-1 at 300°C). This may be explained by a low concentration of sodium or lithium ions and the blocking of their transport by large potassium ions.