PubMed · 6370279
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G R Lewis. 1984-04-21. Metalloceramic technique applied to partial denture construction.. https://doi.org/10.1038/sj.bdj.4805338
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The structural characteristics of Z-DNA were used to challenge the selectivity of guanine oxidation promoted by nickel and cobalt reagents. Base pairing and stacking within all helical structures studied previously had hindered access to guanine and limited its reaction. However, the Z-helix uniquely retains high exposure of guanine N7. This exposure was sufficient to direct oxidation specifically to a plasmid insert -(CG)(13)AATT(CG)(13)- that adopted a Z-conformation under native supercoiling. An alternative insert -(CG)(7)- retained its B-conformation and demonstrated the expected lack of reactivity. For a nickel salen complex made from a particularly bulky ligand, preferential reaction shifted to the junctions within the Z-DNA insert as is common for large reagents. Inactivation of the nickel reagents by high-salt concentrations prevented parallel investigations of Z-DNA, formed by oligonucleotides. However, the activity of Co(2+) was minimally affected by salt and consequently confirmed the high reactivity of 5'-p(CG)(4) in its Z-conformation. These reagents may now be applied to a broad array of targets, since their structural specificity remains predictable for both complex and helical assemblies of nucleic acids.
Nickel-dependent recognition and oxidation of guanine have been linked in part through the paramagnetic effects of nickel on the NMR of model oligonucleotide duplexes. Direct interaction between nickel and guanine N7 had originally been postulated from correlations between the efficiency of guanine oxidation and the environment surrounding its N7 position. (1)H and (31)P NMR spectra of DNA containing a single, isolated extrahelical guanine are consistent with selective binding of nickel to the N7 of this unique base over a background of nonspecific association to the phosphate backbone. The presence of a macrocyclic complex or simple salt of nickel did not detectably alter the structure of the duplex or extrahelical residue. Accordingly, nickel appeared to bind the extrahelical guanine N7 within the major groove as indicated by paramagnetic effects on the proton signals of nucleotides on the 5' but not 3' side of the nickel binding site. Similar (1)H NMR analysis of DNA containing a dynamic equilibrium of extrahelical guanine residues also suggested that the nickel complex did not affect the native distribution of structures. Oxidation of these sites by a nickel-mediated pathway consequently reflected their solvent accessibility in a general and metal-independent manner. The close proximity of the extrahelical guanines produced a composite of paramagnetic effects on each adjacent nucleotide resulting from both direct and proximal coordination of nickel.
OBJECTIVES: The aim of this study was to investigate the bond compatibility between porcelain and titanium, by using three-point bending, oxide adherence and thermal expansion tests, and to compare the results with those of a conventional NiCr alloy-porcelain system. METHODS: The three-point bending test was used and the results were evaluated according to DIN draft 13927. Fractured surfaces of the metal and porcelain were examined macroscopically. The oxide adherence test was applied to titanium and NiCr alloy with appropriate oxidation degrees. After an oxide film was formed on the specimens, tensile strength test was applied. Oxide adherence strength values were set and fractured surfaces were examined macroscopically. In the thermal expansion test, thermal expansion curves and thermal expansion coefficients of titanium, NiCr alloy and tested porcelains were determined. Differences in thermal expansion values (delta alpha) in all metal-porcelain pairs were calculated to allow inferences to be made about residual stress levels. RESULTS: The bending strengths of all groups were found to be within the acceptable standard levels. At the end of the oxide adherence test, the results indicated that the adherence of the formed oxides to the metals were at a desired level. As a result of the thermal expansion test, the titanium-porcelain and NiCr-porcelain systems showed compressive thermal stress. However, the titanium-porcelain pair exhibited large positive delta alpha values. This results is found to be above the proposed thermal compatibility. CONCLUSIONS: It was concluded that the bond compatibility between titanium and porcelain was comparable with the NiCr-porcelain system.