<sup>31</sup>P NMR characterization of terminal phosphates induced on DNA by the artificial nuclease ‘Mn-TMPyP/KHSO<sub>5</sub>’ in comparison with DNases I and II

Gasmi, Geneviève; Pasdeloup, Maurice; Pratviel, Geneviève; Pitié, Marguerite; Bernadou, Jean; Meunier, Bernard

doi:10.1093/nar/19.11.2835

Cited by 21 publications

(7 citation statements)

References 26 publications

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“…The formation of furfural, on the other hand, gives rise to strand scission as shown in Scheme 2. It is commonly known that the glycoside bond is substantially weakened due to the formation of a ribono-lactone, an intermediate leading to 5-MF, and the oxidized G (24)(25)(26)(27)(28)(29)(30)(31)(32)(33). Treatment with piperidine generates the base labile scission due to the weakening of the glycoside bond which we have observed in our polyacrylamide gels.…”

Section: Discussionsupporting

confidence: 53%

Oxidative damage of DNA by chromium(V) complexes: relative importance of base versus sugar oxidation

Bose¹,

Moghaddas²,

Mazzer³

et al. 1999

Nucleic Acids Research

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Chromium(V)-mediated oxidative damage of deoxy-ribonucleic acids was investigated at neutral pH in aqueous solution by utilizing bis(2-ethyl-2-hydroxy-butanato)oxochromate(V) (I) and bis(hydroxyethyl)-amino-tris(hydroxymethyl)methane)oxochromate(V) (II). Single-stranded and double-stranded (ds) calf thymus and human placenta DNA, as well as two oligomers, 5'-GATCTAGTAGGAGGACAAATAGTGTTTG-3' and 5'-GATCCAAGCAAACACTATTTGTCCTCCTACTA-3', were reacted with the chromium(V) complexes. Most products were separated and characterized by chroma-tographic and spectroscopic methods. Polyacrylamide gel electrophoresis experiments reveal more damage at G sites in comparison to other bases. Three primary oxidation products, 5-methylene-2-furanone (5-MF), furfural and 8-oxo-2'-deoxyguanosine, were characterized. A minor product, which appears to be thymine propenal, was also observed. The dsDNA produces more furfural than furanone. The formation of these two products resulted from hydrogen ion or hydride transfer from C1' and C5' positions of the ribose to the oxo-chromium(V) center. Since no enhancements of these products (except propenal) were observed in the presence of oxygen, mechanisms pertaining to the participation of activated oxygen species may be ruled out. The oxidation of the G base is most likely associated with an oxygen atom transfer from the oxo-metallates to the double bond between C8 and N7 of the purine ring. The formation of the propenal may be associated with an oxygen-activated species, since a marginal enhancement of this product was observed in the presence of oxygen. The formation of furfural in higher abundance over 5-MF for dsDNA was attributed to the ease of hydrogen ion (or hydride transfer) from the C5' compared to C1' position of the ribose within a Cr(V)-DNA intermediate in which the metal center is bound to the phosphate diester moiety.

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Section: Discussionsupporting

confidence: 53%

Oxidative damage of DNA by chromium(V) complexes: relative importance of base versus sugar oxidation

Bose¹,

Moghaddas²,

Mazzer³

et al. 1999

Nucleic Acids Research

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“…Oxochromium(V) complexes efficiently cleave ss-DNA predominantly through oxidation of deoxyribose, since 5-MF, an oxidation product of the sugar, was formed in this reaction (8)(9)(10)(28)(29)(30)(31)(32)(33)(34)(35)(36)(37)(38). Oxidation of DNA is accompanied by release of the four bases.…”

Section: Discussionmentioning

confidence: 99%

“…Unfortunately, these oxidized guanine products readily decompose in piperidine (50). Piperidine also accelerates decomposition of the α,β-unsaturated lactone (8)(9)(10)(28)(29)(30), an intermediate formed by hydrogen abstraction at the C1′ position, followed by the first β-elimination reaction. Currently we are using a variety of enzymatic digestion methods to assess the relative contribution of guanine base oxidation (Moghaddas and Bose, work in progress).…”

Section: Discussionmentioning

confidence: 99%

Mechanisms of DNA damage by chromium(V) carcinogens

Bose

Fonkeng

Moghaddas

et al. 1998

Nucleic Acids Research

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Reactions of bis(2-ethyl-2-hydroxy-butanato)oxochromate(V) with pUC19 DNA, single-stranded calf thymus DNA (ss-ctDNA), a synthetic oligonucleotide, 5'-GATCTATGGACTTACTTCAAGGCCGGGTAATGCTA-3' (35mer), deoxyguanosine and guanine were carried out in Bis-Tris buffer at pH 7.0. The plasmid DNA was only nicked, whereas the single-stranded DNA suffered extensive damage due to oxidation of the ribose moiety. The primary oxidation product was characterized as 5-methylene-2-furanone. Although all four bases (A, C, G and T) were released during the oxidation process, the concentration of guanine exceeds the other three. Orthophosphate and 3'-phosphates were also detected in this reaction. Likewise, the synthetic oliogomer exhibits cleavage at all bases with a higher frequecncy at G sites. This increased cleavage at G sites was more apparent after treating the primary oxidation products with piperidine, which may indicate base oxidation as well. DNA oxidation is shown to proceed through a Cr(V)-DNA intermediate in which chromium(V) is coordinated through the phosphodiester moiety. Two alternative mechanisms for DNA oxidation by oxochromate(V) are proposed to account for formation of 5-methylene-2-furanone, based on hydrogen abstraction or hydride transfer from the C1' site of the ribose followed by hydration and two successive beta-eliminations. It appears that phosphate coordination is a prerequisite for DNA oxidation, since no reactions between chromium(V) and deoxyguanosine or guanine were observed. Two other additional pathways, hydrogen abstraction from C4' and guanine base oxidation, are also discussed.

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“…Also, the temperature dependence of the compound's cleavage specificity suggests that it may be a probe for low-melting regions of DNA (Raner et al, 1988(Raner et al, , 1989. A detailed study by Bernadou and Meunier and their coworkers (Pratviel et al, 1991;Gasmi et al, 1991;Pitie et al, 1992) showed that MnTMPyP cleaves DNA from its minor grove. For calf thymus DNA, the activated oxo species attacks Cl'-H, which is located deep within the minor groove.…”

mentioning

confidence: 99%

Interaction of cationic porphyrins with DNA

Sehlstedt¹,

Kim²,

Carter³

et al. 1994

Biochemistry

197

133

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Utilizing linear dichroism (LD), circular dichroism (CD), and fluorescence energy transfer, the binding geometries of a series of Co(3+)-porphyrins and their free ligands were examined. The compounds studied were Co-meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (CoTMPyP) and its free ligand (H2-TMPyP), Co-meso-tetrakis(N-n-butylpyridinium-4-yl)porphyrin (CoTBPyP) and its free ligand (H2TBPyP), and Co-meso-tetrakis(N-n-octylpyridinium-4-yl)porphyrin (CoTOPyP). The two non-metalloporphyrins exhibit negative LD, having angles of roughly 75 degrees relative to the DNA helix axis. They also display negative CD and a significant contact energy transfer from the DNA bases. On the other hand, the three metalloporphyrins display orientation angles of roughly 45 degrees between the porphyrin plane and the helix axis of DNA. Furthermore, they exhibit positive CD and no contact energy transfer from DNA bases. These observations show that the metalloporphyrins are not intercalated whereas non-metalloporphyrins having four freely rotating meso-aryl groups intercalate between the base pairs of DNA. In the presence of KHSO5, the cobalt porphyrins cleave closed circular PM2 DNA in a single strand manner, i.e., a single activation event on the porphyrin leads to a break in one of the DNA strands. A kinetic analysis of the cleavage data revealed that cleavage rates are in the order CoTMPyP > CoTBPyP > CoTOPyP with the difference being due to different DNA affinities rather than differences in cleavage rate-constants. Based on these and earlier observations, the metalloporphyrins appear bound to a partially melted region of DNA.

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³¹P NMR characterization of terminal phosphates induced on DNA by the artificial nuclease ‘Mn-TMPyP/KHSO₅’ in comparison with DNases I and II

Cited by 21 publications

References 26 publications

Oxidative damage of DNA by chromium(V) complexes: relative importance of base versus sugar oxidation

Oxidative damage of DNA by chromium(V) complexes: relative importance of base versus sugar oxidation

Mechanisms of DNA damage by chromium(V) carcinogens

Interaction of cationic porphyrins with DNA

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31P NMR characterization of terminal phosphates induced on DNA by the artificial nuclease ‘Mn-TMPyP/KHSO5’ in comparison with DNases I and II

Cited by 21 publications

References 26 publications

Oxidative damage of DNA by chromium(V) complexes: relative importance of base versus sugar oxidation

Oxidative damage of DNA by chromium(V) complexes: relative importance of base versus sugar oxidation

Mechanisms of DNA damage by chromium(V) carcinogens

Interaction of cationic porphyrins with DNA

Contact Info

Product

Resources

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³¹P NMR characterization of terminal phosphates induced on DNA by the artificial nuclease ‘Mn-TMPyP/KHSO₅’ in comparison with DNases I and II