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Assessment of adenyl residue reactivity within model nucleic acids by surface enhanced Raman spectroscopy

Identifieur interne : 000200 ( France/Extraction ); précédent : 000199; suivant : 000201

Assessment of adenyl residue reactivity within model nucleic acids by surface enhanced Raman spectroscopy

Auteurs : Lydie Grajcar [France] ; Chahrazade El Amri [France] ; Mahmoud Ghomi [France] ; Serge Fermandjian [France] ; Valerie Huteau [France] ; Richard Mandel [États-Unis] ; Sophie Lecomte [France] ; Marie-Hélène Baron [France]

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RBID : ISTEX:EF465BEF4FDDB4A099C7292CB9C1C63451BB4EAA

English descriptors

Abstract

We rank the reactivity of the adenyl residues (A) of model DNA and RNA molecules with electropositive subnano size [Ag] n+ sites as a function of nucleic acid primary sequences and secondary structures and in the presence of biological amounts of Cl− and Na+ or Mg2+ ions. In these conditions A is markedly more reactive than any other nucleic acid bases. A reactivity is higher in ribo (r) than in deoxyribo (d) species [pA > pdA and (pA)n ≫ (pdA)n]. Base pairing decreases A reactivity in corresponding duplexes but much less in r than in d. In linear single and paired dCAG or dGAC loci, base stacking inhibits A reactivity even if A is bulged or mispaired (A.A). dA tracts are highly reactive only when dilution prevents self‐association and duplex structures. In d hairpins the solvent‐exposed A residues are reactive in CAG and GAC triloops and even more in ATC loops. Among the eight rG1N2R3A4 loops, those bearing a single A (A4) are the least reactive. The solvent‐exposed A2 is reactive, but synergistic structural transitions make the initially stacked A residues of any rGNAA loop much more reactive. Mg2+ cross‐bridging single strands via phosphates may screen A reactivity. In contrast d duplexes cross‐bridging enables “A flipping” much more in rA.U pairs than in dA.T. Mg2+ promotes A reactivity in unpaired strands. For hairpins Mg2+ binding stabilizes the stems, but according to A position in the loops, A reactivity may be abolished, reduced, or enhanced. It is emphasized that not only accessibility but also local flexibility, concerted docking, and cation and anion binding control A reactivity. © 2006 Wiley Periodicals, Inc. Biopolymers 82: 6–28, 2006 This article was originally published online as an accepted preprint. The “Published Online” date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com

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DOI: 10.1002/bip.20455

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ISTEX:EF465BEF4FDDB4A099C7292CB9C1C63451BB4EAA

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<term>Adenine</term>
<term>Adenyl</term>
<term>Adenyl residue activity assessment</term>
<term>Adenyl residues</term>
<term>Average base</term>
<term>Base pairing</term>
<term>Base residues</term>
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<term>Biochemistry</term>
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<term>Electropositive</term>
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<term>Exibility</term>
<term>Exible</term>
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<term>Ggga</term>
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<term>Grajcar</term>
<term>Great variety</term>
<term>Guaa</term>
<term>Hairpin</term>
<term>Hairpin stability</term>
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<term>Hairpin structures</term>
<term>High dilution</term>
<term>High ratio</term>
<term>Hyperchromicity</term>
<term>Ipping</term>
<term>Less reactive</term>
<term>Locus</term>
<term>Loop</term>
<term>Lower concentration</term>
<term>Mgcl2</term>
<term>Mgcl2 medium</term>
<term>Mismatch</term>
<term>Mispairing</term>
<term>Moiety</term>
<term>More reactive</term>
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<term>Nacl medium</term>
<term>Nucleic</term>
<term>Nucleic acid</term>
<term>Nucleic acids</term>
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<term>Plasmon spectra</term>
<term>Polymer</term>
<term>Proc natl acad</term>
<term>Racc</term>
<term>Raman</term>
<term>Raman spectrosc</term>
<term>Reactive</term>
<term>Reactivity</term>
<term>Residue</term>
<term>Rgnra loops</term>
<term>Same concentration</term>
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<term>Sers</term>
<term>Silver aggregates</term>
<term>Silver particles</term>
<term>Silver plasmon spectra</term>
<term>Steric hindrance</term>
<term>Struct</term>
<term>Structural stability</term>
<term>Studies show</term>
<term>Triloops</term>
<term>Universite paris</term>
<term>Water molecules</term>
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<div type="abstract" xml:lang="en">We rank the reactivity of the adenyl residues (A) of model DNA and RNA molecules with electropositive subnano size [Ag] n+ sites as a function of nucleic acid primary sequences and secondary structures and in the presence of biological amounts of Cl− and Na+ or Mg2+ ions. In these conditions A is markedly more reactive than any other nucleic acid bases. A reactivity is higher in ribo (r) than in deoxyribo (d) species [pA > pdA and (pA)n ≫ (pdA)n]. Base pairing decreases A reactivity in corresponding duplexes but much less in r than in d. In linear single and paired dCAG or dGAC loci, base stacking inhibits A reactivity even if A is bulged or mispaired (A.A). dA tracts are highly reactive only when dilution prevents self‐association and duplex structures. In d hairpins the solvent‐exposed A residues are reactive in CAG and GAC triloops and even more in ATC loops. Among the eight rG1N2R3A4 loops, those bearing a single A (A4) are the least reactive. The solvent‐exposed A2 is reactive, but synergistic structural transitions make the initially stacked A residues of any rGNAA loop much more reactive. Mg2+ cross‐bridging single strands via phosphates may screen A reactivity. In contrast d duplexes cross‐bridging enables “A flipping” much more in rA.U pairs than in dA.T. Mg2+ promotes A reactivity in unpaired strands. For hairpins Mg2+ binding stabilizes the stems, but according to A position in the loops, A reactivity may be abolished, reduced, or enhanced. It is emphasized that not only accessibility but also local flexibility, concerted docking, and cation and anion binding control A reactivity. © 2006 Wiley Periodicals, Inc. Biopolymers 82: 6–28, 2006 This article was originally published online as an accepted preprint. The “Published Online” date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com</div>
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