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In particular, glyco\u2013oligoamides, a family of DNA minor groove binders, with cooperative and non\u2010cooperative hydrogen\u2010bonding donor centers in the carbohydrate residues have been designed, synthesized, and studied by means of NMR spectroscopy and molecular modeling methods. Indeed, two different sugar moieties, namely, \u03b2\u2010<jats:sc>D<\/jats:sc>\u2010Man\u2010Py\u2010\u03b3\u2010Py\u2010Ind (<jats:bold>1<\/jats:bold>; Ind=indole, Man=mannose, Py=pyrrole) and \u03b2\u2010<jats:sc>D<\/jats:sc>\u2010Tal\u2010Py\u2010\u03b3\u2010Py\u2010Ind (<jats:bold>2<\/jats:bold>; Tal=talose), were chosen according to our design. These sugar molecules should present one\u2010 or two\u2010directional intramolecular hydrogen bonds. The challenge has been to study the conformation of the glyco\u2013oligoamides at low temperature in physiological media by detecting the exchangeable protons (amide NH and OH resonances) by means of NMR spectroscopic analysis. In addition, two more glyco\u2013oligoamides with non\u2010cooperative hydrogen\u2010bonding centers, that is, \u03b2\u2010<jats:sc>D<\/jats:sc>\u2010Glc\u2010Py\u2010\u03b3\u2010Py\u2010Ind (<jats:bold>3<\/jats:bold>; Glc=glucose), \u03b2\u2010<jats:sc>D<\/jats:sc>\u2010Gal\u2010Py\u2010\u03b3\u2010Py\u2010Ind (<jats:bold>4<\/jats:bold>; Gal=galactose), and the model compounds \u03b2\u2010<jats:sc>D<\/jats:sc>\u2010Man\u2010Py\u2010NHAc (<jats:bold>5<\/jats:bold>) and \u03b2\u2010<jats:sc>D<\/jats:sc>\u2010Tal\u2010Py\u2010NHAc (<jats:bold>6<\/jats:bold>) were synthesized and studied for comparison. We have demonstrated the existence of directional intramolecular hydrogen bonds in <jats:bold>1<\/jats:bold> and <jats:bold>2<\/jats:bold> in aqueous media. The unexpected differences in terms of stabilization of the intramolecular hydrogen bonds in <jats:bold>1<\/jats:bold> and <jats:bold>2<\/jats:bold> relative to <jats:bold>5<\/jats:bold> and <jats:bold>6<\/jats:bold> promoted us to evaluate the influence of CH\u2014\u03c0 interactions on the establishment of intramolecular hydrogen bonds by using computational methods. Initial binding studies of <jats:bold>1<\/jats:bold> and <jats:bold>2<\/jats:bold> with calf\u2010thymus DNA and poly(dA\u2010dT)<jats:sub>2<\/jats:sub> by NMR spectroscopic analysis and molecular dynamics simulations were also carried out. Both new sugar\u2013oligoamides are bound in the minor groove of DNA, thus keeping a stable hairpin structure, as in the free state, in which both intramolecular hydrogen\u2010bonding and CH\u2014\u03c0 interactions are present.<\/jats:p>","DOI":"10.1002\/chem.201403911","type":"journal-article","created":{"date-parts":[[2014,10,30]],"date-time":"2014-10-30T10:49:56Z","timestamp":1414666196000},"page":"17640-17652","source":"Crossref","is-referenced-by-count":10,"title":["Cooperative Hydrogen Bonding in Glyco\u2013Oligoamides: DNA Minor Groove Binders in Aqueous Media"],"prefix":"10.1002","volume":"20","author":[{"given":"M. Teresa","family":"Bl\u00e1zquez\u2010S\u00e1nchez","sequence":"first","affiliation":[]},{"given":"Filipa","family":"Marcelo","sequence":"additional","affiliation":[]},{"given":"M. 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