NMR analysis of duplex d(CGCGATCGCG)(2) modified by Lambda- and Delta-[Ru(bpy)(2)(m-GHK)]Cl-2 and DNA photocleavage study

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dc.contributor.authorMyari, A.en
dc.contributor.authorHadjiliadis, N.en
dc.contributor.authorGaroufis, A.en
dc.contributor.authorMalina, J.en
dc.contributor.authorBrabec, V.en
dc.date.accessioned2015-11-24T16:42:45Z
dc.date.available2015-11-24T16:42:45Z
dc.identifier.issn0949-8257-
dc.identifier.urihttps://olympias.lib.uoi.gr/jspui/handle/123456789/8589
dc.rightsDefault Licence-
dc.subjectru(ii)en
dc.subjectpeptideen
dc.subjectDNAen
dc.subjectnmren
dc.subjectphotocleavageen
dc.subjectminor-groove bindingen
dc.subjectnuclear magnetic-resonanceen
dc.subjectcrystal-structureen
dc.subjectenantioselective intercalationen
dc.subjecthexanucleotide d(gtcgac)(2)en
dc.subjectruthenium(ii) complexesen
dc.subjectstereospecific bindingen
dc.subjectpeptide complexesen
dc.subjectsequenceen
dc.subjecth-1-nmren
dc.titleNMR analysis of duplex d(CGCGATCGCG)(2) modified by Lambda- and Delta-[Ru(bpy)(2)(m-GHK)]Cl-2 and DNA photocleavage studyen
heal.abstractThe interaction of the diastereomeric complexes Lambda-[Ru(bpy)(2)(m-GHK)]Cl-2 and Lambda-[Ru(bpy)(2)(m-GHK)]Cl-2 (bpy is 2,2'-bipyridine, GHK is glycine-L-histidine-L-lysine) with the deoxynucleotide duplex d(5'-CGCGATCGCG)(2) was studied by means of H-1 NMR spectroscopy. At a Delta-isomer to DNA ratio of 1:1, significant shifts for the metal complex are observed, whereas there is negligible effect on the oligonucleotide protons and only one intermolecular nuclear Overhauser effect (NOE) is present at the 2D nuclear Overhauser enhancement spectroscopy spectrum. The H-1 NMR spectrum at ratio 2:1 is characterized by a slight shift for the Delta-isomer's bpy aromatic protons as well as significant shifts for the decanucleotide G(4) H1' and H '', A(5) H2, G(10) H1', T-6 NH and G(2) NH protons. Furthermore, at ratio 2:1, 11 intermolecular NOEs are observed. The majority of the NOEs involve the sugar H2' and H '' protons sited in the major groove of the decanucleotide. Increasing the Delta-isomer to d(CGCGATCGCG)(2) ratio to 5:1 results in noteworthy spectral changes. The Delta-isomer's proton shifts are reduced, whereas significant shifts are observed for the decanucleotide protons, especially the sugar protons, as well as for the exchangeable protons. Interaction is characterized by the presence of only one intermolecular NOE. Furthermore, there is significant broadening of the imino proton signals as the ratio of the Delta-isomer to DNA increases, which is attributed to the opening of the two strands of the duplex. The Delta-isomer, on the other hand, approaches the minor groove of the oligonucleotide and interacts only weakly, possibly by electrostatic interactions. Photocleavage studies were also conducted with the plasmid pUC19 and a 158-bp restriction fragment, showing that both diastereomers cleave DNA with similar efficiency, attacking mainly the guanines of the sequence probably by generating active oxygen species.en
heal.accesscampus-
heal.fullTextAvailabilityTRUE-
heal.identifier.primaryDOI 10.1007/s00775-006-0184-8-
heal.identifier.secondary<Go to ISI>://000245457700001-
heal.identifier.secondaryhttp://www.springerlink.com/content/l215416331375441/fulltext.pdf-
heal.journalNameJournal of Biological Inorganic Chemistryen
heal.journalTypepeer reviewed-
heal.languageen-
heal.publicationDate2007-
heal.publisherSpringer Verlag (Germany)en
heal.recordProviderΠανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείαςel
heal.typejournalArticle-
heal.type.elΆρθρο Περιοδικούel
heal.type.enJournal articleen

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