Functionalized Silver-Ion-Mediated -dC/-dC Hybrid Base Pairs with Exceptional Stability: -d-5-Iodo-2-Deoxycytidine and Its Octadiynyl Derivative in Metal DNA

Autor(en): Mueller, Sebastian Lars
Zhou, Xinglong
Leonard, Peter
Korzhenko, Oxana
Daniliuc, Constantin
Seela, Frank
Stichwörter: ALPHA-OLIGODEOXYNUCLEOTIDES; anomeric hybrid base pairs; BINDING; Chemistry; Chemistry, Multidisciplinary; CRYSTAL-STRUCTURE; CYTOSINE; DNA; DUPLEX STABILITY; ENHANCED STABILITY; GLYCOSYLATION; IMPACT; NUCLEIC-ACID; nucleosides; PARALLEL; silver; X-ray structure
Erscheinungsdatum: 2019
Herausgeber: WILEY-V C H VERLAG GMBH
Journal: CHEMISTRY-A EUROPEAN JOURNAL
Volumen: 25
Ausgabe: 12
Startseite: 3077
Seitenende: 3090
Zusammenfassung: 
Silver-mediated -dC-Ag+--dC hybrid base pairs decorated with 5-iodo- or 5-octadiynyl residues are well accommodated in duplex DNA. A strong T-m increase and favorable thermodynamic data for duplex DNA were observed after addition of silver ions. The phenomenon is particularly obvious when both nucleobases of the base pairs are functionalized. Neither the position of the base pair, nor the type of 5-substituent had a negative influence. On the contrary, functionalization of conventional silver-mediated -dC-Ag+--dC homo base pairs showed a negative impact induced by the bulky substituents. To this end, cytosine modified 12-mer oligodeoxynucleotides were prepared by solid-phase synthesis employing new -anomeric 2-deoxycytidine phosphoramidites. A multigram scale synthesis was developed for 5-iodo--d-2-deoxycytidine (1) employing the direct glycosylation of cytosine with Hoffer's -d-halogenose followed by separation of anomeric DMT nucleosides. Regarding base-pair stability and functionalization silver-mediated /-dC hybrid base pairs were found to be superior to /-dC homo pairs. According to their extraordinary properties, they might find applications in DNA diagnostics, material science, or nanotechnology.
ISSN: 09476539
DOI: 10.1002/chem.201805299

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