[en] Attachment of a photoreactive RuII complex to a guanine-containing oligonucleotide has led to an innovative biomolecular tool for gene silencing studies. This conjugate can be selectively photo-cross-linked with its complementary strand but undergoes a se
Disciplines :
Chemistry
Author, co-author :
Le Gac, Stéphane
Rickling, S.
Gerbaux, Pascal ; Université de Mons > Faculté des Sciences > Synthèse et spectrométrie de masse organiques
Defrancq, Eric
Moucheron, Cécile
Kirsch - De Mesmaeker, Andrée
Language :
English
Title :
Photoreactive Ru(II) complex tethered to a guanine-containing oligonucleotide : a biomolecular tool that behaves as a Seppuku molecule
Publication date :
01 January 2009
Journal title :
Angewandte Chemie International Edition
ISSN :
1433-7851
Publisher :
Wiley, Weinheim, Germany
Volume :
48
Issue :
6
Pages :
1122-1125
Peer reviewed :
Peer Reviewed verified by ORBi
Research unit :
S836 - Synthèse et spectrométrie de masse organiques
Commentary :
Publié en ligne le 30 décembre 2008
Lecture en ligne: http://onlinelibrary.wiley.com/doi/10.1002/anie.200804503/pdf
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b) O. Lentzen, J.-F. Constant, E. Defrancq, M. Prévost, S. Schumm, C. Moucheron, P. Dumy, A. Kirsch-De Mesmaeker, ChemBioChem 2003, 4, 195-202;
c) S. Schumm, M. Prévost, D. Garcia-Fresnadillo, O. Lentzen, C. Moucheron, A. Kirsch-De Mesmaeker, J. Phys. Chem. B 2002, 106, 2763-2768.
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[Ru(tap)2phen″]2+, [Ru(phen) 2phen″]2+, and the Ru-ODN conjugates were prepared and purified according to previously reported procedures: M. Villien, S. Deroo, E. Gicquel, E. Defrancq, C. Moucheron, A. Kirsch-De Mesmaeker, P. Dumy, Tetrahedron 2007, 63, 11299-11306. These compounds have been characterized by mass spectrometry (see the Supporting Information).
The position of the guanine base in the sequence of Ru(T)-ODN (G) was chosen such as not being directly accessible by the metal complex without a folding of the strand.
In these cases, the presence of long-lived components, that is, longer than τ0, indicates a protection of the excited state from the aqueous phase, which suggests that the Ru-ODN adopts a secondary structure, see: D. García-Fresnadillo, O. Lentzen, I. Ortmans, E. Defrancq, A. Kirsch-De Mesmaeker, Dalton Trans. 2005, 852-856.
B. Elias, A. Kirsch-De Mesmaeker, Coord. Chem. Rev. 2006, 250, 1627-1641.
Luminescence lifetimes and UV/Vis absorption results (see the Supporting Information) of the Ru(T)-ODN(G)/Targ1 duplex clearly confirm photo-cross-linking. Moreover, bands with the same retarded electrophoretic mobility were obtained upon illumination of duplex Ru(T)-ODN(G)/ Targ1, in which only Targ1 was 5′-end 32P-labeled.
For example, related ruthenium complexes such as [Ru-(tap) 2phen]2+ or [Ru(tap)3]2+ photoreact also with tryptophan to yield a photoadduct, see: E. Gicquel, A. Boisdenghien, E. Defrancq, C. Moucheron, A. Kirsch-De Mesmaeker, Chem. Commun. 2004, 2764-2765.
