Electrochemiluminescent monomers for solid support syntheses of Ru(II)-PNA bioconjugates : multimodal biosensing tools with enhanced duplex stability

Joshi, Tanmaya, Barbante, Gregory J., Francis, Paul S., Hogan, Conor F., Bond, Alan M., Gasser, Gilles and Spiccia, Leone 2012, Electrochemiluminescent monomers for solid support syntheses of Ru(II)-PNA bioconjugates : multimodal biosensing tools with enhanced duplex stability, Inorganic chemistry, vol. 51, no. 5, pp. 3302-3315.

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Title Electrochemiluminescent monomers for solid support syntheses of Ru(II)-PNA bioconjugates : multimodal biosensing tools with enhanced duplex stability
Author(s) Joshi, Tanmaya
Barbante, Gregory J.
Francis, Paul S.
Hogan, Conor F.
Bond, Alan M.
Gasser, Gilles
Spiccia, Leone
Journal name Inorganic chemistry
Volume number 51
Issue number 5
Start page 3302
End page 3315
Total pages 14
Publisher American Chemical Society
Place of publication Washington, D. C.
Publication date 2012-02-16
ISSN 0020-1669
1520-510X
Keyword(s) 2,2'-Dipyridyl
base sequence
DNA
fluorenes
luminescent agents
luminescent measurements
peptide nucleic acids
phenanthrolines
phenazines
ruthenium
solid-phase synthesis techniques
Summary The feasibility of devising a solid support mediated approach to multimodal Ru(II)-peptide nucleic acid (PNA) oligomers is explored. Three Ru(II)-PNA-like monomers, [Ru(bpy)2(Cpp-L-PNA-OH)]2+ (M1), [Ru(phen)2(Cpp-L-PNA-OH)]2+ (M2), and [Ru(dppz)2(Cpp-L-PNA-OH)]2+ (M3) (bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline, dppz = dipyrido[3,2-a:2′,3′-c]phenazine, Cpp-L-PNA-OH = [2-(N-9-fluorenylmethoxycarbonyl)aminoethyl]-N-[6-(2-(pyridin-2yl)pyrimidine-4-carboxamido)hexanoyl]-glycine), have been synthesized as building blocks for Ru(II)-PNA oligomers and characterized by IR and 1H NMR spectroscopy, mass spectrometry, electrochemistry and elemental analysis. As a proof of principle, M1 was incorporated on the solid phase within the PNA sequences H-g-c-a-a-t-a-a-a-a-Lys-NH2 (PNA1) and H-P-K-K-K-R-K-V-g-c-a-a-t-a-a-a-a-lys-NH2 (PNA4) to give PNA2 (H-g-c-a-a-t-a-a-a-a-M1-lys-NH2) and PNA3 (H-P-K-K-K-R-K-V-g-c-a-a-t-a-a-a-a-M1-lys-NH2), respectively. The two Ru(II)-PNA oligomers, PNA2 and PNA3, displayed a metal to ligand charge transfer (MLCT) transition band centered around 445 nm and an emission maximum at about 680 nm following 450 nm excitation in aqueous solutions (10 mM PBS, pH 7.4). The absorption and emission response of the duplexes formed with the cDNA strand (DNA: 5′-T-T-T-T-T-T-T-A-T-T-G-C-T-T-T-3′) showed no major variations, suggesting that the electronic properties of the Ru(II) complexes are largely unaffected by hybridization. The thermal stability of the PNA·DNA duplexes, as evaluated from UV melting experiments, is enhanced compared to the corresponding nonmetalated duplexes. The melting temperature (Tm) was almost 8 °C higher for PNA2·DNA duplex, and 4 °C for PNA3·DNA duplex, with the stabilization attributed to the electrostatic interaction between the cationic residues (Ru(II) unit and positively charged lysine/arginine) and the polyanionic DNA backbone. In presence of tripropylamine (TPA) as co-reactant, PNA2, PNA3, PNA2·DNA and PNA3·DNA displayed strong electrochemiluminescence (ECL) signals even at submicromolar concentrations. Importantly, the combination of spectrochemical, thermal and ECL properties possessed by the Ru(II)-PNA sequences offer an elegant approach for the design of highly sensitive multimodal biosensing tools.
Language eng
Field of Research 030102 Electroanalytical Chemistry
Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences
HERDC Research category C1 Refereed article in a scholarly journal
Copyright notice ©2012, American Chemical Society
Persistent URL http://hdl.handle.net/10536/DRO/DU:30046881

Document type: Journal Article
Collection: School of Life and Environmental Sciences
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