Synthesis, Spectroscopic Properties and Electrochemical Oxidation of Ru<sup>II</sup>‐Polypyridyl Complexes Attached to a Peptide Nucleic Acid Monomer Backbone

Nickita, Nickita; Gasser, Gilles; Bond, Alan M.; Spiccia, Leone

doi:10.1002/ejic.200801259

Cited by 14 publications

(22 citation statements)

References 44 publications

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“…Nucleobases in PNA monomers were also replaced by redoxactive Ru(II) complexes with various linkers in view of the direct and specific insertion of these modified monomers in PNA sequences. 60 The preparation of hetero-bi-metallic thymine PNA monomers was reported using chemically selective reactions at two different sites of the monomer, i.e. ferrocene at the N-and a bis(triphenylphosphine)platinum(0) group at the C-terminus (3, Fig.…”

Section: Metal-containing Pnas For Biosensing Purposesmentioning

confidence: 99%

Metal-containing peptide nucleic acid conjugates

2011

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Peptide Nucleic Acids (PNAs) are non-natural DNA/RNA analogues with favourable physicochemical properties and promising applications. Discovered nearly 20 years ago, PNAs have recently re-gained quite a lot of attention. In this Perspective article, we discuss the latest advances on the preparation and utilisation of PNA monomers and oligomers containing metal complexes. These metalconjugates have found applications in various research fields such as in the sequence-specific detection of nucleic acids, in the hydrolysis of nucleic acids and peptides, as radioactive probes or as modulators of PNA˙DNA hybrid stability, and last but not least as probes for molecular and cell biology.

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Section: Metal-containing Pnas For Biosensing Purposesmentioning

confidence: 99%

Metal-containing peptide nucleic acid conjugates

2011

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“…To allow more versatility in the preparation of PNA oligomers containing multi‐metal complexes we recently proposed an alternative approach. In a manner related to that undertaken, for example, by Achim,10–13 Balasubramanian,14 Spiccia15–17 and Strömberg18,19 and their co‐workers, we envisaged the insertion of modified (metal‐containing) PNA monomers into PNAs. In our case, we successfully inserted, by using an automated oligonucleotide synthesizer, an alkyne‐containing PNA monomer (Fmoc‐1‐OH, Figure 1) into any position in a PNA sequence 20.…”

Section: Introductionmentioning

confidence: 99%

Preparation and Biological Evaluation of Di‐Hetero‐Organometallic‐Containing PNA Bioconjugates

et al. 2011

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Two peptide nucleic acid (PNA) oligomers containing two different organometallic moieties, namely derivatives of azidoferrocene (Fc-N 3 ) and ferrocene carboxylic acid (Fc-COOH) for PNA5 and derivatives of β-cymantrenoylpropionic acid [Cym-CO(CH 2 ) 2 COOH] and the rhenium bisquinoline tricarbonyl complex [Re(BQ-N 3 )(CO) 3 ]Br for PNA6, have been prepared on a solid support by using two different synthetic methods: Peptide coupling and click chemistry. PNA5 and PNA6 were unambiguously characterized by ESI-MS or MALDI-TOF MS and their purity checked by LC-MS. As expected, the bioconjugate PNA6 presents two broad and strong absorption bands at 1933 and 2032 cm -1 in its IR spectrum due to the presence of six metal-carbonyl bonds. It has

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“…The C-terminal labelling of PNA thymine monomers with (h-ethene)bis(triphenylphosphine)platimun(0) has only recently been described by our group. 28 In order to overcome this limitation, several research groups have prepared ferrocene-modified PNA monomers [16][17][18][19][20][21][22][23][24] or ruthenium-modified PNA monomers 32 with the ultimate aim of their subsequent insertion, on the solid phase, into PNA oligomers. This approach would allow the potential synthesis of multi-metal-containing PNA oligomers.…”

Section: Introductionmentioning

confidence: 99%

Thermal melting studies of alkyne- and ferrocene-containing PNA bioconjugates

2009

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The preparation of new metal-containing Peptide Nucleic Acids (PNAs) is currently a field of research intensively studied for various purposes, e.g. DNA biosensors. The role played by the metal centre, notably on the stability of the PNA.DNA hybrid, is obviously crucial, but has not yet been fully investigated. In this work, UV-Vis spectroscopic measurements of solutions of DNA.PNA hybrids, whose 11/12-mer PNA oligomers contained either one or two alkyne- (1) or ferrocene-containing (2) PNA monomers, were carried out to determine the effect of these monomers on the thermal stability of the hybrids (PNA: H-Gly-X-gggtc-Y-agctt-X-Lys-NH2 with X = 1 or and Y = 1 or 2 or blank position). Supplementary CD spectroscopic measurements were performed to gain insight into the structures of the PNA.DNA duplexes formed. The effect of both modified monomers was found to depend on their actual positions within the PNA sequences. Insertions at the N- or C-termini of a PNA oligomer did not change the melting temperatures (T(m) values of about 72 degrees C) of the DNA.PNA hybrids significantly. Insertion of monomers 1 or 2 in the middle of a PNA sequence induced a substantial decrease in the T(m) of the hybrids (by about 23 degrees C) when bound to the same DNA oligomer. Interestingly, it was found that the type of modification, namely alkyne or ferrocene, did not significantly influence the T(m) values in these cases. However, the thermal stability of hybrids with the DNA oligomers containing one to four additional thymines and the PNA oligomers containing the ferrocene moiety in its middle, varied significantly with the number of thymines added compared to its alkyne analogues (DeltaT(m) up to -13 degrees C). The presence of the ferrocene moiety induced a significant decrease in thermal stability of the hybrids, probably due to its bulkiness. In order to assess the effect of PNA backbone rigidity on the stability of DNA.PNA hybrids, PNA oligomers with an internal amino acid, propargylglycine (Pgl) or the dipeptide glycine-propargylglycine (Gly-Pgl), were synthesised. It was assumed that the orientation of the alkyne moiety in the Pgl-containing PNA sequence is not identical to an alkyne-containing PNA sequence, as a significantly higher T(m) value (DeltaT(m) = +10 degrees C) was measured. It is anticipated that the alkyne moiety in Pgl is not facing the DNA base and therefore does not disturb as much the neighbouring nucleobases and base-stacking of the complementary DNA, in contrast to the alkyne moiety of 1. Interestingly, no significant differences in the thermal stability of the hybrids was observed between Pgl-containing and dipeptide-containing PNA oligomers, although the former contracts the PNA backbone by three atoms.

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Synthesis, Spectroscopic Properties and Electrochemical Oxidation of Ru^II‐Polypyridyl Complexes Attached to a Peptide Nucleic Acid Monomer Backbone

Abstract: Keywords: Ruthenium / Peptide nucleic acids / Synthesis / Electrochemistry / Electronic and emission spectroscopy 1 H NMR spectroscopy showed that M1 and M2 are present as rotamers in a 3:1 and

Cited by 14 publications

References 44 publications

Metal-containing peptide nucleic acid conjugates

Metal-containing peptide nucleic acid conjugates

Preparation and Biological Evaluation of Di‐Hetero‐Organometallic‐Containing PNA Bioconjugates

Thermal melting studies of alkyne- and ferrocene-containing PNA bioconjugates

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Synthesis, Spectroscopic Properties and Electrochemical Oxidation of RuII‐Polypyridyl Complexes Attached to a Peptide Nucleic Acid Monomer Backbone

Abstract: Keywords: Ruthenium / Peptide nucleic acids / Synthesis / Electrochemistry / Electronic and emission spectroscopy 1 H NMR spectroscopy showed that M1 and M2 are present as rotamers in a 3:1 and

Cited by 14 publications

References 44 publications

Metal-containing peptide nucleic acid conjugates

Metal-containing peptide nucleic acid conjugates

Preparation and Biological Evaluation of Di‐Hetero‐Organometallic‐Containing PNA Bioconjugates

Thermal melting studies of alkyne- and ferrocene-containing PNA bioconjugates

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Synthesis, Spectroscopic Properties and Electrochemical Oxidation of Ru^II‐Polypyridyl Complexes Attached to a Peptide Nucleic Acid Monomer Backbone