Publications in 2000
Author | Title | Year | Journal/Proceedings | Reftype | DOI/URL |
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Del Guerzo, A., Kirsch-De Mesmaeker, A., Demeunynck, M. and Lhomme, J. | Characterisation of bifunctional ruthenium(II) complexes, potential DNA photo-probes. Presence of folded and unfolded conformers | 2000 | J. Chem. Soc., Dalton Trans., pp. 1173-1180 | article | DOI URL |
Abstract: Novel bifunctional ruthenium(II) complexes, [Ru(TAP)2(POQ-Nmet)]2+ and [Ru(BPY)2(POQ-Nmet)]2+ (1a, 2a), containing a metallic and an organic moiety, have been prepared as photoprobes and photoreagents of DNA (TAP = 1,4,5,8-tetraazaphenanthrene, POQ-Nmet = 5-[6-(7-chloroquinolin-4-yl)-3-thia-6-azaheptanamido]-1,10-phenanthroline). The ES mass spectrometry and 1H NMR data in organic solvents indicate that the quinoline moiety exists in both the protonated and non-protonated form. Moreover, the comparison of the NMR data with those of the corresponding monofunctional complexes (without quinoline) evidences that [Ru(TAP)2(POQ-Nmet)]2+ and [Ru(BPY)2(POQ-Nmet)]2+ are unfolded when the quinoline unit is protonated whereas deprotonation permits folding of the molecule. In the folded state the spatial proximity of the electron donor (the organic moiety) and electron acceptor (the metallic moiety) in [Ru(TAP)2(POQ-Nmet)]2+ favours intramolecular photo-induced electron transfer, which has been shown in a previous study to be responsible for the very low luminescence of 1a in non-protonating solutions. The restoration of the luminescence by protonation of the quinoline moiety as observed previously is in agreement with the unfolding of the molecule demonstrated in this work. The existence of such folding-unfolding processes related to protonation is crucial for studies of 1a with DNA. | |||||
BibTeX:
@article{PUB0237, author = {Del Guerzo, Andre and Kirsch-De Mesmaeker, Andrée and Demeunynck, Martine and Lhomme, Jean}, title = {Characterisation of bifunctional ruthenium(II) complexes, potential DNA photo-probes. Presence of folded and unfolded conformers}, journal = {J. Chem. Soc., Dalton Trans.}, publisher = {The Royal Society of Chemistry}, year = {2000}, pages = {1173-1180}, url = {http://dx.doi.org/10.1039/B000197J}, doi = {http://dx.doi.org/10.1039/B000197J} } |
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Latterini, L., Pourtois, G., Moucheron, C., Lazzaroni, R., Brédas, J.-L., Kirsch-De Mesmaeker, A. and De Schryver, F.C. | STM Imaging of a Heptanuclear Ruthenium(II) Dendrimer, Mono-Add Layer on Graphite | 2000 | Chem. Eur. J. Vol. 6(8), pp. 1331-1336 |
article | DOI URL |
Abstract: Scanning tunneling microscopy (STM) and molecular mechanics calculations were used to investigate the long-range packing and the structure of an heptanuclear ruthenium (II) dendritic species, as a PF6− salt. STM imaging was carried out on a mono-add layer of the ruthenium dendrimer formed by physisorption from a 1,2,4-trichlorobenzene solution at the liquid-graphite interface. The packing of the molecules on the surface was visualised by the formation of ordered patterns and a distance of 27±2 Å was measured between two adjacent lamellae. The comparison of this dimension with the molecular-modelling data indicates that the lamellae were formed by rows of dendrimer molecules in which the counterions (PF6−) were strongly associated with the Ru atoms. The images acquired with higher spatial resolution revealed the presence of repeating units within the lamellae. The comparison of the STM images with the modelling results allowed the attribution of the repeating units observed in the imaged pattern to the STM signature of single dendrimer molecules. | |||||
BibTeX:
@article{PUB1584, author = {Latterini, Loredana and Pourtois, Geoffrey and Moucheron, Cécile and Lazzaroni, Roberto and Brédas, Jean-Luc and Kirsch-De Mesmaeker, Andrée and De Schryver, Frans C.}, title = {STM Imaging of a Heptanuclear Ruthenium(II) Dendrimer, Mono-Add Layer on Graphite}, journal = {Chem. Eur. J.}, publisher = {WILEY-VCH Verlag}, year = {2000}, volume = {6}, number = {8}, pages = {1331--1336}, url = {http://dx.doi.org/10.1002/(SICI)1521-3765(20000417)6:8<1331::AID-CHEM1331>3.0.CO;2-J}, doi = {http://dx.doi.org/10.1002/(SICI)1521-3765(20000417)6:8} } |
Publications in 2001
Author | Title | Year | Journal/Proceedings | Reftype | DOI/URL |
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Coates, C.G., Callaghan, P., McGarvey, J.J., Kelly, J.M., Jacquet, L. and Kirsch-De Mesmaeker, A. | Spectroscopic studies of structurally similar DNA-binding Ruthenium (II) complexes containing the dipyridophenazine ligand | 2001 | J. Mol. Struct. Vol. 598(1), pp. 15-25 |
article | DOI URL |
Abstract: Nanosecond transient resonance Raman and picosecond transient absorption spectroscopic investigations of the two structurally analogous Ru-polypyridyl complexes, [Ru(phen)2dppz]2+ (1) and [Ru(tap)2dppz]2+ (2), are presented (phen=1,10-phenanthroline, dppz=dipyrido [3,2-a:2′,3′-c] phenazine; tap=1,4,5,8 tetraazaphenanthrene). The findings offer insight into the differing nature of the lowest excited states of the two complexes, and describe the role of these states within the very distinct photophysical behaviour of each, both in relation to solvent response and their interaction with DNA (facilitated in each case through the intercalating dppz ligand). The active, solvent-sensitive, dppz-based 3MLCT states involved in the ‘light-switch’ behaviour of (1) are probed, alongside evidence of a progression through a precursor transient state when the complex is in non-aqueous environment. Evidence has been provided of a photophysical pathway for (2), involving formation of a tap-based lowest 3MLCT state. When (2) is bound to DNA through the dppz ligand, a photo-driven electron transfer process ensues between the guanine base of DNA and the lowest 3MLCT state. | |||||
BibTeX:
@article{PUB0228, author = {Colin G. Coates and Phillip Callaghan and John J. McGarvey and John M. Kelly and Luc Jacquet and Kirsch-De Mesmaeker, Andrée}, title = {Spectroscopic studies of structurally similar DNA-binding Ruthenium (II) complexes containing the dipyridophenazine ligand}, journal = {J. Mol. Struct.}, year = {2001}, volume = {598}, number = {1}, pages = {15-25}, url = {http://www.sciencedirect.com/science/article/pii/S0022286001008006}, doi = {http://dx.doi.org/10.1016/S0022-2860(01)00800-6} } |
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Brodkorb, A., Kirsch-De Mesmaeker, A., Rutherford, T.J. and Keene, F.R. | Stereoselective Interactions and Photo-Electron Transfers between Mononucleotides or DNA and the Stereoisomers of a HAT-Bridged Dinuclear RuII Complex (HAT = 1,4,5,8,9,12-hexaazatriphenylene) | 2001 | Eur. J. Inorg. Chem. Vol. 2001(8), pp. 2151-2160 |
article | DOI URL |
Abstract: The dinuclear complex [Ru(phen)22(μ-HAT)]4+ (phen = 1,10-phenanthroline, HAT = 1,4,5,8,9,12-hexaazatriphenylene), can exist in three different stereoisomeric forms: the meso (ΔΛ) and rac diastereoisomers, the latter of which has two enantiomeric forms, namely ΔΔ and ΛΛ. Each of the stereoisomers was studied in the presence of the mononucleotides guanosine 5′-monophosphate (GMP) and adenosine 5′-monophosphate (AMP), and deoxyguanosine (dG) at pH = 7 and 9. Absorption studies revealed the formation of ion pairs or aggregates between the complexes and the mononucleotides (GMP and AMP) and dG. The equilibrium constants for the formation of these species were higher for the meso form than for the ΔΔ and ΛΛ enantiomers. Laser flash photolysis indicated the existence of a stereoselective photo-induced electron-transfer between the guanine of GMP and the stereoisomers. Luminescence data with the purine mononucleotides also indicated the existence of an equilibrium between the free excited complex and a luminescent ion pair or an emitting aggregate between the complex and the mononucleotide. The luminescence of these species depended on the pH and on the identity of the stereoisomer. The investigated spectroscopic behaviour of the complex stereoisomers in the presence of denatured CT-DNA was also isomer-dependent, in agreement with the conclusions drawn from the data with the mononucleotides. The results of this work clearly indicate stereoselectivity of the interaction with the purine mononucleotides and denatured CT-DNA in the ground and excited state of the complex, in favour of the meso form in both cases. | |||||
BibTeX:
@article{PUB0229, author = {Brodkorb, André and Kirsch-De Mesmaeker, Andrée and Rutherford, Todd J. and Keene, F. Richard}, title = {Stereoselective Interactions and Photo-Electron Transfers between Mononucleotides or DNA and the Stereoisomers of a HAT-Bridged Dinuclear RuII Complex (HAT = 1,4,5,8,9,12-hexaazatriphenylene)}, journal = {Eur. J. Inorg. Chem.}, publisher = {WILEY-VCH Verlag GmbH}, year = {2001}, volume = {2001}, number = {8}, pages = {2151-2160}, url = {http://dx.doi.org/10.1002/1099-0682(200108)2001:8<2151::AID-EJIC2151>3.0.CO;2-M}, doi = {http://dx.doi.org/10.1002/1099-0682(200108)2001:8} } |
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Pierard, F., Guerzo, A.D., Kirsch-De Mesmaeker, A., Demeunynck, M. and Lhomme, J. | Quantitative analysis of the effect of derivatisation of [Ru(BPY)2phen]2+ with a quinoline moiety on the interaction with DNA | 2001 | Phys. Chem. Chem. Phys. Vol. 3, pp. 2911-2920 |
article | DOI URL |
Abstract: The bifunctional Ru() complex [Ru(BPY)POQ-Nmet] (), in which the metallic unit is tethered by an aliphatic chain to an organic DNA binder, was designed in order to increase the affinity toward nucleic acids. The interaction of with DNA was characterised from luminescence and absorption data and compared with the binding of its monofunctional metallic and organic analogues, [Ru(BPY)(ac)phen] () and Nmet-quinoline (). The bifunctional complex has a binding affinity one order of magnitude higher than that of each of its separated moieties. Absorption changes induced upon addition of DNA at different pH indicate protonation of the organic sub-unit upon interaction with DNA under neutral conditions. The combination of the luminescence data under steady-state and time-resolved conditions shows that the attachment of the organic unit in induces modifications of the association modes of the metallic unit, owing to the presence of the aliphatic chain which probably hinders the metallic moiety binding. The salt dependence of the binding constants was analysed in order to compare the thermodynamic parameters describing the association with DNA for each complex. This study demonstrates the interest of the derivatisation of a Ru() complex with an organic moiety ( the bifunctional ligand POQ-Nmet) for the development of high affinity DNA probes or photoreactive agents. | |||||
BibTeX:
@article{PUB0241, author = {Pierard, Frederic and Guerzo, André Del and Kirsch-De Mesmaeker, Andrée and Demeunynck, Martine and Lhomme, Jean}, title = {Quantitative analysis of the effect of derivatisation of [Ru(BPY)2phen]2+ with a quinoline moiety on the interaction with DNA}, journal = {Phys. Chem. Chem. Phys.}, publisher = {The Royal Society of Chemistry}, year = {2001}, volume = {3}, pages = {2911-2920}, url = {http://dx.doi.org/10.1039/B101298N}, doi = {http://dx.doi.org/10.1039/B101298N} } |
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van Laar, F., Vos, D.D., Pierard, F., Mesmaeker, A.K.-D., Fiermans, L. and Jacobs, P. | Generation of Singlet Molecular Oxygen from H2O2 with Molybdate-Exchanged Layered Double Hydroxides: Effects of Catalyst Composition and Reaction Conditions
[BibTeX] |
2001 | J. Catal. Vol. 197(1), pp. 139 - 150 |
article | DOI URL |
BibTeX:
@article{PUB1573, author = {F.M.P.R van Laar and D.E De Vos and F Pierard and A Kirsch-De Mesmaeker and L Fiermans and P.A Jacobs}, title = {Generation of Singlet Molecular Oxygen from H2O2 with Molybdate-Exchanged Layered Double Hydroxides: Effects of Catalyst Composition and Reaction Conditions}, journal = {J. Catal.}, year = {2001}, volume = {197}, number = {1}, pages = {139 - 150}, url = {http://www.sciencedirect.com/science/article/pii/S0021951700930707}, doi = {http://dx.doi.org/10.1006/jcat.2000.3070} } |
Publications in 2002
Author | Title | Year | Journal/Proceedings | Reftype | DOI/URL |
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Garcia-Fresnadillo, D., Boutonnet, N., Schumm, S., Moucheron, C., Kirsch-De Mesmaeker, A., Defrancq, E., Constant, J.-F. and Lhomme, J. | Luminescence Quenching of Ru-Labeled Oligonucleotides by Targeted Complementary Strands | 2002 | Biophys. J. Vol. 82(2), pp. 978-987 |
article | DOI |
Abstract: The yield of hole injection into guanines of different oligonucleotide duplexes by a photooxidizing tethered Ru(II) complex is examined by measuring the luminescence quenching of the excited complex. This yield is investigated as a function of the anchoring site of the complex (on a thymine nucleobase in the middle of the sequence or on the 5' terminal phosphate) and the number and position of the guanine bases as compared with the site of attachment of the Ru(II) compound. In contrast to other studies, the tethered complex, [Ru(tap)(2)(dip)](2+), is a non-intercalating compound and has been shown previously to produce an irreversible photocrosslinking between the two strands as the ultimate step of hole injection. The study of luminescence quenching of the anchored complex by emission intensity and lifetime measurements for the different duplexes indicates that a direct contact between the complex and the guanine nucleobase is needed for the electron transfer to take place. Moreover, for none of the sequences a clear contribution of a static quenching is evidenced independently of the two types of attachment of the [Ru(tap)(2)(dip)(2+) complex to the oligonucleoticle. A comparison of the fastest hole-injection process by electron transfer to the excited anchored [Ru(tap)(2)(dip)](2+), with the rate of the photo-electron transfer between the same complex free in solution and guanosine-5'-monophosphate, indicates that the hole injection by the anchored complex is slower by a factor of 10 at least. A bad overlap between donor and acceptor orbitals is probably the cause of this slow rate, which could be attributed to some steric hindrance induced by the complex linker. | |||||
BibTeX:
@article{PUB0060, author = {D. Garcia-Fresnadillo and N. Boutonnet and S. Schumm and C. Moucheron and Kirsch-De Mesmaeker, A. and E. Defrancq and J.-F. Constant and J. Lhomme}, title = {Luminescence Quenching of Ru-Labeled Oligonucleotides by Targeted Complementary Strands}, journal = {Biophys. J.}, year = {2002}, volume = {82}, number = {2}, pages = {978-987}, doi = {http://dx.doi.org/10.1016/S0006-3495(02)75457-X} } |
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Schumm, S., Prévost, M., García-Fresnadillo, D., Lentzen, O., Moucheron, C. and Kirsch-De Mesmaeker, A. | Influence of the Sequence Dependent Ionization Potentials of Guanines on the Luminescence Quenching of Ru-Labeled Oligonucleotides: A Theoretical and Experimental Study | 2002 | J. Phys. Chem. B Vol. 106(10), pp. 2763-2768 |
article | DOI URL |
Abstract: The luminescence quenching by electron transfer of a nonintercalating [Ru(TAP)2DIP]2+ complex, which is covalently linked to different guanine containing oligonucleotide duplexes, is compared to the sequence dependent ionization potentials of guanines as estimated from Hartree−Fock calculations on regular B-DNA by means of Koopmans theorem. From these experimental and theoretical results, it is demonstrated that the ionization potential of the guanines has a major influence on the efficiency of hole injection by the groove binding [Ru(TAP)2DIP]2+ complex in a type I photooxidation of DNA. Because the photoelectron transfer between the complex and DNA takes place on a nanosecond time scale, nanosecond molecular dynamics simulations were performed for two of the sequences in order to check for the possible influence of the dynamical fluctuations in the DNA structure on the ionization potential. IP fluctuations up to 0.5 eV were observed on a picosecond time scale along the molecular dynamics trajectories. However, these fluctuations scatter statistically around the value calculated for regular B-DNA and are thus not relevant for the slow photoelectron transfer with a nonintercalating [Ru(TAP)2DIP]2+complex. | |||||
BibTeX:
@article{PUB0075, author = {Schumm, S. and Prévost, M. and García-Fresnadillo, D. and Lentzen, O. and Moucheron, C. and Kirsch-De Mesmaeker, A.}, title = {Influence of the Sequence Dependent Ionization Potentials of Guanines on the Luminescence Quenching of Ru-Labeled Oligonucleotides: A Theoretical and Experimental Study}, journal = {J. Phys. Chem. B}, year = {2002}, volume = {106}, number = {10}, pages = {2763-2768}, url = {http://pubs.acs.org/doi/abs/10.1021/jp013185k}, doi = {http://dx.doi.org/10.1021/jp013185k} } |
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Demeunynck, M., Moucheron, C. and Kirsch-De Mesmaeker, A. | Tetrapyrido[3,2-a:2′,3′-c:3″,2″-h:2‴,3‴-j]acridine (tpac): a new extended polycyclic bis-phenanthroline ligand | 2002 | Tetrahedron Lett. Vol. 43(2), pp. 261-264 |
article | DOI URL |
Abstract: A new heptacyclic planar molecule has been synthesized in a very efficient one-pot reaction from 5-aminophenanthroline. Ru(II) mono- and dinuclear complexes based on this new bridging ligand, Tpac, have been prepared. | |||||
BibTeX:
@article{PUB0099, author = {Martine Demeunynck and Cécile Moucheron and Kirsch-De Mesmaeker, Andrée}, title = {Tetrapyrido[3,2-a:2′,3′-c:3″,2″-h:2‴,3‴-j]acridine (tpac): a new extended polycyclic bis-phenanthroline ligand}, journal = {Tetrahedron Lett.}, year = {2002}, volume = {43}, number = {2}, pages = {261-264}, url = {http://www.sciencedirect.com/science/article/pii/S0040403901021311}, doi = {http://dx.doi.org/10.1016/S0040-4039(01)02131-1} } |
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Pauly, M., Kayser, I., Schmitz, M., Dicato, M., Guerzo, A.D., Kolber, I., Moucheron, C. and Kirsch-De Mesmaeker, A. | In vitro inhibition of gene transcription by novel photo-activated polyazaaromatic ruthenium(II) complexes | 2002 | Chem. Commun., pp. 1086-1087 | article | DOI URL |
Abstract: Under visible irradiation, [Ru(TAP)2(phen)]2+(Cl−)2, [Ru(TAP)2(POQ-Nmet)]2+(Cl−)2 and [Ru(bpy)2(phen)]2+(Cl−)2 were able to dramatically reduce the in vitro transcription of a plasmid DNA template by a bacteriophage RNA polymerase. This photoactivity is related to two different mechanisms of reactivity towards DNA exhibited by these complexes under illumination. | |||||
BibTeX:
@article{PUB0511, author = {Pauly, Marc and Kayser, Isabelle and Schmitz, Martine and Dicato, Mario and Guerzo, Andre Del and Kolber, Isabelle and Moucheron, Cecile and Kirsch-De Mesmaeker, Andrée}, title = {In vitro inhibition of gene transcription by novel photo-activated polyazaaromatic ruthenium(II) complexes}, journal = {Chem. Commun.}, year = {2002}, pages = {1086-1087}, url = {http://dx.doi.org/10.1039/B202905G}, doi = {http://dx.doi.org/10.1039/B202905G} } |
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Guerzo, A.D. and Kirsch-De Mesmaeker, A. | Novel DNA Sensor for Guanine Content | 2002 | Inorg. Chem. Vol. 41(4), pp. 938-945 |
article | DOI |
Abstract: The bifunctional complex [Ru(TAP)2POQ-Nmet]2+, 1, formed with a [Ru(TAP)2Phen]2+ metallic unit linked to a quinoline moiety, and [Ru(TAP)2Phen]2+, 2, as reference, have been tested as photoprobes of DNA. Interestingly, 1 exhibits an emission enhancement of a factor of 16-17 upon binding to calf thymus DNA. Moreover, this emission is modulated by the nucleic base content of the polynucleotide. It varies by almost an order of magnitude from a polynucleotide containing 100% of G-C to a guanine-free nucleic acid where the excited-state lifetime reaches about 2 ís. The origins of these interesting properties are analyzed by comparing 1 with reference 2 in the presence of different polynucleotides. | |||||
BibTeX:
@article{PUB0607, author = {A. Del Guerzo and Kirsch-De Mesmaeker, A.}, title = {Novel DNA Sensor for Guanine Content}, journal = {Inorg. Chem.}, year = {2002}, volume = {41}, number = {4}, pages = {938-945}, doi = {http://dx.doi.org/10.1021/ic0108944} } |
Publications in 2003
Author | Title | Year | Journal/Proceedings | Reftype | DOI/URL |
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Lentzen, O., Constant, J.-F., Defrancq, E., Prévost, M., Schumm, S., Moucheron, C., Dumy, P. and Kirsch-De Mesmaeker, A. | Photocrosslinking in Ruthenium-Labelled Duplex Oligonucleotides | 2003 | ChemBioChem Vol. 4(2-3), pp. 195-202 |
article | DOI URL |
Abstract: The formation of a photoadduct between a [Ru(1,4,5,8-tetraazaphenanthrene)24,7-diphenylphenanthroline]2+complex chemically attached to a synthetic oligonucleotide, and a guanine moiety in a complementary targeted single-stranded DNA molecule was studied for ten 17-mer duplexes by denaturing gel electrophoresis. This photoadduct formation leads to photocrosslinking of the two strands. The percentage quenching of luminescence of the complex by electron transfer was compared to the resulting yield of photocrosslinked product. This yield does not only depend on the ionisation potential of the guanine bases, which are electron donors, but also on other factors, such as the position of the guanine bases as compared to the site of attachment of the complex. The photocrosslinking yield is higher when the guanine moieties are towards the 3′ end on the complementary strand as compared to the tethering site. Computer modelling results are in agreement with this preference for the 3′ side for the photoreaction. Interestingly, the photocrosslink is not alkali labile. Moreover, a type III exonuclease enzyme is blocked at the position of photocrosslinking. | |||||
BibTeX:
@article{PUB0003, author = {Lentzen, O. and Constant, J.-F. and Defrancq, E. and Prévost, M. and Schumm, S. and Moucheron, C. and Dumy, P. and Kirsch-De Mesmaeker, A.}, title = {Photocrosslinking in Ruthenium-Labelled Duplex Oligonucleotides}, journal = {ChemBioChem}, publisher = {WILEY-VCH Verlag}, year = {2003}, volume = {4}, number = {2-3}, pages = {195-202}, url = {http://dx.doi.org/10.1002/cbic.200390031}, doi = {http://dx.doi.org/10.1002/cbic.200390031} } |
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Deroo, S., Defrancq, E., Moucheron, C., Kirsch-De Mesmaeker, A. and Dumy, P. | Synthesis of an oxyamino-containing phenanthroline derivative for the efficient preparation of phenanthroline oligonucleotide oxime conjugates | 2003 | Tetrahedron Lett. Vol. 44(46), pp. 8379-8382 |
article | DOI URL |
Abstract: A phenanthroline derivative bearing an oxyamino linker was efficiently prepared from commercial 5-nitro-1,10-phenanthroline. The subsequent reaction with an oligonucleotide containing an aldehyde either at the 5′ end or the 3′ end afforded, in good yield, the phenanthroline–oligonucleotide conjugates through oxime bond formation. | |||||
BibTeX:
@article{PUB0011, author = {Stéphanie Deroo and Eric Defrancq and Cécile Moucheron and Kirsch-De Mesmaeker, Andrée and Pascal Dumy}, title = {Synthesis of an oxyamino-containing phenanthroline derivative for the efficient preparation of phenanthroline oligonucleotide oxime conjugates}, journal = {Tetrahedron Lett.}, year = {2003}, volume = {44}, number = {46}, pages = {8379-8382}, url = {http://www.sciencedirect.com/science/article/pii/S0040403903022615}, doi = {http://dx.doi.org/10.1016/j.tetlet.2003.09.128} } |
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Lentzen, O., Constant, J.-F., Defrancq, E., Moucheron, C., Dumy, P. and Kirsch-De Mesmaeker, A. | Photoadduct Leading to Crosslinking in RuII-Derivatized Oligonucleotides
[BibTeX] |
2003 | Nucleosides Nucleotides Nucleic Acids Vol. 22(5-8), pp. 1487-1489 |
article | DOI URL |
BibTeX:
@article{PUB0076, author = {Lentzen, O. and Constant, J.-F. and Defrancq, E. and Moucheron, C. and Dumy, P. and Kirsch-De Mesmaeker, A.}, title = {Photoadduct Leading to Crosslinking in RuII-Derivatized Oligonucleotides}, journal = {Nucleosides Nucleotides Nucleic Acids}, year = {2003}, volume = {22}, number = {5-8}, pages = {1487-1489}, url = {http://www.tandfonline.com/doi/abs/10.1081/NCN-120023017}, doi = {http://dx.doi.org/10.1081/NCN-120023017} } |
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Ghizdavu, L., Lentzen, O., Schumm, S., Brodkorb, A., Moucheron, C. and Kirsch-De Mesmaeker, A. | Synthesis and Characterization of Optically Active and Racemic Forms of Cyclometalated Rh(III) Complexes. An Experimental and Theoretical Emission Study | 2003 | Inorg. Chem. Vol. 42(6), pp. 1935-1944 |
article | DOI URL |
Abstract: The optically active cyclometalated Rh(III) complexes, Δ[Rh(thpy4,5p(R,R)py)2TAP]Cl, Λ[Rh(thpy4,5p(S,S)py)2TAP]Cl, and Δ[Rh(phpy4,5p(R,R)py)2TAP]Cl (where TAP = 1,4,5,8-tetraazaphenanthrene, thpy4,5p(R,R)py = (8R,10R)-2-(2‘-thienyl)-4,5-pinenopyridine and phpy4,5p(R,R)py = (8R,10R)-2-(2‘-phenyl)-4,5-pinenopyridine) have been prepared and characterized. Their photophysics has been examined in parallel with that of rac[Rh(thpy)2TAP]Cl and rac[Rh(phpy)2TAP]Cl. Their behaviors have been rationalized from results of TD-DFT calculations. The complexes with thienylpyridine (thpy) as cyclometalating ligands exhibit 3CT (from thpy to TAP) and 3LCπ-π* (centered on thpy) emissions in a solvent matrix at 77 K and one 3CT luminescence at room temperature. In contrast, with phenylpyridine (phpy), the complexes show only one 3CT emission (from phpy to TAP) at both temperatures. | |||||
BibTeX:
@article{PUB0586, author = {Ghizdavu, Liana and Lentzen, Olivier and Schumm, Stephan and Brodkorb, André and Moucheron, Cécile and Kirsch-De Mesmaeker, Andrée}, title = {Synthesis and Characterization of Optically Active and Racemic Forms of Cyclometalated Rh(III) Complexes. An Experimental and Theoretical Emission Study}, journal = {Inorg. Chem.}, year = {2003}, volume = {42}, number = {6}, pages = {1935-1944}, url = {http://PUB0s.acs.org/doi/abs/10.1021/ic020435i}, doi = {http://dx.doi.org/10.1021/ic020435i} } |
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Pourtois, G., Beljonne, D., Moucheron, C., Schumm, S., Kirsch-De Mesmaeker, A., Lazzaroni, R. and Brédas, J. | Photophysical Properties of Ruthenium(II) Polyazaaromatic Compounds: A Theoretical Insight | 2003 | J. Am. Chem. Soc. Vol. 126(2), pp. 683-692 |
article | DOI |
Abstract: Quantum-chemical methods are applied to study the nature of the excited states relevant in the photophysical processes (absorption and emission) of a series of polyazaaromatic-ligand-based ruthenium(II) complexes. The electronic and optical properties of the free polyazaaromatic ligands and their corresponding ruthenium(II) complexes are determined on the basis of correlated Hartree−Fock semiempirical approaches. While the emission of complexes containing small-size ligands, such as 1,10-phenanthroline or 2,2‘-bipyridine, arises from a manifold of metal-to-ligand charge-transfer triplet states (3MLCTs), an additional ligand-centered triplet state (3L) is identified in the triplet manifold of complexes containing a π-extended ligand such as dipyrido[3,2-a:2‘,3‘-c]phenazine, tetrapyrido[3,2-a:2‘,3‘-c:3‘ ‘,2‘ ‘-h:2‘ ‘‘,3‘ ‘‘-j]phenazine, and 1,10-phenanthrolino[5,6-b]-1,4,5,8,9,12-hexaazatriphenylene. Recent experimental data are interpreted in light of these theoretical results; namely, the origin for the abnormal solvent- and temperature-dependent emission measured in π-extended Ru complexes is revisited. | |||||
BibTeX:
@article{PUB0616, author = {G. Pourtois and D. Beljonne and C. Moucheron and S. Schumm and Kirsch-De Mesmaeker, A. and R. Lazzaroni and J.L. Brédas}, title = {Photophysical Properties of Ruthenium(II) Polyazaaromatic Compounds: A Theoretical Insight}, journal = {J. Am. Chem. Soc.}, year = {2003}, volume = {126}, number = {2}, pages = {683-692}, doi = {http://dx.doi.org/10.1021/ja034444h} } |
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Creely, C.M., Kelly, J.M., Feeney, M.M., Hudson, S., Penedo, J.C., Blau, W.J., Elias, B., Kirsch-De Mesmaeker, A., Matousek, P., Towrie, M., Parker, A.W., Dyer, J.S., George, M.W., Coates, C.G. and McGarvey, J.J. | Ultrafast transient absorption studies of ruthenium and rhenium dipyridophenazine complexes bound to DNA and polynucleotides | 2003 | Proc. SPIE Vol. 4876, pp. 92-102 |
article | DOI URL |
Abstract: We report on ultrafast pump and probe studies of biological systems, in the form of polynucleotide and calf thymus DNA complexes. Molecules for study are bound to the polynucleotides and probed in the visible region to observe changes in the absorption over time. Various dipyridophenazine metal complexes are studied alone and complexed with DNA or synthetic polynucleotides to investigate changes occurring in their excited states upon interacting with nucleobases. Transient absorption measurements are performed pumping at 400nm and probing from 450-700nm with pulse duration of 400fs. | |||||
BibTeX:
@article{PUB1583, author = {Creely, Caitriona M. and Kelly, John M. and Feeney, M. M. and Hudson, S. and Penedo, J. C. and Blau, Werner J. and Elias, B. and Kirsch-De Mesmaeker, Andree and Matousek, P. and Towrie, M. and Parker, A. W. and Dyer, J. S. and George, Mikhael W. and Coates, C. G. and McGarvey, John J.}, title = {Ultrafast transient absorption studies of ruthenium and rhenium dipyridophenazine complexes bound to DNA and polynucleotides}, journal = {Proc. SPIE}, year = {2003}, volume = {4876}, pages = {92-102}, url = { http://dx.doi.org/10.1117/12.463625}, doi = {http://dx.doi.org/10.1117/12.463625} } |
Publications in 2004
Author | Title | Year | Journal/Proceedings | Reftype | DOI/URL |
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Lentzen, O., Defrancq, E., Constant, J.-F., Schumm, S., García-Fresnadillo, D., Moucheron, C., Dumy, P. and Kirsch-De Mesmaeker, A. | Determination of DNA guanine sites forming photo-adducts with Ru(II)-labeled oligonucleotides; DNA polymerase inhibition by the resulting photo-crosslinking | 2004 | J. Biol. Inorg. Chem. Vol. 9, pp. 100-108 |
article | URL |
Abstract: The influence of the distance between the anchoring site of the tethered [Ru(TAP) 2 dip] 2+ complex (TAP=1,4,5,8-tetraazaphenanthrene; dip=4,7-diphenyl-1,10-phenanthroline) on a probe sequence and the guanines of the complementary target strand was studied by (1) the luminescence quenching of the complex (by electron transfer) and (2) the oligodeoxyribonucleotide adduct (ODN adduct) formation which results in photo-crosslinking of the two strands. Moving the guanine moieties away from the complex induces an important decrease of the efficiency of both processes, but clearly affects the ODN adduct formation more specifically than the quenching process. From these results, we determined the positions of the guanine bases in the duplex ODN that are able to form a photo-adduct with the tethered complex. We also examined the possible competition between a long-range hole migration in the duplex ODN and the formation of a photo-adduct by using a sequence labeled with the complex at the 5′-phosphate end. Such a hole migration appears to be inefficient as compared to the ODN adduct formation. Finally, we studied the influence of the photo-crosslinking on the function of two different DNA polymerases. A 17-mer Ru(II)-labeled ODN was hybridized to its complementary sequence located on the 5′-side of a 40-mer matrix. After illumination, the elongation of a 13-mer DNA primer hybridized to the 3′-extremity of the same matrix was stopped at a position corresponding to the formation of the ODN adduct. | |||||
BibTeX:
@article{PUB0004, author = {Lentzen, Olivier and Defrancq, Eric and Constant, Jean-François and Schumm, Stephan and García-Fresnadillo, David and Moucheron, Cécile and Dumy, Pascal and Kirsch-De Mesmaeker, Andrée}, title = {Determination of DNA guanine sites forming photo-adducts with Ru(II)-labeled oligonucleotides; DNA polymerase inhibition by the resulting photo-crosslinking}, journal = {J. Biol. Inorg. Chem.}, publisher = {Springer Berlin / Heidelberg}, year = {2004}, volume = {9}, pages = {100-108}, url = {http://dx.doi.org/10.1007/s00775-003-0502-3} } |
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Blasius, R., Moucheron, C. and Kirsch-De Mesmaeker, A. | Photoadducts of Metallic Compounds with Nucleic Acids − Role Played by the Photoelectron Transfer Process and by the TAP and HAT Ligands in the RuII Complexes | 2004 | Eur. J. Inorg. Chem. Vol. 2004(20), pp. 3971-3979 |
article | DOI URL |
Abstract: The properties that are characteristic of TAP (1,4,5,8-tetraazaphenanthrene) and HAT (1,4,5,8,9,12-hexaazatriphenylene) RuII complexes under illumination are highlighted and compared with those of other metallic complexes. In particular, the photo-oxidizing power of their 3MLCT states leads to a quenching of luminescence accompanied by a photoreaction when they are in presence of nucleic acids. The proton-coupled photoinduced electron transfer with the guanine nucleobases produces metallic adducts on DNA guanine units. The mechanism of formation, structure, and possible applications of these photoadducts are discussed and compared with other DNA metallic adducts currently in the literature. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) | |||||
BibTeX:
@article{PUB0005, author = {Blasius, Romain and Moucheron, Cécile and Kirsch-De Mesmaeker, Andrée}, title = {Photoadducts of Metallic Compounds with Nucleic Acids − Role Played by the Photoelectron Transfer Process and by the TAP and HAT Ligands in the RuII Complexes}, journal = {Eur. J. Inorg. Chem.}, publisher = {WILEY-VCH Verlag}, year = {2004}, volume = {2004}, number = {20}, pages = {3971-3979}, url = {http://dx.doi.org/10.1002/ejic.200400489}, doi = {http://dx.doi.org/10.1002/ejic.200400489} } |
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Gicquel, E., Boisdenghien, A., Defrancq, E., Moucheron, C. and Kirsch-De Mesmaeker, A. | Adduct formation by photo-induced electron transfer between photo-oxidising Ru(ii) complexes and tryptophan | 2004 | Chem. Commun., pp. 2764-2765 | article | DOI URL |
Abstract: The MLCT excited state of Ru() complexes with 1,4,5,8-tetraazaphenanthrene (TAP) ligands in the presence of tryptophan gives rise to an electron transfer process from the amino acid with subsequent formation of an adduct between the two partners, strongly influenced by oxygen. | |||||
BibTeX:
@article{PUB0026, author = {Gicquel, Etienne and Boisdenghien, Arnaud and Defrancq, Eric and Moucheron, Cecile and Kirsch-De Mesmaeker, Andrée}, title = {Adduct formation by photo-induced electron transfer between photo-oxidising Ru(ii) complexes and tryptophan}, journal = {Chem. Commun.}, publisher = {The Royal Society of Chemistry}, year = {2004}, pages = {2764-2765}, url = {http://dx.doi.org/10.1039/B411686K}, doi = {http://dx.doi.org/10.1039/B411686K} } |
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Ortmans, I., Elias, B., Kelly, J.M., Moucheron, C. and Kirsch-De Mesmaeker, A. | [Ru(TAP)2 (dppz)]2+: a DNA intercalating complex, which luminesces strongly in water and undergoes photo-induced proton-coupled electron transfer with guanosine-5'-monophosphate | 2004 | Dalton Trans., pp. 668-676 | article | DOI URL |
Abstract: The lowest excited state of [Ru(TAP)2(dppz)]2+ (TAP = 1,4,5,8-tetraazaphenanthrene, dppz = dipyrido[3,2-a:2[prime or minute],3[prime or minute]-c]phenazine) 1 is strongly luminescent, even in water, and very oxidizing. Therefore it is able to oxidise not only guanosine-5[prime or minute]-monophosphate (GMP), as demonstrated by laser flash photolysis, but also guanine-containing polynucleotides such as calf thymus DNA and [poly(dG-dC)]2. The luminescence quenching was found to be faster in H2O than in D2O, as is the back reaction, indicating that both processes probably proceed by proton-coupled electron transfer. These properties, that are controlled by the triplet MLCT state in which the charge has been transferred from the Ru to a TAP ligand, contrast with those of the well known [Ru(phen)2(dppz)]2+2. | |||||
BibTeX:
@article{PUB0047, author = {Ortmans, Isabelle and Elias, Benjamin and Kelly, John M. and Moucheron, Cecile and Kirsch-De Mesmaeker, Andrée}, title = {[Ru(TAP)2 (dppz)]2+: a DNA intercalating complex, which luminesces strongly in water and undergoes photo-induced proton-coupled electron transfer with guanosine-5'-monophosphate}, journal = {Dalton Trans.}, publisher = {The Royal Society of Chemistry}, year = {2004}, pages = {668-676}, url = {http://dx.doi.org/10.1039/B313213G}, doi = {http://dx.doi.org/10.1039/B313213G} } |
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Pourtois, G., Beljonne, D., Moucheron, C., Schumm, S., Kirsch-De Mesmaeker, A., Lazzaroni, R. and Brédas, J.-L. | Photophysical Properties of Ruthenium(II) Polyazaaromatic Compounds: A Theoretical Insight | 2004 | J. Am. Chem. Soc. Vol. 126(2), pp. 683-692 |
article | DOI URL |
Abstract: Quantum-chemical methods are applied to study the nature of the excited states relevant in the photophysical processes (absorption and emission) of a series of polyazaaromatic-ligand-based ruthenium(II) complexes. The electronic and optical properties of the free polyazaaromatic ligands and their corresponding ruthenium(II) complexes are determined on the basis of correlated Hartree−Fock semiempirical approaches. While the emission of complexes containing small-size ligands, such as 1,10-phenanthroline or 2,2‘-bipyridine, arises from a manifold of metal-to-ligand charge-transfer triplet states (3MLCTs), an additional ligand-centered triplet state (3L) is identified in the triplet manifold of complexes containing a π-extended ligand such as dipyrido[3,2-a:2‘,3‘-c]phenazine, tetrapyrido[3,2-a:2‘,3‘-c:3‘ ‘,2‘ ‘-h:2‘ ‘‘,3‘ ‘‘-j]phenazine, and 1,10-phenanthrolino[5,6-b]-1,4,5,8,9,12-hexaazatriphenylene. Recent experimental data are interpreted in light of these theoretical results; namely, the origin for the abnormal solvent- and temperature-dependent emission measured in π-extended Ru complexes is revisited. | |||||
BibTeX:
@article{PUB1570, author = {Pourtois, Geoffrey and Beljonne, David and Moucheron, Cécile and Schumm, Stephan and Kirsch-De Mesmaeker, Andrée and Lazzaroni, Roberto and Brédas, Jean-Luc}, title = {Photophysical Properties of Ruthenium(II) Polyazaaromatic Compounds: A Theoretical Insight}, journal = {J. Am. Chem. Soc.}, year = {2004}, volume = {126}, number = {2}, pages = {683-692}, note = {PMID: 14719968}, url = {http://pubs.acs.org/doi/abs/10.1021/ja034444h}, doi = {http://dx.doi.org/10.1021/ja034444h} } |
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Leveque, J., Moucheron, C., Kirsch-De Mesmaeker, A., Loiseau, F., Serroni, S., Puntoriero, F., Campagna, S., Nierengarten, H. and Van Dorsselaer, A. | A mixed-bridging ligand nonanuclear Ru(ii) dendrimer containing a tris- chelating core. Synthesis and redox properties | 2004 | Chem. Commun., pp. 878-879 | article | DOI URL |
Abstract: The first ligand-cored dendrimer based on branching Ru() centers and containing mixed polypyridine bridging ligands has been prepared; redox experiments suggest that the redox-active core is not reduced at the expected potential, probably as a consequence of shielding induced by the rigid dendritic array. | |||||
BibTeX:
@article{PUB1571, author = {Leveque, Julien and Moucheron, Cecile and Kirsch-De Mesmaeker, Andree and Loiseau, Frederique and Serroni, Scolastica and Puntoriero, Fausto and Campagna, Sebastiano and Nierengarten, Helene and Van Dorsselaer, Alain}, title = {A mixed-bridging ligand nonanuclear Ru(ii) dendrimer containing a tris- chelating core. Synthesis and redox properties}, journal = {Chem. Commun.}, publisher = {The Royal Society of Chemistry}, year = {2004}, pages = {878-879}, url = {http://dx.doi.org/10.1039/B400311J}, doi = {http://dx.doi.org/10.1039/B400311J} } |
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Bresson, C., Luhmer, M., Demeunynck, M., Mesmaeker, A.K.-D. and Pierard, F. | The diastereoisomeric forms of a mononuclear Ru(II) complex bearing a bis-phenanthroline Troger's base
[BibTeX] |
2004 | Tetrahedron Lett. Vol. 45(13), pp. 2863 - 2866 |
article | DOI URL |
BibTeX:
@article{PUB1572, author = {Carole Bresson and Michel Luhmer and Martine Demeunynck and Andrée Kirsch-De Mesmaeker and Frédéric Pierard}, title = {The diastereoisomeric forms of a mononuclear Ru(II) complex bearing a bis-phenanthroline Troger's base}, journal = {Tetrahedron Lett.}, year = {2004}, volume = {45}, number = {13}, pages = {2863 - 2866}, url = {http://www.sciencedirect.com/science/article/pii/S0040403904001923}, doi = {http://dx.doi.org/10.1016/j.tetlet.2004.01.096} } |