Bioinorganic Chemistry and Redox Homeostasis
Our website :
Metals in Biology and Redox Homeostasis
A new name for our research group: METROX
CONGRATULATIONS to our former PhD students:
Jean Bouvet for his selection to the MBA « collège des ingénieurs » (jan. 2024)
Paul Demay-Drouhard, who was appointed as a CNRS researcher (section 12, ICOA Orléans) in 2023
Martha Zoumpoulaki for her selection to the MBA « collège des ingénieurs » (oct. 2021) and her recruitment at Air Liquide in 2023.
Koudedja Coulibaly, who was recruited by Air Liquide in 2021
Emilie Mathieu, who was appointed as a CNRS researcher (section 16, LCC Toulouse) in 2021
Sarah Hostachy, who was appointed as a CEAEA researcher (LCBM, Grenoble) in 2020
Our personal webpages and resumes:
Alice Balfourier (ORCID: 0000-0002-4801-1388)
Hélène Bertrand (ORCID: 0000-0002-3841-022X)
Nicolas Delsuc (ORCID: 0000-0001-5570-8311)
Clotilde Policar (ORCID: 0000-0003-0255-1650)
Christine Rampon (ORCID: 0000-0002-1444-3166)
Michel Volovitch (ORCID: 0000-0002-7488-764X)
Sophie Vriz
Some news about our work:
About our work and equity in science (in French): https://www.youtube.com/watch?v=ZfyFIkh_G4k
https://www.inc.cnrs.fr/fr/cnrsinfo/des-complexes-bio-inspires-dans-le-vent
https://www.ens.psl.eu/actualites/des-catalyseurs-bio-inspires-pour-lutter-contre-le-stress-oxydant
Publications of the group:
((Go back to the publication page of the ens-bic website))
2014 |
From IR-Spectromicroscopy using AFM-IR and SR-FTIR to Bimodal Spectromicroscopy using SCoMPIs - Single Core Multimodal Probe for Imaging Article de journal C Policar; C Sylvain; F Lambert; N Delsuc; C Sandt; P Dumas; M Refregiers; M Plamont; A Vessieres; Z Gueroui; A Dazzi Journal of Biological Inorganic Chemistry, 19 , p. S182-S182, 2014, ISSN: 0949-8257. @article{RN23c, title = {From IR-Spectromicroscopy using AFM-IR and SR-FTIR to Bimodal Spectromicroscopy using SCoMPIs - Single Core Multimodal Probe for Imaging}, author = {C Policar and C Sylvain and F Lambert and N Delsuc and C Sandt and P Dumas and M Refregiers and M Plamont and A Vessieres and Z Gueroui and A Dazzi}, url = {<Go to ISI>://WOS:000332835300124}, issn = {0949-8257}, year = {2014}, date = {2014-01-01}, journal = {Journal of Biological Inorganic Chemistry}, volume = {19}, pages = {S182-S182}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
How to Control Proteins with Light in Living Systems Article de journal Arnaud Gautier; Carole Gauron; Michel Volovitch; David Bensimon; Ludovic Jullien; Sophie Vriz Nature Chemical Biology, 10 , p. 533, 2014. @article{RN42, title = {How to Control Proteins with Light in Living Systems}, author = {Arnaud Gautier and Carole Gauron and Michel Volovitch and David Bensimon and Ludovic Jullien and Sophie Vriz}, doi = {10.1038/nchembio.1534}, year = {2014}, date = {2014-01-01}, journal = {Nature Chemical Biology}, volume = {10}, pages = {533}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Anti-oxidant Mn-complexes: evaluation in cellular models of oxidative stress Article de journal Clotilde Policar; Anne-Sophie Bernard; Nicolas Delsuc; Geraldine Gazzah; Manon Guille; Frederic Lemaitre; Christian Amatore; Maria Bachelet; Joelle Masliah Journal of Biological Inorganic Chemistry, 19 , p. S739-S740, 2014, (Times Cited: 0 2 12th European Biological Inorganic Chemistry Conference (EuroBIC) Aug 24-28, 2014 Zurich, SWITZERLAND Univ Zurich). @article{, title = {Anti-oxidant Mn-complexes: evaluation in cellular models of oxidative stress}, author = {Clotilde Policar and Anne-Sophie Bernard and Nicolas Delsuc and Geraldine Gazzah and Manon Guille and Frederic Lemaitre and Christian Amatore and Maria Bachelet and Joelle Masliah}, year = {2014}, date = {2014-01-01}, journal = {Journal of Biological Inorganic Chemistry}, volume = {19}, pages = {S739-S740}, note = {Times Cited: 0 2 12th European Biological Inorganic Chemistry Conference (EuroBIC) Aug 24-28, 2014 Zurich, SWITZERLAND Univ Zurich}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
2013 |
Synthesis, Properties, and Remarkable 2 D Self-Assembly at the Liquid/Solid Interface of a Series of Triskele-Shaped 5,11,17-Triazatrinaphthylenes (TrisK) Article de journal Hélène Bertrand; Régis Guillot; Marie-Paule Teulade-Fichou; Denis Fichou Chemistry – A European Journal, 19 (43), p. 14654–14664, 2013, ISSN: 0947-6539. @article{Bertrand2013, title = {Synthesis, Properties, and Remarkable 2 D Self-Assembly at the Liquid/Solid Interface of a Series of Triskele-Shaped 5,11,17-Triazatrinaphthylenes (TrisK)}, author = {H\'{e}l{\`{e}}ne Bertrand and R\'{e}gis Guillot and Marie-Paule Teulade-Fichou and Denis Fichou}, url = {https://doi.org/10.1002/chem.201300705}, doi = {10.1002/chem.201300705}, issn = {0947-6539}, year = {2013}, date = {2013-10-01}, journal = {Chemistry \textendash A European Journal}, volume = {19}, number = {43}, pages = {14654--14664}, publisher = {John Wiley & Sons, Ltd}, abstract = {Abstract A series of 5,11,17-triazatrinaphthylene (TrisK) derivatives, large disk-like $pi$-conjugated molecules with C3h symmetry, has been synthesised by following an optimised synthetic pathway. The synthesis was performed by a four-step protocol based on the N-arylation of 1,3,5-tribromobenzene with appropriate anthranilate derivatives. This strategy permits the generation of either chlorinated (TrisK-Cl-OCn) or non-chlorinated (TrisK-H-OCn) alkoxy-substituted derivatives (OCnH2n+1 with n=3, 10, 12 and 16), thus providing additional versatility in the control of the structure?property relationships. The electronic properties of the various TrisK compounds have been characterised in solution by absorption and emission spectroscopies as well as cyclic voltammetry. The crystal structure of 2,8,14-propyloxy-5,11,17-triazatrinaphthylene TrisK-H-OC3 has been determined by X-ray diffraction analysis, which revealed the presence of stabilising weak intermolecular H bonds. Scanning tunnelling microscopy (STM) at the liquid/solid interface has revealed the remarkable 2D self-assembling properties of the TrisK compounds. In particular, it has shown that TrisK-H-OC12 forms three concomitant self-organised 2D phases with different row-packing arrangements. This 2D polymorphism arises from slow ordering due to the presence of three long dodecyloxy chains on the molecular backbone. Individual molecules can be imaged with spectacular intramolecular resolution, thus providing the possibility of correlating the STM features with the calculated charge density distribution.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Abstract A series of 5,11,17-triazatrinaphthylene (TrisK) derivatives, large disk-like $pi$-conjugated molecules with C3h symmetry, has been synthesised by following an optimised synthetic pathway. The synthesis was performed by a four-step protocol based on the N-arylation of 1,3,5-tribromobenzene with appropriate anthranilate derivatives. This strategy permits the generation of either chlorinated (TrisK-Cl-OCn) or non-chlorinated (TrisK-H-OCn) alkoxy-substituted derivatives (OCnH2n+1 with n=3, 10, 12 and 16), thus providing additional versatility in the control of the structure?property relationships. The electronic properties of the various TrisK compounds have been characterised in solution by absorption and emission spectroscopies as well as cyclic voltammetry. The crystal structure of 2,8,14-propyloxy-5,11,17-triazatrinaphthylene TrisK-H-OC3 has been determined by X-ray diffraction analysis, which revealed the presence of stabilising weak intermolecular H bonds. Scanning tunnelling microscopy (STM) at the liquid/solid interface has revealed the remarkable 2D self-assembling properties of the TrisK compounds. In particular, it has shown that TrisK-H-OC12 forms three concomitant self-organised 2D phases with different row-packing arrangements. This 2D polymorphism arises from slow ordering due to the presence of three long dodecyloxy chains on the molecular backbone. Individual molecules can be imaged with spectacular intramolecular resolution, thus providing the possibility of correlating the STM features with the calculated charge density distribution. |
Toward optimal spatial and spectral quality in widefield infrared spectromicroscopy of IR labelled single cells Article de journal E C Mattson; M Unger; S Clède; F Lambert; C Policar; A Imtiaz; R D'Souza; C J Hirschmugl Analyst, 138 (19), p. 5610–5618, 2013. @article{Mattson:2013, title = {Toward optimal spatial and spectral quality in widefield infrared spectromicroscopy of IR labelled single cells}, author = {E C Mattson and M Unger and S Cl\`{e}de and F Lambert and C Policar and A Imtiaz and R D'Souza and C J Hirschmugl}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84883213711&doi=10.1039%2fc3an00383c&partnerID=40&md5=77ab18447e02b2a40b9a4b70fb8f05b0}, doi = {10.1039/c3an00383c}, year = {2013}, date = {2013-01-01}, journal = {Analyst}, volume = {138}, number = {19}, pages = {5610--5618}, abstract = {Advancements in widefield infrared spectromicroscopy have recently been demonstrated following the commissioning of IRENI (InfraRed ENvironmental Imaging), a Fourier Transform infrared (FTIR) chemical imaging beamline at the Synchrotron Radiation Center. The present study demonstrates the effects of magnification, spatial oversampling, spectral pre-processing and deconvolution, focusing on the intracellular detection and distribution of an exogenous metal tris-carbonyl derivative 1 in a single MDA-MB-231 breast cancer cell. We demonstrate here that spatial oversampling for synchrotron-based infrared imaging is critical to obtain accurate diffraction-limited images at all wavelengths simultaneously. Resolution criteria and results from raw and deconvoluted images for two Schwarzschild objectives (36×, NA 0.5 and 74×, NA 0.65) are compared to each other and to prior reports for raster-scanned, confocal microscopes. The resolution of the imaging data can be improved by deconvolving the instrumental broadening that is determined with the measured PSFs, which is implemented with GPU programming architecture for fast hyperspectral processing. High definition, rapidly acquired, FTIR chemical images of respective spectral signatures of the cell and 1 shows that 1 is localized next to the phosphate- and Amide-rich regions, in agreement with previous infrared and luminescence studies. The infrared image contrast, localization and definition are improved after applying proven spectral pre-processing (principal component analysis based noise reduction and RMie scattering correction algorithms) to individual pixel spectra in the hyperspectral cube. © The Royal Society of Chemistry.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Advancements in widefield infrared spectromicroscopy have recently been demonstrated following the commissioning of IRENI (InfraRed ENvironmental Imaging), a Fourier Transform infrared (FTIR) chemical imaging beamline at the Synchrotron Radiation Center. The present study demonstrates the effects of magnification, spatial oversampling, spectral pre-processing and deconvolution, focusing on the intracellular detection and distribution of an exogenous metal tris-carbonyl derivative 1 in a single MDA-MB-231 breast cancer cell. We demonstrate here that spatial oversampling for synchrotron-based infrared imaging is critical to obtain accurate diffraction-limited images at all wavelengths simultaneously. Resolution criteria and results from raw and deconvoluted images for two Schwarzschild objectives (36×, NA 0.5 and 74×, NA 0.65) are compared to each other and to prior reports for raster-scanned, confocal microscopes. The resolution of the imaging data can be improved by deconvolving the instrumental broadening that is determined with the measured PSFs, which is implemented with GPU programming architecture for fast hyperspectral processing. High definition, rapidly acquired, FTIR chemical images of respective spectral signatures of the cell and 1 shows that 1 is localized next to the phosphate- and Amide-rich regions, in agreement with previous infrared and luminescence studies. The infrared image contrast, localization and definition are improved after applying proven spectral pre-processing (principal component analysis based noise reduction and RMie scattering correction algorithms) to individual pixel spectra in the hyperspectral cube. © The Royal Society of Chemistry. |
Polypyrrole functionalized with new copper complex as platform for His-tag antibody immobilization and direct antigen detection Article de journal S Chebil; A Miodek; V Ambike; H Sauriat-Dorizon; C Policar; H Korri-Youssoufi Sensors and Actuators, B: Chemical, 185 , p. 762–770, 2013. @article{Chebil:2013, title = {Polypyrrole functionalized with new copper complex as platform for His-tag antibody immobilization and direct antigen detection}, author = {S Chebil and A Miodek and V Ambike and H Sauriat-Dorizon and C Policar and H Korri-Youssoufi}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84879243477&doi=10.1016%2fj.snb.2013.05.024&partnerID=40&md5=3d177c3bfb5d34b53cdc0265fd462968}, doi = {10.1016/j.snb.2013.05.024}, year = {2013}, date = {2013-01-01}, journal = {Sensors and Actuators, B: Chemical}, volume = {185}, pages = {762--770}, abstract = {A biomaterial based on a copper complex covalently attached to a polypyrrole backbone was designed for monitoring a glycoprotein, D-dimer, used as a marker of the deep vein thrombosis (DVT) condition. For this purpose a new copper complex has been developed based on the ligand N-(2-hydroxybenzyl)- N′-(6-aminohexyl)-N,N′-bis[2-(N-methylimidazolyl)methyl]ethane-1, 2-diamine (3) that is able to coordinate copper ions through two imidazole, two amine and one phenolato moieties - this coordination sphere will be labeled enPI2. The complex conjugated with a polypyrrole layer allows the His-tag antibody immobilization onto the conducting polymer substrate and immunosensor evaluation. The biomaterial shows a remarkable variation in redox activity of the Cu(II) complex after the D-dimer interaction. The redox activity of the [(enPi2)Cu(II)] complex decreases after the antigen interaction providing a linear response between 0.01 and 500 ng mL-1 with a detection limit of 10 pg mL-1. The chemical structure of copper complex demonstrates the ability to avoid non specific-interaction leading to anti fouling surface. Such biolayer architecture offers high measurement stability over time and the biomaterial could be stocked for several weeks without any modification of the electrochemical properties. © 2013 Elsevier B.V.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A biomaterial based on a copper complex covalently attached to a polypyrrole backbone was designed for monitoring a glycoprotein, D-dimer, used as a marker of the deep vein thrombosis (DVT) condition. For this purpose a new copper complex has been developed based on the ligand N-(2-hydroxybenzyl)- N′-(6-aminohexyl)-N,N′-bis[2-(N-methylimidazolyl)methyl]ethane-1, 2-diamine (3) that is able to coordinate copper ions through two imidazole, two amine and one phenolato moieties - this coordination sphere will be labeled enPI2. The complex conjugated with a polypyrrole layer allows the His-tag antibody immobilization onto the conducting polymer substrate and immunosensor evaluation. The biomaterial shows a remarkable variation in redox activity of the Cu(II) complex after the D-dimer interaction. The redox activity of the [(enPi2)Cu(II)] complex decreases after the antigen interaction providing a linear response between 0.01 and 500 ng mL-1 with a detection limit of 10 pg mL-1. The chemical structure of copper complex demonstrates the ability to avoid non specific-interaction leading to anti fouling surface. Such biolayer architecture offers high measurement stability over time and the biomaterial could be stocked for several weeks without any modification of the electrochemical properties. © 2013 Elsevier B.V. |
Synchrotron radiation FTIR detection of a metal-carbonyl tamoxifen analog. Correlation with luminescence microscopy to study its subcellular distribution Article de journal S Clède; F Lambert; C Sandt; Z Gueroui; N Delsuc; P Dumas; A Vessières; C Policar Biotechnology Advances, 31 (3), p. 393–395, 2013. @article{Clede:2013, title = {Synchrotron radiation FTIR detection of a metal-carbonyl tamoxifen analog. Correlation with luminescence microscopy to study its subcellular distribution}, author = {S Cl\`{e}de and F Lambert and C Sandt and Z Gueroui and N Delsuc and P Dumas and A Vessi\`{e}res and C Policar}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84875055388&doi=10.1016%2fj.biotechadv.2012.01.023&partnerID=40&md5=064b36e2db4e1260e17d3abc8b07bbd6}, doi = {10.1016/j.biotechadv.2012.01.023}, year = {2013}, date = {2013-01-01}, journal = {Biotechnology Advances}, volume = {31}, number = {3}, pages = {393--395}, abstract = {1,1-Di(4-hydroxyphenyl)-2-cyrhetrenylbut-1-ene 1 is an organometallic conjugate where a [(Cp)Re(CO)3] unit is linked to a hydroxytamoxifen-like structure. Its subcellular nuclear distribution was previously observed in a single cell using the near-field technique AFMIR. We show here that synchrotron radiation FTIR spectromicroscopy (SR-FTIR-SM) enabled the mapping of 1 based on its IR-signature (characteristic bands in the 1850-2200cm-1 range) and pointed out the colocalization of 1 with an area of high amide density. Fluorescence microscopy using DAPI staining performed on the same cells confirmed that this area corresponds to the cell nucleus. © 2012 Elsevier Inc.}, keywords = {}, pubstate = {published}, tppubtype = {article} } 1,1-Di(4-hydroxyphenyl)-2-cyrhetrenylbut-1-ene 1 is an organometallic conjugate where a [(Cp)Re(CO)3] unit is linked to a hydroxytamoxifen-like structure. Its subcellular nuclear distribution was previously observed in a single cell using the near-field technique AFMIR. We show here that synchrotron radiation FTIR spectromicroscopy (SR-FTIR-SM) enabled the mapping of 1 based on its IR-signature (characteristic bands in the 1850-2200cm-1 range) and pointed out the colocalization of 1 with an area of high amide density. Fluorescence microscopy using DAPI staining performed on the same cells confirmed that this area corresponds to the cell nucleus. © 2012 Elsevier Inc. |
An intrinsically fluorescent glycoligand for direct imaging of ligand trafficking in artificial and living cell systems Article de journal L Garcia; M Lazzaretti; A Diguet; F Mussi; F Bisceglie; J Xie; G Pelosi; A Buschini; D Baigl; C Policar New Journal of Chemistry, 37 (10), p. 3030–3034, 2013. @article{Garcia:2013, title = {An intrinsically fluorescent glycoligand for direct imaging of ligand trafficking in artificial and living cell systems}, author = {L Garcia and M Lazzaretti and A Diguet and F Mussi and F Bisceglie and J Xie and G Pelosi and A Buschini and D Baigl and C Policar}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84884338239&doi=10.1039%2fc3nj00380a&partnerID=40&md5=227adf277b66a18d63bfec3b8a13ff09}, doi = {10.1039/c3nj00380a}, year = {2013}, date = {2013-01-01}, journal = {New Journal of Chemistry}, volume = {37}, number = {10}, pages = {3030--3034}, abstract = {Glycoligands, sugar-based molecules able to complex metal cations, constitute a new class of molecules with great potential for biological and biochemical applications. To analyze their behaviour in a biological environment, we have synthesized an intrinsically fluorescent glycoligand and analyzed its trafficking in both living (U937 human cancer cells) and artificial (giant unilamellar vesicles) cell systems. We have found that this ligand has moderate cytotoxicity accompanied by specific accumulation in both living and reconstituted membranes, which it can cross to reach inner compartments. © 2013 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Glycoligands, sugar-based molecules able to complex metal cations, constitute a new class of molecules with great potential for biological and biochemical applications. To analyze their behaviour in a biological environment, we have synthesized an intrinsically fluorescent glycoligand and analyzed its trafficking in both living (U937 human cancer cells) and artificial (giant unilamellar vesicles) cell systems. We have found that this ligand has moderate cytotoxicity accompanied by specific accumulation in both living and reconstituted membranes, which it can cross to reach inner compartments. © 2013 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique. |
S Clède; F Lambert; C Sandt; S Kascakova; M Unger; E Harté; M -A Plamont; R Saint-Fort; A Deniset-Besseau; Z Gueroui; C Hirschmugl; S Lecomte; A Dazzi; A Vessières; C Policar Analyst, 138 (19), p. 5627–5638, 2013. @article{Clede:2013a, title = {Detection of an estrogen derivative in two breast cancer cell lines using a single core multimodal probe for imaging (SCoMPI) imaged by a panel of luminescent and vibrational techniques}, author = {S Cl\`{e}de and F Lambert and C Sandt and S Kascakova and M Unger and E Hart\'{e} and M -A Plamont and R Saint-Fort and A Deniset-Besseau and Z Gueroui and C Hirschmugl and S Lecomte and A Dazzi and A Vessi\`{e}res and C Policar}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84883254315&doi=10.1039%2fc3an00807j&partnerID=40&md5=02420b772ef22a07206b5ae31c42dd2e}, doi = {10.1039/c3an00807j}, year = {2013}, date = {2013-01-01}, journal = {Analyst}, volume = {138}, number = {19}, pages = {5627--5638}, abstract = {3-Methoxy-17α-ethynylestradiol or mestranol is a prodrug for ethynylestradiol and the estrogen component of some oral contraceptive formulations. We demonstrate here that a single core multimodal probe for imaging-SCoMPI-can be efficiently grafted onto mestranol allowing its tracking in two breast cancer cell lines, MDA-MB-231 and MCF-7 fixed cells. Correlative imaging studies based on luminescence (synchrotron UV spectromicroscopy, wide field and confocal fluorescence microscopies) and vibrational (AFMIR, synchrotron FTIR spectromicroscopy, synchrotron-based multiple beam FTIR imaging, confocal Raman microspectroscopy) spectroscopies were consistent with one another and showed a Golgi apparatus distribution of the SCoMPI-mestranol conjugate in both cell lines. © The Royal Society of Chemistry.}, keywords = {}, pubstate = {published}, tppubtype = {article} } 3-Methoxy-17α-ethynylestradiol or mestranol is a prodrug for ethynylestradiol and the estrogen component of some oral contraceptive formulations. We demonstrate here that a single core multimodal probe for imaging-SCoMPI-can be efficiently grafted onto mestranol allowing its tracking in two breast cancer cell lines, MDA-MB-231 and MCF-7 fixed cells. Correlative imaging studies based on luminescence (synchrotron UV spectromicroscopy, wide field and confocal fluorescence microscopies) and vibrational (AFMIR, synchrotron FTIR spectromicroscopy, synchrotron-based multiple beam FTIR imaging, confocal Raman microspectroscopy) spectroscopies were consistent with one another and showed a Golgi apparatus distribution of the SCoMPI-mestranol conjugate in both cell lines. © The Royal Society of Chemistry. |
Homooligomers of substituted prolines and β-prolines: Syntheses and secondary structure investigation Article de journal C Caumes; N Delsuc; R B Azza; I Correia; F Chemla; F Ferreira; L Carlier; A P Luna; R Moumné; O Lequin; P Karoyan New Journal of Chemistry, 37 (5), p. 1312–1319, 2013. @article{Caumes:2013, title = {Homooligomers of substituted prolines and β-prolines: Syntheses and secondary structure investigation}, author = {C Caumes and N Delsuc and R B Azza and I Correia and F Chemla and F Ferreira and L Carlier and A P Luna and R Moumn\'{e} and O Lequin and P Karoyan}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84876740702&doi=10.1039%2fc3nj00127j&partnerID=40&md5=dbda08d94a12bcb6b260393c90dd6af4}, doi = {10.1039/c3nj00127j}, year = {2013}, date = {2013-01-01}, journal = {New Journal of Chemistry}, volume = {37}, number = {5}, pages = {1312--1319}, abstract = {Homooligomers of enantiomerically pure (2S,3R)-3-methyl-proline, (3R,4R)-4-methyl-β-proline and (3R,4S)-3,4-dimethyl-β-proline were synthesized and studied using circular dichroism (CD) in water, methanol and propanol and using NMR in water. Changes in the far-UV CD spectrum were observed from dimers to hexamers, but little change was observed from hexamers to octa- or nonamers, both in water and methanol. CD and NMR data allowed us to conclude that oligomers of 3-substituted prolines with more than six residues adopt a characteristic PPII secondary structure both in water and aliphatic alcohols. Oligomers of (3R,4R)-4-methyl-β-proline bear the same CD signature as non-substituted β-proline oligomers, suggesting that substitution at position 3 is not sufficient to reduce conformational heterogeneity in β-proline oligomers. In the case of 3,4-disubstituted-β-proline oligomers, an atypical signature with an extra negative band at around 225 nm was observed, together with a concentration dependent CD spectrum indicating association properties. Nevertheless, NMR studies of 13C labelled oligomers of 3,4-disubstituted-β-prolines revealed a complex mixture of cis-trans conformers even for longer oligomers. © 2913 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Homooligomers of enantiomerically pure (2S,3R)-3-methyl-proline, (3R,4R)-4-methyl-β-proline and (3R,4S)-3,4-dimethyl-β-proline were synthesized and studied using circular dichroism (CD) in water, methanol and propanol and using NMR in water. Changes in the far-UV CD spectrum were observed from dimers to hexamers, but little change was observed from hexamers to octa- or nonamers, both in water and methanol. CD and NMR data allowed us to conclude that oligomers of 3-substituted prolines with more than six residues adopt a characteristic PPII secondary structure both in water and aliphatic alcohols. Oligomers of (3R,4R)-4-methyl-β-proline bear the same CD signature as non-substituted β-proline oligomers, suggesting that substitution at position 3 is not sufficient to reduce conformational heterogeneity in β-proline oligomers. In the case of 3,4-disubstituted-β-proline oligomers, an atypical signature with an extra negative band at around 225 nm was observed, together with a concentration dependent CD spectrum indicating association properties. Nevertheless, NMR studies of 13C labelled oligomers of 3,4-disubstituted-β-prolines revealed a complex mixture of cis-trans conformers even for longer oligomers. © 2913 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique. |
3-substituted prolines: From synthesis to structural applications, from peptides to foldamers Article de journal C Mothes; C Caumes; A Guez; H Boullet; T Gendrineau; S Darses; N Delsuc; R Moumné; B Oswald; O Lequin; P Karoyan Molecules, 18 (2), p. 2307–2327, 2013. @article{Mothes:2013, title = {3-substituted prolines: From synthesis to structural applications, from peptides to foldamers}, author = {C Mothes and C Caumes and A Guez and H Boullet and T Gendrineau and S Darses and N Delsuc and R Moumn\'{e} and B Oswald and O Lequin and P Karoyan}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84874605320&doi=10.3390%2fmolecules18022307&partnerID=40&md5=05828aecf601bf07f9a0a6a3fec4e28c}, doi = {10.3390/molecules18022307}, year = {2013}, date = {2013-01-01}, journal = {Molecules}, volume = {18}, number = {2}, pages = {2307--2327}, abstract = {Among the twenty natural proteinogenic amino acids, proline is unique as its secondary amine forms a tertiary amide when incorporated into biopolymers, thus preventing hydrogen bond formation. Despite the lack of hydrogen bonds and thanks to conformational restriction of flexibility linked to the pyrrolidine ring, proline is able to stabilize peptide secondary structures such as -turns or polyproline helices. These unique conformational properties have aroused a great interest in the development of proline analogues. Among them, proline chimeras are tools combining the proline restriction of flexibility together with the information brought by natural amino acids side chains. This review will focus on the chemical syntheses of 3-substituted proline chimeras of potential use for peptide syntheses and as potential use as tools for SAR studies of biologically active peptides and the development of secondary structure mimetics. Their influence on peptide structure will be briefly described. © 2013 by the authors.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Among the twenty natural proteinogenic amino acids, proline is unique as its secondary amine forms a tertiary amide when incorporated into biopolymers, thus preventing hydrogen bond formation. Despite the lack of hydrogen bonds and thanks to conformational restriction of flexibility linked to the pyrrolidine ring, proline is able to stabilize peptide secondary structures such as -turns or polyproline helices. These unique conformational properties have aroused a great interest in the development of proline analogues. Among them, proline chimeras are tools combining the proline restriction of flexibility together with the information brought by natural amino acids side chains. This review will focus on the chemical syntheses of 3-substituted proline chimeras of potential use for peptide syntheses and as potential use as tools for SAR studies of biologically active peptides and the development of secondary structure mimetics. Their influence on peptide structure will be briefly described. © 2013 by the authors. |
A blue-absorbing photolabile protecting group for in vivo chromatically orthogonal photoactivation Article de journal L Fournier; C Gauron; L Xu; I Aujard; T Le Saux; N Gagey-Eilstein; S Maurin; S Dubruille; J -B Baudin; D Bensimon; M Volovitch; S Vriz; L Jullien ACS Chemical Biology, 8 (7), p. 1528–1536, 2013. @article{Fournier:2013a, title = {A blue-absorbing photolabile protecting group for in vivo chromatically orthogonal photoactivation}, author = {L Fournier and C Gauron and L Xu and I Aujard and T Le Saux and N Gagey-Eilstein and S Maurin and S Dubruille and J -B Baudin and D Bensimon and M Volovitch and S Vriz and L Jullien}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84880534465&doi=10.1021%2fcb400178m&partnerID=40&md5=a6d82b0b12d74445d9235b43207903ed}, doi = {10.1021/cb400178m}, year = {2013}, date = {2013-01-01}, journal = {ACS Chemical Biology}, volume = {8}, number = {7}, pages = {1528--1536}, abstract = {The small and synthetically easily accessible 7-diethylamino-4- thiocoumarinylmethyl photolabile protecting group has been validated for uncaging with blue light. It exhibits a significant action cross-section for uncaging in the 470-500 nm wavelength range and a low light absorption between 350 and 400 nm. These attractive features have been implemented in living zebrafish embryos to perform chromatic orthogonal photoactivation of two biologically active species controlling biological development with UV and blue-cyan light sources, respectively. © 2013 American Chemical Society.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The small and synthetically easily accessible 7-diethylamino-4- thiocoumarinylmethyl photolabile protecting group has been validated for uncaging with blue light. It exhibits a significant action cross-section for uncaging in the 470-500 nm wavelength range and a low light absorption between 350 and 400 nm. These attractive features have been implemented in living zebrafish embryos to perform chromatic orthogonal photoactivation of two biologically active species controlling biological development with UV and blue-cyan light sources, respectively. © 2013 American Chemical Society. |
2012 |
A rhenium tris-carbonyl derivative as a single core multimodal probe for imaging (SCoMPI) combining infrared and luminescent properties Article de journal S Clède; F Lambert; C Sandt; Z Gueroui; M Réfrégiers; M -A Plamont; P Dumas; A Vessières; C Policar Chemical Communications, 48 (62), p. 7729–7731, 2012. @article{Clede:2012, title = {A rhenium tris-carbonyl derivative as a single core multimodal probe for imaging (SCoMPI) combining infrared and luminescent properties}, author = {S Cl\`{e}de and F Lambert and C Sandt and Z Gueroui and M R\'{e}fr\'{e}giers and M -A Plamont and P Dumas and A Vessi\`{e}res and C Policar}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84863947366&doi=10.1039%2fc2cc32163g&partnerID=40&md5=289388c6720aee80e800fb8ad80cdb27}, doi = {10.1039/c2cc32163g}, year = {2012}, date = {2012-01-01}, journal = {Chemical Communications}, volume = {48}, number = {62}, pages = {7729--7731}, abstract = {A rhenium tris-carbonyl derivative has been designed to couple infrared and luminescent detection in cells. Both spectroscopies are consistent with one another; they point out the reliability of the present SCoMPI (for Single Core Multimodal Probe for Imaging) for bimodal imaging and unambiguously indicate a localization at the Golgi apparatus in MDA-MB-231 breast cancer cells. © 2012 The Royal Society of Chemistry.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A rhenium tris-carbonyl derivative has been designed to couple infrared and luminescent detection in cells. Both spectroscopies are consistent with one another; they point out the reliability of the present SCoMPI (for Single Core Multimodal Probe for Imaging) for bimodal imaging and unambiguously indicate a localization at the Golgi apparatus in MDA-MB-231 breast cancer cells. © 2012 The Royal Society of Chemistry. |
Glycosiderophores: Synthesis of tris-hydroxamate siderophores based on a galactose or glycero central scaffold, Fe(III) complexation studies Article de journal C Neff; F Bellot; J -B Waern; F Lambert; J Brandel; G Serratrice; F Gaboriau; C Policar Journal of Inorganic Biochemistry, 112 , p. 59–67, 2012. @article{Neff:2012, title = {Glycosiderophores: Synthesis of tris-hydroxamate siderophores based on a galactose or glycero central scaffold, Fe(III) complexation studies}, author = {C Neff and F Bellot and J -B Waern and F Lambert and J Brandel and G Serratrice and F Gaboriau and C Policar}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84860271202&doi=10.1016%2fj.jinorgbio.2012.02.030&partnerID=40&md5=67094ead67163b2ab05f9eed02b54bbd}, doi = {10.1016/j.jinorgbio.2012.02.030}, year = {2012}, date = {2012-01-01}, journal = {Journal of Inorganic Biochemistry}, volume = {112}, pages = {59--67}, abstract = {A series of five new hexadentate tris-hydroxamate ligands based on a d-galactose or a glycerol scaffold have been synthesized. Protonation and ferric complex formation constants have been determined from solution studies by potentiometric and spectrophotometric titrations. All ligands form 1:1 Fe:L complexes. The calculated pFe values at pH 7.4 span over the range 19.2-23.0 depending on the scaffold and on the length of the spacers between hydroxamate and central scaffold and on the N-methyl substitution. This new kind of artificial siderophores based on a glycoscaffold is of interest as it opens up an easy way to modulate the pFe. © 2012 Elsevier Inc.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A series of five new hexadentate tris-hydroxamate ligands based on a d-galactose or a glycerol scaffold have been synthesized. Protonation and ferric complex formation constants have been determined from solution studies by potentiometric and spectrophotometric titrations. All ligands form 1:1 Fe:L complexes. The calculated pFe values at pH 7.4 span over the range 19.2-23.0 depending on the scaffold and on the length of the spacers between hydroxamate and central scaffold and on the N-methyl substitution. This new kind of artificial siderophores based on a glycoscaffold is of interest as it opens up an easy way to modulate the pFe. © 2012 Elsevier Inc. |
Recent analytical applications of molecular spectroscopy in bioorganometallic chemistrypart I: Metal carbonyls Article de journal I S Butler; R P Kengne-Momo; G Jaouen; C Policar; A Vessières Applied Spectroscopy Reviews, 47 (7), p. 531–549, 2012. @article{Butler:2012, title = {Recent analytical applications of molecular spectroscopy in bioorganometallic chemistrypart I: Metal carbonyls}, author = {I S Butler and R P Kengne-Momo and G Jaouen and C Policar and A Vessi\`{e}res}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84865204418&doi=10.1080%2f05704928.2012.673189&partnerID=40&md5=520598e533375e3ff67b73f9e50d4386}, doi = {10.1080/05704928.2012.673189}, year = {2012}, date = {2012-01-01}, journal = {Applied Spectroscopy Reviews}, volume = {47}, number = {7}, pages = {531--549}, abstract = {This is the first part of a two-part review on the analytical applications of molecular spectroscopy in bioorganometallic chemistry since 2005. In this case, radiopharmaceutical studies are included and the review is focused particularly on biological molecules labeled with metal carbonyl fragments. Copyright © Taylor & Francis Group, LLC.}, keywords = {}, pubstate = {published}, tppubtype = {article} } This is the first part of a two-part review on the analytical applications of molecular spectroscopy in bioorganometallic chemistry since 2005. In this case, radiopharmaceutical studies are included and the review is focused particularly on biological molecules labeled with metal carbonyl fragments. Copyright © Taylor & Francis Group, LLC. |
Recent applications of molecular spectroscopy in bioorganometallic chemistry-Part 2: Ferrocenes and other organometallic complexes Article de journal I S Butler; R P Kengne-Momo; A Vessières; G Jaouen; C Policar Applied Spectroscopy Reviews, 47 (8), p. 620–632, 2012. @article{Butler:2012a, title = {Recent applications of molecular spectroscopy in bioorganometallic chemistry-Part 2: Ferrocenes and other organometallic complexes}, author = {I S Butler and R P Kengne-Momo and A Vessi\`{e}res and G Jaouen and C Policar}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84867002904&doi=10.1080%2f05704928.2012.697088&partnerID=40&md5=9a894613d259bfe47cd1f47469a86497}, doi = {10.1080/05704928.2012.697088}, year = {2012}, date = {2012-01-01}, journal = {Applied Spectroscopy Reviews}, volume = {47}, number = {8}, pages = {620--632}, abstract = {This is the second part of an overview of the applications of the various molecular spectroscopic methods that have been employed in bioorganometallic chemistry research since 2005 focusing on ferrocenes and other non-metal carbonyl organometallic complexes. These spectroscopic methods encompass infrared (IR), nuclear magnetic resonance (NMR), mass, Raman, ultraviolet-visible (UV-Vis), and several other less common spectroscopic techniques. © 2012 Taylor & Francis Group, LLC.}, keywords = {}, pubstate = {published}, tppubtype = {article} } This is the second part of an overview of the applications of the various molecular spectroscopic methods that have been employed in bioorganometallic chemistry research since 2005 focusing on ferrocenes and other non-metal carbonyl organometallic complexes. These spectroscopic methods encompass infrared (IR), nuclear magnetic resonance (NMR), mass, Raman, ultraviolet-visible (UV-Vis), and several other less common spectroscopic techniques. © 2012 Taylor & Francis Group, LLC. |
Metal complexation of a Đ -ribose-based ligand decoded by experimental and theoretical studies Article de journal F Cisnetti; J -D Maréchal; M Nicaise; R Guillot; M Desmadril; F Lambert; C Policar European Journal of Inorganic Chemistry, (20), p. 3308–3319, 2012. @article{Cisnetti:2012, title = {Metal complexation of a {D} -ribose-based ligand decoded by experimental and theoretical studies}, author = {F Cisnetti and J -D Mar\'{e}chal and M Nicaise and R Guillot and M Desmadril and F Lambert and C Policar}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84863687434&doi=10.1002%2fejic.201200322&partnerID=40&md5=0682fc752866de140dd4439a4be02cdd}, doi = {10.1002/ejic.201200322}, year = {2012}, date = {2012-01-01}, journal = {European Journal of Inorganic Chemistry}, number = {20}, pages = {3308--3319}, abstract = {A combination of experimental and theoretical methods have been used to elucidate the complexation properties of a new sugar-derived hexadentate ligand, namely methyl 2,3,4-tri-O-(2-picolyl)-β-D-ribopyranoside (L). The coordination bond lengths in the complexes with Mn II, Co II, Ni II, and Zn II show substantial deviations from ideal octahedra with deformation towards trigonal-prismatic geometries, which is indicative of a conformationally constrained ligand. The metal-cation-ligand interactions were studied for L and the acyclic analogue L' [1,2,3-tri-O-(2-picolyl)-1,2,3-propanetriol] by spectroscopic methods and isothermal calorimetric titrations for the series Mn II, Co II, Ni II, Zn II, and Cu II. The results indicate a stabilization of the complexes obtained with L compared with L', depending on the nature of the metal. Molecular modeling studies showed that the presence of the sugar moiety strongly favors conformations compatible with metal binding, which suggests an entropic origin of the stabilization of L complexes with regards to L' complexes. Moreover, the differences in the metal chelation profiles of L and L' are related to the constraints in the sugar group in the metal-bound structures. This study shows that foreseeing the degree of preorganization of flexible ligands may drive the design of a new generation of chelating compounds. A new sugar-derived ligand, with its coordination site embedded in a pyranoside cycle in the chair conformation, has been designed. Its transition-metal complexes were characterized by experimental and complexation methods and revealed a dramatic impact of the preorganization and complementarity of the carbohydrate scaffold on the metal binding. © 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A combination of experimental and theoretical methods have been used to elucidate the complexation properties of a new sugar-derived hexadentate ligand, namely methyl 2,3,4-tri-O-(2-picolyl)-β-D-ribopyranoside (L). The coordination bond lengths in the complexes with Mn II, Co II, Ni II, and Zn II show substantial deviations from ideal octahedra with deformation towards trigonal-prismatic geometries, which is indicative of a conformationally constrained ligand. The metal-cation-ligand interactions were studied for L and the acyclic analogue L' [1,2,3-tri-O-(2-picolyl)-1,2,3-propanetriol] by spectroscopic methods and isothermal calorimetric titrations for the series Mn II, Co II, Ni II, Zn II, and Cu II. The results indicate a stabilization of the complexes obtained with L compared with L', depending on the nature of the metal. Molecular modeling studies showed that the presence of the sugar moiety strongly favors conformations compatible with metal binding, which suggests an entropic origin of the stabilization of L complexes with regards to L' complexes. Moreover, the differences in the metal chelation profiles of L and L' are related to the constraints in the sugar group in the metal-bound structures. This study shows that foreseeing the degree of preorganization of flexible ligands may drive the design of a new generation of chelating compounds. A new sugar-derived ligand, with its coordination site embedded in a pyranoside cycle in the chair conformation, has been designed. Its transition-metal complexes were characterized by experimental and complexation methods and revealed a dramatic impact of the preorganization and complementarity of the carbohydrate scaffold on the metal binding. © 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. |
Evaluation of the anti-oxidant properties of a SOD-mimic Mn-complex in activated macrophages Article de journal Anne-Sophie Bernard; Claire Giroud; Vincent H Y Ching; Anne Meunier; Vinita Ambike; Christian Amatore; Manon Guille-Collignon; Frederic Lemaitre; Clotilde Policar Dalton Transactions, 41 (21), p. 6399-6403, 2012, (Times Cited: 23). @article{, title = {Evaluation of the anti-oxidant properties of a SOD-mimic Mn-complex in activated macrophages}, author = {Anne-Sophie Bernard and Claire Giroud and Vincent H Y Ching and Anne Meunier and Vinita Ambike and Christian Amatore and Manon Guille-Collignon and Frederic Lemaitre and Clotilde Policar}, year = {2012}, date = {2012-01-01}, journal = {Dalton Transactions}, volume = {41}, number = {21}, pages = {6399-6403}, note = {Times Cited: 23}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
2011 |
Recognition of G-Quadruplex DNA by Triangular Star-Shaped Compounds: With or Without Side Chains? Article de journal Hélène Bertrand; Anton Granzhan; David Monchaud; Nicolas Saettel; Régis Guillot; Sarah Clifford; Aurore Guédin; Jean-Louis Mergny; Marie-Paule Teulade-Fichou Chemistry – A European Journal, 17 (16), p. 4529–4539, 2011, ISSN: 0947-6539. @article{Bertrand2011a, title = {Recognition of G-Quadruplex DNA by Triangular Star-Shaped Compounds: With or Without Side Chains?}, author = {H\'{e}l{\`{e}}ne Bertrand and Anton Granzhan and David Monchaud and Nicolas Saettel and R\'{e}gis Guillot and Sarah Clifford and Aurore Gu\'{e}din and Jean-Louis Mergny and Marie-Paule Teulade-Fichou}, url = {https://doi.org/10.1002/chem.201002810}, doi = {10.1002/chem.201002810}, issn = {0947-6539}, year = {2011}, date = {2011-04-01}, journal = {Chemistry \textendash A European Journal}, volume = {17}, number = {16}, pages = {4529--4539}, publisher = {John Wiley & Sons, Ltd}, abstract = {Abstract We report the synthesis of two new series of triangular aromatic platforms, either with three aminoalkyl side chains (triazatrinaphthylene series, TrisK: six compounds), or without side chains (triazoniatrinaphthylene, TrisQ). The quadruplex?DNA binding behavior of the two series, which differ essentially by the localization of the cationic charges, was evaluated by means of FRET-melting and G4-FID assays. For the trisubstituted triazatrinaphthylenes (TrisK), the length of the substituents and the presence of terminal hydrogen-bond-donor groups (NH2) were shown to be crucial for ensuring a high quadruplex affinity (?T1/2 values of up to 20?°C at 1??M for the best candidate, TrisK3-NH) and selectivity versus duplex DNA. Subsequently, comparison of data collected on both the telomeric- and c-myc-quadruplex showed that the nonsubstituted TrisQ is even more efficient than TrisK3-NH, both in terms of quadruplex affinity (?T1/2=26?°C in K+ buffer) and selectivity versus duplex DNA. Structural considerations conducted with the c-myc quadruplex indicate that both TrisK3-NH and TrisQ stack well onto the G-quartet but in an offset position, which might be influenced by the formation of multiple hydrogen bonds with the target in the former case. Finally, the nonsubstituted TrisQ displays a binding profile very similar to some of the best quadruplex binders, BRACO-19 and bisquinolinium 360A, used herein as references, and thereby represents a highly promising novel molecular design for quadruplex recognition.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Abstract We report the synthesis of two new series of triangular aromatic platforms, either with three aminoalkyl side chains (triazatrinaphthylene series, TrisK: six compounds), or without side chains (triazoniatrinaphthylene, TrisQ). The quadruplex?DNA binding behavior of the two series, which differ essentially by the localization of the cationic charges, was evaluated by means of FRET-melting and G4-FID assays. For the trisubstituted triazatrinaphthylenes (TrisK), the length of the substituents and the presence of terminal hydrogen-bond-donor groups (NH2) were shown to be crucial for ensuring a high quadruplex affinity (?T1/2 values of up to 20?°C at 1??M for the best candidate, TrisK3-NH) and selectivity versus duplex DNA. Subsequently, comparison of data collected on both the telomeric- and c-myc-quadruplex showed that the nonsubstituted TrisQ is even more efficient than TrisK3-NH, both in terms of quadruplex affinity (?T1/2=26?°C in K+ buffer) and selectivity versus duplex DNA. Structural considerations conducted with the c-myc quadruplex indicate that both TrisK3-NH and TrisQ stack well onto the G-quartet but in an offset position, which might be influenced by the formation of multiple hydrogen bonds with the target in the former case. Finally, the nonsubstituted TrisQ displays a binding profile very similar to some of the best quadruplex binders, BRACO-19 and bisquinolinium 360A, used herein as references, and thereby represents a highly promising novel molecular design for quadruplex recognition. |
Subcellular IR imaging of a metal-carbonyl moiety using photothermally induced resonance Article de journal C Policar; J B Waern; M -A Plamont; S Clède; C Mayet; R Prazeres; J -M Ortega; A Vessières; A Dazzi Angewandte Chemie - International Edition, 50 (4), p. 860–864, 2011. @article{Policar:2011, title = {Subcellular IR imaging of a metal-carbonyl moiety using photothermally induced resonance}, author = {C Policar and J B Waern and M -A Plamont and S Cl\`{e}de and C Mayet and R Prazeres and J -M Ortega and A Vessi\`{e}res and A Dazzi}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-78650905440&doi=10.1002%2fanie.201003161&partnerID=40&md5=68f3379717f4b84ab8336cdb50461a5f}, doi = {10.1002/anie.201003161}, year = {2011}, date = {2011-01-01}, journal = {Angewandte Chemie - International Edition}, volume = {50}, number = {4}, pages = {860--864}, abstract = {Some like it hot! The photothermally induced resonance technique, in which an AFM microscope is coupled to a tunable pulsed IR laser, allows IR mapping and gives access to local IR spectra at the subcellular level. A metal-carbonyl compound was internalized in cells and detected in the cell nucleus thanks to its IR signature. The local IR spectrum at the nucleus showed the characteristic IR bands of the Re(CO)3 unit. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Some like it hot! The photothermally induced resonance technique, in which an AFM microscope is coupled to a tunable pulsed IR laser, allows IR mapping and gives access to local IR spectra at the subcellular level. A metal-carbonyl compound was internalized in cells and detected in the cell nucleus thanks to its IR signature. The local IR spectrum at the nucleus showed the characteristic IR bands of the Re(CO)3 unit. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
Proton-coupled electron transfers in biomimetic water bound metal complexes. the electrochemical approach Article de journal E Anxolabéhère-Mallart; C Costentin; C Policar; M Robert; J -M Savéant; A -L Teillout Faraday Discussions, 148 , p. 83–95, 2011. @article{Anxolabehere-Mallart:2011, title = {Proton-coupled electron transfers in biomimetic water bound metal complexes. the electrochemical approach}, author = {E Anxolab\'{e}h\`{e}re-Mallart and C Costentin and C Policar and M Robert and J -M Sav\'{e}ant and A -L Teillout}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-79952268478&doi=10.1039%2fc004276e&partnerID=40&md5=24036168d6b9ca482d1b9f949b3a5995}, doi = {10.1039/c004276e}, year = {2011}, date = {2011-01-01}, journal = {Faraday Discussions}, volume = {148}, pages = {83--95}, abstract = {Water-bound metal (M) complexes play a central role in the catalytic centers of natural systems such as Photosystem II (PSII), superoxide dismutase, cytochrome c oxidase and others. In these systems, electron transfer reactions involving the metal center are coupled to proton transfers. Besides its fundamental interest, comprehension of these reactions and of possible bio-inspired catalytic devices is an additional motivation for studying the coupling between proton and electron transfer (proton-coupled electron transfers, PCET), starting with an aqua-MII/hydroxo-MIII couple, and going to higher oxidation degrees as in the case of PSII (hydroxo-MIII/oxo-MIV couple). Factors that determine the occurrence of the stepwise and concerted pathways are recalled from the illustrating example of a recently described mononuclear osmium complex, thus opening perspectives for further studies of the biomimicking complex. PCET in a mononuclear aqua/hydroxo manganese couple was then studied using the electrochemical approach. © 2011 The Royal Society of Chemistry.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Water-bound metal (M) complexes play a central role in the catalytic centers of natural systems such as Photosystem II (PSII), superoxide dismutase, cytochrome c oxidase and others. In these systems, electron transfer reactions involving the metal center are coupled to proton transfers. Besides its fundamental interest, comprehension of these reactions and of possible bio-inspired catalytic devices is an additional motivation for studying the coupling between proton and electron transfer (proton-coupled electron transfers, PCET), starting with an aqua-MII/hydroxo-MIII couple, and going to higher oxidation degrees as in the case of PSII (hydroxo-MIII/oxo-MIV couple). Factors that determine the occurrence of the stepwise and concerted pathways are recalled from the illustrating example of a recently described mononuclear osmium complex, thus opening perspectives for further studies of the biomimicking complex. PCET in a mononuclear aqua/hydroxo manganese couple was then studied using the electrochemical approach. © 2011 The Royal Society of Chemistry. |
Intrinsically fluorescent glycoligands to study metal selectivity Article de journal L Garcia; S Maisonneuve; J Oudinet-Sin Marcu; R Guillot; F Lambert; J Xie; C Policar Inorganic Chemistry, 50 (22), p. 11353–11362, 2011. @article{Garcia:2011, title = {Intrinsically fluorescent glycoligands to study metal selectivity}, author = {L Garcia and S Maisonneuve and J Oudinet-Sin Marcu and R Guillot and F Lambert and J Xie and C Policar}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-81255195281&doi=10.1021%2fic200897v&partnerID=40&md5=2d82616942d473b2774c71363fb8ff6a}, doi = {10.1021/ic200897v}, year = {2011}, date = {2011-01-01}, journal = {Inorganic Chemistry}, volume = {50}, number = {22}, pages = {11353--11362}, abstract = {Glycoligands are a versatile family of ligands centered on a sugar platform and functionalized by Lewis bases. In this article, pentofuranoses were appended with the fluoroionophores 4-(pyridin-2′-yl)-1,2,3-triazol-1-yl and 4-(2′,1′,3′-benzothiadiazol-4′-yl)-1,2,3-triazol-1- yl using the "click-like" cycloaddition [2 + 3] of Huisgen catalyzed by copper(I). Their fluorescence properties were used to study metal cation complexation. A possible selective functionalization of furanoscaffolds allows the synthesis of "mixed" glycoligands with the successive insertion of these different fluoroionophores. The metal selectivity and the chelating behavior of these six resulting intrinsically fluorescent glycoligands were investigated. The change in the configuration at the carbon C3 of furanose did not influence either the metal selectivity or the binding constants. However, different selectivities and binding constants were found to depend on the nature of the fluoroionophore moieties. Overall, the triazolylbenzothiadiazolyl chelating group was shown to be less efficient than the triazolylpyridyl claw for complexation. Interestingly enough, the triazolylbenzothiadiazolyl claw, which fluoresces in the visible range, did not interfere in the binding and selectivity of the more efficient triazolylpyridyl claw. This study suggests that the triazolylbenzothiadiazolyl moiety could be used as an adequate fluorescent reporter to qualitatively monitor complexation of other moieties. © 2011 American Chemical Society.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Glycoligands are a versatile family of ligands centered on a sugar platform and functionalized by Lewis bases. In this article, pentofuranoses were appended with the fluoroionophores 4-(pyridin-2′-yl)-1,2,3-triazol-1-yl and 4-(2′,1′,3′-benzothiadiazol-4′-yl)-1,2,3-triazol-1- yl using the "click-like" cycloaddition [2 + 3] of Huisgen catalyzed by copper(I). Their fluorescence properties were used to study metal cation complexation. A possible selective functionalization of furanoscaffolds allows the synthesis of "mixed" glycoligands with the successive insertion of these different fluoroionophores. The metal selectivity and the chelating behavior of these six resulting intrinsically fluorescent glycoligands were investigated. The change in the configuration at the carbon C3 of furanose did not influence either the metal selectivity or the binding constants. However, different selectivities and binding constants were found to depend on the nature of the fluoroionophore moieties. Overall, the triazolylbenzothiadiazolyl chelating group was shown to be less efficient than the triazolylpyridyl claw for complexation. Interestingly enough, the triazolylbenzothiadiazolyl claw, which fluoresces in the visible range, did not interfere in the binding and selectivity of the more efficient triazolylpyridyl claw. This study suggests that the triazolylbenzothiadiazolyl moiety could be used as an adequate fluorescent reporter to qualitatively monitor complexation of other moieties. © 2011 American Chemical Society. |
Relative helix-helix conformations in branched aromatic oligoamide foldamers Article de journal N Delsuc; S Massip; J -M Léger; B Kauffmann; I Huc Journal of the American Chemical Society, 133 (9), p. 3165–3172, 2011. @article{Delsuc:2011, title = {Relative helix-helix conformations in branched aromatic oligoamide foldamers}, author = {N Delsuc and S Massip and J -M L\'{e}ger and B Kauffmann and I Huc}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-79952263733&doi=10.1021%2fja110677a&partnerID=40&md5=36f1e84ade60bac4aee1c82b34b28b99}, doi = {10.1021/ja110677a}, year = {2011}, date = {2011-01-01}, journal = {Journal of the American Chemical Society}, volume = {133}, number = {9}, pages = {3165--3172}, abstract = {The de novo design and synthesis of large and well-organized, tertiary-like, α-peptidic folded architectures is difficult because it relies on multiple cooperative interactions within and between secondary folded motifs of relatively weak intrinsic stability. The very stable helical structures of oligoamides of 8-amino-2-quinoline carboxylic acid offer a way to circumvent this difficulty thanks to their ability to fold into predictable and stable secondary motifs. Branched architectures comprised of two pairs of tetrameric (1), pentameric (2), or octameric (3) oligomers connected via an ethylene glycol spacer were designed and synthesized. The short spacer holds two helices in close proximity, thus enabling interactions between them. Degrees of freedom allowed in the system are well-defined: the relative P or M handedness of the two helices; the relative orientation of the helix axes; and the gauche or anti conformation of the ethylene spacer. Investigating the structures of 1-3 in the solid state and in solution allowed a detailed picture to be drawn of their conformational preferences and dynamics. The high variability of the solid state structures provides many snapshots of possible solution conformations. Helix-helix handedness communication was evidenced and shown to depend both on solvent and on a defined set of side chains at the helix-helix interface. Interdigitation of the side chains was found to restrict free rotation about the ethylene spacer. One solid state structure shows a high level of symmetry and provides a firm basis to further design specific side chain/side chain directional interactions. © 2011 American Chemical Society.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The de novo design and synthesis of large and well-organized, tertiary-like, α-peptidic folded architectures is difficult because it relies on multiple cooperative interactions within and between secondary folded motifs of relatively weak intrinsic stability. The very stable helical structures of oligoamides of 8-amino-2-quinoline carboxylic acid offer a way to circumvent this difficulty thanks to their ability to fold into predictable and stable secondary motifs. Branched architectures comprised of two pairs of tetrameric (1), pentameric (2), or octameric (3) oligomers connected via an ethylene glycol spacer were designed and synthesized. The short spacer holds two helices in close proximity, thus enabling interactions between them. Degrees of freedom allowed in the system are well-defined: the relative P or M handedness of the two helices; the relative orientation of the helix axes; and the gauche or anti conformation of the ethylene spacer. Investigating the structures of 1-3 in the solid state and in solution allowed a detailed picture to be drawn of their conformational preferences and dynamics. The high variability of the solid state structures provides many snapshots of possible solution conformations. Helix-helix handedness communication was evidenced and shown to depend both on solvent and on a defined set of side chains at the helix-helix interface. Interdigitation of the side chains was found to restrict free rotation about the ethylene spacer. One solid state structure shows a high level of symmetry and provides a firm basis to further design specific side chain/side chain directional interactions. © 2011 American Chemical Society. |
Locking the free-rotation of a prochiral star-shaped guest molecule inside a two-dimensional nanoporous network by introduction of chlorine atoms Article de journal Hélène Bertrand; Fabien Silly; Marie-Paule Teulade-Fichou; Ludovic Tortech; Denis Fichou Chemical Communications, 47 (36), p. 10091–10093, 2011, ISSN: 1359-7345. @article{Bertrand2011, title = {Locking the free-rotation of a prochiral star-shaped guest molecule inside a two-dimensional nanoporous network by introduction of chlorine atoms}, author = {H\'{e}l{\`{e}}ne Bertrand and Fabien Silly and Marie-Paule Teulade-Fichou and Ludovic Tortech and Denis Fichou}, url = {http://dx.doi.org/10.1039/C1CC12951A}, doi = {10.1039/C1CC12951A}, issn = {1359-7345}, year = {2011}, date = {2011-01-01}, journal = {Chemical Communications}, volume = {47}, number = {36}, pages = {10091--10093}, publisher = {The Royal Society of Chemistry}, abstract = {Two star-shaped triazatrinaphthylene (TrisK) derivatives form highly-organized nanoporous honeycomb networks when adsorbed at the n-tetradecane/HOPG interface. STM reveals that replacing three H-atoms by three Cl-atoms in the chemical structure of the TrisK skeleton results in locking the free-rotation of the guest molecules inside the pore of the host network as a result of symmetry breaking.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Two star-shaped triazatrinaphthylene (TrisK) derivatives form highly-organized nanoporous honeycomb networks when adsorbed at the n-tetradecane/HOPG interface. STM reveals that replacing three H-atoms by three Cl-atoms in the chemical structure of the TrisK skeleton results in locking the free-rotation of the guest molecules inside the pore of the host network as a result of symmetry breaking. |
2010 |
Sugars to control ligand shape in metal complexes: Conformationally constrained glycoligands with a predetermination of stereochemistry and a structural control Article de journal L Garcia; S Maisonneuve; J Xie; R Guillot; P Dorlet; E Rivière; M Desmadril; F Lambert; C Policar Inorganic Chemistry, 49 (16), p. 7282–7288, 2010. @article{Garcia:2010, title = {Sugars to control ligand shape in metal complexes: Conformationally constrained glycoligands with a predetermination of stereochemistry and a structural control}, author = {L Garcia and S Maisonneuve and J Xie and R Guillot and P Dorlet and E Rivi\`{e}re and M Desmadril and F Lambert and C Policar}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-77955475481&doi=10.1021%2fic1002379&partnerID=40&md5=d7e719000261dc5be94c8bbf72ce40ca}, doi = {10.1021/ic1002379}, year = {2010}, date = {2010-01-01}, journal = {Inorganic Chemistry}, volume = {49}, number = {16}, pages = {7282--7288}, abstract = {In coordination chemistry, ligand shape can be used to tune properties, such as metal selectivity, coordination number, electronic structure, redox potential, and metal center stereochemistry including coordination helicates formation, and also to generate cavities for encapsulation. The results presented in this article indicate that two epimeric glycoligands (3 and 4) based on the conformationally restrained xylo-and ribo-1,2-O- isopropylidenefurano scaffolds are preorganized in water through π-π stacking due to hydrophobic interactions, as evidenced from excimer observation. The structure obtained in the solid state for one of the Cu(II) complexes (5) is chiral, with an original helical chirality arising from the coiling of the two ligands around the Cu-Cu axis. It shows an unusual double-deck type structure, with π-π interaction between two triazoyl-pyridyl rings and with a small cavity between the two Cu(II) ions able to host a bridging water molecule, as suggested by electron paramagnetic resonance. The Cu(II) complex from the epimeric ligand (6) shows similar properties with a mirror-image CD spectrum in the d-d region of the Cu(II). There is a predetermination of chirality at the metal center by the glycoligand induced by the C3 configuration, 6 and 5 being pseudoenantiomers. Interestingly, the stereochemistry at the metal center is here controlled by the combination of π-stacking and chiral backbone. © 2010 American Chemical Society.}, keywords = {}, pubstate = {published}, tppubtype = {article} } In coordination chemistry, ligand shape can be used to tune properties, such as metal selectivity, coordination number, electronic structure, redox potential, and metal center stereochemistry including coordination helicates formation, and also to generate cavities for encapsulation. The results presented in this article indicate that two epimeric glycoligands (3 and 4) based on the conformationally restrained xylo-and ribo-1,2-O- isopropylidenefurano scaffolds are preorganized in water through π-π stacking due to hydrophobic interactions, as evidenced from excimer observation. The structure obtained in the solid state for one of the Cu(II) complexes (5) is chiral, with an original helical chirality arising from the coiling of the two ligands around the Cu-Cu axis. It shows an unusual double-deck type structure, with π-π interaction between two triazoyl-pyridyl rings and with a small cavity between the two Cu(II) ions able to host a bridging water molecule, as suggested by electron paramagnetic resonance. The Cu(II) complex from the epimeric ligand (6) shows similar properties with a mirror-image CD spectrum in the d-d region of the Cu(II). There is a predetermination of chirality at the metal center by the glycoligand induced by the C3 configuration, 6 and 5 being pseudoenantiomers. Interestingly, the stereochemistry at the metal center is here controlled by the combination of π-stacking and chiral backbone. © 2010 American Chemical Society. |
Photocontrol of protein activity in cultured cells and zebrafish with one- and two-photon illumination Article de journal D K Sinha; P Neveu; N Gagey; I Aujard; C Benbrahim-Bouzidi; T Le Saux; C Rampon; C Gauron; B Goetz; S Dubruille; M Baaden; M Volovitch; D Bensimon; S Vriz; L Jullien ChemBioChem, 11 (5), p. 653–663, 2010. @article{Sinha:2010, title = {Photocontrol of protein activity in cultured cells and zebrafish with one- and two-photon illumination}, author = {D K Sinha and P Neveu and N Gagey and I Aujard and C Benbrahim-Bouzidi and T Le Saux and C Rampon and C Gauron and B Goetz and S Dubruille and M Baaden and M Volovitch and D Bensimon and S Vriz and L Jullien}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-77949823382&doi=10.1002%2fcbic.201000008&partnerID=40&md5=4ac50ebf9ae4f10b80cc91f729b23969}, doi = {10.1002/cbic.201000008}, year = {2010}, date = {2010-01-01}, journal = {ChemBioChem}, volume = {11}, number = {5}, pages = {653--663}, abstract = {We have implemented a noninvasive optical method for the fast control of protein activity in a live zebrafish embryo. It relies on releasing a protein fused to a modified estrogen receptor ligand binding domain from its complex with cytoplasmic chaperones, upon the local photoactivation of a nonendogenous caged inducer. Molecular dynamics simulations were used to design cyclofen-OH, a photochemically stable inducer of the receptor specific for 4-hydroxy-tamoxifen (ERT2). Cyclofen-OH was easily synthesized in two steps with good yields. At submicromolar concentrations, it activates proteins fused to the ERT2 receptor. This was shown in cultured cells and in zebrafish embryos through emission properties and subcellular localization of properly engineered fluorescent proteins. Cyclofen-OH was successfully caged with various photolabile protecting groups. One particular caged compound was efficient in photoinducing the nuclear translocation of fluorescent proteins either globally (with 365 nm UV illumination) or locally (with a focused UV laser or with two-photon illumination at 750 nm). The present method for photocontrol of protein activity could be used more generally to investigate important physiological processes (e.g., in embryogenesis, organ regeneration and carcinogenesis) with high spatiotemporal resolution. © 2010 Wiley-VCH Verlag GmbH& Co. KGaA.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We have implemented a noninvasive optical method for the fast control of protein activity in a live zebrafish embryo. It relies on releasing a protein fused to a modified estrogen receptor ligand binding domain from its complex with cytoplasmic chaperones, upon the local photoactivation of a nonendogenous caged inducer. Molecular dynamics simulations were used to design cyclofen-OH, a photochemically stable inducer of the receptor specific for 4-hydroxy-tamoxifen (ERT2). Cyclofen-OH was easily synthesized in two steps with good yields. At submicromolar concentrations, it activates proteins fused to the ERT2 receptor. This was shown in cultured cells and in zebrafish embryos through emission properties and subcellular localization of properly engineered fluorescent proteins. Cyclofen-OH was successfully caged with various photolabile protecting groups. One particular caged compound was efficient in photoinducing the nuclear translocation of fluorescent proteins either globally (with 365 nm UV illumination) or locally (with a focused UV laser or with two-photon illumination at 750 nm). The present method for photocontrol of protein activity could be used more generally to investigate important physiological processes (e.g., in embryogenesis, organ regeneration and carcinogenesis) with high spatiotemporal resolution. © 2010 Wiley-VCH Verlag GmbH& Co. KGaA. |
Photoactivation of the CreERT2 recombinase for conditional site-specific recombination with high spatiotemporal resolution Article de journal D K Sinha; P Neveu; N Gagey; I Aujard; T Le Saux; C Rampon; C Gauron; K Kawakami; C Leucht; L Bally-Cuif; M Volovitch; D Bensimon; L Jullien; S Vriz Zebrafish, 7 (2), p. 199–204, 2010. @article{Sinha:2010a, title = {Photoactivation of the CreERT2 recombinase for conditional site-specific recombination with high spatiotemporal resolution}, author = {D K Sinha and P Neveu and N Gagey and I Aujard and T Le Saux and C Rampon and C Gauron and K Kawakami and C Leucht and L Bally-Cuif and M Volovitch and D Bensimon and L Jullien and S Vriz}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-77953623529&doi=10.1089%2fzeb.2009.0632&partnerID=40&md5=e5fb039a397abb6510140bcd6b2b258b}, doi = {10.1089/zeb.2009.0632}, year = {2010}, date = {2010-01-01}, journal = {Zebrafish}, volume = {7}, number = {2}, pages = {199--204}, abstract = {We implemented a noninvasive optical method for the fast control of Cre recombinase in single cells of a live zebrafish embryo. Optical uncaging of the caged precursor of a nonendogeneous steroid by one- or two-photon illumination was used to restore Cre activity of the CreERT2 fusion protein in specific target cells. This method labels single cells irreversibly by inducing recombination in an appropriate reporter transgenic animal and thereby can achieve high spatiotemporal resolution in the control of gene expression. This technique could be used more generally to investigate important physiological processes (e.g., in embryogenesis, organ regeneration, or carcinogenesis) with high spatiotemporal resolution (single cell and 10-min scales). © Copyright 2010, Mary Ann Liebert, Inc.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We implemented a noninvasive optical method for the fast control of Cre recombinase in single cells of a live zebrafish embryo. Optical uncaging of the caged precursor of a nonendogeneous steroid by one- or two-photon illumination was used to restore Cre activity of the CreERT2 fusion protein in specific target cells. This method labels single cells irreversibly by inducing recombination in an appropriate reporter transgenic animal and thereby can achieve high spatiotemporal resolution in the control of gene expression. This technique could be used more generally to investigate important physiological processes (e.g., in embryogenesis, organ regeneration, or carcinogenesis) with high spatiotemporal resolution (single cell and 10-min scales). © Copyright 2010, Mary Ann Liebert, Inc. |
Cascading transformations within a dynamic self-assembled system Article de journal Victoria E Campbell; Xavier de Hatten; Nicolas Delsuc; Brice Kauffmann; Ivan Huc; Jonathan R Nitschke Nature Chemistry, 2 (8), p. 684–687, 2010, ISSN: 1755-4349. @article{campbell_cascading_2010, title = {Cascading transformations within a dynamic self-assembled system}, author = {Victoria E Campbell and Xavier de Hatten and Nicolas Delsuc and Brice Kauffmann and Ivan Huc and Jonathan R Nitschke}, url = {https://www.nature.com/articles/nchem.693}, doi = {10.1038/nchem.693}, issn = {1755-4349}, year = {2010}, date = {2010-01-01}, urldate = {2018-03-06}, journal = {Nature Chemistry}, volume = {2}, number = {8}, pages = {684--687}, abstract = {Molecular subcomponents such as phosphate groups are often passed between biomolecules during complex signalling cascades, the flow of which define the motion of the machinery of life. Here, we show how an abiological system consisting of organic subcomponents knitted together by metal-ion coordination can respond to simple signals in complex ways. A CuI3 helicate transformed into its ZnII2CuI analogue following the addition of zinc(II), and the ejected copper(I) went on to induce the self-assembly of a CuI2 helicate from other free subcomponents present in solution. The addition of an additional subcomponent, 8-aminoquinoline, resulted in the formation of a third, more stable CuI3 helicate, requiring the destruction of both the ZnII2CuI and CuI2 helicates to scavenge sufficient CuI for the new structure. This system thus demonstrates two examples in which the application of one signal provokes two distinct responses involving the creation or destruction of complex assemblies as the system seeks thermodynamic equilibrium following perturbation.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Molecular subcomponents such as phosphate groups are often passed between biomolecules during complex signalling cascades, the flow of which define the motion of the machinery of life. Here, we show how an abiological system consisting of organic subcomponents knitted together by metal-ion coordination can respond to simple signals in complex ways. A CuI3 helicate transformed into its ZnII2CuI analogue following the addition of zinc(II), and the ejected copper(I) went on to induce the self-assembly of a CuI2 helicate from other free subcomponents present in solution. The addition of an additional subcomponent, 8-aminoquinoline, resulted in the formation of a third, more stable CuI3 helicate, requiring the destruction of both the ZnII2CuI and CuI2 helicates to scavenge sufficient CuI for the new structure. This system thus demonstrates two examples in which the application of one signal provokes two distinct responses involving the creation or destruction of complex assemblies as the system seeks thermodynamic equilibrium following perturbation. |
2009 |
Design, self-assembly, and molecular structures of 3D copper(II) capsules templated by BF4 - guest anions Article de journal C Desmarets; C Policar; L -M Chamoreau; H Amouri European Journal of Inorganic Chemistry, (29-30), p. 4396–4400, 2009. @article{Desmarets:2009, title = {Design, self-assembly, and molecular structures of 3D copper(II) capsules templated by BF4 - guest anions}, author = {C Desmarets and C Policar and L -M Chamoreau and H Amouri}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-70350150888&doi=10.1002%2fejic.200900606&partnerID=40&md5=a0e5525563850dda7c2083f3b040390c}, doi = {10.1002/ejic.200900606}, year = {2009}, date = {2009-01-01}, journal = {European Journal of Inorganic Chemistry}, number = {29-30}, pages = {4396--4400}, abstract = {The synthesis of two 3D M2L4 copper(II) capsules, [BF4C(CH3CN)2Cu2(L 1)4][BF4]3 (1) and ([BF 4C(BF4J2Cu2(L1) 4][BF4]) (2), by using l,3-(benzimidazol-l-ylmethyl)-2, 5dimethoxy-4,6-dimethylbenzene (L1) as a semirigid exobidentate ligand and [Cu(CH3CN)4][BF4]2 as a metallobrick is reported. Single-crystal X-ray diffraction studies show the encapsulation of a BF4 - anion in 1 and 2. Moreover, 2 dis-played three coordinated BF4 - anions, which is rare in supramolecular coordination host-guest chemistry. Remarkably, in both metallocages the weakly coordinated BF4 - anion acts as a template and interacts with the metal center through a weak Cu⋯F contact. © Wiley-VCH Verlag GmbH & Co. KGaA.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The synthesis of two 3D M2L4 copper(II) capsules, [BF4C(CH3CN)2Cu2(L 1)4][BF4]3 (1) and ([BF 4C(BF4J2Cu2(L1) 4][BF4]) (2), by using l,3-(benzimidazol-l-ylmethyl)-2, 5dimethoxy-4,6-dimethylbenzene (L1) as a semirigid exobidentate ligand and [Cu(CH3CN)4][BF4]2 as a metallobrick is reported. Single-crystal X-ray diffraction studies show the encapsulation of a BF4 - anion in 1 and 2. Moreover, 2 dis-played three coordinated BF4 - anions, which is rare in supramolecular coordination host-guest chemistry. Remarkably, in both metallocages the weakly coordinated BF4 - anion acts as a template and interacts with the metal center through a weak Cu⋯F contact. © Wiley-VCH Verlag GmbH & Co. KGaA. |
Exclusive platination of loop adenines in the human telomeric G-quadruplex Article de journal Hélène Bertrand; Sophie Bombard; David Monchaud; Eric Talbot; Aurore Guédin; Jean-Louis Mergny; Renate Grünert; Patrick J Bednarski; Marie-Paule Teulade-Fichou Organic & Biomolecular Chemistry, 7 (14), p. 2864–2871, 2009, ISSN: 1477-0520. @article{Bertrand2009, title = {Exclusive platination of loop adenines in the human telomeric G-quadruplex}, author = {H\'{e}l{\`{e}}ne Bertrand and Sophie Bombard and David Monchaud and Eric Talbot and Aurore Gu\'{e}din and Jean-Louis Mergny and Renate Gr\"{u}nert and Patrick J Bednarski and Marie-Paule Teulade-Fichou}, url = {http://dx.doi.org/10.1039/B904599F}, doi = {10.1039/B904599F}, issn = {1477-0520}, year = {2009}, date = {2009-01-01}, journal = {Organic & Biomolecular Chemistry}, volume = {7}, number = {14}, pages = {2864--2871}, publisher = {The Royal Society of Chemistry}, abstract = {The present article reports on the platination of the human telomeric G-quadruplex by three Pt-terpyridine complexes. It is shown that extension of the aromatic surface of the terpyridine moiety surrounding the platinum atom influences both the binding affinity and the platination activity. Remarkably, the most strongly bound complex Pt-ttpy coordinates exclusively the adenine nucleobases present in the loop of the G-quadruplex. This exclusive single-site platination reflects the interaction of the compound with both the G-tetrad and the loop residues. In addition Pt-ttpy showed promising antiproliferative activity on a panel of cancer cell lines in a parallel study using cisplatin derivatives currently in clinical use.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The present article reports on the platination of the human telomeric G-quadruplex by three Pt-terpyridine complexes. It is shown that extension of the aromatic surface of the terpyridine moiety surrounding the platinum atom influences both the binding affinity and the platination activity. Remarkably, the most strongly bound complex Pt-ttpy coordinates exclusively the adenine nucleobases present in the loop of the G-quadruplex. This exclusive single-site platination reflects the interaction of the compound with both the G-tetrad and the loop residues. In addition Pt-ttpy showed promising antiproliferative activity on a panel of cancer cell lines in a parallel study using cisplatin derivatives currently in clinical use. |