Chargé de Recherche CNRS – Maître de conférence attaché à l’ENS
ENS – Département de chimie
24 rue Lhomond, 75005 Paris
Email: nicolas.delsuc@ens.psl.eu
Phone: +33 144322424
Office: E037a
Our website: https://www.chimie.ens.fr/bic/
Short bio
I have been trained in chemistry at Bordeaux University. I did a PhD from 2004 to 2007 in supramolecular chemistry under the supervision of Dr. Ivan Huc. I worked on the development of proteomimetic structures using abiotic foldamers. I then obtained a fellowship from the Japan Society for the Promotion of Sciences (JSPS) to join the group of Prof. Itaru Hamachi at Kyoto University where I worked on new peptidyl receptors for peptide recognition. In 2009, I came back to France as temporary lecturer (ATER) at the Laboratoire des Biomolécules (LBM, UMR 7203), where I worked with Prof. Philippe Karoyan to develop foldamers based on proline derivatives. I have been appointed as CNRS researcher in 2010 and joined the group of Clotilde Policar at the LBM. I first worked on the conjugation of bioactive molecules with peptide to enhance their penetration and bioavaibality as well on the development of multimodal metal-based probes. Now I want to combine peptide and metal ions to synergistically take advantages of the properties of both classes of molecules by developing new peptidyl metalloprobes and metallodrugs.
Education and professional experience
- Sept 2020-now: Assitant Professor associate. ENS
- Oct 2010-now: Associate researcher. Laboratoire des BioMolécules, UMR7203 CNRS-SU-ENS. In the Inorganic Cellular Chemistry group within the team 1.
- Sept 2009-Sept 2010: Teaching assistant. Laboratoire des BioMolécules, UMR7203 UPMC-ENS. In the group of P. Karoyan, « Conception of enzyme mimics with foldamers »
- Nov 2007-Jul 2009: Post-doctoral fellow of the JSPS. Kyoto University, Japan. In the group of I. Hamachi. « Development of molecular receptors for specific peptides recognition »
- Oct 2004-Oct 2007: PhD in Organic chemistry, Bordeaux1 University under the supervision of I. Huc. »Development of proteomimetic tertiary structures with aromatic oligoamide foldamers »
- Sept 2005- Sept 2007: M.Sc. in Organic chemistry, Bordeaux1 University
Research interests
- Development of peptidyl metal complexes mimicking metalloenzymes
- Development of metal-centered probes for bio-imaging or diagnostic
Awards and distinctions
- 2016: ANR JCJC
- 2007: JSPS Postodoctoral Fellowship
Supervised PhD and post-doctoral students
- Current: Gabrielle Schanne (2019)
- Formers: Martha Zoumpoulaki (2017-2021), Koudedja Coulibaly (2017-2020), Amandine Vincent (2016-2019), Emilie Mathieu (2014-2017), Sarah Hostachy (2012-2015), May Lee Low (2011-2014, cotutelle with Malaysia), Anne-Sophie Bernard (2010-2014)
Publications
2022 |
SOD mimics: From the tool box of the chemists to cellular studies Article de journal Clotilde Policar; Jean Bouvet; Hélène C Bertrand; Nicolas Delsuc Current Opinion in Chemical Biology, 67 , p. 102109, 2022, ISSN: 1367-5931. @article{POLICAR2022102109, title = {SOD mimics: From the tool box of the chemists to cellular studies}, author = {Clotilde Policar and Jean Bouvet and H\'{e}l\`{e}ne C Bertrand and Nicolas Delsuc}, url = {https://www.sciencedirect.com/science/article/pii/S136759312100154X}, doi = {https://doi.org/10.1016/j.cbpa.2021.102109}, issn = {1367-5931}, year = {2022}, date = {2022-01-01}, journal = {Current Opinion in Chemical Biology}, volume = {67}, pages = {102109}, abstract = {Superoxide dismutases (SODs) are metalloproteins that protect cells against oxidative stress by controlling the concentration of superoxide (O2−) through catalysis of its dismutation. The activity of superoxide dismutases can be mimicked by low-molecular-weight complexes having potential therapeutic applications. This review presents recent strategies for designing efficient SOD mimics, from molecular metal complexes to nanomaterials. Studies of these systems in cells reveal that some SOD mimics, designed to react directly with superoxide, may also indirectly enhance the cellular antioxidant arsenal. Finally, a good understanding of the bioactivity requires information on the cell-penetration, speciation, and subcellular location of the SOD mimics: we will describe recent studies and new techniques that open opportunities for characterizing SOD mimics in biological environments.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Superoxide dismutases (SODs) are metalloproteins that protect cells against oxidative stress by controlling the concentration of superoxide (O2−) through catalysis of its dismutation. The activity of superoxide dismutases can be mimicked by low-molecular-weight complexes having potential therapeutic applications. This review presents recent strategies for designing efficient SOD mimics, from molecular metal complexes to nanomaterials. Studies of these systems in cells reveal that some SOD mimics, designed to react directly with superoxide, may also indirectly enhance the cellular antioxidant arsenal. Finally, a good understanding of the bioactivity requires information on the cell-penetration, speciation, and subcellular location of the SOD mimics: we will describe recent studies and new techniques that open opportunities for characterizing SOD mimics in biological environments. |
2021 |
Evaluation of the compounds commonly known as superoxide dismutase and catalase mimics in cellular models Article de journal Amandine Vincent; Marion Thauvin; Elodie Quévrain; Emilie Mathieu; Sarah Layani; Philippe Seksik; Ines Batinic-Haberle; Sophie Vriz; Clotilde Policar; Nicolas Delsuc Journal of Inorganic Biochemistry, p. 111431, 2021, ISSN: 0162-0134. @article{VINCENT2021111431, title = {Evaluation of the compounds commonly known as superoxide dismutase and catalase mimics in cellular models}, author = {Amandine Vincent and Marion Thauvin and Elodie Qu\'{e}vrain and Emilie Mathieu and Sarah Layani and Philippe Seksik and Ines Batinic-Haberle and Sophie Vriz and Clotilde Policar and Nicolas Delsuc}, url = {https://www.sciencedirect.com/science/article/pii/S0162013421000787}, doi = {https://doi.org/10.1016/j.jinorgbio.2021.111431}, issn = {0162-0134}, year = {2021}, date = {2021-01-01}, journal = {Journal of Inorganic Biochemistry}, pages = {111431}, abstract = {Oxidative stress that results from an imbalance between the concentrations of reactive species (RS) and antioxidant defenses is associated with many pathologies. Superoxide dismutase (SOD), catalase (CAT), and glutathione peroxidase are among the key enzymes that maintain the low nanomolar physiological concentrations of superoxide and hydrogen peroxide. The increase in the levels of these species and their progeny could have deleterious effects. In this context, chemists have developed SOD and CAT mimics to supplement them when cells are overwhelmed with oxidative stress. However, the beneficial activity of such molecules in cells depends not only on their intrinsic catalytic activities but also on their stability in biological context, their cell penetration and their cellular localization. We have employed cellular assays to characterize several compounds that possess SOD and CAT activities and have been frequently used in cellular and animal models. We used cellular assays that address SOD and CAT activities of the compounds. Finally, we determined the effect of compounds on the suppression of the inflammation in HT29-MD2 cells challenged by lipopolysaccharide. When the assay requires penetration inside cells, the SOD mimics Mn(III) meso-tetrakis(N-(2′-nbutoxyethyl)pyridinium-2-yl)porphyrin (MnTnBuOE-2-PyP5+) and Mn(II) dichloro[(4aR,13aR,17aR,21aR)-1,2,3,4,4a,5, 6,12,13,13a,14,15,16,17,17a,18,19,20,21,21a-eicosahydro-11,7-nitrilo-7Hdibenzo[b,h] [1, 4, 7, 10] tetra--azacycloheptadecine-κN5,κN13,κN18,κN21,κN22] (Imisopasem manganese, M40403, CG4419) were found efficacious at 10 μM, while Mn(II) chloro N-(phenolato)-N,N′-bis[2-(N-methyl-imidazolyl)methyl]-ethane-1,2-diamine (Mn1) requires an incubation at 100 μM. This study thus demonstrates that MnTnBuOE-2-PyP5+, M40403 and Mn1 were efficacious in suppressing inflammatory response in HT29-MD2 cells and such action appears to be related to their ability to enter the cells and modulate reactive oxygen species (ROS) levels.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Oxidative stress that results from an imbalance between the concentrations of reactive species (RS) and antioxidant defenses is associated with many pathologies. Superoxide dismutase (SOD), catalase (CAT), and glutathione peroxidase are among the key enzymes that maintain the low nanomolar physiological concentrations of superoxide and hydrogen peroxide. The increase in the levels of these species and their progeny could have deleterious effects. In this context, chemists have developed SOD and CAT mimics to supplement them when cells are overwhelmed with oxidative stress. However, the beneficial activity of such molecules in cells depends not only on their intrinsic catalytic activities but also on their stability in biological context, their cell penetration and their cellular localization. We have employed cellular assays to characterize several compounds that possess SOD and CAT activities and have been frequently used in cellular and animal models. We used cellular assays that address SOD and CAT activities of the compounds. Finally, we determined the effect of compounds on the suppression of the inflammation in HT29-MD2 cells challenged by lipopolysaccharide. When the assay requires penetration inside cells, the SOD mimics Mn(III) meso-tetrakis(N-(2′-nbutoxyethyl)pyridinium-2-yl)porphyrin (MnTnBuOE-2-PyP5+) and Mn(II) dichloro[(4aR,13aR,17aR,21aR)-1,2,3,4,4a,5, 6,12,13,13a,14,15,16,17,17a,18,19,20,21,21a-eicosahydro-11,7-nitrilo-7Hdibenzo[b,h] [1, 4, 7, 10] tetra--azacycloheptadecine-κN5,κN13,κN18,κN21,κN22] (Imisopasem manganese, M40403, CG4419) were found efficacious at 10 μM, while Mn(II) chloro N-(phenolato)-N,N′-bis[2-(N-methyl-imidazolyl)methyl]-ethane-1,2-diamine (Mn1) requires an incubation at 100 μM. This study thus demonstrates that MnTnBuOE-2-PyP5+, M40403 and Mn1 were efficacious in suppressing inflammatory response in HT29-MD2 cells and such action appears to be related to their ability to enter the cells and modulate reactive oxygen species (ROS) levels. |
Rhenium carbonyl complexes bearing methylated triphenylphosphonium cations as antibody-free mitochondria trackers for X-ray fluorescence imaging Article de journal Gabrielle Schanne; Lucas Henry; How Chee Ong; Andrea Somogyi; Kadda Medjoubi; Nicolas Delsuc; Clotilde Policar; Felipe García; Helene C Bertrand Inorg. Chem. Front., 8 , p. 3905-3915, 2021. @article{D1QI00542A, title = {Rhenium carbonyl complexes bearing methylated triphenylphosphonium cations as antibody-free mitochondria trackers for X-ray fluorescence imaging}, author = {Gabrielle Schanne and Lucas Henry and How Chee Ong and Andrea Somogyi and Kadda Medjoubi and Nicolas Delsuc and Clotilde Policar and Felipe Garc\'{i}a and Helene C Bertrand}, url = {http://dx.doi.org/10.1039/D1QI00542A}, doi = {10.1039/D1QI00542A}, year = {2021}, date = {2021-01-01}, journal = {Inorg. Chem. Front.}, volume = {8}, pages = {3905-3915}, publisher = {The Royal Society of Chemistry}, abstract = {Synchrotron Radiation X-ray Fluorescence (SXRF) imaging is a powerful technique for the visualization of metal complexes in biological systems. However, due to the lack of an endogenous elemental signature for mitochondria, probes for the localization of this organelle are required for colocalization studies. In this work, we designed and synthesized rhenium pyta tricarbonyl complexes conjugated to methylated triphenylphosphonium TP*P+ cations as multimodal probes for the visualization of mitochondria, suitable for fluorescence and SXRF imaging and quantification. Accumulation of the methylated triphenylphosphonium TP*P+-based conjugates in cells was observed in fixed A549 cells, and the amount of mitochondrial uptake was linked to the lipophilicity of the TPP+ vector. Our work highlights a convenient rhenium-based multimodal mitochondrial-targeted probe compatible with SXRF nano-imaging.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Synchrotron Radiation X-ray Fluorescence (SXRF) imaging is a powerful technique for the visualization of metal complexes in biological systems. However, due to the lack of an endogenous elemental signature for mitochondria, probes for the localization of this organelle are required for colocalization studies. In this work, we designed and synthesized rhenium pyta tricarbonyl complexes conjugated to methylated triphenylphosphonium TP*P+ cations as multimodal probes for the visualization of mitochondria, suitable for fluorescence and SXRF imaging and quantification. Accumulation of the methylated triphenylphosphonium TP*P+-based conjugates in cells was observed in fixed A549 cells, and the amount of mitochondrial uptake was linked to the lipophilicity of the TPP+ vector. Our work highlights a convenient rhenium-based multimodal mitochondrial-targeted probe compatible with SXRF nano-imaging. |
A di-Copper Peptidyl Complex Mimics the Activity of Catalase, a Key Antioxidant Metalloenzyme Article de journal Koudedja Coulibaly; Marion Thauvin; Adyn Melenbacher; Clara Testard; Evangelina Trigoni; Amandine Vincent; Martin J Stillman; Sophie Vriz; Clotilde Policar; Nicolas Delsuc Inorganic Chemistry, 60 (13), p. 9309-9319, 2021. @article{doi:10.1021/acs.inorgchem.0c03718b, title = {A di-Copper Peptidyl Complex Mimics the Activity of Catalase, a Key Antioxidant Metalloenzyme}, author = {Koudedja Coulibaly and Marion Thauvin and Adyn Melenbacher and Clara Testard and Evangelina Trigoni and Amandine Vincent and Martin J Stillman and Sophie Vriz and Clotilde Policar and Nicolas Delsuc}, url = {https://doi.org/10.1021/acs.inorgchem.0c03718}, doi = {10.1021/acs.inorgchem.0c03718}, year = {2021}, date = {2021-01-01}, journal = {Inorganic Chemistry}, volume = {60}, number = {13}, pages = {9309-9319}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
2020 |
An easy-to-implement combinatorial approach involving an activity-based assay for the discovery of a peptidyl copper complex mimicking superoxide dismutase Article de journal Amandine Vincent; Jennifer Rodon Fores; Elodie Tauziet; Elodie Quévrain; Ágnes Dancs; Amandine Conte-Daban; Anne-Sophie Bernard; Philippe Pelupessy; Koudedja Coulibaly; Philippe Seksik; Christelle Hureau; Katalin Selmeczi; Clotilde Policar; Nicolas Delsuc Chem. Commun., 56 , p. 399-402, 2020. @article{C9CC07920C, title = {An easy-to-implement combinatorial approach involving an activity-based assay for the discovery of a peptidyl copper complex mimicking superoxide dismutase}, author = {Amandine Vincent and Jennifer Rodon Fores and Elodie Tauziet and Elodie Qu\'{e}vrain and \'{A}gnes Dancs and Amandine Conte-Daban and Anne-Sophie Bernard and Philippe Pelupessy and Koudedja Coulibaly and Philippe Seksik and Christelle Hureau and Katalin Selmeczi and Clotilde Policar and Nicolas Delsuc}, url = {http://dx.doi.org/10.1039/C9CC07920C}, doi = {10.1039/C9CC07920C}, year = {2020}, date = {2020-01-01}, journal = {Chem. Commun.}, volume = {56}, pages = {399-402}, publisher = {The Royal Society of Chemistry}, abstract = {A combinatorial approach using a one-bead-one-compound method and a screening based on a SOD-activity assay was set up for the discovery of an efficient peptidyl copper complex. The complex exhibited good stability constants, suitable redox potentials and excellent intrinsic activity. This complex was further assayed in cells for its antioxidant properties and showed beneficial effects when cells were subjected to oxidative stress.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A combinatorial approach using a one-bead-one-compound method and a screening based on a SOD-activity assay was set up for the discovery of an efficient peptidyl copper complex. The complex exhibited good stability constants, suitable redox potentials and excellent intrinsic activity. This complex was further assayed in cells for its antioxidant properties and showed beneficial effects when cells were subjected to oxidative stress. |
Intracellular location matters: rationalization of the anti-inflammatory activity of a manganese(ii) superoxide dismutase mimic complex Article de journal Emilie Mathieu; Anne-Sophie Bernard; Elodie Quévrain; Martha Zoumpoulaki; Sébastien Iriart; Caroline Lung-Soong; Barry Lai; Kadda Medjoubi; Lucas Henry; Sounderya Nagarajan; Florent Poyer; Andreas Scheitler; Ivana Ivanović-Burmazović; Sergio Marco; Andrea Somogyi; Philippe Seksik; Nicolas Delsuc; Clotilde Policar Chem. Commun., p. -, 2020. @article{D0CC03398G, title = {Intracellular location matters: rationalization of the anti-inflammatory activity of a manganese(ii) superoxide dismutase mimic complex}, author = {Emilie Mathieu and Anne-Sophie Bernard and Elodie Qu\'{e}vrain and Martha Zoumpoulaki and S\'{e}bastien Iriart and Caroline Lung-Soong and Barry Lai and Kadda Medjoubi and Lucas Henry and Sounderya Nagarajan and Florent Poyer and Andreas Scheitler and Ivana Ivanovi\'{c}-Burmazovi\'{c} and Sergio Marco and Andrea Somogyi and Philippe Seksik and Nicolas Delsuc and Clotilde Policar}, url = {http://dx.doi.org/10.1039/D0CC03398G}, doi = {10.1039/D0CC03398G}, year = {2020}, date = {2020-01-01}, journal = {Chem. Commun.}, pages = {-}, publisher = {The Royal Society of Chemistry}, abstract = {A conjugate of a Mn-based superoxide dismutase mimic with a Re-based multimodal probe ̲ was studied in a cellular model of oxidative stress. Its speciation was investigated using Re and Mn X-fluorescence. Interestingly, ̲ shows a distribution different from its unconjugated analogue but a similar concentration in mitochondria and a similar bioactivity.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A conjugate of a Mn-based superoxide dismutase mimic with a Re-based multimodal probe ̲ was studied in a cellular model of oxidative stress. Its speciation was investigated using Re and Mn X-fluorescence. Interestingly, ̲ shows a distribution different from its unconjugated analogue but a similar concentration in mitochondria and a similar bioactivity. |
Anti-inflammatory activity of superoxide dismutase mimics functionalized with cell-penetrating peptides Article de journal Emilie Mathieu; Anne-Sophie Bernard; Vincent H Y Ching; Andrea Somogyi; Kadda Medjoubi; Jennifer Rodon Fores; Hélène C Bertrand; Amandine Vincent; Sylvain Trépout; Jean-Luc Guerquin-Kern; Andreas Scheitler; Ivana Ivanović-Burmazović; Philippe Seksik; Nicolas Delsuc; Clotilde Policar Dalton Trans., 49 , p. 2323-2330, 2020. @article{C9DT04619Db, title = {Anti-inflammatory activity of superoxide dismutase mimics functionalized with cell-penetrating peptides}, author = {Emilie Mathieu and Anne-Sophie Bernard and Vincent H Y Ching and Andrea Somogyi and Kadda Medjoubi and Jennifer Rodon Fores and H\'{e}l\`{e}ne C Bertrand and Amandine Vincent and Sylvain Tr\'{e}pout and Jean-Luc Guerquin-Kern and Andreas Scheitler and Ivana Ivanovi\'{c}-Burmazovi\'{c} and Philippe Seksik and Nicolas Delsuc and Clotilde Policar}, url = {http://dx.doi.org/10.1039/C9DT04619D}, doi = {10.1039/C9DT04619D}, year = {2020}, date = {2020-01-01}, journal = {Dalton Trans.}, volume = {49}, pages = {2323-2330}, publisher = {The Royal Society of Chemistry}, abstract = {A superoxide dismutase mimic (Mn1) was functionalized with three positively charged-peptides: RRRRRRRRR (Mn1-R9), RRWWWRRWRR (Mn1-RW9) or Fx-r-Fx-K (Mn1-MPP). Characterization of the physico-chemical properties of the complexes show that they share similar binding affinity for Mn2+, apparent reduction potential and intrinsic superoxide dismutase activity. However, their accumulation in cells is different (Mn1-R9 < Mn1-MPP < Mn1-RW9 < Mn1), as well as their subcellular distribution. In addition, the three functionalized-complexes display a better anti-inflammatory activity than Mn1 when assayed at 10 μM. This improvement is due to a combination of an anti-inflammatory effect of the peptidyl moiety itself, and of the SOD mimic for Mn1-RW9 and Mn1-MPP. In contrast, the enhanced anti-inflammatory activity of Mn1-R9 is solely due to the SOD mimic.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A superoxide dismutase mimic (Mn1) was functionalized with three positively charged-peptides: RRRRRRRRR (Mn1-R9), RRWWWRRWRR (Mn1-RW9) or Fx-r-Fx-K (Mn1-MPP). Characterization of the physico-chemical properties of the complexes show that they share similar binding affinity for Mn2+, apparent reduction potential and intrinsic superoxide dismutase activity. However, their accumulation in cells is different (Mn1-R9 < Mn1-MPP < Mn1-RW9 < Mn1), as well as their subcellular distribution. In addition, the three functionalized-complexes display a better anti-inflammatory activity than Mn1 when assayed at 10 μM. This improvement is due to a combination of an anti-inflammatory effect of the peptidyl moiety itself, and of the SOD mimic for Mn1-RW9 and Mn1-MPP. In contrast, the enhanced anti-inflammatory activity of Mn1-R9 is solely due to the SOD mimic. |
Differentiation of neural-type cells on multi-scale ordered collagen-silica bionanocomposites Article de journal Nicolas Debons; Dounia Dems; Christophe Hélary; Sylvain Le Grill; Lise Picaut; Flore Renaud; Nicolas Delsuc; Marie-Claire Schanne-Klein; Thibaud Coradin; Carole Aimé Biomater. Sci., 8 , p. 569-576, 2020. @article{C9BM01029Gb, title = {Differentiation of neural-type cells on multi-scale ordered collagen-silica bionanocomposites}, author = {Nicolas Debons and Dounia Dems and Christophe H\'{e}lary and Sylvain Le Grill and Lise Picaut and Flore Renaud and Nicolas Delsuc and Marie-Claire Schanne-Klein and Thibaud Coradin and Carole Aim\'{e}}, url = {http://dx.doi.org/10.1039/C9BM01029G}, doi = {10.1039/C9BM01029G}, year = {2020}, date = {2020-01-01}, journal = {Biomater. Sci.}, volume = {8}, pages = {569-576}, publisher = {The Royal Society of Chemistry}, abstract = {Cells respond to biophysical and biochemical signals. We developed a composite filament from collagen and silica particles modified to interact with collagen and/or present a laminin epitope (IKVAV) crucial for cell\textendashmatrix adhesion and signal transduction. This combines scaffolding and signaling and shows that local tuning of collagen organization enhances cell differentiation.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Cells respond to biophysical and biochemical signals. We developed a composite filament from collagen and silica particles modified to interact with collagen and/or present a laminin epitope (IKVAV) crucial for cell–matrix adhesion and signal transduction. This combines scaffolding and signaling and shows that local tuning of collagen organization enhances cell differentiation. |
Recent Emergence of Rhenium(I) Tricarbonyl Complexes as Photosensitisers for Cancer Therapy Article de journal Hui Shan Liew; Chun-Wai Mai; Mohd Zulkefeli; Thiagarajan Madheswaran; Lik Voon Kiew; Nicolas Delsuc; May Lee Low Molecules, 25 (18), 2020, ISSN: 1420-3049. @article{molecules25184176, title = {Recent Emergence of Rhenium(I) Tricarbonyl Complexes as Photosensitisers for Cancer Therapy}, author = {Hui Shan Liew and Chun-Wai Mai and Mohd Zulkefeli and Thiagarajan Madheswaran and Lik Voon Kiew and Nicolas Delsuc and May Lee Low}, url = {https://www.mdpi.com/1420-3049/25/18/4176}, doi = {10.3390/molecules25184176}, issn = {1420-3049}, year = {2020}, date = {2020-01-01}, journal = {Molecules}, volume = {25}, number = {18}, abstract = {Photodynamic therapy (PDT) is emerging as a significant complementary or alternative approach for cancer treatment. PDT drugs act as photosensitisers, which upon using appropriate wavelength light and in the presence of molecular oxygen, can lead to cell death. Herein, we reviewed the general characteristics of the different generation of photosensitisers. We also outlined the emergence of rhenium (Re) and more specifically, Re(I) tricarbonyl complexes as a new generation of metal-based photosensitisers for photodynamic therapy that are of great interest in multidisciplinary research. The photophysical properties and structures of Re(I) complexes discussed in this review are summarised to determine basic features and similarities among the structures that are important for their phototoxic activity and future investigations. We further examined the in vitro and in vivo efficacies of the Re(I) complexes that have been synthesised for anticancer purposes. We also discussed Re(I) complexes in conjunction with the advancement of two-photon PDT, drug combination study, nanomedicine, and photothermal therapy to overcome the limitation of such complexes, which generally absorb short wavelengths.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Photodynamic therapy (PDT) is emerging as a significant complementary or alternative approach for cancer treatment. PDT drugs act as photosensitisers, which upon using appropriate wavelength light and in the presence of molecular oxygen, can lead to cell death. Herein, we reviewed the general characteristics of the different generation of photosensitisers. We also outlined the emergence of rhenium (Re) and more specifically, Re(I) tricarbonyl complexes as a new generation of metal-based photosensitisers for photodynamic therapy that are of great interest in multidisciplinary research. The photophysical properties and structures of Re(I) complexes discussed in this review are summarised to determine basic features and similarities among the structures that are important for their phototoxic activity and future investigations. We further examined the in vitro and in vivo efficacies of the Re(I) complexes that have been synthesised for anticancer purposes. We also discussed Re(I) complexes in conjunction with the advancement of two-photon PDT, drug combination study, nanomedicine, and photothermal therapy to overcome the limitation of such complexes, which generally absorb short wavelengths. |
2018 |
A Metallo Pro-Drug to Target CuII in the Context of Alzheimer's Disease Article de journal A Conte-Daban; V Ambike; R Guillot; N Delsuc; C Policar; C Hureau Chemistry - A European Journal, 24 (20), p. 5095–5099, 2018. @article{Conte-Daban:2018, title = {A Metallo Pro-Drug to Target CuII in the Context of Alzheimer's Disease}, author = {A Conte-Daban and V Ambike and R Guillot and N Delsuc and C Policar and C Hureau}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85045131927&doi=10.1002%2fchem.201706049&partnerID=40&md5=5dc310a9e12535e296ba5429250159d3}, doi = {10.1002/chem.201706049}, year = {2018}, date = {2018-01-01}, journal = {Chemistry - A European Journal}, volume = {24}, number = {20}, pages = {5095--5099}, abstract = {Alzheimer's disease and oxidative stress are connected. In the present communication, we report the use of a MnII-based superoxide dismutase (SOD) mimic ([MnII(L)]+, 1+) as a pro-drug candidate to target CuII-associated events, namely, CuII-induced formation of reactive oxygen species (ROS) and modulation of the amyloid-β (Aβ) peptide aggregation. Complex 1+ is able to remove CuII from Aβ, stop ROS and prevent alteration of Aβ aggregation as would do the corresponding free ligand LH. Using 1+ instead of LH in further biological applications would have the double advantage to avoid the cell toxicity of LH and to benefit from its proved SOD-like activity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim}, keywords = {}, pubstate = {published}, tppubtype = {article} } Alzheimer's disease and oxidative stress are connected. In the present communication, we report the use of a MnII-based superoxide dismutase (SOD) mimic ([MnII(L)]+, 1+) as a pro-drug candidate to target CuII-associated events, namely, CuII-induced formation of reactive oxygen species (ROS) and modulation of the amyloid-β (Aβ) peptide aggregation. Complex 1+ is able to remove CuII from Aβ, stop ROS and prevent alteration of Aβ aggregation as would do the corresponding free ligand LH. Using 1+ instead of LH in further biological applications would have the double advantage to avoid the cell toxicity of LH and to benefit from its proved SOD-like activity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim |
Labeling of Hyaluronic Acids with a Rhenium-tricarbonyl Tag and Percutaneous Penetration Studied by Multimodal Imaging Article de journal L Henry; N Delsuc; C Laugel; F Lambert; C Sandt; S Hostachy; A -S Bernard; H C Bertrand; L Grimaud; A Baillet-Guffroy; C Policar Bioconjugate Chemistry, 29 (4), p. 987–991, 2018. @article{Henry:2018, title = {Labeling of Hyaluronic Acids with a Rhenium-tricarbonyl Tag and Percutaneous Penetration Studied by Multimodal Imaging}, author = {L Henry and N Delsuc and C Laugel and F Lambert and C Sandt and S Hostachy and A -S Bernard and H C Bertrand and L Grimaud and A Baillet-Guffroy and C Policar}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85045549363&doi=10.1021%2facs.bioconjchem.7b00825&partnerID=40&md5=87140714a264358836c5f4c7734e49a3}, doi = {10.1021/acs.bioconjchem.7b00825}, year = {2018}, date = {2018-01-01}, journal = {Bioconjugate Chemistry}, volume = {29}, number = {4}, pages = {987--991}, abstract = {Hyaluronic acids were labeled with a rhenium-tricarbonyl used as single core multimodal probe for imaging and their penetration into human skin biopsies was studied using IR microscopy and fluorescence imaging (labeled SCoMPI). The penetration was shown to be dependent on the molecular weight of the molecule and limited to the upper layer of the skin. © 2018 American Chemical Society.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Hyaluronic acids were labeled with a rhenium-tricarbonyl used as single core multimodal probe for imaging and their penetration into human skin biopsies was studied using IR microscopy and fluorescence imaging (labeled SCoMPI). The penetration was shown to be dependent on the molecular weight of the molecule and limited to the upper layer of the skin. © 2018 American Chemical Society. |
Graftable SCoMPIs enable the labeling and X-ray fluorescence imaging of proteins Article de journal S Hostachy; M Masuda; T Miki; I Hamachi; S Sagan; O Lequin; K Medjoubi; A Somogyi; N Delsuc; C Policar Chemical Science, 9 (19), p. 4483–4487, 2018. @article{Hostachy:2018, title = {Graftable SCoMPIs enable the labeling and X-ray fluorescence imaging of proteins}, author = {S Hostachy and M Masuda and T Miki and I Hamachi and S Sagan and O Lequin and K Medjoubi and A Somogyi and N Delsuc and C Policar}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85047244059&doi=10.1039%2fc8sc00886h&partnerID=40&md5=4625eaa891ccc665a2357b73e20e3541}, doi = {10.1039/c8sc00886h}, year = {2018}, date = {2018-01-01}, journal = {Chemical Science}, volume = {9}, number = {19}, pages = {4483--4487}, abstract = {Bio-imaging techniques alternative to fluorescence microscopy are gaining increasing interest as complementary tools to visualize and analyze biological systems. Among them, X-ray fluorescence microspectroscopy provides information on the local content and distribution of heavy elements (Z ≥ 14) in cells or biological samples. In this context, similar tools to those developed for fluorescence microscopy are desired, including chemical probes or tags. In this work, we study rhenium complexes as a convenient and sensitive probe for X-ray fluorescence microspectroscopy. We demonstrate their ability to label and sense exogenously incubated or endogenous proteins inside cells. © The Royal Society of Chemistry 2018.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Bio-imaging techniques alternative to fluorescence microscopy are gaining increasing interest as complementary tools to visualize and analyze biological systems. Among them, X-ray fluorescence microspectroscopy provides information on the local content and distribution of heavy elements (Z ≥ 14) in cells or biological samples. In this context, similar tools to those developed for fluorescence microscopy are desired, including chemical probes or tags. In this work, we study rhenium complexes as a convenient and sensitive probe for X-ray fluorescence microspectroscopy. We demonstrate their ability to label and sense exogenously incubated or endogenous proteins inside cells. © The Royal Society of Chemistry 2018. |
2017 |
Re(I) carbonyl complexes: Multimodal platforms for inorganic chemical biology Article de journal S Hostachy; C Policar; N Delsuc Coordination Chemistry Reviews, 351 , p. 172–188, 2017. @article{Hostachy:2017, title = {Re(I) carbonyl complexes: Multimodal platforms for inorganic chemical biology}, author = {S Hostachy and C Policar and N Delsuc}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85020033654&doi=10.1016%2fj.ccr.2017.05.004&partnerID=40&md5=ea1241c6f9199448b3fbb2bfc259b363}, doi = {10.1016/j.ccr.2017.05.004}, year = {2017}, date = {2017-01-01}, journal = {Coordination Chemistry Reviews}, volume = {351}, pages = {172--188}, abstract = {Bio-imaging, by enabling the visualization of biomolecules of interest, has proved to be highly informative in the study of biological processes. Although fluorescence microscopy is probably one of the most used techniques, alternative methods of imaging, providing complementary information, are emerging. In this context, metal complexes represent valuable platforms for multimodal imaging, since they may combine interesting spectroscopic features and biologically relevant functionalization on a single molecular core. In particular, d6 low-spin rhenium tri-carbonyl complexes display unique luminescence and vibrational properties, and can be readily functionalized. Here we review their applications and potential as probes or drugs relying on their photophysical properties, before focusing on their use as multimodal probes for the labelling and imaging of peptides and proteins. © 2017 Elsevier B.V.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Bio-imaging, by enabling the visualization of biomolecules of interest, has proved to be highly informative in the study of biological processes. Although fluorescence microscopy is probably one of the most used techniques, alternative methods of imaging, providing complementary information, are emerging. In this context, metal complexes represent valuable platforms for multimodal imaging, since they may combine interesting spectroscopic features and biologically relevant functionalization on a single molecular core. In particular, d6 low-spin rhenium tri-carbonyl complexes display unique luminescence and vibrational properties, and can be readily functionalized. Here we review their applications and potential as probes or drugs relying on their photophysical properties, before focusing on their use as multimodal probes for the labelling and imaging of peptides and proteins. © 2017 Elsevier B.V. |
An All-in-One Molecule for the One-Step Synthesis of Functional Hybrid Silica Particles with Tunable Sizes Article de journal J Graffion; D Dems; M Demirelli; T Coradin; N Delsuc; C Aimé European Journal of Inorganic Chemistry, 2017 (43), p. 5047–5051, 2017. @article{Graffion:2017, title = {An All-in-One Molecule for the One-Step Synthesis of Functional Hybrid Silica Particles with Tunable Sizes}, author = {J Graffion and D Dems and M Demirelli and T Coradin and N Delsuc and C Aim\'{e}}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85035047611&doi=10.1002%2fejic.201701181&partnerID=40&md5=249333f958412776dc6966b033242102}, doi = {10.1002/ejic.201701181}, year = {2017}, date = {2017-01-01}, journal = {European Journal of Inorganic Chemistry}, volume = {2017}, number = {43}, pages = {5047--5051}, abstract = {Spherical particles with well-defined diameters were obtained by self-assembly of trityl-based molecules. Thanks to the robustness of the organic scaffold, a variety of modifications could be covalently introduced into the network so as to stabilize the supramolecular structure by a sol\textendashgel route. Using supramolecular chemistry, we showed that the synthesis of hybrid small molecules allowed engineering nanomaterials with tunable size and functionality. The use of a combination of different characterization techniques, including dynamic light scattering, cryoTEM, and solid-state NMR spectroscopy, provided careful understanding of the relationship between the molecular and supramolecular structures for further chemical engineering of supramolecular hybrid materials. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim}, keywords = {}, pubstate = {published}, tppubtype = {article} } Spherical particles with well-defined diameters were obtained by self-assembly of trityl-based molecules. Thanks to the robustness of the organic scaffold, a variety of modifications could be covalently introduced into the network so as to stabilize the supramolecular structure by a sol–gel route. Using supramolecular chemistry, we showed that the synthesis of hybrid small molecules allowed engineering nanomaterials with tunable size and functionality. The use of a combination of different characterization techniques, including dynamic light scattering, cryoTEM, and solid-state NMR spectroscopy, provided careful understanding of the relationship between the molecular and supramolecular structures for further chemical engineering of supramolecular hybrid materials. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim |
A host-guest system based on collagen-like triple-helix hybridization Article de journal N Delsuc; S Uchinomiya; A Ojida; I Hamachi Chemical Communications, 53 (51), p. 6856–6859, 2017. @article{Delsuc:2017, title = {A host-guest system based on collagen-like triple-helix hybridization}, author = {N Delsuc and S Uchinomiya and A Ojida and I Hamachi}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85021764142&doi=10.1039%2fc7cc03055j&partnerID=40&md5=702ef29356b9c2adcdde22eeaaafb981}, doi = {10.1039/c7cc03055j}, year = {2017}, date = {2017-01-01}, journal = {Chemical Communications}, volume = {53}, number = {51}, pages = {6856--6859}, abstract = {A strategy inspired by tweezer receptors has been employed to develop a new host-guest system. The hybridization into a collagen-like triple helix is the driving force for the recognition that occurs with high affinity and selectivity. Several systems have been screened to find the best host-guest pair and this strategy may be implemented for tag fused protein recognition. © 2017 The Royal Society of Chemistry.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A strategy inspired by tweezer receptors has been employed to develop a new host-guest system. The hybridization into a collagen-like triple helix is the driving force for the recognition that occurs with high affinity and selectivity. Several systems have been screened to find the best host-guest pair and this strategy may be implemented for tag fused protein recognition. © 2017 The Royal Society of Chemistry. |
E Mathieu; A -S Bernard; N Delsuc; E Quévrain; G Gazzah; B Lai; F Chain; P Langella; M Bachelet; J Masliah; P Seksik; C Policar Inorganic Chemistry, 56 (5), p. 2545–2555, 2017. @article{Mathieu:2017, title = {A Cell-Penetrant Manganese Superoxide Dismutase (MnSOD) Mimic Is Able to Complement MnSOD and Exerts an Antiinflammatory Effect on Cellular and Animal Models of Inflammatory Bowel Diseases}, author = {E Mathieu and A -S Bernard and N Delsuc and E Qu\'{e}vrain and G Gazzah and B Lai and F Chain and P Langella and M Bachelet and J Masliah and P Seksik and C Policar}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85014763334&doi=10.1021%2facs.inorgchem.6b02695&partnerID=40&md5=acd51065ea36d5da707ec8c1915634a0}, doi = {10.1021/acs.inorgchem.6b02695}, year = {2017}, date = {2017-01-01}, journal = {Inorganic Chemistry}, volume = {56}, number = {5}, pages = {2545--2555}, abstract = {Inorganic complexes are increasingly used for biological and medicinal applications, and the question of the cell penetration and distribution of metallodrugs is key to understanding their biological activity. Oxidative stress is known to be involved in inflammation and in inflammatory bowel diseases for which antioxidative defenses are weakened. We report here the study of the manganese complex Mn1 mimicking superoxide dismutase (SOD), a protein involved in cell protection against oxidative stress, using an approach in inorganic cellular chemistry combining the investigation of Mn1 intracellular speciation using mass spectrometry and of its quantification and distribution using electron paramagnetic resonance and spatially resolved X-ray fluorescence with evaluation of its biological activity. More precisely, we have looked for and found the MS signature of Mn1 in cell lysates and quantified the overall manganese content. Intestinal epithelial cells activated by bacterial lipopolysaccharide were taken as a cellular model of oxidative stress and inflammation. DNBS-induced colitis in mice was used to investigate Mn1 activity in vivo. Mn1 exerts an intracellular antiinflammatory activity, remains at least partially coordinated, with diffuse distribution over the whole cell, and functionally complements mitochondrial MnSOD. © 2017 American Chemical Society.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Inorganic complexes are increasingly used for biological and medicinal applications, and the question of the cell penetration and distribution of metallodrugs is key to understanding their biological activity. Oxidative stress is known to be involved in inflammation and in inflammatory bowel diseases for which antioxidative defenses are weakened. We report here the study of the manganese complex Mn1 mimicking superoxide dismutase (SOD), a protein involved in cell protection against oxidative stress, using an approach in inorganic cellular chemistry combining the investigation of Mn1 intracellular speciation using mass spectrometry and of its quantification and distribution using electron paramagnetic resonance and spatially resolved X-ray fluorescence with evaluation of its biological activity. More precisely, we have looked for and found the MS signature of Mn1 in cell lysates and quantified the overall manganese content. Intestinal epithelial cells activated by bacterial lipopolysaccharide were taken as a cellular model of oxidative stress and inflammation. DNBS-induced colitis in mice was used to investigate Mn1 activity in vivo. Mn1 exerts an intracellular antiinflammatory activity, remains at least partially coordinated, with diffuse distribution over the whole cell, and functionally complements mitochondrial MnSOD. © 2017 American Chemical Society. |
2016 |
Photophysical properties of single core multimodal probe for imaging (SCoMPI) in a membrane model and in cells Article de journal S Hostachy; J -M Swiecicki; C Sandt; N Delsuc; C Policar Dalton Transactions, 45 (7), p. 2791–2795, 2016. @article{Hostachy:2016, title = {Photophysical properties of single core multimodal probe for imaging (SCoMPI) in a membrane model and in cells}, author = {S Hostachy and J -M Swiecicki and C Sandt and N Delsuc and C Policar}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84958064177&doi=10.1039%2fc5dt03819g&partnerID=40&md5=fb027086e6424b54b23cc2c11098e273}, doi = {10.1039/c5dt03819g}, year = {2016}, date = {2016-01-01}, journal = {Dalton Transactions}, volume = {45}, number = {7}, pages = {2791--2795}, abstract = {The spectroscopic properties of two luminescent Re(i) tricarbonyl complexes conjugated with two cell-penetrating peptides were examined. Fluorescence experiments and IR quantification in membrane models and in cells showed unexpectedly strong luminescence enhancement for one of the complexes in a lipid environment. © The Royal Society of Chemistry 2016.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The spectroscopic properties of two luminescent Re(i) tricarbonyl complexes conjugated with two cell-penetrating peptides were examined. Fluorescence experiments and IR quantification in membrane models and in cells showed unexpectedly strong luminescence enhancement for one of the complexes in a lipid environment. © The Royal Society of Chemistry 2016. |
New insight into the structural, electrochemical and biological aspects of macroacyclic Cu(II) complexes derived from S-substituted dithiocarbazate schiff bases Article de journal M L Low; L Maigre; M I M Tahir; E R T Tiekink; P Dorlet; R Guillot; T B Ravoof; R Rosli; J -M Pagès; C Policar; N Delsuc; K A Crouse European Journal of Medicinal Chemistry, 120 , p. 1–12, 2016. @article{Low:2016, title = {New insight into the structural, electrochemical and biological aspects of macroacyclic Cu(II) complexes derived from S-substituted dithiocarbazate schiff bases}, author = {M L Low and L Maigre and M I M Tahir and E R T Tiekink and P Dorlet and R Guillot and T B Ravoof and R Rosli and J -M Pag\`{e}s and C Policar and N Delsuc and K A Crouse}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84967102584&doi=10.1016%2fj.ejmech.2016.04.027&partnerID=40&md5=71cde180942655ac9c57205e82887fcf}, doi = {10.1016/j.ejmech.2016.04.027}, year = {2016}, date = {2016-01-01}, journal = {European Journal of Medicinal Chemistry}, volume = {120}, pages = {1--12}, abstract = {Copper (II) complexes synthesized from the products of condensation of S-methyl- and S-benzyldithiocarbazate with 2,5-hexanedione (SMHDH2 and SBHDH2 respectively) have been characterized using various physicochemical (elemental analysis, molar conductivity, magnetic susceptibility) and spectroscopic (infrared, electronic) methods. The structures of SMHDH2, its copper (II) complex, CuSMHD, and the related CuSBHD complex as well as a pyrrole byproduct, SBPY, have been determined by single crystal X-ray diffraction. In order to provide more insight into the behaviour of the complexes in solution, electron paramagnetic resonance (EPR) and electrochemical experiments were performed. Antibacterial activity and cytotoxicity were evaluated. The compounds, dissolved in 0.5% and 5% DMSO, showed a wide range of antibacterial activity against 10 strains of Gram-positive and Gram-negative bacteria. Investigations of the effects of efflux pumps and membrane penetration on antibacterial activity are reported herein. Antiproliferation activity was observed to be enhanced by complexation with copper. Preliminary screening showed Cu complexes are strongly active against human breast adenocarcinoma cancer cell lines MDA-MB-231 and MCF-7. © 2016 Published by Elsevier Masson SAS.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Copper (II) complexes synthesized from the products of condensation of S-methyl- and S-benzyldithiocarbazate with 2,5-hexanedione (SMHDH2 and SBHDH2 respectively) have been characterized using various physicochemical (elemental analysis, molar conductivity, magnetic susceptibility) and spectroscopic (infrared, electronic) methods. The structures of SMHDH2, its copper (II) complex, CuSMHD, and the related CuSBHD complex as well as a pyrrole byproduct, SBPY, have been determined by single crystal X-ray diffraction. In order to provide more insight into the behaviour of the complexes in solution, electron paramagnetic resonance (EPR) and electrochemical experiments were performed. Antibacterial activity and cytotoxicity were evaluated. The compounds, dissolved in 0.5% and 5% DMSO, showed a wide range of antibacterial activity against 10 strains of Gram-positive and Gram-negative bacteria. Investigations of the effects of efflux pumps and membrane penetration on antibacterial activity are reported herein. Antiproliferation activity was observed to be enhanced by complexation with copper. Preliminary screening showed Cu complexes are strongly active against human breast adenocarcinoma cancer cell lines MDA-MB-231 and MCF-7. © 2016 Published by Elsevier Masson SAS. |
Bioinspired superoxide-dismutase mimics: The effects of functionalization with cationic polyarginine peptides Article de journal H Y V Ching; I Kenkel; N Delsuc; E Mathieu; I Ivanović-Burmazović; C Policar Journal of Inorganic Biochemistry, 160 , p. 172–179, 2016. @article{Ching:2016a, title = {Bioinspired superoxide-dismutase mimics: The effects of functionalization with cationic polyarginine peptides}, author = {H Y V Ching and I Kenkel and N Delsuc and E Mathieu and I Ivanovi\'{c}-Burmazovi\'{c} and C Policar}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84964372716&doi=10.1016%2fj.jinorgbio.2016.01.025&partnerID=40&md5=035d0c2b5ffd4ee0b6fb74df285838da}, doi = {10.1016/j.jinorgbio.2016.01.025}, year = {2016}, date = {2016-01-01}, journal = {Journal of Inorganic Biochemistry}, volume = {160}, pages = {172--179}, abstract = {Continuing a bio-mimetic approach, we have prepared peptide conjugates of a superoxide dismutase (SOD) mimic [MnL]+ (where HL = N-(2-hydroxybenzyl)-N,N'-bis[2-(N-methylimidazolyl)methyl]ethane-1,2-diamine), namely [MnL'-Arg(n-1)]n+ (where n = 2, 4, 7 and 10) and [MnL'-Gly1]+. [MnL'-Arg(n-1)]n+ contained cationic residue(s) that emulate the electrostatic channel of the enzyme. Physicochemical methods showed that functionalization at the secondary amine of HL did not impair coordination to MnII with association constants (Kassoc) between 1.6 and 3.3 × 106 M- 1. The MnIII/MnII redox potential of the conjugates was between 0.27 and 0.30 V vs SCE, slightly higher than [MnL]+ under the same conditions, but remain at a value that facilitates O2•- dismutation. The catalytic rate constant (kcat) of the dismutation for the series was studied using a direct stopped-flow method, which showed that for compounds with the same overall charge, the alkylation of the secondary amine of [MnL]+ (kcat = 5.0 ± 0.1 × 106 M- 1 s- 1) led to a lower value (i.e. for [MnL'Gly]+}, keywords = {}, pubstate = {published}, tppubtype = {article} } Continuing a bio-mimetic approach, we have prepared peptide conjugates of a superoxide dismutase (SOD) mimic [MnL]+ (where HL = N-(2-hydroxybenzyl)-N,N'-bis[2-(N-methylimidazolyl)methyl]ethane-1,2-diamine), namely [MnL'-Arg(n-1)]n+ (where n = 2, 4, 7 and 10) and [MnL'-Gly1]+. [MnL'-Arg(n-1)]n+ contained cationic residue(s) that emulate the electrostatic channel of the enzyme. Physicochemical methods showed that functionalization at the secondary amine of HL did not impair coordination to MnII with association constants (Kassoc) between 1.6 and 3.3 × 106 M- 1. The MnIII/MnII redox potential of the conjugates was between 0.27 and 0.30 V vs SCE, slightly higher than [MnL]+ under the same conditions, but remain at a value that facilitates O2•- dismutation. The catalytic rate constant (kcat) of the dismutation for the series was studied using a direct stopped-flow method, which showed that for compounds with the same overall charge, the alkylation of the secondary amine of [MnL]+ (kcat = 5.0 ± 0.1 × 106 M- 1 s- 1) led to a lower value (i.e. for [MnL'Gly]+ |
2015 |
Synthesis, characterization and biological activity of Cu(II), Zn(II) and Re(I) complexes derived from S-benzyldithiocarbazate and 3-acetylcoumarin Article de journal M L Low; G Paulus; P Dorlet; R Guillot; R Rosli; N Delsuc; K A Crouse; C Policar BioMetals, 28 (3), p. 553–566, 2015. @article{Low:2015, title = {Synthesis, characterization and biological activity of Cu(II), Zn(II) and Re(I) complexes derived from S-benzyldithiocarbazate and 3-acetylcoumarin}, author = {M L Low and G Paulus and P Dorlet and R Guillot and R Rosli and N Delsuc and K A Crouse and C Policar}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84939939059&doi=10.1007%2fs10534-015-9831-2&partnerID=40&md5=8d0220a2a88cc9eb122f191d65c87199}, doi = {10.1007/s10534-015-9831-2}, year = {2015}, date = {2015-01-01}, journal = {BioMetals}, volume = {28}, number = {3}, pages = {553--566}, abstract = {Cu(II), Zn(II) and Re(I) complexes have been synthesized with the Schiff base, N′-[1-(2-oxo-2H-chromen-3-yl)-ethylidene]-hydrazinecarbodithioic acid benzyl ester (SBCM-H) which was prepared by condensation of S-benzyldithiocarbazate and 3-acetylcoumarin. The metal complexes were characterized on the basis of various physico-chemical and spectroscopic techniques including elemental analysis and electrochemical studies, and FT-IR, UV-Vis, NMR, EPR and mass spectroscopy. The Schiff base was found to behave as a bidentate ligand coordinating with Cu(II) and Zn(II) in the thiolate form with 1:2 metal to ligand stoichiometry. Crystals suitable for X-ray diffractometry (XRD) were obtained from the reaction of ReCl(CO)5 with SBCM-H forming a centrosymmetric dimeric complex Re2L2(CO)6 linked by Re-S-Re bridges, where S is the thiolate sulfur of the N,S-bidentate ligand. This Re(I) complex is the first metal carbonyl complex with a bidentate dithiocarbazate ligand to have been characterized by XRD. Cytotoxicity assays revealed enhancement of the bioactivity of SBCM-H upon complexation. Both Cu(II) and Re(I) complexes are found to be active against human breast adenocarcinoma cancer cell lines MDA-MB-231 and MCF-7. Graphical Abstract: TOC diagram [Figure not available: see fulltext.] © 2015 Springer Science+Business Media New York.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Cu(II), Zn(II) and Re(I) complexes have been synthesized with the Schiff base, N′-[1-(2-oxo-2H-chromen-3-yl)-ethylidene]-hydrazinecarbodithioic acid benzyl ester (SBCM-H) which was prepared by condensation of S-benzyldithiocarbazate and 3-acetylcoumarin. The metal complexes were characterized on the basis of various physico-chemical and spectroscopic techniques including elemental analysis and electrochemical studies, and FT-IR, UV-Vis, NMR, EPR and mass spectroscopy. The Schiff base was found to behave as a bidentate ligand coordinating with Cu(II) and Zn(II) in the thiolate form with 1:2 metal to ligand stoichiometry. Crystals suitable for X-ray diffractometry (XRD) were obtained from the reaction of ReCl(CO)5 with SBCM-H forming a centrosymmetric dimeric complex Re2L2(CO)6 linked by Re-S-Re bridges, where S is the thiolate sulfur of the N,S-bidentate ligand. This Re(I) complex is the first metal carbonyl complex with a bidentate dithiocarbazate ligand to have been characterized by XRD. Cytotoxicity assays revealed enhancement of the bioactivity of SBCM-H upon complexation. Both Cu(II) and Re(I) complexes are found to be active against human breast adenocarcinoma cancer cell lines MDA-MB-231 and MCF-7. Graphical Abstract: TOC diagram [Figure not available: see fulltext.] © 2015 Springer Science+Business Media New York. |
An easy-to-detect nona-arginine peptide for epidermal targeting Article de journal S Clède; N Delsuc; C Laugel; F Lambert; C Sandt; A Baillet-Guffroy; C Policar Chemical Communications, 51 (13), p. 2687–2689, 2015. @article{Clede:2015a, title = {An easy-to-detect nona-arginine peptide for epidermal targeting}, author = {S Cl\`{e}de and N Delsuc and C Laugel and F Lambert and C Sandt and A Baillet-Guffroy and C Policar}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84922637409&doi=10.1039%2fc4cc08737b&partnerID=40&md5=a0e333e8498570e4d4ceb500066d9c1e}, doi = {10.1039/c4cc08737b}, year = {2015}, date = {2015-01-01}, journal = {Chemical Communications}, volume = {51}, number = {13}, pages = {2687--2689}, abstract = {A correlative approach combining synchrotron radiation based IR microscopy and fluorescence microscopy enabled the successful detection and quantification of a nona-arginine peptide labelled with a Single Core Multimodal Probe for Imaging (SCoMPI) in skin biopsies. The topical penetration of the conjugate appeared to be time dependent and occurred most probably via the extracellular matrix. This journal is © The Royal Society of Chemistry 2015.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A correlative approach combining synchrotron radiation based IR microscopy and fluorescence microscopy enabled the successful detection and quantification of a nona-arginine peptide labelled with a Single Core Multimodal Probe for Imaging (SCoMPI) in skin biopsies. The topical penetration of the conjugate appeared to be time dependent and occurred most probably via the extracellular matrix. This journal is © The Royal Society of Chemistry 2015. |
2014 |
Conjugation of a new series of dithiocarbazate schiff base copper(II) complexes with vectors selected to enhance antibacterial activity Article de journal M L Low; L Maigre; P Dorlet; R Guillot; J -M Pagès; K A Crouse; C Policar; N Delsuc Bioconjugate Chemistry, 25 (12), p. 2269–2284, 2014. @article{Low:2014, title = {Conjugation of a new series of dithiocarbazate schiff base copper(II) complexes with vectors selected to enhance antibacterial activity}, author = {M L Low and L Maigre and P Dorlet and R Guillot and J -M Pag\`{e}s and K A Crouse and C Policar and N Delsuc}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84918505283&doi=10.1021%2fbc5004907&partnerID=40&md5=d51ad81235fa7fd9aec14b7acd2c908a}, doi = {10.1021/bc5004907}, year = {2014}, date = {2014-01-01}, journal = {Bioconjugate Chemistry}, volume = {25}, number = {12}, pages = {2269--2284}, abstract = {A new series of six Schiff bases derived from S-methyldithiocarbazate (SMDTC) and S-benzyldithiocarbazate (SBDTC) with methyl levulinate (SMML, SBML), levulinic acid (SMLA, SBLA), and 4-carboxybenzaldehyde (SM4CB, SB4CB) were reacted with copper(II), producing complexes of general formula MLtextlessinftextgreater2textless/inftextgreater (M = Cu(II)}, keywords = {}, pubstate = {published}, tppubtype = {article} } A new series of six Schiff bases derived from S-methyldithiocarbazate (SMDTC) and S-benzyldithiocarbazate (SBDTC) with methyl levulinate (SMML, SBML), levulinic acid (SMLA, SBLA), and 4-carboxybenzaldehyde (SM4CB, SB4CB) were reacted with copper(II), producing complexes of general formula MLtextlessinftextgreater2textless/inftextgreater (M = Cu(II) |
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} } |
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 |
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. |
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. |
2011 |
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. |
2010 |
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 |
Interplay of Interactions Governing the Dynamic Conversions of Acyclic and Macrocyclic Helicates Article de journal Victoria E. Campbell; Xavier de Hatten; Nicolas Delsuc; Brice Kauffmann; Ivan Huc; Jonathan R. Nitschke Chemistry - A European Journal, 15 (25), p. 6138–6142, 2009, ISSN: 09476539, 15213765. @article{campbell_interplay_2009, title = {Interplay of Interactions Governing the Dynamic Conversions of Acyclic and Macrocyclic Helicates}, author = {Victoria E. Campbell and Xavier de Hatten and Nicolas Delsuc and Brice Kauffmann and Ivan Huc and Jonathan R. Nitschke}, url = {http://doi.wiley.com/10.1002/chem.200900693}, doi = {10.1002/chem.200900693}, issn = {09476539, 15213765}, year = {2009}, date = {2009-01-01}, urldate = {2018-02-18}, journal = {Chemistry - A European Journal}, volume = {15}, number = {25}, pages = {6138--6142}, keywords = {}, pubstate = {published}, tppubtype = {article} } |