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175 results on '"Loïc J. Charbonnière"'

1. Yb to Tb Cooperative Upconversion in Supramolecularly Assembled Complexes in a Solution

Author

Lohona K. Soro, Cyrille Charpentier, Frédéric Przybilla, Yves Mély, Aline M. Nonat, and Loïc J. Charbonnière

Subjects
lanthanides, luminescence, upconversion, supramolecular chemistry, cooperative sensitization, Chemistry, QD1-999
Abstract

The podand-type ligand L, based on a tertiary amine substituted by three pyridyl-6-phosphonic acid functions, forms hydrated complexes with Ln3+ cations. The luminescence properties of the YbL complex were studied in D2O as a function of the pD and temperature. In basic conditions, increases in the luminescence quantum yield and the excited state lifetime of the Yb centered emission associated with the 2F5/2 → 2F7/2 transition were observed and attributed to a change in the hydration number from two water molecules in the first coordination sphere of Yb at acidic pH to a single one in basic conditions. Upon the addition of TbCl3 salts to a solution containing the YbL complex in D2O, heteropolynuclear Yb/Tb species formed, and excitation of the Yb at 980 nm resulted in the observation of the typical visible emission of Tb as a result of a cooperative upconversion (UC) photosensitization process. The UC was further evidenced by the quadratic dependence of the UC emission as a function of the laser power density.

Published
2021
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2. Optical spin-state polarization in a binuclear europium complex towards molecule-based coherent light-spin interfaces

Author

Kuppusamy Senthil Kumar, Diana Serrano, Aline M. Nonat, Benoît Heinrich, Lydia Karmazin, Loïc J. Charbonnière, Philippe Goldner, and Mario Ruben

Subjects
Science
Abstract

Rare-earth ion (REI)-doped systems are well suited for realising coherent light-spin interfaces, but demonstrations of spectral hole burning (SHB) in optical transitions of REI-based systems have been so far limited to REIs dispersed in matrices. Here, the authors report on transient SHB in a binuclear Eu(III) complex.

Published
2021
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4. 55/52Mn2+ Complexes with a Bispidine-Phosphonate Ligand: High Kinetic Inertness for Imaging Applications

Author

Maryame Sy, Daouda Ndiaye, Isidro da Silva, Sara Lacerda, Loïc J. Charbonnière, Éva Tóth, Aline M. Nonat, Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), and HEP, INSPIRE

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Inorganic Chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, [SDV.IB.IMA] Life Sciences [q-bio]/Bioengineering/Imaging, [SDV.IB.IMA]Life Sciences [q-bio]/Bioengineering/Imaging, [CHIM.COOR]Chemical Sciences/Coordination chemistry, [CHIM.COOR] Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry
Abstract

International audience; Bispidine (3,7-diazabicyclo[3.3.1]nonane) provides a rigid and preorganized scaffold that is particularly interesting for the stable and inert complexation of metal ions, especially for their application in medical imaging. In this study, we present the synthesis of two bispidine ligands with N-methanephosphonate (H4L1) and N-methanecarboxylate (H3L2) substituents as well as the physico-chemical properties of the corresponding Mn2+ and Zn2+ complexes. The two complexes [Mn(L-1)](2- )and [Mn(L-2)](-) have relatively moderate thermodynamic stability constants according to potentiometric titration data. However, they both display an exceptional kinetic inertness, as assessed by transmetallation experiments in the presence of 50 equiv excess of Zn2+, showing only similar to 40 and 20% of dissociation for [Mn(L-1)](2- ) and [Mn(L-2)](-), respectively, after 150 days at pH 6 and 37°C. Proton relaxivities amount to r(1 )= 4.31 mM(-1 )s(-1 )([Mn(L-1)](2-)) and 3.64 mM(-1) s(-1 )([Mn(L-2)](-)) at 20 MHz, 25°C, and are remarkable for Mn2+ complexes with one inner-sphere water molecule (q = 1); they are comparable to that of the commercial contrast agent [Gd(DOTA)(H2O)](-). The presence of one inner-sphere water molecule and an associative water exchange mechanism was confirmed by temperature-dependent transverse O-17 relaxation rate measurements, which yielded k(ex)(298) = 0.12 x 10(7) and 5.5 x 10(7) s(-1 )for the water exchange rate of the phosphonate and the carboxylate complex, respectively. In addition, radiolabeling experiments with Mn-52 were also performed with H-2(L-1)(2-) showing excellent radiolabeling properties and quantitative complexation at pH 7 in 15 min at room temperature as well as excellent stability of the complex in various biological media over 24 h.

Published
2022

5. Upconversion in a d–f [RuYb3] Supramolecular Assembly

Author

Richard C. Knighton, Lohona K. Soro, Waygen Thor, Jean-Marc Strub, Sarah Cianférani, Yves Mély, Marc Lenertz, Ka-Leung Wong, Carlos Platas-Iglesias, Frédéric Przybilla, and Loïc J. Charbonnière

Subjects
Colloid and Surface Chemistry, General Chemistry, Biochemistry, Catalysis
Published
2022

6. Room temperature molecular up conversion in solution

Author

Aline Nonat, Chi Fai Chan, Tao Liu, Carlos Platas-Iglesias, Zhenyu Liu, Wing-Tak Wong, Wai-Kwok Wong, Ka-Leung Wong, and Loïc J. Charbonnière

Subjects
Science
Abstract

Up conversion is an Anti-Stokes luminescent process by which photons of low energy are piled up to generate light at a higher energy. Here, the authors report a supramolecular assembly of fluoride-bridged erbium complexes which exhibit this behaviour in D2O solution at room temperature.

Published
2016
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8. Dye-sensitized lanthanide containing nanoparticles for luminescence based applications

Author

Clémence Cheignon, Ali A. Kassir, Lohona K. Soro, and Loïc J. Charbonnière

Subjects
Aucun, General Materials Science
Abstract

Due to their exceptional luminescent properties, lanthanide (Ln) complexes represent a unique palette of probes in the spectroscopic toolkit. Their extremely weak brightness due to forbidden Ln electronic transitions can be overcome by indirect dye-sensitization from the antenna effect brought by organic ligands. Despite the improvement brought by the antenna effect, (bio)analytical applications with discrete Ln complexes as luminescent markers still suffers from low sensitivity as they are limited by the complex brightness. Thus, there is a need to develop nano-objects that cumulate the spectroscopic properties of multiple Ln ions. This review firstly gives a brief introduction of the spectral properties of lanthanides both in complexes and in nanoparticles (NPs). Then, the research progress of the design of Ln-doped inorganic NPs with capping antennas, Ln-complex encapsulated NPs and Ln-complex surface functionalized NPs is presented along with a summary of the various photosensitizing ligands and of the spectroscopic properties (excited-state lifetime, brightness, quantum yield). The review also emphasizes the problems and limitations encountered over the years and the solutions provided to address them. Finally, a comparison of the advantages and drawbacks of the three types of NP is provided as well as a conclusion about the remaining challenges both in the design of brighter NPs and in the luminescence based applications.

Published
2022

11. Solution-State Cooperative Luminescence Upconversion in Molecular Ytterbium Dimers

Author

Lohona K. Soro, Richard C. Knighton, Fernando Avecilla, Waygen Thor, Frédéric Przybilla, Olivier Jeannin, David Esteban‐Gomez, Carlos Platas‐Iglesias, Loïc J. Charbonnière, Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Universidade da Coruña, Laboratoire de Bioimagerie et Pathologies (LBP), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), French Ministere de l'Education Nationale et de la Recherche, French Canada Research Fund, Frontier Research in Chemistry Foundation (LabEx CSC) [ANR-10-LABX-0026_CSC], French National research agency [ANR-20-CE09-0021-02, ANR-19-CE29-0014-01], Ministerio de Ciencia e Innovacion [PID2019-104626GB-I00], ANR-20-CE09-0021,LaPin,Nanoparticules polymériques chargées en lanthanides pour la détection et l'imagerie in vitro et in vivo sans autofluorescence(2020), ANR-10-LABX-0026,CSC,Center of Chemistry of Complex System(2010), and ANR-19-CE29-0014,LUCAS,Assemblages moléculaires et supramoléculaires pour la conversion ascendante de photons(2019)

Subjects
upconversion, [CHIM]Chemical Sciences, Chimie/Autre, cooperative luminescence, lanthanides, photoluminescence, Atomic and Molecular Physics, and Optics, Electronic, Optical and Magnetic Materials
Abstract

International audience; Two homometallic ytterbium dimers are prepared and their solution-state photoluminescence and upconversion properties are investigated. Both complexes exhibit two-photon cooperative luminescence upconversion in the visible region (lambda(em) approximate to 510 nm) upon excitation into the near-infrared Yb F-2(5/2)

Published
2022

12. Intracellular accumulation and immunological response of NIR-II polymeric nanoparticles

Author

Iryna Moskalevska, Virginie Faure, Lucie Haye, Marion Mercey-Ressejac, Arindam K. Dey, Benoit Chovelon, Lohona K. Soro, Loïc J. Charbonnière, Andreas Reisch, Andrey S. Klymchenko, Patrice N. Marche, Jean-Luc Coll, Zuzana Macek Jilkova, and Xavier le Guével

Subjects
Pharmaceutical Science
Abstract

Polymeric nanoparticles (NPs) are extremely promising for theranostic applications. However, their interest depends largely on their interactions with immune system, including the capacity to activate inflammation after their capture by macrophages. In the present study, we generated monodisperse poly(ethyl methacrylate) (PEMA) NPs loaded with hydrophobic photoluminescent gold nanoclusters (Au NCs) emitting in the NIR-II optical windows and studied their interaction in vitro with J774.1A macrophages. PEMA NPs showed an efficient time and dose dependent cellular uptake with up to 70 % of macrophages labelled in 24 h without detectable cell death. Interestingly, PEMA and Au-PEMA NPs induced an anti-inflammatory response and a strong down-regulation of nitric oxide level on lipopolysacharides (LPS) activated macrophages, but without influence on the levels of reactive oxygen species (ROS). These polymeric NPs may thus present a potential interest for the treatment of inflammatory diseases.

Published
2023

13. Cooperative Luminescence and Cooperative Sensitisation Upconversion of Lanthanide Complexes in Solution

Author

Richard C. Knighton, Niko Hildebrandt, Guillaume Pilet, Carlos Platas-Iglesias, Lohona K. Soro, Loïc J. Charbonnière, Aurora Rodríguez-Rodríguez, Marc Lenertz, and Laura Francés-Soriano

Subjects
Lanthanide, Quenching (fluorescence), Materials science, Quantum yield, General Chemistry, 02 engineering and technology, General Medicine, Photochemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 7. Clean energy, Catalysis, Photon upconversion, 0104 chemical sciences, Upconversion nanoparticles, Excited state, Solar energy conversion, Luminescence, 0210 nano-technology
Abstract

Upconversion nanoparticles have led to various breakthrough applications in solar energy conversion, imaging, and biomedicine. One key impediment is the facilitation of such processes at the molecular scale in solution where quenching effects are much more pronounced. In this work, molecular solution-state cooperative luminescence (CL) upconversion arising from a Yb excited state is explored and the mechanistic origin behind cooperative sensitisation (CS) upconversion in Yb/ Tb systems is investigated. Counterintuitively, the best UC performances were obtained for Yb/Tb ratios close to parity, resulting in the brightest molecular upconversion complexes with a quantum yield of 2.8 × 10-6 at a low laser power density of 2.86 W/cm2.

Published
2021

14. Investigation of the Supramolecular Assembly of Luminescent Lanthanide Nanoparticles Surface Functionalized by p‐ Sulfonato‐Calix[4]arenes with Charged Aromatic Compounds

Author

Aline Nonat, Câline Christine, Anne Boos, Alexandre Lecointre, Loïc J. Charbonnière, Zouhair Asfari, Clémence Cheignon, Richard C. Knighton, Ali A. Kassir, Margaux Heurté, Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Lanthanide, Photoluminescence, Quenching (fluorescence), 010405 organic chemistry, Chemistry, Aucun, Antenna effect, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Supramolecular assembly, Inorganic Chemistry, Rhodamine 6G, Crystallography, chemistry.chemical_compound, Calixarene, [CHIM]Chemical Sciences, Luminescence, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; The surface coordination of p-sulfonato- (C[4]), p-sulfonatothia- (SC[4]) and p-sulfonato-sulfoxocalix[4]arene (SO2C[4]) on La0.9Tb0.1F3 nanoparticles (TbNP) was investigated by UV-Vis absorption and luminescence spectroscopies. SO2C[4] displayed the strongest affinity towards the NPs and a significant antenna effect leading to observation of the characteristic Tb emission bands upon calixarene excitation. NPs decorated by a shell of SO2C[4] were prepared and the interaction with rhodamine 6G (R6G) was studied. The progressive addition of R6G resulted in a strong Tb to R6G energy transfer process, as revealed by a long lived emission of R6G upon SO2C[4] excitation. The FRET efficiency was almost quantitative (87-90 %), pointing to an average distance of 28 to 32 Å between the R6G and the Tb emitting centres of the NP. An association of one R6G per SO2C[4] was deduced with a very strong apparent affinity (K = 2.5 107 M-1) in water. Similar interactions were observed with paraquat, resulting in TbNP luminescence quenching. In both cases, an unexpected increase of the association constant of the cation with SO2C[4] was observed when SO2C[4] is anchored at the surface of the NP.

Published
2021

15. Elucidating Cooperative Luminescence and Cooperative Sensitisation Upconversion of Nonanuclear Lanthanide Complexes in Solution

Author

Richard C. Knighton, Niko Hildebrandt, Aurora Rodríguez-Rodríguez, Laura Francés-Soriano, Loïc J. Charbonnière, Lohona K. Soro, Guillaume Pilet, Carlos Platas-Iglesias, and Marc Lenertz

Subjects
Lanthanide, Laser power density, Materials science, Quenching (fluorescence), Excited state, Quantum yield, Luminescence, Photochemistry, Spectroscopy, Photon upconversion
Abstract

Upconversion nanoparticles have led to various breakthrough applications in solar energy conversion, imaging, and biomedicine. One key impediment is the facilitation of such processes at the molecular scale in solution where quenching effects are much more pronounced. In this work we explore, for the first time, molecular solution-state cooperative luminescence (CL) upconversion arising from a Yb excited state and investigate the mechanistic origin behind cooperative sensitisation (CS) upconversion in Yb/ Tb systems. Counterintuitively, the best UC performances were obtained for Yb/Tb ratios close to parity, resulting in the brightest molecular upconversion complexes with an unprecedented quantum yield of 2.8 × 10-6 at a low laser power density of 2.86 W/cm2.

Published
2021

16. Yb to Tb Cooperative Upconversion in Supramolecularly Assembled Complexes in a Solution

Author

Yves Mély, Cyrille Charpentier, Lohona K. Soro, Frédéric Przybilla, Aline Nonat, Loïc J. Charbonnière, Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Bioimagerie et Pathologies (LBP), and Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Lanthanide, upconversion, Coordination sphere, Tertiary amine, 010405 organic chemistry, Chemistry, Ligand, General Medicine, 010402 general chemistry, 01 natural sciences, Photon upconversion, supramolecular chemistry, 0104 chemical sciences, Crystallography, Excited state, luminescence, Molecule, [CHIM]Chemical Sciences, lanthanides, cooperative sensitization, Luminescence, QD1-999
Abstract

The podand-type ligand L, based on a tertiary amine substituted by three pyridyl-6-phosphonic acid functions, forms hydrated complexes with Ln3+ cations. The luminescence properties of the YbL complex were studied in D2O as a function of the pD and temperature. In basic conditions, increases in the luminescence quantum yield and the excited state lifetime of the Yb centered emission associated with the 2F5/2 → 2F7/2 transition were observed and attributed to a change in the hydration number from two water molecules in the first coordination sphere of Yb at acidic pH to a single one in basic conditions. Upon the addition of TbCl3 salts to a solution containing the YbL complex in D2O, heteropolynuclear Yb/Tb species formed, and excitation of the Yb at 980 nm resulted in the observation of the typical visible emission of Tb as a result of a cooperative upconversion (UC) photosensitization process. The UC was further evidenced by the quadratic dependence of the UC emission as a function of the laser power density.

Published
2021

17. From Mono- to Polynuclear Coordination Complexes with a 2,2’-Bipyrimidine-4,4’-dicarboxylate Ligand

Author

Thomas Fix, Olivier Jeannin, Piotr W. Zabierowski, Jean-François Guillemoles, Aline Nonat, Loïc J. Charbonnière, Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des sciences de l'ingénieur, de l'informatique et de l'imagerie (ICube), École Nationale du Génie de l'Eau et de l'Environnement de Strasbourg (ENGEES)-Université de Strasbourg (UNISTRA)-Institut National des Sciences Appliquées - Strasbourg (INSA Strasbourg), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut National de Recherche en Informatique et en Automatique (Inria)-Les Hôpitaux Universitaires de Strasbourg (HUS)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut Photovoltaïque d’Ile-de-France (ITE) (IPVF), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut National des Sciences Appliquées - Strasbourg (INSA Strasbourg), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-École Nationale du Génie de l'Eau et de l'Environnement de Strasbourg (ENGEES)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), and Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Lanthanide, chemistry.chemical_classification, Chloroform, Aqueous solution, 010405 organic chemistry, Ligand, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Dicarboxylic acid, chemistry, Proton NMR, [CHIM]Chemical Sciences, Titration, Chelation, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

The coordination properties of the ligand 2,2'-bipyrimidine-4,4'-dicarboxylic acid (H2bpd) with lanthanide(III) ions (Ln = Eu, Tb, or Lu) were investigated. The syntheses of the H2bpd ligand and its salts, [K2(bpd)(H2O)2] (1) and [(AlkNH)Lu(bpd)2] (Alk = Et, Hex, or en), are described. In the presence of LnCl3 salts (Ln = Lu, Eu, or Tb), the formation of [Ln(bpd)2]- and [Ln(bpd)(H2O)x]+ species was assessed by 1H nuclear magnetic resonance (NMR), spectrophotometry, and spectrofluorometric titrations in aqueous solution. The solid state structure of 1, [K(H2O)2][Lu(bpd)2] (2), and [(Et3NH)Lu(bpd)2] (3) could be determined by X-ray diffraction, showing the ligand to act as a tetradentate unit with formation of three five-membered chelate rings around the central Ln(III). With the aim of building polynuclear assemblies, the coordination between [Lu(bdp)2]- and [Lu(tta)3(H2O)] units (tta = thenoyltrifluoroacetylacetonate) was also investigated. In methanol, 1H NMR titration experiments revealed the formation of complex mixtures from which two new species could be identified, [Lu2(bpd)(tta)4] (4) and H[Lu(bpd)(tta)2] (5), as confirmed by their solid state structure analysis. Using highly lipophilic cations in chloroform, the octametallic complex [enH]4[Lu8(bpd)4(tta)18] (6) could be isolated and its X-ray structure determined.

Published
2021

18. Phosphonated Podand Type Ligand for the Complexation of Lanthanide CationsPhosphonated Podand Type Ligand for the Complexation of Lanthanide Cations

Author

Olivier Jeannin, Cyrille Charpentier, Alexandre Lecointre, Aline Nonat, Jérémy Salaam, and Loïc J. Charbonnière

Subjects
Inorganic Chemistry, Lanthanide, chemistry.chemical_classification, chemistry, 010405 organic chemistry, Ligand, Polymer chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Coordination complex
Published
2019

19. Molecular Upconversion in Water in Heteropolynuclear Supramolecular Tb/Yb Assemblies

Author

Franck Camerel, Loïc J. Charbonnière, Carlos Platas-Iglesias, Sylvana Bahamyirou, Frédéric Przybilla, Yves Mély, Alexandre Lecointre, Aline Nonat, Olivier Jeannin, Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Bioimagerie et Pathologies (LBP), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Universidade da Coruña, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Doctor Robert Pansu (Ecole Normal Superieure de Cachan, ́France) is gratefully acknowledged for his advice and fruitful discussions concerning the determination of the luminescence UC QY. C.P.-I. thanks Centro de Supercomputacion de Galicia for providing the computer facilities., Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Quenching (fluorescence), Aqueous solution, Chemistry, Supramolecular chemistry, General Chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Biochemistry, Catalysis, Photon upconversion, 0104 chemical sciences, Supramolecular assembly, Colloid and Surface Chemistry, Absorption band, Excited state, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Luminescence
Abstract

Piling up excited states to reach upconversion (UC) is severely restricted by vibrational quenching mechanisms, especially when one looks at discrete molecular entities in solution. By carefully controlling the supramolecular assembly processes resulting from the strong electrostatic interactions between negatively charged Yb complexes and Tb3+ cations in aqueous solutions, we engineered the formation of heteropolynuclear complexes of [(YbL)2Tb x] compositions ( x = 1 and 2). These edifices display a phenomenon of cooperative photosensitization UC with green emission of the Tb cations upon NIR excitation at 980 nm in the Yb absorption band. The photophysical properties of the complexes were carefully investigated by steady-state and time-resolved luminescence experiments in D2O, allowing one to quantify the impact of the composition and pD of the solution on the emission intensity as well as clarifying the exact cooperative photosensitization upconversion mechanism. Using optimized conditions, the energy transfer UC process could be observed for the first time in nondeuterated water with discrete molecular compounds.

Published
2019

20. Structural and Thermodynamics Studies on Polyaminophosphonate Ligands for Uranyl Decorporation

Author

Pier-Lorenzo Solari, E. Simoni, Loïc J. Charbonnière, Wangsuo Wu, Jérémy Brandel, Christophe Den Auwer, Jérôme Roques, Aurélie Jeanson, Gaoyang Ye, Laboratoire de Physique des 2 Infinis Irène Joliot-Curie (IJCLab), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Nice (ICN), Université Nice Sophia Antipolis (... - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA), Institut Pluridisciplinaire Hubert Curien (IPHC), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA)-Université Nice Sophia Antipolis (... - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA), and Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[PHYS]Physics [physics], 010405 organic chemistry, Chemistry, Ligand, Inorganic chemistry, chemistry.chemical_element, Actinide, Uranium, 010402 general chemistry, Uranyl, 01 natural sciences, 7. Clean energy, Fluorescence spectroscopy, 0104 chemical sciences, X-ray absorption fine structure, Inorganic Chemistry, chemistry.chemical_compound, Chelation, Physical and Theoretical Chemistry, Coordination geometry
Abstract

International audience; The development of actinide decorporation agents with high complexation affinity, high tissue specificity, and low biological toxicity is of vital importance for the sustained and healthy development of nuclear energy. After accidental actinide intake, sequestration by chelation therapy to reduce acute damage is considered as the most effective method. In this work, a series of bis- and tetra-phosphonated pyridine ligands have been designed, synthesized, and characterized for uranyl (UO22+) decorporation. Owing to the absorption of the ligand and the luminescence of the uranyl ion, UV–vis spectroscopy and time-resolved laser-induced fluorescence spectroscopy (TRLFS) were used to probe in situ complexation and structure variation of the complexes formed by the ligands with uranyl. Density functional theory (DFT) calculations and X-ray absorption fine structure (XAFS) spectroscopy on uranyl–ligand complexes revealed the coordination geometry around the uranyl center at pH 3 and 7.4. High affinity constants (log K ∼17) toward the uranyl ion were determined by displacement titration. A preliminary in vitro chelation study proves that bis-phosphonated pyridine ligands can remove uranium from calmodulin (CaM) at a low dose and in the short term, which supports further uranyl decorporation applications of these ligands

Published
2021

21. Cyclam-Based Chelators Bearing Phosphonated Pyridine Pendants for

Author

Richard C, Knighton, Thibault, Troadec, Valérie, Mazan, Patricia, Le Saëc, Séverine, Marionneau-Lambot, Thomas, Le Bihan, Nathalie, Saffon-Merceron, Nathalie, Le Bris, Michel, Chérel, Alain, Faivre-Chauvet, Mourad, Elhabiri, Loïc J, Charbonnière, and Raphaël, Tripier

Subjects
Kinetics, Mice, Mice, Inbred BALB C, Copper Radioisotopes, Heterocyclic Compounds, Phosphorous Acids, Pyridines, Positron-Emission Tomography, Electron Spin Resonance Spectroscopy, Animals, Crystallography, X-Ray, Ligands, Chelating Agents
Abstract

Herein we present the preparation of two novel cyclam-based macrocycles (

Published
2021

22. Cyclam-Based Chelators Bearing Phosphonated Pyridine Pendants for 64Cu-PET Imaging : Synthesis, Physico-Chemical Studies, Radiolabeling and Bioimaging

Author

Richard Knighton, Thibault Troadec, Valerie Mazan, Patricia Le Saëc, Séverine Marionneau-Lambot, Thomas Le Bihan, Nathalie Saffon-Merceron, Nathalie Le Bris, Michel Chérel, Alain Faivre-Chauvet, Mourad Elhabiri, Loïc J. Charbonnière, Raphael Tripier, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Laboratoire d'innovation moléculaire et applications (LIMA), Centre National de la Recherche Scientifique (CNRS)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Université de Strasbourg (UNISTRA), Centre de Recherche en Cancérologie et Immunologie Nantes-Angers (CRCINA), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Nantes - UFR de Médecine et des Techniques Médicales (UFR MEDECINE), Université de Nantes (UN)-Université de Nantes (UN)-Centre hospitalier universitaire de Nantes (CHU Nantes)-Centre National de la Recherche Scientifique (CNRS)-Université d'Angers (UA), Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), Institut Pluridisciplinaire Hubert Curien (IPHC), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Nuclear Oncology (CRCINA-ÉQUIPE 13), Université de Nantes (UN)-Université de Nantes (UN)-Centre hospitalier universitaire de Nantes (CHU Nantes)-Centre National de la Recherche Scientifique (CNRS)-Université d'Angers (UA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Nantes - UFR de Médecine et des Techniques Médicales (UFR MEDECINE), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Troadec, Thibault, Université d'Angers (UA)-Université de Nantes (UN)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre hospitalier universitaire de Nantes (CHU Nantes)-Université d'Angers (UA)-Université de Nantes (UN)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre hospitalier universitaire de Nantes (CHU Nantes), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées, and Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[SDV.CAN] Life Sciences [q-bio]/Cancer, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.RADIO] Chemical Sciences/Radiochemistry, [CHIM]Chemical Sciences, [SDV.CAN]Life Sciences [q-bio]/Cancer, [CHIM.COOR]Chemical Sciences/Coordination chemistry, [CHIM.COOR] Chemical Sciences/Coordination chemistry, [CHIM.RADIO]Chemical Sciences/Radiochemistry
Abstract

Herein we present the preparation of two novel cyclam-based macrocycles (te1pyp and cb-te1pyp), bearing phosphonate-appended pyridine side-arms for the coordination of copper(II) ions in the context of 64Cu PET imaging. The two ligands have been prepared through conventional protection-alkylation sequences on cyclam, and their coordination properties have been thoroughly investigated. The corresponding copper complexes have been fully characterized in the solid-state (X-Ray diffraction analysis) and in solution (EPR and UV-Vis spectroscopies). Potentiometric studies, combined with spectrometry, have also allowed us to determine their thermodynamic stability constants, confirming their high affinity for copper(II) cations. The kinetic inertness of the complexes has also been verified by acid-assisted dissociation experiments, enabling their use in 64Cu-PET imaging in mice for the first time. Indeed, the two ligands could be quantitatively radiolabeled under mild conditions, and the resulting 64Cu complexes have demonstrated excellent stability in serum. PET imaging demon-strated a set of features emerging from the combination of picolinates and phosphonate units: high stability in vivo, fast clear-ance from the body via renal elimination, and most interestingly, very low fixation in the liver. The latter is in contrast with what was observed for monopicolinate cyclam (te1pa), that had a non-negligible accumulation in the liver, owing probably to its different charge and lipophillicity. These results thus pave the way for the use of such phosphonated pyridine chelators for in vivo 64Cu-PET imaging.

Published
2021

23. Cyclam-Based Chelators Bearing Phosphonated Pyridine Pendants for 64 Cu-PET Imaging: Synthesis, Physicochemical Studies, Radiolabeling, and Bioimaging

Author

Séverine Marionneau-Lambot, Nathalie Saffon-Merceron, Michel Chérel, Mourad Elhabiri, Valérie Mazan, Nathalie Le Bris, Richard C. Knighton, Loïc J. Charbonnière, Thibault Troadec, Thomas Le Bihan, Patricia Le Saëc, Raphaël Tripier, Alain Faivre-Chauvet, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Laboratoire d'innovation moléculaire et applications (LIMA), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de Recherche en Cancérologie et Immunologie Nantes-Angers (CRCINA), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Nantes - UFR de Médecine et des Techniques Médicales (UFR MEDECINE), Université de Nantes (UN)-Université de Nantes (UN)-Centre hospitalier universitaire de Nantes (CHU Nantes)-Centre National de la Recherche Scientifique (CNRS)-Université d'Angers (UA), Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Institut Pluridisciplinaire Hubert Curien (IPHC), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Université d'Angers (UA)-Université de Nantes (UN)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre hospitalier universitaire de Nantes (CHU Nantes), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées, Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Troadec, Thibault, Institut de Chimie de Toulouse (ICT), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), and ANR-16-IDEX-0007,NExT (I-SITE),NExT (I-SITE)(2016)

Subjects
Organophosphorus compounds, [SDV.IB.IMA]Life Sciences [q-bio]/Bioengineering/Imaging, Reaction mechanisms, Potentiometric titration, chemistry.chemical_element, 010402 general chemistry, Ligands, 01 natural sciences, Dissociation (chemistry), Inorganic Chemistry, chemistry.chemical_compound, Cyclam, Pyridine, [CHIM.RADIO] Chemical Sciences/Radiochemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, 010405 organic chemistry, [CHIM.COOR] Chemical Sciences/Coordination chemistry, Combinatorial chemistry, Copper, Phosphonate, 0104 chemical sciences, [SDV.IB.IMA] Life Sciences [q-bio]/Bioengineering/Imaging, chemistry, Lipophilicity, Chemical stability, Stability, [CHIM.RADIO]Chemical Sciences/Radiochemistry
Abstract

International audience; Herein we present the preparation of two novel cyclam-based macrocycles (te1pyp and cb-te1pyp), bearing phosphonate-appended pyridine side arms for the coordination of copper(II) ions in the context of 64Cu PET imaging. The two ligands have been prepared through conventional protection–alkylation sequences on cyclam, and their coordination properties have been thoroughly investigated. The corresponding copper complexes have been fully characterized in the solid state (X-ray diffraction analysis) and in solution (EPR and UV–vis spectroscopies). Potentiometric studies combined with spectrometry have also allowed us to determine their thermodynamic stability constants, confirming their high affinity for copper(II) cations. The kinetic inertness of the complexes has been verified by acid-assisted dissociation experiments, enabling their use in 64Cu-PET imaging in mice for the first time. Indeed, the two ligands could be quantitatively radiolabeled under mild conditions, and the resulting 64Cu complexes have demonstrated excellent stability in serum. PET imaging demonstrated a set of features emerging from the combination of picolinates and phosphonate units: high stability in vivo, fast clearance from the body via renal elimination, and most interestingly, very low fixation in the liver. This is in contrast with what was observed for monopicolinate cyclam (te1pa), which had a non-negligible accumulation in the liver, owing probably to its different charge and lipophilicity. These results thus pave the way for the use of such phosphonated pyridine chelators for in vivo64Cu-PET imaging.

Published
2021

24. Upconversion in molecular hetero-nonanuclear lanthanide complexes in solution

Author

Niko Hildebrandt, Richard C. Knighton, Lohona K. Soro, Alexandre Lecointre, Guillaume Pilet, Alexandra Fateeva, Loïc J. Charbonnière, Laura Francés-Soriano, Laurie Pontille, Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Institut Pluridisciplinaire Hubert Curien (IPHC), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Lanthanide, Materials science, Solution state, Metals and Alloys, 02 engineering and technology, General Chemistry, Molecular systems, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Catalysis, Photon upconversion, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Materials Chemistry, Ceramics and Composites, Physical chemistry, Molecule, [CHIM.COOR]Chemical Sciences/Coordination chemistry, 0210 nano-technology, Luminescence, Excitation
Abstract

International audience; Here we show that nonanuclear lanthanide complexes respresent a new class of solution state upconversion (UC) molecules. For a composition of one Tb per eight Yb the nonanuclear complexes display a very efficient UC phenomenon with Tb luminescence in the visible region upon 980 nm NIR excitation of Yb. An unprecedented value of 1.0 × 10−7 was obtained for the UC efficiency at only 2.86 W cm−2, demonstrating these new molecular complexes to be up to 26 times more efficient than the best current molecular systems, the UC being observed down to a concentration of 10 nM.

Published
2021

25. Upconversion in Molecular Hetero-Nonanuclear Lanthanide Clusters in Solution

Author

Richard Knighton, Lohona K. Soro, Alexandre Lecointre, Guillaume Pilet, Alexandra Fateeva, laurie pontille, Laura Laura Francés-Soriano, Niko Hildebrandt, and Loïc J. Charbonnière

Abstract

Up until now restricted to solid state chemistry and nanoparticles, upconversion (UC) phenomena by which low energy photons are piled up to engender higher energy emission, are progressively entering the field of molecular probes with a handful of molecular/supramolecular discrete complexes. Here we show that nonanuclear lanthanide complexes respresent a new class of solution state UC materials, and are straightforwardly crystalized from LnCl3.6H2O salts, triethylamine and acetylacetone, retaining their structural integrity in solution. For a composition of one Tb per eight Yb the nonanuclear clusters display a very efficient upconversion phenomenon with Tb luminescence in the visible region upon 980 nm NIR excitation of Yb. An unprecedented value of 1.0×10-7 was obtained for the UC efficiency at only 2.86 W/cm2, demonstrating these new molecular clusters to be up to 26 times more efficient than the best current molecular systems, the UC being observed down to a concentration of 10 nM.

Published
2020

27. Molecule-based coherent light-spin interfaces for quantum information processing -- optical spin state polarization in a binuclear Europium complex

Author

Kuppusamy Senthil Kumar, Mario Ruben, Benoît Heinrich, Lydia Karmazin, Aline Nonat, Diana Serrano, Loïc J. Charbonnière, and Philippe Goldner

Subjects
Physics, Quantum Physics, Spin states, Spins, Condensed Matter - Mesoscale and Nanoscale Physics, FOS: Physical sciences, Quantum channel, 010402 general chemistry, 010403 inorganic & nuclear chemistry, Polarization (waves), 01 natural sciences, 3. Good health, 0104 chemical sciences, Laser linewidth, Mesoscale and Nanoscale Physics (cond-mat.mes-hall), Atomic physics, Quantum Physics (quant-ph), Ground state, Quantum, Optics (physics.optics), Coherence (physics), Physics - Optics
Abstract

The success of the emerging field of solid-state optical quantum information processing (QIP) critically depends on the access to resonant optical materials. Rare-earth ions (REIs) are suitable candidates for QIP protocols due to their extraordinary photo-physical and magnetic quantum properties such as long optical and spin coherence lifetimes ($T_2$). However, molecules incorporating REIs, despite having advantageous properties such as atomically exact quantum tunability, inherent scalability, and large portability, have not yet been studied for QIP applications. As a first testimony of the usefulness of REI molecules for optical QIP applications, we demonstrate in this study that narrow spectral holes can be burned in the inhomogeneously broadened $^5$D$_0\to^7$F$_0$ optical transition of a binuclear Eu(III) complex, rendering a homogeneous linewidth ($\Gamma_h$) = 22 $\pm$ 1 MHz, which translates as $T_2 = 14.5$ $\pm$ 0.7 ns at 1.4 K. Moreover, long-lived spectral holes are observed, demonstrating efficient polarization of Eu(III) ground state nuclear spins, a fundamental requirement for all-optical spin initialization and addressing. These results elucidate the usefulness of REI-based molecular complexes as versatile coherent light-spin interfaces for applications in quantum communications and processing., Comment: 31 pages, 9 figures

Published
2020

28. Unprecedented Kinetic Inertness for a Mn

Author

Daouda, Ndiaye, Maryame, Sy, Agnès, Pallier, Sandra, Même, Isidro, de Silva, Sara, Lacerda, Aline M, Nonat, Loïc J, Charbonnière, and Éva, Tóth

Abstract

The search for more biocompatible alternatives to Gd

Published
2020

29. pH dependent hydration change in a Gd based MRI contrast agent with a phosphonated ligand

Author

Isabel Brandariz, Cyrille Charpentier, Mauro Botta, David Esteban-Gómez, Aline Nonat, Loïc J. Charbonnière, Jérémy Salaam, Fabio Carniato, Olivier Jeannin, Carlos Platas-Iglesias, Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Università degli Studi del Piemonte Orientale - Amedeo Avogadro (UPO), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universidade da Coruña, 16-CE09-0015-02, Agence Nationale de la Recherche, ED431B 2017/59, Xunta de Galicia, 2017A2KEPL_002, Ministero dell’Istruzione, dell’Università e della Ricerca, ANR-16-CE09-0015,NEUTRINOS,Suivi des interactions biologiques par détection optique ultrasensible à base de nanoparticules(2016), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
010405 organic chemistry, Chemistry, Ligand, Gadolinium, MRI contrast agent, Organic Chemistry, pH sensing, Ph dependent, chemistry.chemical_element, General Chemistry, Crystal structure, Nuclear magnetic resonance spectroscopy, contrast agent, 010402 general chemistry, 01 natural sciences, Catalysis, NMR, 0104 chemical sciences, Crystallography, relaxivity, Molecule, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Luminescence
Abstract

International audience; The heptadentate ligand L was shown to form extremely stable Gd complex at neutral pH with a pGd value of 18.4 at pH 7.4. The X-ray crystal structures of the complexes formed with Gd and Tb displayed two very different coordination behaviors being respectively octa-and nonacoordinated. The relaxometric properties of the Gd complex were studied by field dependent relaxivity measurements at various temperatures and by 17 O NMR spectroscopy. The pH dependence of the longitudinal relaxivity profile indicated large changes around neutral pH leading to a very large value of 10.1 mM-1. s-1 (60 MHz, 298 K) at pH 4.7. The changes were attributed to an increase of the hydration number from one water molecule in basic conditions to two at acidic pH. A similar trend was observed for the luminescence of the Eu complex, confirming the change in hydration state. DOSY experiments were performed on the Lu analogue, pointing to the absence of dimers in solution in the considered pH range. A breathing mode of the complex was postulated, further supported by 1 H and 31 P-NMR spectroscopy of the Yb complex at varying pH and was finally modeled by DFT calculations.

Published
2020

30. Leveraging Immunotherapy with Nanomedicine

Author

Mainak Banerjee, Alexandre Detappe, Xavier Pivot, Vincent Mittelheisser, Loïc J. Charbonnière, Jacky G. Goetz, Immuno-Rhumatologie Moléculaire, Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM), Centre Paul Strauss, CRLCC Paul Strauss, Institut de Cancérologie de Strasbourg Europe (ICANS), Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), and Charbonnière, Loïc

Subjects
Pharmacology, 0303 health sciences, business.industry, medicine.medical_treatment, [SDV]Life Sciences [q-bio], Biochemistry (medical), Pharmaceutical Science, Medicine (miscellaneous), Immunotherapy, 3. Good health, [SDV] Life Sciences [q-bio], 03 medical and health sciences, 0302 clinical medicine, Immune system, 030220 oncology & carcinogenesis, medicine, Cancer research, Nanomedicine, Pharmacology (medical), business, Genetics (clinical), 030304 developmental biology
Abstract

International audience; Considerable progress has been made in the development and understanding of immunotherapy, notably with the emergence of novel chimeric antigen receptor T cells (CAR‐T) which changed the perception of personalized therapy. However, cell‐based immunotherapy not only lacks therapeutic efficiency in various solid cancers but also raises concerns related to important side effects. The convergence of immunotherapy and nanomedicine is timely as nanoparticles can now be easily conjugated to various antibodies and peptides enabling outstanding abilities to target specific cell populations in vivo. Here, the state of the art of immunonanotherapy that activates the immune system in vivo, by acting either as vaccines or as tumor microenvironment (TME) activators is described. Then, the development of ex vivo immune‐cell surface labeling strategies is discussed to exploit immune cells as trojan horses and thereby improving the delivery of the therapeutics in the TME. Such a strategy is likely to considerably amplify the efficacy of immunotherapy.

Published
2020

31. Unprecedented kinetic inertness for a Mn2+‐bispidine chelate: a novel structural entry for Mn2+‐based imaging agents

Author

Aline Nonat, Éva Tóth, Daouda Ndiaye, Loïc J. Charbonnière, Sandra Même, Maryame Sy, Isidro de Silva, Sara Lacerda, Agnès Pallier, Martins Vasco de Lacerda, Sara, Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO)

Subjects
010405 organic chemistry, Chemistry, Ligand, [SDV.IB.IMA]Life Sciences [q-bio]/Bioengineering/Imaging, chemistry.chemical_element, General Medicine, General Chemistry, Manganese, Pet imaging, [CHIM.COOR] Chemical Sciences/Coordination chemistry, 010402 general chemistry, Biocompatible material, Kinetic energy, 01 natural sciences, Combinatorial chemistry, Catalysis, Dissociation (chemistry), 3. Good health, 0104 chemical sciences, [SDV.IB.IMA] Life Sciences [q-bio]/Bioengineering/Imaging, Chelation, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Clearance
Abstract

International audience; The search for more biocompatible alternatives to Gd 3+-based MRI agents, and the interest in 52 Mn for PET imaging call for ligands that form inert Mn 2+ chelates. Given the labile nature of Mn 2+ , high inertness is challenging to achieve. The strongly preorganized structure of the 2,4-pyridyl-disubstituted bispidol ligand L1 endows its Mn 2+ complex with exceptional kinetic inertness. Indeed, MnL1 did not show any dissociation for 140 days in the presence of 50 eq. of Zn 2+ (37°C, pH 6), while recently reported potential MRI agents MnPyC3A and MnPC2A-EA have dissociation half-lives of 0.285 h and 54.4 h under similar conditions. In addition, the relaxivity of MnL1 (4.28 mM-1 s-1 at 25°C, 20 MHz) is remarkable for a monohydrated, small Mn 2+ chelate. In vivo MRI experiments in mice and determination of the tissue Mn content evidence rapid renal clearance of MnL1. Additionally, L1 could be radiolabeled with 52 Mn and the complex revealed good stability in biological media.

Published
2020

32. Ultrabright Terbium Nanoparticles for FRET Biosensing and in Situ Imaging of Epidermal Growth Factor Receptors

Author

Laura Francés-Soriano, Vjona Cifliku, Cyrille Charpentier, Clémence Cheignon, Joan Goetz, Aline Nonat, Loïc J. Charbonnière, Niko Hildebrandt, Ka-Leung Wong, Marcelina Cardoso Dos Santos, Centre National de la Recherche Scientifique (CNRS), Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Institut de Biologie Intégrative de la Cellule (I2BC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), POLY-DTECH, Reconnaissance Ionique et Chimie de Coordination (RICC), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Centre National de la Recherche Scientifique (CNRS), Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées, Hong Kong Baptist University (HKBU), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), NanoBioPhotonics (NANO), Département Biochimie, Biophysique et Biologie Structurale (B3S), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Biologie Intégrative de la Cellule (I2BC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), ANR‐11‐IDEX‐0003‐02/ Saclay Plant Sciences, ANR-16-CE09-0015,NEUTRINOS,Suivi des interactions biologiques par détection optique ultrasensible à base de nanoparticules(2016), ANR-11-EQPX-0029,MORPHOSCOPE 2,Imagerie et reconstruction multiéchelles de la morphogenèse. (Plateforme d'innovation technologique et méthodologique pour l'imagerie in vivo et la reconstruction des dynamiques multiéchelles de la morphogenèse)(2011), and ANR-10-INBS-0004,France-BioImaging,Développment d'une infrastructure française distribuée coordonnée(2010)

Subjects
EGF Family of Proteins, [SDV]Life Sciences [q-bio], Biosensing Techniques, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Catalysis, Mice, Epidermal growth factor, Fluorescence Resonance Energy Transfer, Animals, [CHIM]Chemical Sciences, Terbium, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, [PHYS]Physics [physics], Bioconjugation, 010405 organic chemistry, Chemistry, Biomolecule, Organic Chemistry, General Chemistry, 0104 chemical sciences, ErbB Receptors, Förster resonance energy transfer, Biotinylation, Biophysics, NIH 3T3 Cells, Nanoparticles, Biosensor, Linker, A431 cells
Abstract

International audience; Lanthanide‐doped nanoparticles (LnNPs) have become an important class of fluorophores for advanced biosensing and bioimaging. LnNPs that are photosensitized by surface‐attached antenna ligands can possess exceptional brightness. However, their functional bioconjugation remains an important challenge for their translation into bioanalytical applications. To solve this problem, we designed a ligand that can be simultaneously applied as efficient light harvesting antenna for Tb surface ions and strong linker of biomolecules to the LnNPs surfaces. To demonstrate generic applicability of the photosensitized TbNP‐bioconjugates, we applied them in two prototypical applications for biosensing and bioimaging. First, in‐solution biorecognition was shown by time‐resolved Förster resonance energy transfer (FRET) between streptavidin‐functionalized TbNPs to biotinylated dyes (ATTO 610). Second, in‐situ detection of ligand‐receptor binding on cells was accomplished with TbNP‐antibody (Matuzumab) conjugates that could specifically bind to transmembrane epidermal growth factor receptors (EGFR). High specificity and sensitivity were demonstrated by time‐gated imaging of EGFR on both strongly (A431) and weakly (HeLa and Cos7) EGFR‐expressing cell lines, whereas non‐expressing cell lines (NIH3T3) and EGFR‐passivated A431 cells did not show any signals. Despite the relatively large size of TbNP‐antibody conjugates, they could be internalized by A431 cells upon binding to extracellular EGFR, which showed their potential as bright and stable luminescence markers for intracellular signalling.

Published
2020

33. Corrosion Protection of Mild Steel by a New Phosphonated Pyridines Inhibitor System in HCl Solution

Author

Lilia Tabti, Embarek Bentouhami, Aline Nonat, Alexandre Lecointre, Nadjib Chafai, Redha M. Khelladi, Loïc J. Charbonnière, Université Ferhat-Abbas Sétif 1 [Sétif] (UFAS1), Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Institut Pluridisciplinaire Hubert Curien (IPHC), and Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Inhibitor, Cyclic voltammetry, Chemistry, 02 engineering and technology, General Medicine, Phosphonated Pyridines, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, DFT calculations, 01 natural sciences, 0104 chemical sciences, Corrosion, TPP, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, 0210 nano-technology, Nuclear chemistry
Abstract

International audience; The adsorption behavior and inhibition mechanism of (1, 4, 7-Tris [hydrogen (6-methylpyridin-2-yl) phosphonate] -1, 4, 7-triazacyclononane) (TPP) on the corrosion of mild steel in 1 M HCl were investigated by weight loss technique, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS) methods for different concentrations at 25°C. The results show that the inhibition efficiency values depend on the amount of immersion times and the concentration. A 90% efficiency is found at the highest concentration of the studied compound according to weight loss measurements. The adsorption of the investigated inhibitor on the mild steel surface was well supported using an AFM study. For the assignment of the absorption sites, we performed quantum chemical calculations with (DFT) method. The interaction between the inhibitor and iron surface were performed by molecular dynamic (MD) simulations. In this paper, experimental methods and results used to assess the efficiency of the studied compound are presented.

Published
2020

34. Evaluation of a Bispidine‐Based Chelator for Gallium‐68 and of the Porphyrin Conjugate as PET/PDT Theranostic Agent

Author

Steven Y. Yap, Huguette Savoie, Aline Nonat, Ross W. Boyle, Thomas W. Price, Graeme J. Stasiuk, Raphaël Gillet, Loïc J. Charbonnière, University of Hull, Institut Pluridisciplinaire Hubert Curien (IPHC), and Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Porphyrins, theranostic, chemistry.chemical_element, Gallium, Gallium Radioisotopes, Conjugated system, 010402 general chemistry, Ligands, 01 natural sciences, Catalysis, Theranostic Nanomedicine, chemistry.chemical_compound, gallium-68, medicine, Humans, [CHIM]Chemical Sciences, Chelation, bispidine, radiochemistry, Chelating Agents, medicine.diagnostic_test, 010405 organic chemistry, Organic Chemistry, General Chemistry, Ligand (biochemistry), Bridged Bicyclo Compounds, Heterocyclic, Combinatorial chemistry, Porphyrin, 3. Good health, 0104 chemical sciences, chemistry, Positron emission tomography, Positron-Emission Tomography, Bifunctional chelator, porphyrin, Conjugate
Abstract

International audience; In this study a bispidine ligand has been applied to the complexation of gallium(III) and radiolabelled with gallium-68 for the first time. Despite its 5-coordinate nature, the resulting complex is stable in serum for over two hours, demonstrating a ligand system well matched to the imaging window of gallium-68 positron emission tomography (PET). To show the versatility of the bispidine ligand and its potential use in PET, the bifunctional chelator was conjugated to a porphyrin, producing a PET/PDT-theranostic, which showed the same level of stability to serum as the non-conjugated gallium-68 complex. The PET/PDT complex killed >90 % of HT-29 cells upon light irradiation at 50 mu m. This study shows bispidines have the versatility to be used as a ligand system for gallium-68 in PET.

Published
2020

35. 2,4-Substituted bispidines as rigid hosts for versatile applications: from κ-opioid receptor to metal coordination

Author

Amandine Roux, Loïc J. Charbonnière, Aline Nonat, Maryame Sy, Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Institut Pluridisciplinaire Hubert Curien (IPHC), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and ANR-18-CE18-0008,MANGA,Complexes de manganèse pour TEP et IRM : production du 52Mn et conception de ligands pour une complexation stable et inerte(2018)

Subjects
Ketone, medicine.drug_class, Molecular Conformation, 010402 general chemistry, 01 natural sciences, Catalysis, Coordination complex, Inorganic Chemistry, Metal, Transition metal, Coordination Complexes, Opioid receptor, Transition Elements, medicine, Animals, Humans, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Conformational isomerism, chemistry.chemical_classification, Radiotherapy, Bicyclic molecule, 010405 organic chemistry, Receptors, Opioid, kappa, Bridged Bicyclo Compounds, Heterocyclic, Combinatorial chemistry, 0104 chemical sciences, chemistry, visual_art, visual_art.visual_art_medium, Metals, Rare Earth
Abstract

International audience; a Bispidones (3,7-diazabicyclo[3.3.1]nonan-9-one) are bicyclic analogues of the natural antiarrythmic agent, spartein. They can straightforwardly be obtained from two successive Mannich reactions. Reduction of the ketone gives the corresponding bispidol. Substituted bispidones and bispidols offer a large playground by varying the substituents, the configuration of the carbon atoms in position 2 and 4 as well as the conformation of the bicycle. While chair-boat conformers display a strong affinity for κ-opioid receptors, chair-chair bispidines provide adaptable coordination spheres for transition metal and rare-earth ions. Because of their very rich coordination chemistry, substituted bispidines have emerged in various applications of coordination chemistry, such as catalysis, magnetism and medical imaging.

Published
2019

36. Formation of Mono- and Polynuclear Luminescent Lanthanide Complexes based on the Coordination of Preorganized Phosphonated Pyridines

Author

Franck Camerel, Embarek Bentouhami, Olivier Jeannin, Loïc J. Charbonnière, Jérémy Salaam, Lilia Tabti, Sylvana Bahamyirou, Sarah Cianférani, Oscar Hernandez Alba, Alexandre Lecointre, Aline Nonat, Institut Pluridisciplinaire Hubert Curien ( IPHC ), Université de Strasbourg ( UNISTRA ) -Centre National de la Recherche Scientifique ( CNRS ), Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Sciences Analytiques et Interactions Ioniques et Biomoléculaires ( DSA-IPHC ), Université de Strasbourg ( UNISTRA ) -Centre National de la Recherche Scientifique ( CNRS ) -Université de Strasbourg ( UNISTRA ) -Centre National de la Recherche Scientifique ( CNRS ), University of Ferhat Abbas Setif 1, CNRS, Centre National de la Recherche Scientifique, Université de Strasbourg, GIS, Genome Institute of Singapore, Institut Pluridisciplinaire Hubert Curien (IPHC), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Université Ferhat-Abbas Sétif 1 [Sétif] (UFAS1), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)

Subjects
pyridine, Lanthanide, lanthanide, Hydrogen, 010405 organic chemistry, Chemistry, Hydrogen bond, Ligand, Quantum yield, chemistry.chemical_element, 010402 general chemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Phosphonate, 0104 chemical sciences, Inorganic Chemistry, polynuclear assemblies, Crystallography, chemistry.chemical_compound, luminescence, phosphonate, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Luminescence, Stoichiometry
Abstract

International audience; A series of polynuclear assemblies based on ligand L (1,4,7-tris[hydrogen (6-methylpyridin-2-yl)phosphonate]-1,4,7-triazacyclononane) has been developed. The coordination properties of ligand L with LnIII (Ln = La, Eu, Tb, Yb, Lu) have been studied in water (pH = 7.0) and in D2O (pD = 7.0) by UV-absorption spectrometry, spectrofluorimetry, 1H and 31P NMR, DOSY, ESI-mass spectrometry, and X-ray diffraction. This nonadentate ligand forms highly stable mononuclear complexes in water and provides a very efficient shielding of the Ln cations, as emphasized by the very good luminescence properties of the Yb complex in D2O, especially regarding its lifetime (τD2O = 10.2 μs) and quantum yield (φD2O = 0.42%). In the presence of excess LnIII cation, polynuclar complexes of [(LnL)2Lnx] stoichiometry (x = 1 and x = 2) are observed in solution. In the solid state, a dinuclear complex of La could be isolated and structurally characterized by X-ray diffraction, unraveling the presence of strong hydrogen bonding interactions between a La(H2O)9 3+ cation and the [LaL]3- complex. © 2018 American Chemical Society.

Published
2018

37. Bringing upconversion down to the molecular scale

Author

Loïc J. Charbonnière, Institut Pluridisciplinaire Hubert Curien (IPHC), and Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Computer science, Scale (chemistry), Solid-state, Supramolecular chemistry, Nanotechnology, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Photon upconversion, 0104 chemical sciences, Inorganic Chemistry, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, 0210 nano-technology
Abstract

International audience; After solid state and nanoparticles, discrete molecular and supramolecular systems displaying upconversion (UC) in solution have recently emerged in the literature. This frontier article intends to recall the roots of molecular UC and will try to draw perspectives to improve the actual state of the art.

Published
2018

38. Lanthanide-Complex-Loaded Polymer Nanoparticles for Background-Free Single-Particle and Live-Cell Imaging

Author

Andrey S. Klymchenko, Loïc J. Charbonnière, Anne Runser, Hortense Bartenlian, Niko Hildebrandt, Marcelina Cardoso Dos Santos, Andreas Reisch, Aline Nonat, Institut de Biologie Intégrative de la Cellule (I2BC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Bioimagerie et Pathologies (LBP), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), ANR-16-CE09-0007,supertrack,Nanoparticules polymériques fluorescentes ultrabrillantes et biocompatibles pour l'imagerie rapide intracellulaire à haute-résolution(2016), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Université Paris-Sud - Paris 11 (UP11)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay, NanoBioPhotonics (NANO), Département Biochimie, Biophysique et Biologie Structurale (B3S), Université Paris-Sud - Paris 11 (UP11)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay-Université Paris-Sud - Paris 11 (UP11)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay-Institut de Biologie Intégrative de la Cellule (I2BC), Université Paris-Sud - Paris 11 (UP11)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay-Université Paris-Sud - Paris 11 (UP11)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay, Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Université Paris-Sud - Paris 11 (UP11), Laboratoire de Biophotonique et Pharmacologie - UMR 7213 (LBP), Réseau nanophotonique et optique, and Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)

Subjects
Lanthanide, General Chemical Engineering, [SDV]Life Sciences [q-bio], Nanoparticle, Nanotechnology, quantum dots, 02 engineering and technology, bright, in-vitro, 010402 general chemistry, 01 natural sciences, dyes, Live cell imaging, emission, Materials Chemistry, luminescence, Molecule, [CHIM.COOR]Chemical Sciences/Coordination chemistry, ComputingMilieux_MISCELLANEOUS, time-resolved fluorescence, chemistry.chemical_classification, General Chemistry, Polymer, tracking, 021001 nanoscience & nanotechnology, 0104 chemical sciences, agents, Autofluorescence, chemistry, Particle, photoluminescence, Time-resolved spectroscopy, 0210 nano-technology
Abstract

WOS:000471728200021; International audience; Imaging single molecules and nanoparticles in complex biological media is highly challenging notably due to autofluorescence of cells and tissues. Lanthanides and lanthanide complexes, with their particularly long luminescence lifetimes, offer the possibility to perform time-gated imaging and thus to strongly reduce the autofluorescence background. However, their very low brightness and photon flux have limited their use in single-molecule imaging. Here, we encapsulate high amounts of Europium complexes into poly(methyl methacrylate)-based particles of 10, 20, and 30 nm size. The resulting particles contain up to 5000 copies of the complex with a quantum yield of \textgreater= 0.2, resulting in a per particle brightness of up to 4 x 10(7) M-1 cm(-1). They can be imaged at the single-particle level using low illumination intensities (0.24 W cm(-2)) and low acquisition times (300 ms) and internalize well into living cells, where they can be monitored through time-gated imaging at illumination conditions compatible with living specimen. These Eu-complex-loaded nanoparticles can thus be applied for highly sensitive and autofluorescence-free imaging and have the potential to become very performant probes for fast intracellular tracking of single biomolecules.

Published
2019
Full Text
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39. The role of ligand to metal charge-transfer states on the luminescence of Europium complexes with 18-membered macrocyclic ligands

Author

Paulo Pérez-Lourido, Aline Nonat, David Esteban-Gómez, Laura Valencia, Carlos Platas-Iglesias, Loïc J. Charbonnière, José L. Barriada, Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Centro de Investigacións Científicas Avanzadas (CICA), Departamento de Química Fundamental, Universidade da Coruña, Departamento de Química Inorgánica, Universidade de Vigo, and Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Quenching (fluorescence), Aqueous solution, 010405 organic chemistry, Chemistry, Ligand, Quantum yield, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Crystallography, [CHIM]Chemical Sciences, Density functional theory, Emission spectrum, Luminescence, Europium, ComputingMilieux_MISCELLANEOUS
Abstract

[Abstract] We report a detailed study of the photophysical properties of EuIII and TbIII complexes with two ligands based on a 3,6,10,13-tetraaza-1,8(2,6)-dipyridinacyclotetradecaphane platform containing either four pyridine-2yl-methyl (L1) or four hydroxyethyl (L2) pendant arms. The [TbL1]3+ and [TbL2]3+ complexes present moderate luminescence quantum yields upon excitation through the ligand bands (ϕH2O = 7.4 and 21%, respectively). The [EuL2]3+ complex displays a relatively low quantum yield in H2O (ϕH2O = 1.6%) that increases considerably in D2O (ϕD2O = 5.3%), which highlights the strong quenching effect of the four ligand O–H oscillators. The emission spectrum of [EuL1]3+ is rather unusual in that it shows a relatively high intensity of the 5D0 → 7F5,6 transitions, which appears to be also related to the distorted D4d symmetry of the coordination polyhedron. Surprisingly, the quantum yield of the [EuL1]3+ complex is very low (ϕH2O = 0.10%), considering the good protection of the EuIII coordination environment offered by the ligand. Cyclic voltammograms recorded from aqueous solutions of [EuL1]3+ display a reversible curve with a half-wave potential of −620 mV (versus Ag/AgCl), while [EuL2]3+ presents a reduction peak at more negative potential (−1040 mV). Thus, the L1 ligand provides a rather good stabilisation of divalent Eu compared to the L2 analogue, suggesting that the presence of a low-lying ligand-to-metal charge-transfer (LMCT) state might be responsible for the low quantum yield determined for [EuL1]3+. A density functional theory (DFT) study provides very similar energies for the ligand-centered excited singlet (1ππ*) and triplet (3ππ*) states of [EuL1]3+ and [EuL2]3+. The energy of the 9LMCT state of [EuL1]3+ was estimated to be 20 760 cm−1 by using all-electron relativistic calculations based on the DKH2 approach, a value that decreases to 15 940 cm−1 upon geometry relaxation. Ministerio de Economía y Competitividad; CTQ2016-76756-P Xunta de Galicia; ED431B 2017/59 Xunta de Galicia; ED431D 2017/01

Published
2019

40. Luminescent Materials: Metal Complexes, Clusters, and Nanomaterials

Author

Loïc J. Charbonnière, Kenneth Kam-Wing Lo, Institut Pluridisciplinaire Hubert Curien (IPHC), and Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Chemistry, Nanotechnology, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Nanomaterials, Inorganic Chemistry, Metal, visual_art, visual_art.visual_art_medium, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, 0210 nano-technology, Luminescence, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2017

41. Enhancement of silicon solar cells by downshifting with Eu and Tb coordination complexes

Author

Thomas Fix, Daniel Imbert, Abdelilah Slaoui, Loïc J. Charbonnière, Marinella Mazzanti, S. Di Pietro, and Aline Nonat

Subjects
Materials science, Physics::Optics, 02 engineering and technology, Quantum dot solar cell, 010402 general chemistry, 01 natural sciences, Polymer solar cell, law.invention, law, Solar cell, Astrophysics::Solar and Stellar Astrophysics, Electrical and Electronic Engineering, Renewable Energy, Sustainability and the Environment, business.industry, Energy conversion efficiency, Hybrid solar cell, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Copper indium gallium selenide solar cells, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, Downshifting, Multiple exciton generation, Optoelectronics, 0210 nano-technology, business
Abstract

Luminescent lanthanide-doped oxides, nanoparticles, nanocrystals, and coordination complexes are major tools in the fields of optical and laser materials, telecommunications, medical imaging, and fluoroimmunoassays. In particular, coordination complexes are efficient energy converters with high photostability, large ligand-induced Stokes shifts, and tunable excitation and emission spectra. However, their application as light downshifting materials for solar cells has not yet been widely explored. This third generation solar cell concept enables to increase the efficiency of standard solar cells—such as Si or copper indium gallium (di)selenide (CIGS)—that have low performance for ultraviolet photons. The incorporation of such a converter in solar module encapsulants can provide a cheap and effective way to integrate photon conversion. Here, encapsulants functionalised by photon downshifting coordination complexes have been spin-coated on silicon solar cells. For all the coordination complexes, an increase of the spectral response of the solar cells is observed in the ultraviolet region. In the best case, a relative increase of 8% of the conversion efficiency of the solar cell is observed.

Published
2016

42. [C–H⋯anion] interactions mediate the templation and anion binding properties of topologically non-trivial metal–organic structures in aqueous solutions

Author

Rana A. Bilbeisi, Mourad Elhabiri, Ali Trabolsi, John Carl Olsen, Loïc J. Charbonnière, Roberto El Khoury, Carlos Platas-Iglesias, Matteo Lusi, and Thirumurugan Prakasam

Subjects
Anion binding, Knots, chemistry.chemical_classification, Aqueous solution, 010405 organic chemistry, Hydrogen bond, Template, Catenane, Inorganic chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, Hydrogen bonds, 0104 chemical sciences, Zinc, Crystallography, chemistry.chemical_compound, chemistry, Heteronuclear molecule, Bromide, Counterion, Trifluoromethanesulfonate
Abstract

[Abstract] Two synthetic approaches—temperature variation and anion templation—allowed for the selective formation of a [2]catenane ([2]C4+) or a trefoil knot (TK6+), or for the enhanced formation of a Solomon link (SL8+), all from a simple set of starting materials (Zn(II) acetate, diformylpyridine (DFP) and a diamino-2,2′-bipyridine (DAB)) in mixed aqueous solutions. The catenane formed exclusively at 90 °C in a 1 : 1 mixed solvent of D2O and MeOD. In the presence of bromide ion as template, TK6+ formed exclusively at 50 °C in the same solvent. In the solid state, TK6+ hosts two bromide ions in its central cavity by forming six Csp2–H hydrogen bonds. In D2O, TK6+, which was originally prepared as a trifluoroacetate (TFA) salt, was found to exchange two TFA counterions for two monovalent anions of different sizes and shapes, which lodged within the knot's central cavity. In contrast to bromide, the larger triflate anion (CF3SO3−) promoted the formation of SL8+, which was characterized by 1H NMR spectroscopy and mass spectrometry. Two dimensional heteronuclear 19F-1H-HOSEY NMR experiments detected CH⋯F interactions inside the cavity of SL8+. Thus, the product distribution of this dynamic link forming system is sensitive to temperature and the size and shape of the anion template, and one of the products, TK6+, is capable of binding a variety of monovalent anions in D2O with high affinity (with log β2 values of 4 to 6 being typical).

Published
2016

43. Cover Feature: Ultrabright Terbium Nanoparticles for FRET Biosensing and in Situ Imaging of Epidermal Growth Factor Receptors (Chem. Eur. J. 64/2020)

Author

Niko Hildebrandt, Joan Goetz, Laura Francés-Soriano, Vjona Cifliku, Clémence Cheignon, Cyrille Charpentier, Loïc J. Charbonnière, Ka-Leung Wong, Aline Nonat, and Marcelina Cardoso Dos Santos

Subjects
In situ, Chemistry, Organic Chemistry, chemistry.chemical_element, Nanoparticle, Terbium, General Chemistry, Catalysis, Förster resonance energy transfer, Epidermal growth factor, Feature (computer vision), Biophysics, Cover (algebra), Biosensor
Published
2020

46. Upconversion of light with molecular and supramolecular lanthanide complexes

Author

Loïc J. Charbonnière, Aline Nonat, Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), and Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Lanthanide, Luminescence, Photon, 010405 organic chemistry, Chemistry, Solid-state, Supramolecular chemistry, Nanoparticle, 010402 general chemistry, 01 natural sciences, Ray, Photon upconversion, 0104 chemical sciences, Inorganic Chemistry, Molecular level, Chemical physics, Lanthanides, Materials Chemistry, [CHIM]Chemical Sciences, Photosensitization, Physical and Theoretical Chemistry, Upconversion
Abstract

International audience; Upconversion (UC) is the process by which the energy of multiple photons is absorbed by a compound and restored in the form of a photon of higher energy than the incident light, resulting in an anti-Stokes process. Although studied theoretically since the middle of the last century and experimentally observed in the 1960′s, the process was up to recently mainly restricted to solid state devices and ultimately to nanoparticles at the end of the century. At the same period, different researches were directed towards the possibility to observe UC at the molecular level and it is only recently that the phenomenon could be observed in discrete molecular entities in solution with still very few examples. This review aims at explaining the difficulties encountered at the molecular level compared to the solid state and summarizes the results reported to date on UC at the molecular scale.

Published
2020

47. Cover Feature: pH‐Dependent Hydration Change in a Gd‐Based MRI Contrast Agent with a Phosphonated Ligand (Chem. Eur. J. 24/2020)

Author

David Esteban-Gómez, Isabel Brandariz, Loïc J. Charbonnière, Jérémy Salaam, Aline Nonat, Olivier Jeannin, Fabio Carniato, Cyrille Charpentier, Carlos Platas-Iglesias, and Mauro Botta

Subjects
Crystallography, Chemistry, Feature (computer vision), Ligand, Gadolinium, MRI contrast agent, Organic Chemistry, chemistry.chemical_element, Ph dependent, Cover (algebra), General Chemistry, Catalysis
Published
2020

48. Correction: Luminescent imidazolium–naphthalene salts in liquid and solid states

Author

Youssef Atoini, Loïc J. Charbonnière, Emilie Bordes, Benoît Heinrich, Luisa De Cola, Matthieu L’Her, Emma Scrafton, Lydia Karmazin, Nicolas Del-Giudice, Laurent Douce, and Julien Fouchet

Subjects
Chemistry, Inorganic chemistry, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Materials Chemistry, 0210 nano-technology, Luminescence, Naphthalene
Abstract

Correction for ‘Luminescent imidazolium–naphthalene salts in liquid and solid states’ by Matthieu L’Her et al., New J. Chem., 2019, 43, 12529–12532.

Published
2020

49. Sensing Uranyl(VI) Ions by Coordination and Energy Transfer to a Luminescent Europium(III) Complex

Author

Peter Harvey, Aline Nonat, Carlos Platas-Iglesias, Louise S. Natrajan, Loïc J. Charbonnière, University of Manchester [Manchester], Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Departamento de Química Fundamental, and Universidade da Coruña

Subjects
energy transfer, Luminescence, 010405 organic chemistry, Sensors, Communication, General Medicine, 010402 general chemistry, sensors, 7. Clean energy, 01 natural sciences, Communications, 0104 chemical sciences, Uranyl, Europium, Energy transfer, uranyl, luminescence, [CHIM]Chemical Sciences, Uranyl Ion Detection, europium
Abstract

International audience; The release of uranyl(VI) is a hazardous environmental issue, with limited ways to monitor accumulation in situ. Here, we present a method for the detection of uranyl(VI) ions through the utilization of a unique fluorescence energy transfer process to europium(III). Our system displays the first example of a “turn‐on” europium(III) emission process with a small, water‐soluble lanthanide complex triggered by uranyl(VI) ions.

Published
2018

50. Autofluorescence-Free Live-Cell Imaging Using Terbium Nanoparticles

Author

M. Cardoso Dos Santos, Ka-Leung Wong, Loïc J. Charbonnière, Joan Goetz, Niko Hildebrandt, H. Bartenlian, Institut de Biologie Intégrative de la Cellule (I2BC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), NanoBioPhotonics (NANO), Département Biochimie, Biophysique et Biologie Structurale (B3S), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Biologie Intégrative de la Cellule (I2BC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), and ANR-16-CE09-0015,NEUTRINOS,Suivi des interactions biologiques par détection optique ultrasensible à base de nanoparticules(2016)

Subjects
Cell Survival, [SDV]Life Sciences [q-bio], Biomedical Engineering, Pharmaceutical Science, chemistry.chemical_element, Nanoparticle, Bioengineering, Terbium, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Fluorescence, Live cell imaging, Microscopy, Humans, ComputingMilieux_MISCELLANEOUS, Fluorescent Dyes, Pharmacology, Chemistry, Vesicle, Organic Chemistry, Optical Imaging, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Autofluorescence, Microscopy, Fluorescence, Biophysics, Nanoparticles, 0210 nano-technology, Biotechnology, Visible spectrum, HeLa Cells
Abstract

Fluorescent nanoparticles (NPs) have become irreplaceable tools for advanced cellular and subcellular imaging. While very bright NPs require excitation with UV or visible light, which can create strong autofluorescence of biological components, NIR-excitable NPs without autofluorescence issues exhibit much lower brightness. Here, we show the application of a new type of surface-photosensitized terbium NPs (Tb-NPs) for autofluorescence-free intracellular imaging in live HeLa cells. The combination of exceptionally high brightness, high photostability, and long photoluminecence (PL) lifetimes for highly efficient suppression of the short-lived autofluorescence allowed for time-gated PL imaging of intracellular vesicles over 72 h without toxicity and at extremely low Tb-NP concentrations down to 12 pM. Detection of highly resolved long-lifetime (ms) PL decay curves from small (∼10 μm2) areas within single cells within a few seconds emphasized the unprecedented photophysical properties of Tb-NPs for live-cell...

Published
2018

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