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1. Synthesis and Characterization of Tetraphenylethene AIEgen-Based Push–Pull Chromophores for Photothermal Applications: Could the Cycloaddition–Retroelectrocyclization Click Reaction Make Any Molecule Photothermally Active?

Author

Maxime Roger, Yann Bretonnière, Yann Trolez, Antoine Vacher, Imane Arbouch, Jérôme Cornil, Gautier Félix, Julien De Winter, Sébastien Richeter, Sébastien Clément, and Philippe Gerbier

Subjects
TPE, AIEgen, cycloaddition-retroelectrocyclization, click chemistry, photothermal applications, Biology (General), QH301-705.5, Chemistry, QD1-999
Abstract

Three new tetraphenylethene (TPE) push–pull chromophores exhibiting strong intramolecular charge transfer (ICT) are described. They were obtained via [2 + 2] cycloaddition–retroelectrocyclization (CA-RE) click reactions on an electron-rich alkyne-tetrafunctionalized TPE (TPE-alkyne) using both 1,1,2,2-tetracyanoethene (TCNE), 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) as electron-deficient alkenes. Only the starting TPE-alkyne displayed significant AIE behavior, whereas for TPE-TCNE, a faint effect was observed, and for TPE-TCNQ and TPE-F4-TCNQ, no fluorescence was observed in any conditions. The main ICT bands that dominate the UV–Visible absorption spectra underwent a pronounced red-shift beyond the near-infrared (NIR) region for TPE-F4-TCNQ. Based on TD-DFT calculations, it was shown that the ICT character shown by the compounds exclusively originated from the clicked moieties independently of the nature of the central molecular platform. Photothermal (PT) studies conducted on both TPE-TCNQ and TPE-F4-TCNQ in the solid state revealed excellent properties, especially for TPE-F4-TCNQ. These results indicated that CA-RE reaction of TCNQ or F4-TCNQ with donor-substituted are promising candidates for PT applications.

Published
2023
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2. Fluorescent Dynamic Covalent Polymers for DNA Complexation and Templated Assembly

Author

Clément Kotras, Maxime Leclercq, Maxime Roger, Camille Bouillon, Antonio Recupido, Aurélien Lebrun, Yannick Bessin, Philippe Gerbier, Sébastien Richeter, Sébastien Ulrich, Sébastien Clément, and Mathieu Surin

Subjects
dynamic covalent polymers, fluorescence, DNA complexation, templated assembly, Organic chemistry, QD241-441
Abstract

Dynamic covalent polymers (DCPs) offer opportunities as adaptive materials of particular interest for targeting, sensing and delivery of biological molecules. In this view, combining cationic units and fluorescent units along DCP chains is attractive for achieving optical probes for the recognition and delivery of nucleic acids. Here, we report on the design of acylhydrazone-based DCPs combining cationic arginine units with π-conjugated fluorescent moieties based on thiophene-ethynyl-fluorene cores. Two types of fluorescent building blocks bearing neutral or cationic side groups on the fluorene moiety are considered in order to assess the role of the number of cationic units on complexation with DNA. The (chir)optical properties of the building blocks, the DCPs, and their complexes with several types of DNA are explored, providing details on the formation of supramolecular complexes and on their stability in aqueous solutions. The DNA-templated formation of DCPs is demonstrated, which provides new perspectives on the assembly of fluorescent DCP based on the nucleic acid structure.

Published
2022
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3. Factors affecting the accuracy of genomic selection for growth and wood quality traits in an advanced-breeding population of black spruce (Picea mariana)

Author

Patrick R.N. Lenz, Jean Beaulieu, Shawn D. Mansfield, Sébastien Clément, Mireille Desponts, and Jean Bousquet

Subjects
Genomic selection, Black spruce, Wood properties, Tree improvement and breeding, Genomic-estimated breeding values, Gene SNPs, Biotechnology, TP248.13-248.65, Genetics, QH426-470
Abstract

Abstract Background Genomic selection (GS) uses information from genomic signatures consisting of thousands of genetic markers to predict complex traits. As such, GS represents a promising approach to accelerate tree breeding, which is especially relevant for the genetic improvement of boreal conifers characterized by long breeding cycles. In the present study, we tested GS in an advanced-breeding population of the boreal black spruce (Picea mariana [Mill.] BSP) for growth and wood quality traits, and concurrently examined factors affecting GS model accuracy. Results The study relied on 734 25-year-old trees belonging to 34 full-sib families derived from 27 parents and that were established on two contrasting sites. Genomic profiles were obtained from 4993 Single Nucleotide Polymorphisms (SNPs) representative of as many gene loci distributed among the 12 linkage groups common to spruce. GS models were obtained for four growth and wood traits. Validation using independent sets of trees showed that GS model accuracy was high, related to trait heritability and equivalent to that of conventional pedigree-based models. In forward selection, gains per unit of time were three times higher with the GS approach than with conventional selection. In addition, models were also accurate across sites, indicating little genotype-by-environment interaction in the area investigated. Using information from half-sibs instead of full-sibs led to a significant reduction in model accuracy, indicating that the inclusion of relatedness in the model contributed to its higher accuracies. About 500 to 1000 markers were sufficient to obtain GS model accuracy almost equivalent to that obtained with all markers, whether they were well spread across the genome or from a single linkage group, further confirming the implication of relatedness and potential long-range linkage disequilibrium (LD) in the high accuracy estimates obtained. Only slightly higher model accuracy was obtained when using marker subsets that were identified to carry large effects, indicating a minor role for short-range LD in this population. Conclusions This study supports the integration of GS models in advanced-generation tree breeding programs, given that high genomic prediction accuracy was obtained with a relatively small number of markers due to high relatedness and family structure in the population. In boreal spruce breeding programs and similar ones with long breeding cycles, much larger gain per unit of time can be obtained from genomic selection at an early age than by the conventional approach. GS thus appears highly profitable, especially in the context of forward selection in species which are amenable to mass vegetative propagation of selected stock, such as spruces.

Published
2017
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4. A Cationic Tetraphenylethene as a Light-Up Supramolecular Probe for DNA G-Quadruplexes

Author

Clément Kotras, Mathieu Fossépré, Maxime Roger, Virginie Gervais, Sébastien Richeter, Philippe Gerbier, Sébastien Ulrich, Mathieu Surin, and Sébastien Clément

Subjects
tetraphenylethene, G-quadruplexes, fluorescence, light-up probe, supramolecular, Chemistry, QD1-999
Abstract

Guanine-quadruplexes (G4s) are targets for anticancer therapeutics. In this context, human telomeric DNA (HT-DNA) that can fold into G4s sequences are of particular interest, and their stabilization with small molecules through a visualizable process has become a challenge. As a new type of ligand for HT-G4, we designed a tetraimidazolium tetraphenylethene (TPE-Im) as a water-soluble light-up G4 probe. We study its G4-binding properties with HT-DNA by UV-Visible absorption, circular dichroism and fluorescence spectroscopies, which provide insights into the interactions between TPE-Im and G4-DNA. Remarkably, TPE-Im shows a strong fluorescence enhancement and large shifts upon binding to G4, which is valuable for detecting G4s. The association constants for the TPE-Im/G4 complex were evaluated in different solution conditions via isothermal titration calorimetry (ITC), and its binding modes were explored by molecular modeling showing a groove-binding mechanism. The stabilization of G4 by TPE-Im has been assessed by Fluorescence Resonance Energy Transfer (FRET) melting assays, which show a strong stabilization (ΔT1/2 around +20°C), together with a specificity toward G4 with respect to double-stranded DNA.

Published
2019
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5. Polythiophenes with Cationic Phosphonium Groups as Vectors for Imaging, siRNA Delivery, and Photodynamic Therapy

Author

Laure Lichon, Clément Kotras, Bauyrzhan Myrzakhmetov, Philippe Arnoux, Morgane Daurat, Christophe Nguyen, Denis Durand, Karim Bouchmella, Lamiaa Mohamed Ahmed Ali, Jean-Olivier Durand, Sébastien Richeter, Céline Frochot, Magali Gary-Bobo, Mathieu Surin, and Sébastien Clément

Subjects
combined therapy, conjugated polyelectrolyte, imaging, photodynamic therapy, polythiophenes, siRNA delivery, Chemistry, QD1-999
Abstract

In this work, we exploit the versatile function of cationic phosphonium-conjugated polythiophenes to develop multifunctional platforms for imaging and combined therapy (siRNA delivery and photodynamic therapy). The photophysical properties (absorption, emission and light-induced generation of singlet oxygen) of these cationic polythiophenes were found to be sensitive to molecular weight. Upon light irradiation, low molecular weight cationic polythiophenes were able to light-sensitize surrounding oxygen into reactive oxygen species (ROS) while the highest were not due to its aggregation in aqueous media. These polymers are also fluorescent, allowing one to visualize their intracellular location through confocal microscopy. The most promising polymers were then used as vectors for siRNA delivery. Due to their cationic and amphipathic features, these polymers were found to effectively self-assemble with siRNA targeting the luciferase gene and deliver it in MDA-MB-231 cancer cells expressing luciferase, leading to 30–50% of the gene-silencing effect. In parallel, the photodynamic therapy (PDT) activity of these cationic polymers was restored after siRNA delivery, demonstrating their potential for combined PDT and gene therapy.

Published
2020
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6. Sol-Gel Chemistry: From Molecule to Functional Materials

Author

Sébastien Clément and Ahmad Mehdi

Subjects
sol-gel, hydrolytic, non-hydrolytic, self-assembly, catalysis, titanium dioxide, Organic chemistry, QD241-441
Abstract

Through this Special Issue, you will discover the potentiality of inorganic polymerization (sol-gel process) which is a unique and versatile way for the preparation of materials [...]

Published
2020
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7. In Depth Analysis of Photovoltaic Performance of Chlorophyll Derivative-Based 'All Solid-State' Dye-Sensitized Solar Cells

Author

Michèle Chevrier, Alberto Fattori, Laurent Lasser, Clément Kotras, Clémence Rose, Michela Cangiotti, David Beljonne, Ahmad Mehdi, Mathieu Surin, Roberto Lazzaroni, Philippe Dubois, Maria Francesca Ottaviani, Sébastien Richeter, Johann Bouclé, and Sébastien Clément

Subjects
solid state dye sensitized solar cells, spirulina, chlorophyll, anchoring groups, epr, Organic chemistry, QD241-441
Abstract

Chlorophyll a derivatives were integrated in “all solid-state” dye sensitized solar cells (DSSCs) with a mesoporous TiO2 electrode and 2′,2′,7,7′-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9′-spirobifluorene as the hole-transport material. Despite modest power conversion efficiencies (PCEs) between 0.26% and 0.55% achieved for these chlorin dyes, a systematic investigation was carried out in order to elucidate their main limitations. To provide a comprehensive understanding of the parameters (structure, nature of the anchoring group, adsorption …) and their relationship with the PCEs, density functional theory (DFT) calculations, optical and photovoltaic studies and electron paramagnetic resonance analysis exploiting the 4-carboxy-TEMPO spin probe were combined. The recombination kinetics, the frontier molecular orbitals of these DSSCs and the adsorption efficiency onto the TiO2 surface were found to be the key parameters that govern their photovoltaic response.

Published
2020
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8. New Layered Polythiophene-Silica Composite Through the Self-Assembly and Polymerization of Thiophene-Based Silylated Molecular Precursors

Author

Marie-José Zacca, Danielle Laurencin, Sébastien Richeter, Sébastien Clément, and Ahmad Mehdi

Subjects
self-assembly, lamellar, polythiophene, silica, sol-gel, hybrid material, Organic chemistry, QD241-441
Abstract

A new layered hybrid polythiophene-silica material was obtained directly by hydrolysis and polycondensation (sol-gel) of a silylated-thiophene bifunctional precursor, and its subsequent oxidative polymerization by FeCl3. This precursor was judiciously designed to guarantee its self-assembly and the formation of a lamellar polymer-silica structure, exploiting the cooperative effect between the hydrogen bonding interactions, originating from the ureido groups and the π-stacking interactions between the thiophene units. The lamellar structure of the polythiophene-silica composite was confirmed by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM) analyses. The solid-state nuclear magnetic resonance (NMR), UV-Vis, and photoluminescence spectra unambiguously indicate the incorporation of polythiophene into the silica matrix. Our work demonstrates that using a polymerizable silylated-thiophene precursor is an efficient approach towards the formation of nanostructured conjugated polymer-based hybrid materials.

Published
2018
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9. (E)-3-(2,3,4,5,6-Pentafluorostyryl)thiophene

Author

Sébastien Clément, Olivier Coulembier, Franck Meyer, Matthias Zeller, and Christophe M. L. Vande Velde

Subjects
Crystallography, QD901-999
Abstract

The reaction of thiophene-3-carboxaldehyde and perfluorobenzyltriphenylphosphonium bromide in the presence of sodium hydride gave the title compound, C12H5F5S, in 70% yield. The thiophene and perfluorophenyl groups form a dihedral angle of 5.4 (2)°. The structure is characterized by a head-to-tail organization in a columnar arrangement due to π–π interactions between the thiophene and pentafluorophenyl rings with centroid–centroid distances in the range 3.698 (2)–3.802 (2) Å.

Published
2010
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11. Enquête sur les jardins et savoirs jardiniers de La Réunion : premiers résultats d’une recherche sur la biodiversité « cultivée »

Author

Sébastien Clément

Subjects
Reunion Island, biodiversity, landscape, garden, knowledge, Environmental sciences, GE1-350, Social Sciences
Abstract

This article, resulting from doctoral research, proposes to bring landmarks on the dynamics of biodiversity in the private gardens of Reunion Island. The aim is to examine the conditions for the production of a "cultivated" biodiversity, which is inseparable from the local way of life, from the knowledge and know-how inscribed in cultural heritages, and from the social relations woven around the gardens. The approach proposes the study of a measurement of the level of biodiversity through a precise scientific protocol combined with the analysis of practices and knowledge invested in the creation and maintenance of gardens. This approach makes it possible to evaluate the impact of the transmission of gardeners' knowledge and their interactions with living species. It is based on interviews with gardeners and on an experiment consisting of the collective creation of a garden on an uncultivated plot in the west of the island at an altitude of 350 meters, and a quantitative survey of changes in the species of flora and fauna. The initial results of this research reveal an increase in the number of species and the genesis of a "cultivated" biodiversity.

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12. Halogen-Bonded Thiophene Derivatives Prepared by Solution and/or Mechanochemical Synthesis. Evidence of N···S Chalcogen Bonds in Homo- and Cocrystals

Author

Shiv Kumar, Carole Body, Tom Leyssens, Kristof Van Hecke, Gilles Berger, Arie Van der Lee, Danielle Laurencin, Sébastien Richeter, Sébastien Clément, Franck Meyer, and UCL - SST/IMCN/MOST - Molecular Chemistry, Materials and Catalysis

Subjects
General Materials Science, General Chemistry, Condensed Matter Physics
Abstract

Thiophene, a key building block for the construction of conjugated materials, has been scarcely studied in halogen bonding (XB)-driven self-assemblies. In the present study, two thiophene derivatives modified at position 3 were (co-)crystallized using complementary XB donor/acceptor functional groups. Single-crystal X-ray diffraction analysis confirmed the presence of halogen and chalcogen bonding acting, in most cases, concomitantly. While the majority of the structures are governed by the conventional N···I motif, additional S···N and S···S contacts encouraged the cohesion of the supramolecular architectures. Density functional theory calculations shed the light on interaction energy, their respective contributions of the motifs to these non-covalent bonds, and the overall stability of these assemblies. To gain further insight into the formation and evidence of XB interactions, solution and mechanochemical syntheses of polymorphic adducts were performed, followed by 13C solid-state NMR analysis. Further, 1H and 19F{1H} solution-state NMR spectroscopy studies were carried out to highlight these interactions in the solution phase. The strength and directionality of halogen bonding thus reaffirm its role as a structure-directing agent for designing functional materials. The evidence of N···S chalcogen bonds in thiophene derivatives also broadens up the horizon of supramolecular chemistry in S-heterocycles, while necessitating further investigation for rational application in materials science.

Published
2023

13. Synthesis and Characterization of Tetraphenylethene AIEgen-Based Push-Pull Chromophores for Photothermal Applications: Do the Cycloaddition – Retroelectrocyclization Click Reaction Could Make any Molecule Photothermally Active?

Author

Maxime Roger, Yann Bretonnière, Yann Trolez, Antoine Vacher, Imane Arbouch, Jérôme Cornil, Gautier Félix, Julien De Winter, Sébastien Richeter, Sébastien Clément, and Philippe Gerbier

Abstract

Three new tetraphenylethene (TPE) push-pull chromophores exhibiting strong intramolecular charge transfer (ICT) are described. They were obtained via [2+2] cycloaddition - retroelectrocyclization (CA-RE) click reactions on an electron-rich alkyne-tetrafunctionalized TPE (TPE-alkyne) using both 1,1,2,2-tetracyanoethene (TCNE), 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) as electron-deficient alkene. Only the starting TPE-alkyne displayed a significant AIE behavior, whereas for TPE-TCNE,a faint effect was observed and for TPE-TCNQ and TPE-F4-TCNQ, no fluorescence was observed in any conditions. The main ICT bands that dominate the UV-Visible absorption spectra underwent a pronounced red-shift beyond the near-infrared (NIR) region for TPE-F4-TCNQ. Based on TD-DFT calculations, it was shown that the ICT character shown by the compounds exclusively originated from the clicked moieties independently of the nature of the central molecular platform. Photothermal (PT) studies conducted on both TPE-TCNQ and TPE-F4-TCNQ in the solid state revealed excellent properties, especially for TPE-F4-TCNQ. These results indicated that CA-RE reaction of TCNQ or F4-TCNQ with donor-substituted are promising candidates for PT applications.

Published
2023

14. Electronic, steric and catalytic properties of N-heterocyclic carbene rhodium(<scp>i</scp>) complexes linked to (metallo)porphyrins

Author

Ludivine Poyac, Stefano Scoditti, Xavier Dumail, Michel Granier, Sébastien Clément, Rafael Gramage-Doria, Charles H. Devillers, Sébastien Richeter, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Università della Calabria [Arcavacata di Rende] (Unical), 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), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and ANR-19-CE07-0039,REMOTCAT,Fonctionalisation 'remote' des molecules par catalyse supramoleculaire(2019)

Subjects
Porphyrins, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Metals and Alloys, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Heterocyclic Compounds, Materials Chemistry, Ceramics and Composites, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Rhodium, Electronics
Abstract

International audience; Electronic and steric properties of NHC ligands functionalized with porphyrins were investigated. When porphyrins are used as NHCwingtips, nickel(II) in the macrocyle significantly improves the catalytic activity of the neighbouring NHC-Rh(I) complex in the conjugate addition of phenylboronic acid to cyclohexen-2-one.

Published
2022

15. D-Mannose-appended 5,15-diazaporphyrin for photodynamic therapy

Author

Lamiaa M. A. Ali, Kazuya Miyagawa, Norihito Fukui, Mélanie Onofre, Khaled El Cheikh, Alain Morère, Sébastien Clément, Magali Gary-Bobo, Sébastien Richeter, and Hiroshi Shinokubo

Subjects
Photosensitizing Agents, Photochemotherapy, Cell Line, Tumor, Organic Chemistry, Humans, Female, Breast Neoplasms, Physical and Theoretical Chemistry, Biochemistry, Mannose
Abstract

5,15-Diazaporphyrin appended with d-mannose moieties was prepared through Suzuki–Miyaura cross-coupling reaction and SN2 alkylation.

Published
2022

16. Raman resonance tuning of quaterthiophene in filled carbon nanotubes at high pressures

Author

Rafael S. Alencar, Bruno Jousselme, Romain Chambard, R. Aznar, Laurent Alvarez, J.-L. Bantignies, A. G. Souza Filho, Denis Machon, C. Weigel, A. L. Aguiar, R.S. Ferreira, Alfonso San-Miguel, Sébastien Clément, Laboratoire Charles Coulomb (L2C), and Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Quaterthiophene, Nanotube, Materials science, Resonance Raman spectroscopy, Carbon nanotubes, 02 engineering and technology, Carbon nanotube, Electronic structure, 010402 general chemistry, 01 natural sciences, law.invention, [SPI]Engineering Sciences [physics], symbols.namesake, law, [CHIM]Chemical Sciences, General Materials Science, Straintronics, [PHYS]Physics [physics], Intermolecular force, Resonance, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, High pressure, Chemical physics, symbols, Density functional theory, 0210 nano-technology, Raman spectroscopy
Abstract

Filling carbon nanotubes with molecules is a route for the development of electronically modified one-dimensional hybrid structures for which the interplay between the electronic structure of molecules and nanotubes is a key factor. Tuning these energy levels with external parameters is an interesting strategy for the engineering of new devices and materials. Here we show that the hybrid system composed by quaterthiophene (4T) molecules confined in single-walled carbon nanotubes, presents a piezo-Raman-resonance of the molecule vibrational pattern. This behavior manifests as a rapid pressure induced enhancement of the 4T Raman mode intensities compared to the tubes G-band Raman modes. Density functional theory calculations allow to explain the spectral behaviour through the pressure-enhanced quaterthiophene resonance evolution. By increasing pressure, the tube cross-section deformation leads to a reduction of the intermolecular distance, to the splitting of the molecular levels and then to an increase of resonance channels. Calculations and experiments converge to the 4T piezo-resonance scenario associated with the pressure-induced nanotube radial collapse observed at about 0.8 GPa. Our findings offer possibilities for the development of pressure transducers based on molecule-filled carbon nanotubes.

Published
2021

17. Molecular Systems Combining Porphyrinoids and N‐Heterocyclic Carbenes

Author

Sébastien Clément, Sébastien Richeter, Jean-François Longevial, Ludivine Poyac, Clémence Rose, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), ANR, ANR-19-CE07-0009,COmPaCt,Propriétés Catalytiques de Systèmes Moléculaires Combinant Porphyrines et Complexes Métalliques de Carbènes N-hétérocycliques(2019), and ANR-09-JCJC-0089,PORPH-NHC,Ligands ' Porphyrine-Carbène N-Hétérocyclique ' Réglables et Réactifs à des Stimuli Externes pour la Catalyse(2009)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Structural diversity, Molecular electronics, Homogeneous catalysis, [CHIM.CATA]Chemical Sciences/Catalysis, Molecular systems, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Porphyrin, 0104 chemical sciences, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Covalent bond, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Organometallic chemistry
Abstract

International audience; Porphyrins and N-heterocyclic carbenes (NHCs) are both relevant ligands in the fields of coordination and organometallic chemistry. Despite evident structural differences, porphyrins and NHCs have a lot in common such as their ability to form strong metalligand bonds and their use in catalysis, materials science and biomedicine. During the last decade, several molecular systems combining porphyrins and NHC ligands were reported in the literature. The present review gathers relevant examples where NHC ligands are either axially bonded to metalloporphyrins or covalently attached to the porphyrin cores. Structural diversity, electronic interplay between porphyrins and NHCs and some relevant applications in catalysis and biomedicine are notably described. Finally, molecular systems combining NHCs with other original porphyrinoids such as Nconfused porphyrins, subporphyrins and norcorroles are also presented.

Published
2021

18. Fluorescent P-Hydroxyphosphole for Peptide Labeling through P-N Bond Formation

Author

Emmanuelle Rémond, Jean‐Alain Fehrentz, Laure Liénart, Sébastien Clément, Jean‐Louis Banères, and Florine Cavelier

Subjects
Organic Chemistry, Oxides, General Chemistry, Sulfides, Ligands, Peptides, Receptors, Ghrelin, Catalysis
Abstract

Synthesis of fluorescent P-hydroxybinaphtylphosphole-oxide or -sulfide was achieved by trapping a binaphtyl dianion with methyl dichlorophosphite or P-(N,N-diethylamino)dichlorophosphine, followed by oxidation or sulfuration of the P-center. After saponification or acid hydrolysis, the P-hydroxyphospholes were coupled to peptides using the coupling agent BOP, under the conditions required for the synthesis in solution or on a solid support. This new method was illustrated by the labeling of the JMV2959, a potent antagonist of the Growth Hormone Secretagogue Receptor type 1a (GHS-R1a). The labeled conjugates were used to characterize GHSR ligands by competition assays, based on Fluorescence Resonance Energy Transfer (FRET). Such P-hydroxyphosphole-oxide or -sulfide constitute a promising new class of compact fluorophores with large Stokes shift, for labeling biomolecules by grafting through the phosphorus atom.

Published
2022

19. Bio-based porphyrins pyropheophorbide a and its Zn-complex as visible-light photosensitizers for free-radical photopolymerization

Author

Louise Breloy, Vlasta Brezová, Sébastien Richeter, Sébastien Clément, Jean-Pierre Malval, Samir Abbad Andaloussi, Davy-Louis Versace, Institut de Chimie et des Matériaux Paris-Est (ICMPE), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Slovak University of Technology in Bratislava, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Institut de Science des Matériaux de Mulhouse (IS2M), 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)-Matériaux et nanosciences d'Alsace (FMNGE), 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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-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), Laboratoire de Chimie Biologique, and Hôpital de la Timone [CHU - APHM] (TIMONE)

Subjects
Polymers and Plastics, Organic Chemistry, [CHIM]Chemical Sciences, Bioengineering, Biochemistry
Abstract

Two chlorophyll a derivatives, namely pyropheophorbide a and its corresponding zinc(ii) complex, are used as visible-light photosensitizers for free-radical photopolymerization.

Published
2022

21. Synthesis, Characterization, and Encapsulation Properties of Rigid and Flexible Porphyrin Cages Assembled from N -Heterocyclic Carbene–Metal Bonds

Author

Ludivine Poyac, Clémence Rose, Mohammad Wahiduzzaman, Aurélien Lebrun, Guillaume Cazals, Charles H. Devillers, Pascal G. Yot, Sébastien Clément, Sébastien Richeter, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Laboratoire de Météorologie Physique (LaMP), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Clermont Auvergne (UCA), Laboratoire de Mesures Physiques, Université de Montpellier (UM), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), Centre National de la Recherche Scientifique (CNRS)-Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)

Subjects
Inorganic Chemistry, 010405 organic chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, 010402 general chemistry, 01 natural sciences, ComputingMilieux_MISCELLANEOUS, 0104 chemical sciences
Abstract

International audience

Published
2021

22. Importance of lattice softness and phonon anharmonicity for the optoelectronic properties of 3D, 2D and 0D halide perovskites

Author

Even, Jacky, Da Cunha Ferreira, Afonso, Paofai, Serge, Létoublon, Antoine, Ollivier, Jacques, Raymond, stéphane, Sébastien, Clément, VIALLA, Remy, HEHLEN, Bernard, RUFFLE, Benoit, Cordier, Stéphane, Katan, Claudine, Bourges, Philippe, Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), 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), Institut Laue-Langevin (ILL), Magnétisme et Diffusion Neutronique (MDN ), Modélisation et Exploration des Matériaux (MEM), 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 (UGA)-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 (UGA), Laboratoire Charles Coulomb (L2C), Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Léon Brillouin (LLB - UMR 12), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), European Project: 899141,PoLLoC, European Project: PeroCUBE, European Project: 862656,DROPIT, Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-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)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), 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), ILL, and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay

Subjects
[PHYS]Physics [physics], [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

National audience

Published
2021

23. Detection of the Enzymatic Cleavage of DNA through Supramolecular Chiral Induction to a Cationic Polythiophene

Author

David Beljonne, Sébastien Richeter, Mathieu Surin, Mathieu Fossépré, Marie Trevisan, Valentine Cyriaque, Ruddy Wattiez, Sébastien Clément, Laboratory for Chemistry of Novel Materials, Université de Mons (UMons), Proteomics and Microbiology Laboratory, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Univers, Transport, Interfaces, Nanostructures, Atmosphère et environnement, Molécules (UMR 6213) (UTINAM), Université de Franche-Comté (UFC), Université Bourgogne Franche-Comté [COMUE] (UBFC)-Université Bourgogne Franche-Comté [COMUE] (UBFC)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), and Univ Mons, Belgique, Serv Chim Mat Nouveaux

Subjects
Circular dichroism, Molecular model, Biomedical Engineering, Supramolecular chemistry, macromolecular substances, 02 engineering and technology, 010402 general chemistry, Cleavage (embryo), 01 natural sciences, Biomaterials, chemistry.chemical_compound, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Chemistry, Biochemistry (medical), technology, industry, and agriculture, Cationic polymerization, General Chemistry, Polymer, 021001 nanoscience & nanotechnology, Combinatorial chemistry, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, Polythiophene, 0210 nano-technology, Biosensor
Abstract

Water-soluble π-conjugated polymers are increasingly envisioned in biosensors, in which their unique optical and electronic properties permit a highly sensitive detection of biomolecular targets. In particular, cationic π-conjugated polymers are attractive for DNA sensing technologies, through the use of the fluorescence signals either in physiological solutions or in thin films. However, in the context of enzymatic activity assays, fluorescence-based methods require covalently labeling DNA with a dye or an antibody and are limited to short time scale due to dye photobleaching. In this frame, we report here a novel possible approach to probe the cleavage of DNA by a restriction enzyme, in continuous and without covalently labeled DNA substrate. This is achieved by exploiting unique chiroptical signals arising from the chiral induction of DNA to a poly[3-(6'-(trimethylphosphonium)hexyl)thiophene-2,5-diyl] upon interaction. The cleavage of DNA by

Published
2019

24. Silole Amino Acids with Aggregation-Induced Emission Features Synthesized by Hydrosilylation

Author

Florine Cavelier, Emmanuelle Rémond, Mathieu Arribat, Sébastien Richeter, Sébastien Clément, and Philippe Gerbier

Subjects
Alanine, chemistry.chemical_classification, 010405 organic chemistry, Hydrosilylation, Carboxylic acid, Organic Chemistry, Peptide, Tripeptide, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Amino acid, chemistry.chemical_compound, Solid-phase synthesis, chemistry, Moiety, Physical and Theoretical Chemistry
Abstract

The synthesis of silole amino acids was achieved through hydrosilylation of alkene or alkyne‐containing amino acids with 1‐methyl‐2,3,4,5‐tetraphenyl‐1H‐silole, using Karstedt's catalyst with yield up to 95 % and without epimerization. After selective deprotection of carboxylic acid or amine functions respectively, C‐ or N‐peptide coupling with an alanine moiety proved their possible incorporation into peptides. A model tripeptide was synthesized by solid phase synthesis with the N‐Fmoc protected silole amino acid version. The silole moiety can be also grafted on a precursor peptide directly on the solid support. These amino acids and peptides exhibit AIE properties with λem ca. 500 nm and Δλ ca. 100 nm. This approach constitutes an alternative and promising strategy for incorporation of such AIE fluorogens to peptides.

Published
2019

25. Synthesis, characterization and use of a POSS-arylamine based push–pull octamer

Author

Clément Cabanetos, Sébastien Richeter, Sylvie Dabos-Seignon, Amir Hossein Habibi, Sébastien Clément, Pablo Simón Marqués, Ahmad Mehdi, José María Andrés Castán, Philippe Blanchard, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), MOLTECH-Anjou, and Université d'Angers (UA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Organic solar cell, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 02 engineering and technology, General Chemistry, Polymer, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Small molecule, Catalysis, Silsesquioxane, Polymer solar cell, 0104 chemical sciences, Characterization (materials science), chemistry.chemical_compound, chemistry, Chemical engineering, Materials Chemistry, Histone octamer, 0210 nano-technology, Push pull
Abstract

International audience; The first synthesis of an original octamer consisting of a central polyhedral oligomeric silsesquioxane (POSS) cage decorated with electro- and optically active arylamine-based push–pull building-blocks is reported herein. Once fully characterized, the potential of the new compound was evaluated as donor material in bulk heterojunction organic solar cells. With promising power conversion efficiencies, good processability and film forming properties, such multimer architectures turns out to be potential candidates to bridge the gap between small molecules and polymers.

Published
2021

26. Phosphonium-based polythiophene conjugated polyelectrolytes with different surfactant counterions: thermal properties, self-assembly and photovoltaic performances

Author

Sylvain Chambon, M. Chevrier, Roberto Lazzaroni, Niko Van den Brande, Sébastien Clément, Rachel C. Evans, Bruno Van Mele, Jurgen Kesters, Philippe Dubois, Thomas Arnold, Ahmad Mehdi, Wouter Maes, Sébastien Richeter, Judith E. Houston, Materials and Chemistry, Vriendenkring VUB, Physical Chemistry and Polymer Science, Biology, Faculty of Economic and Social Sciences and Solvay Business School, Kesters, J [0000-0003-2095-8411], Houston, JE [0000-0001-5205-3620], Van den Brande, N [0000-0002-5324-6261], Chambon, S [0000-0003-0703-7407], Richeter, S [0000-0001-5284-0931], Mehdi, A [0000-0002-7830-2012], Lazzaroni, R [0000-0002-6334-4068], Dubois, P [0000-0003-1534-1564], Evans, RC [0000-0003-2956-4857], Maes, W [0000-0001-7883-3393], Clément, S [0000-0002-8473-8197], Apollo - University of Cambridge Repository, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Centre d'Innovation et de Recherche en Matériaux Polymères (CIRMAP), Université de Mons (UMons), Hasselt University (UHasselt), Jülich Centre for Neutron Science (JCNS), Physical Chemistry and Polymer Science (FYSC), Vrije Universiteit Brussel (VUB), Laboratoire de l'intégration, du matériau au système (IMS), Université Sciences et Technologies - Bordeaux 1-Institut Polytechnique de Bordeaux-Centre National de la Recherche Scientifique (CNRS), Diamond Light Source Limited [Didcot, UK], Harwell Science and Innovation Campus [Didcot, UK], European Spallat Source ERIC, POB 176, SE-22100 Lund, Sweden, Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, Rutherford Appleton Lab, ISIS Neutron & Muon Source, Didcot OX11 0QX, Oxon, England, Department of Materials Science and Metallurgy [Cambridge University] (DMSM), University of Cambridge [UK] (CAM), MEHDI, Ahmad/0000-0002-7830-2012, Houston, Judith/0000-0001-5205-3620, Arnold, Thomas/0000-0001-8295-3822, Van den Brande, Niko/0000-0002-5324-6261, and Chambon, Sylvain/0000-0003-0703-7407

Subjects
Materials science, Polymers and Plastics, Organic solar cell, conjugated polyelectrolytes, 02 engineering and technology, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Polymer solar cell, [SPI.MAT]Engineering Sciences [physics]/Materials, chemistry.chemical_compound, Photoactive layer, Materials Chemistry, Phosphonium, chemistry.chemical_classification, surfactant counteranion, Organic Chemistry, organic solar cells, self-assembly, 021001 nanoscience & nanotechnology, Conjugated Polyelectrolytes, 0104 chemical sciences, chemistry, Chemical engineering, thin films, cathode interlayers, Polythiophene, Counterion, 0210 nano-technology, Glass transition
Abstract

Phosphonium-based polythiophene conjugated polyelectrolytes (CPEs) with three different counterions (dodecylsulfate, octylsulfate and perfluorooctane sulfonate) are synthesized to determine how the nature of the counterion affects the thermal properties, the self-assembly in thin films and the performance as the cathode interfacial layer in polymer solar cells (PSCs). The counterion has a significant effect on the thermal properties of the CPEs, affecting both their glass transition and crystalline behaviour. Grazing-incidence wide-angle X-ray scattering studies also indicate that changing the nature of the counterion influences the microstructural organization in thin films (face-onversusedge-on orientation). The affinity of the CPEs with the underlying photoactive layer in PSCs is highly correlated with the counterion species. Finally, in addition to an increase of the power conversion efficiency ofca15% when using these CPEs as cathode interfacial layers in PSCs, a higher device stability is noted, compared to a reference device with a calcium interlayer. (c) 2020 Society of Industrial Chemistry This work was supported by the CNRS and the Universite de Montpellier. This work was also supported in part by the Science Foundation Ireland under grant no. 12/IP/1608. Research in Mons is supported by FNRS-FRFC (2Dto3D project - EOS programme) and Region Wallonne (OPTI2MAT excellence programme). The University of Mons and Hasselt University co-authors are grateful for financial support by the Science Policy Office of the Belgian Federal Government (BELSPO; PAI/IAP 7/05). JK is a postdoctoral fellow of the Research Foundation - Flanders (FWO Vlaanderen). NVdB thanks the Vrije Universiteit Brussel for a post-doctoral grant. The HINT COST action MP1202 and French-Irish programme 'Hubert Curien Ulysses' (31998ZF) are also acknowledged for support. This research has also been supported by the European Commission under the 7th Framework Programme through the 'Research Infrastructures' action of the 'Capacities' programme (contract no. CP-CSA_INFRA-2008-1.1.1 Number 226507-NM13). We further thank the Diamond Light Source for beamtime at the I07 beamline (experiment SI13868) and TA Instruments for the RHC equipment. Clement, S (corresponding author), Univ Montpellier, ENSCM, CNRS, ICGM, Montpellier, France. sebastien.clement1@umontpellier.fr

Published
2021

27. Revealing the Complex Nature of Bonding in the Binary High-Pressure Compound FeO 2

Author

Sébastien Clément, Georgios Aprilis, Stella Chariton, Ivan Leonov, Hanns-Peter Liermann, R. Torchio, Egor Koemets, Valerio Cerantola, Julien Haines, Vitali B. Prakapenka, Timofey Fedotenko, Natalia Dubrovinskaia, Angelika Dorothea Rosa, Catherine McCammon, Volodymyr Svitlyk, Maxim Bykov, Igor A. Abrikosov, Tetsuo Irifune, A. V. Ponomareva, Jérôme Rouquette, Michael Hanfland, Leonid Dubrovinsky, Elena Bykova, Konstantin Glazyrin, Bayerisches Geoinstitut (BGI), Universität Bayreuth, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Ural Division of the Russian Academy of Sciences Institute of Metal Physics, Carnegie Institution for Science, Earth and Planets Laboratory, Laboratoire Charles Coulomb (L2C), Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), European Synchroton Radiation Facility [Grenoble] (ESRF), Deutsches Elektronen-Synchrotron [Hamburg] (DESY), Center for Advanced Radiation Sources [University of Chicago] (CARS), University of Chicago, Geodynamics Research Center [Ehime], Ehime University [Matsuyama], National University of Science and Technology (MISIS), Department of Physics, Chemistry and Biology [Linköping] (IFM), Linköping University (LIU), Koemets, E, Leonov, I, Bykov, M, Bykova, E, Chariton, S, Aprilis, G, Fedotenko, T, Clément, S, Rouquette, J, Haines, J, Cerantola, V, Glazyrin, K, Mccammon, C, Prakapenka, V, Hanfland, M, Liermann, H, Svitlyk, V, Torchio, R, Rosa, A, Irifune, T, Ponomareva, A, Abrikosov, I, Dubrovinskaia, N, and Dubrovinsky, L

Subjects
FORMAL VALENCES, Diffraction, iron oxide, Absorption spectroscopy, XRD, XAS, EXTREME PRESSURE, General Physics and Astronomy, Binary number, REDUCTION OF OXYGEN, DYNAMICAL MEAN-FIELD THEORY, 01 natural sciences, DFT, CHEMICAL BONDS, OXYGEN, Homologous series, chemistry.chemical_compound, MEAN FIELD THEORY, extreme condition, IRON METALLOGRAPHY, 0103 physical sciences, synchrotron, [CHIM]Chemical Sciences, ddc:530, DENSITY FUNCTIONAL THEORY, Isostructural, IRON OXIDES, 010306 general physics, Spectroscopy, Valence (chemistry), Mössbauer spectroscopy, SINGLE CRYSTALS, 16. Peace & justice, laser heating, 3. Good health, Crystallography, HOMOLOGOUS SERIES, SINGLE CRYSTAL X-RAY DIFFRACTION, chemistry, diamond anvil cell, X RAY ABSORPTION SPECTROSCOPY, High pressure, COMPLEX NATURE, LOCALIZED HOLES
Abstract

Extreme pressures and temperatures are known to drastically affect the chemistry of iron oxides, resulting in numerous compounds forming homologous series nFeOmFe2O3 and the appearance of FeO2. Here, based on the results of in situ single-crystal x-ray diffraction, Mössbauer spectroscopy, x-ray absorption spectroscopy, and density-functional theory+dynamical mean-field theory calculations, we demonstrate that iron in high-pressure cubic FeO2 and isostructural FeO2H0.5 is ferric (Fe3+), and oxygen has a formal valence less than 2. Reduction of oxygen valence from 2, common for oxides, down to 1.5 can be explained by a formation of a localized hole at oxygen sites. © 2021 American Physical Society. We acknowledge the Deutsches Elektronen-Synchrotron (DESY, PETRA III), the European Synchrotron Radiation Facility (ESRF), and the Advance Photon Source (APS) for provision of beamtime. N. D. and L. D. thank the Federal Ministry of Education and Research, Germany (BMBF, Grant No. 05K19WC1) and the Deutsche Forschungsgemeinschaft (DFG Projects No. DU 954–11/1, No. DU 393–9/2, and No. DU 393–13/1) for financial support. N. D. and I. A. A. thank the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO-Mat-LiU No. 2009 00971). Electronic structure calculations were supported by the Russian Science Foundation (Project No. 18-12-00492). Theoretical analysis of chemical bonding was supported by the Ministry of Science and Higher Education of the Russian Federation in the framework of Increase Competitiveness Program of NUST “MISIS” (No. K2-2019-001) implemented by a governmental decree, No. 211. Support from the Knut and Alice Wallenberg Foundation (Wallenberg Scholar Grant No. KAW-2018.0194), the Swedish Government Strategic Research Areas and SeRC, and the Swedish Research Council (VR) Grant No. 2019-05600 is gratefully acknowledged.

Published
2021

28. Synthesis, Self‐Assembly, and Nucleic Acid Recognition of an Acylhydrazone‐Conjugated Cationic Tetraphenylethene Ligand

Author

Mathieu Fossépré, Virginie Gervais, Maxime Leclercq, Sébastien Clément, Clément Kotras, Maëva Coste, Sébastien Ulrich, Mathieu Surin, David Dellemme, Sébastien Richeter, Yannick Bessin, Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut de pharmacologie et de biologie structurale (IPBS), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées, Laboratory for Chemistry of Novel Materials, Université de Mons (UMons), and Univ Mons, Belgique, Serv Chim Mat Nouveaux

Subjects
010405 organic chemistry, Chemistry, Organic Chemistry, Cationic polymerization, Conjugated system, 010402 general chemistry, Ligand (biochemistry), G-quadruplex, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Molecular recognition, Nucleic acid, [CHIM]Chemical Sciences, Self-assembly, Physical and Theoretical Chemistry, Aggregation-induced emission, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2021

29. In vitro toxicity and photodynamic properties of porphyrinoids bearing imidazolium salts and N-heterocyclic carbene gold(I) complexes

Author

Clémence Rose, Laure Lichon, Sébastien Clément, Morgane Daurat, Magali Gary-Bobo, Sébastien Richeter, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), and NanoMedSyn

Subjects
Bearing (mechanical), 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Porphyrinoids, Building and Construction, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, In vitro, Photodynamic therapy, 0104 chemical sciences, law.invention, chemistry.chemical_compound, chemistry, law, Toxicity, [CHIM.COOR]Chemical Sciences/Coordination chemistry, N-heterocyclic carbenes, Electrical and Electronic Engineering, Gold complexes, Carbene
Abstract

International audience; Porphyrins bearing imidazolium salts were synthesized and used as N-heterocylic carbene (NHC) precursors for the preparation of gold(I) complexes. The dark toxicity and phototoxicity of the obtained compounds were investigated in vitro on MCF-7 breast cancer cells. The obtained data showed that porphyrins equipped with imidazolium salts are non-toxic in the dark and present interesting photodynamic properties. On the contrary, corresponding NHC gold(I) complexes are not suitable photosensitizers for photodynamic therapy (PDT) applications. Their dark toxicity strongly depends of the nature of the linker between the porphyrin core and the NHC. This work was extended to the synthesis of a pyropheophorbide a derivative with a pendant imidazolium group for PDT applications using excitation wavelengths of 450 nm, 545 nm, and importantly of 650 nm.

Published
2021

31. Lattice Dynamics Study of Elemental Bismuth under High Pressure

Author

Romain Viennois, Sébastien Clément, Julien Haines, Yixuan Zhao, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Lattice dynamics, Materials science, High Energy Physics::Lattice, Thermodynamics, chemistry.chemical_element, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, Pressure dependence, 021001 nanoscience & nanotechnology, 01 natural sciences, 3. Good health, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Bismuth, General Energy, chemistry, High pressure, 0103 physical sciences, Physical and Theoretical Chemistry, 010306 general physics, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

We report a combined experimental and theoretical study of the lattice dynamics of different high-pressure phases of bismuth and their pressure dependence. The stability and the lattice dynamics of...

Published
2020

32. Binding Mode Multiplicity and Multiscale Chirality in the Supramolecular Assembly of DNA and a π-Conjugated Polymer

Author

Mathieu Fossépré, Sébastien Clément, David Beljonne, Sébastien Richeter, Mathieu Surin, and Inbal Tuvi-Arad

Subjects
Circular dichroism, Binding Sites, Chemistry, Macromolecular Substances, Polymers, Supramolecular chemistry, DNA, Thiophenes, Molecular Dynamics Simulation, Atomic and Molecular Physics, and Optics, Supramolecular assembly, symbols.namesake, Molecular dynamics, Chemical physics, Cations, symbols, heterocyclic compounds, Physical and Theoretical Chemistry, Multiplicity (chemistry), van der Waals force, Chirality (chemistry), Macromolecule
Abstract

Water-soluble π-conjugated polymers are increasingly considered for DNA biosensing. However, the conformational rearrangement, supramolecular organization and dynamics upon interaction with DNA have been overlooked, which prevents the rational design of such detection tools. To elucidate the binding of a cationic polythiophene (CPT) to DNA with atomistic resolution, we performed molecular simulations of their supramolecular assembly. Comparison of replicated simulations show a multiplicity of CPT binding geometries that contribute to the wrapping of CPT around DNA. The different binding geometries are stabilized by both electrostatic interactions between CPT lateral cations and DNA phosphodiesters and van der Waals interactions between the CPT backbone and the DNA grooves. Simulated circular dichroism (CD) spectra show that the induced CD signal stems from a conserved geometrical feature across the replicated simulations, i. e. the presence of segments of syn configurations between thiophene units along the CPT chain. At the macromolecular scale, we inspected the different shapes related to the CPT binding modes around the DNA through symmetry metrics. Altogether, molecular dynamics (MD) simulations, model Hamiltonian calculations of the CD spectra, and symmetry indices provide insights into the origin of induced chirality from the atomic to the macromolecular scale. Our multidisciplinary approach points out the hierarchical aspect of CPT chiral organization induced by DNA.

Published
2020

33. Sol-Gel Chemistry: From Molecule to Functional Materials

Author

Ahmad Mehdi, Sébastien Clément, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Pharmaceutical Science, Biocompatible Materials, coatings, 02 engineering and technology, 01 natural sciences, Analytical Chemistry, Biofouling, chemistry.chemical_compound, Materials Testing, Drug Discovery, Nanotechnology, anticorrosion, Optical Fibers, ComputingMilieux_MISCELLANEOUS, dye-sensitized solar cells (DSSCs), antifouling, Temperature, [CHIM.MATE]Chemical Sciences/Material chemistry, self-assembly, Hydrogen-Ion Concentration, Silicon Dioxide, 021001 nanoscience & nanotechnology, Anti-Bacterial Agents, Corrosion, Chemistry, Editorial, Chemistry (miscellaneous), Scientific method, Molecular Medicine, 0210 nano-technology, hydrolytic, Materials science, Surface Properties, Phase Transition, Catalysis, non-hydrolytic, lcsh:QD241-441, lcsh:Organic chemistry, Escherichia coli, Molecule, sol-gel, Physical and Theoretical Chemistry, Sol-gel, catalysis, 010405 organic chemistry, titanium dioxide, Organic Chemistry, PAHs adsorption, 0104 chemical sciences, Kinetics, Chemical engineering, Polymerization, chemistry, Titanium dioxide, Biocatalysis, Self-assembly, Reactive Oxygen Species, Hydrogen
Abstract

Through this Special Issue, you will discover the potentiality of inorganic polymerization (sol-gel process) which is a unique and versatile way for the preparation of materials [...]

Published
2020

34. Molecular complexes and main-chain organometallic polymers based on Janus bis(carbenes) fused to metalloporphyrins

Author

Jean-François Longevial, Aurélien Lebrun, Danielle Laurencin, Sébastien Richeter, Sébastien Clément, Mamadou Lo, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Ligand, Singlet oxygen, chemistry.chemical_element, Zinc, Polymer, 010402 general chemistry, 01 natural sciences, Porphyrin, Chloride, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymer chemistry, medicine, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Janus, Carbene, medicine.drug
Abstract

Janus bis(N-heterocyclic carbenes) composed of a porphyrin core with two N-heterocyclic carbene (NHC) heads fused to opposite pyrroles were used as bridging ligands for the preparation of metal complexes. We first focused our attention on the synthesis of gold(i) chloride complexes [(NHC)AuCl] and investigated the substitution of the chloride ligand by acetylides to obtain the corresponding [(NHC)AuC[triple bond, length as m-dash]CR] complexes. Polyacetylides were then used to obtain molecular multiporphyrinic systems with porphyrins fused to only one NHC ligand, while main-chain organometallic polymers (MCOPs) were obtained when using Janus porphyrin bis(NHCs). Interestingly, MCOPs incorporating zinc(ii) porphyrins proved to be efficient as heterogeneous photocatalysts for the generation of singlet oxygen upon visible light irradiation.

Published
2020

35. High-pressure, high temperature synthesis of a mesoporous α-quartz/bismuth nanowire composite

Author

M. Cambon, Pierre Toulemonde, Romain Viennois, Gaël Talbi, Thomas Hansen, Mickael Beaudhuin, Olivier Cambon, Yixuan Zhao, Sébastien Clément, Julien Haines, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Laboratoire Charles Coulomb (L2C), Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Matériaux, Rayonnements, Structure (MRS), Institut Néel (NEEL), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA), Institut Laue-Langevin (ILL), and ILL

Subjects
Materials science, Guest Insertion, Composite number, Nanowire, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Bismuth, Nanocomposites, Silica nanotubes, General Materials Science, Quartz, Nanocomposite, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Amorphous solid, chemistry, Chemical engineering, Transmission electron microscopy, 0210 nano-technology, Mesoporous material, High Pressure
Abstract

International audience; High temperature, high pressure conditions were used to insert liquid bismuth in 4-6 nm diameter amorphous silica nanotubes. A combination of transmission electron microscopy and neutron powder diffrac-tion indicate that the final composite consists in 5-6 nm semi-conducting Bi nanowires confined in insulating mesoporous -quartz. Such a nanostructured material could be of considerable interest for thermo-electric applications. HIGHLIGHTS:  Bismuth was inserted into 4-6 nm silica nanotubes under high-pressure, high-temperature conditions  The host amorphous nanotubes crystallize in the form of -quartz  The obtained nanocomposite consists of 5-6 nm Bi nanowires imbedded in mesoporous -quartz  The formation of Bi nanowires modifies their physical properties compared to bulk Bi

Published
2020

36. Conductive multilayer film based on composite materials made of conjugated polyelectrolytes and inorganic particles

Author

Boris Lakard, C.C. Buron, Sébastien Clément, C. Filiâtre, Ahmad Mehdi, F.E. Jurin, Nicolas Martin, Univers, Transport, Interfaces, Nanostructures, Atmosphère et environnement, Molécules (UMR 6213) (UTINAM), Université de Franche-Comté (UFC), Université Bourgogne Franche-Comté [COMUE] (UBFC)-Université Bourgogne Franche-Comté [COMUE] (UBFC)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Franche-Comté Électronique Mécanique, Thermique et Optique - Sciences et Technologies (UMR 6174) (FEMTO-ST), Université de Technologie de Belfort-Montbeliard (UTBM)-Ecole Nationale Supérieure de Mécanique et des Microtechniques (ENSMM)-Université de Franche-Comté (UFC), Université Bourgogne Franche-Comté [COMUE] (UBFC)-Université Bourgogne Franche-Comté [COMUE] (UBFC)-Centre National de la Recherche Scientifique (CNRS), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Franche-Comté (UFC), Université Bourgogne Franche-Comté [COMUE] (UBFC)-Université Bourgogne Franche-Comté [COMUE] (UBFC), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2), and Université de Technologie de Belfort-Montbeliard (UTBM)-Ecole Nationale Supérieure de Mécanique et des Microtechniques (ENSMM)-Centre National de la Recherche Scientifique (CNRS)-Université de Franche-Comté (UFC)

Subjects
Materials science, Inorganic colloidal particle, Composite film, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, [SPI.MAT]Engineering Sciences [physics]/Materials, Polystyrene sulfonate, chemistry.chemical_compound, Colloid and Surface Chemistry, PEDOT:PSS, Multilayer, Zeta potential, [CHIM]Chemical Sciences, Surface charge, Composite material, [SPI.NANO]Engineering Sciences [physics]/Micro and nanotechnologies/Microelectronics, [SPI.ACOU]Engineering Sciences [physics]/Acoustics [physics.class-ph], Conductivity, Conjugated polyelectrolyte, 021001 nanoscience & nanotechnology, Conjugated Polyelectrolytes, Polythiophene, Polyelectrolyte, 0104 chemical sciences, chemistry, Particle, 0210 nano-technology
Abstract

International audience; Poly(3,4-ethylenedioxythiophene)–polystyrene sulfonate (PEDOT:PSS) conjugated polymer blend and a cationic poly(3-hexylthiophene) (P3HT)-based conjugated polyelectrolyte incorporating imidazolium ionic side groups were first adsorbed as monolayer on inorganic colloidal particles. At the plateau of adsorption isotherm, adsorbed amount of PEDOT:PSS on alumina particles appears lower than the adsorbed amount of P3HT on silica particles. Both polyelectrolytes strongly modify the surface charge of particles as reveals by zeta potential variation. Functionalized particles were then assembled using Layer-by-Layer method in order to prepare (PDDA/Al2O3-PEDOT:PSS)n and (SiO2-P3HT/PEDOT:PSS)n conductive multilayer film. Thicker PDDA/Al2O3-PEDOT:PSS films were elaborated when a drying step was added during the LbL build-up. The same effect was observed when composite particle concentration was increased from 1 to 10 g.L−1. Electrical behavior of film was completely modified in comparison with PDDA/PEDOT:PSS assembly. After heating at 150 °C, no conductivity was detected due to microcracks visible on SEM images. For SiO2-P3HT/PEDOT:PSS assembly, thickness is higher than for PDDA/Al2O3-PEDOT:PSS assembly using the same experimental procedure. However, even if two conductive polyelectrolytes were embedded into the film, conductivity was too low at 30 °C to be measured by van der Pauw technique probably due to the cracking of the film induced by incorporation of silica particles.

Published
2020

37. A la Réunion, un jardin-école pour la planète

Author

Sébastien, Clément, Passages, Centre National de la Recherche Scientifique (CNRS)-Université Bordeaux Montaigne-Université de Pau et des Pays de l'Adour (UPPA)-Ministère de la Culture et de la Communication (MCC)-Université de Bordeaux (UB), and Université de Bordeaux (UB)-Ministère de la Culture et de la Communication (MCC)-Université de Pau et des Pays de l'Adour (UPPA)-Université Bordeaux Montaigne-Centre National de la Recherche Scientifique (CNRS)

Subjects
[SHS.ARCHI]Humanities and Social Sciences/Architecture, space management, [SDE.IE]Environmental Sciences/Environmental Engineering, [SDE.MCG]Environmental Sciences/Global Changes, [SHS.EDU]Humanities and Social Sciences/Education, [SDE.BE]Environmental Sciences/Biodiversity and Ecology, [SDE.ES]Environmental Sciences/Environmental and Society, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2020

38. Design of metalloporphyrins fused to imidazolium rings for binding DNA G-quadruplexes

Author

Jenifer Rubio-Magnieto, Clémence Rose, Francesca Caporaletti, Arie van der Lee, Sébastien Clément, Sébastien Richeter, Mamadou Lo, Jean-François Longevial, Mathieu Surin, Univ Mons, Belgique, Serv Chim Mat Nouveaux, Université de Mons (UMons), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut Européen des membranes (IEM), and Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)

Subjects
Circular dichroism, G-quadruplex, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, porphyrinoids, chemistry.chemical_element, General Chemistry, circular dichroism spectroscopy, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Porphyrin, human telomeric DNA, 0104 chemical sciences, FRET melting assay, chemistry.chemical_compound, Crystallography, Nickel, chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, DNA, ComputingMilieux_MISCELLANEOUS, Pyrrole
Abstract

Synthesis and characterization of nickel(II) meso-tetraarylporphyrins fused to imidazolium rings across [Formula: see text],[Formula: see text]-pyrrolic positions and X-ray structure of the porphyrin where two opposed pyrrole units are fused to an imidazolium ring are presented. The interactions between these mono-, bis-, tris- and tetrakis(imidazolium) porphyrins with human telomeric DNA G-quadruplexes (G4) were investigated using UV-vis absorption spectroscopy, Circular Dichroism (CD) spectroscopy and Fluorescence Resonance Energy Transfer (FRET) melting assay. Possible binding modes between cationic porphyrins and a selected G4 sequence (d[AG3(T2AG[Formula: see text]]), and relative stabilities of porphyrin/G4 complexes are discussed. Excepting porphyrins fused to one imidazolium ring, the other derivatives interact with G4 structures and their stabilization strongly depends on the porphyrin structure (number and localization of the imidazolium rings).

Published
2020

39. Synthesis, photophysical and electropolymerization properties of thiophene-substituted 2,3-diphenylbuta-1,3-dienes

Author

Joëlle Rault-Berthelot, Arie van der Lee, Philippe Gerbier, Sébastien Clément, Mathias Quiot, Sébastien Richeter, Maxime Roger, Cyril Poriel, Kassem Amro, Centre d'Energétique et de Thermique de Lyon (CETHIL), Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), 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), Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Université de Montpellier, Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-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), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-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)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), and Université de Montpellier (UM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Molecular interactions, 010405 organic chemistry, Band gap, Solid-state, New materials, General Chemistry, Polymer, 010402 general chemistry, Electrochemistry, Photochemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Materials Chemistry, Thiophene, [CHIM]Chemical Sciences, Aggregation-induced emission, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; A series of 2,3-diphenylbuta-1,3-dienes (DPBs) bearing thiophene (T-DPB), bithiophene (BT-DPB) and ethylenedioxythiophene (EDOT-DPB) electropolymerizable units were prepared through desilylation reactions of the corresponding 3,4-diphenylsiloles derivatives. These DPBs derivatives exhibit remarkable different aggregation induced emission (AIE) or aggregation enhanced emission (AEE) behaviour depending on the strength of the molecular interactions occuring in the solid state. Indeed, T-DPB and EDOT-DPB were found to be good AIEgens while BT-DPB exhibited AEE behaviour. Finally, the electrochemical properties of these new materials were investigated revealing for all DPBs the occurrence of electropolymerization processes leading potentially to low band gap polymers.

Published
2020

40. Synthesis, characterization and modeling of self-assembled porphyrin nanorods

Author

Christel Gervais, Danielle Laurencin, Didier Cot, Sébastien Richeter, Yannick Guari, Sébastien Clément, Matthieu Paillet, Pascal G. Yot, Erik Elkaim, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Spectroscopie, Modélisation, Interfaces pour L'Environnement et la Santé (LCMCP-SMiLES), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Laboratoire Charles Coulomb (L2C), Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut Européen des membranes (IEM), and Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)

Subjects
NMR crystallography, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, law.invention, chemistry.chemical_compound, law, DFT modeling Tel : ++(33)467143971, Spectroscopy, solid state NMR, Tetraphenylborate, Chemistry, NMR cristallography, General Chemistry, self-assembly, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Porphyrin, Synchrotron, 0104 chemical sciences, Crystallography, Solid-state nuclear magnetic resonance, Nanorod, Self-assembly, 0210 nano-technology, nanorods, DFT modeling, porphyrin, Powder diffraction
Abstract

Porphyrin nanorods were prepared by ion-association between free-base meso 5,10,15,20-tetrakis-(4-[Formula: see text]-methylpyridinium)porphyrin cations and tetraphenylborate anions. The nanorods have variable lengths (up to a few micrometers long) and diameters ([Formula: see text]50–500 nm). Their structure at the molecular level was elucidated by combining multinuclear solid state NMR spectroscopy, synchrotron X-ray powder diffraction and DFT calculations.

Published
2019

41. Peripherally Metalated Porphyrins with Applications in Catalysis, Molecular Electronics and Biomedicine

Author

Jean Weiss, Jennifer A. Wytko, Sébastien Clément, Romain Ruppert, Sébastien Richeter, Jean-François Longevial, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut de Chimie de Strasbourg, 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 Louis Pasteur - Strasbourg I-Institut de Chimie du CNRS (INC), Incoming International Master program of IdEx (Univ. of Strasbourg), FRC-Labex CSC (ANR-10-LABX-0026 CSC), Région Languedoc-Roussillon (Research Grant 'Chercheur(se)s d’Avenir -2015–005984), ANR-14-JTIC-0002,MECANO,Ingenierie moléculaire et assemblages contrôlés de nanoobjets fonctionnels à base de porphyrines(2014), ANR-09-JCJC-0089,PORPH-NHC,Ligands ' Porphyrine-Carbène N-Hétérocyclique ' Réglables et Réactifs à des Stimuli Externes pour la Catalyse(2009), European Project: FEDER, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Louis Pasteur - Strasbourg I-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Porphyrins, Metal ions in aqueous solution, Biomedical Technology, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, Conjugated system, 010402 general chemistry, 01 natural sciences, Catalysis, Transition metal, Coordination Complexes, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, polycyclic compounds, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Electronic properties, Molecular Structure, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Molecular electronics, General Chemistry, Chromophore, Combinatorial chemistry, 3. Good health, 0104 chemical sciences, Intramolecular force, Electronics
Abstract

Porphyrins are conjugated, stable chromophores with a central core that binds a variety of metal ions and an easily functionalized peripheral framework. By combining the catalytic, electronic or cytotoxic properties of selected transition metal complexes with the binding and electronic properties of porphyrins, enhanced characteristics of the ensemble are generated. This review article focuses on porphyrins bearing one or more peripheral transition metal complexes and discusses their potential applications in catalysis or biomedicine. Modulation of the electronic properties and intramolecular communication through coordination bond linkages in bis-porphyrin scaffolds is also presented.

Published
2018

42. Cofacial porphyrin dimers assembled from N-heterocyclic carbene–metal bonds

Author

Clémence Rose, Sébastien Clément, Aurélien Lebrun, Sébastien Richeter, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Metals and Alloys, General Chemistry, 010402 general chemistry, 01 natural sciences, Porphyrin, Catalysis, 0104 chemical sciences, 3. Good health, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, chemistry, Polymer chemistry, Materials Chemistry, Ceramics and Composites, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Carbene, ComputingMilieux_MISCELLANEOUS, Metallic bonding
Abstract

A porphyrin bearing four imidazolium rings on the meso positions was used as an N-heterocyclic carbene (NHC) precursor for the synthesis of porphyrin dimers with face-to-face orientations. The porphyrins are connected through the formation of eight M-CNHC bonds, with M = AgI or AuI.

Published
2018

43. Diazachlorin and diazabacteriochlorin for one- and two-photon photodynamic therapy

Author

Morgane Daurat, Jean-François Longevial, Tsubasa Nishimura, Dongho Kim, Juwon Oh, Sébastien Richeter, Wen Xi Chia, Ayaka Yamaji, Yoshihiro Miyake, Magali Gary-Bobo, Christophe Nguyen, Gakhyun Kim, Dina Aggad, Hiroshi Shinokubo, Sébastien Clément, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), and Soongsil University

Subjects
Models, Molecular, medicine.medical_treatment, education, Breast Neoplasms, Photodynamic therapy, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, Two-photon excitation microscopy, In vivo, Cell Line, Tumor, Materials Chemistry, medicine, Animals, Humans, Zebrafish, health care economics and organizations, Photons, Photosensitizing Agents, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Chemistry, Metals and Alloys, General Chemistry, 021001 nanoscience & nanotechnology, In vitro, 3. Good health, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Photochemotherapy, MCF-7 Cells, Ceramics and Composites, Cancer research, Female, 0210 nano-technology
Abstract

International audience; Diazachlorin and diazabacteriochlorin have been prepared through reduction of diazaporphyrin and their in vitro and in vivo activity in photodynamic therapy has been investigated.

Published
2018

44. Molecular design of interfacial layers based on conjugated polythiophenes for polymer and hybrid solar cells

Author

Rachel C. Evans, Sébastien Richeter, Judith E. Houston, and Sébastien Clément

Subjects
chemistry.chemical_classification, Materials science, Polymers and Plastics, Organic Chemistry, Photovoltaic system, Nanotechnology, 02 engineering and technology, Polymer, Hybrid solar cell, Conjugated system, 010402 general chemistry, 021001 nanoscience & nanotechnology, 7. Clean energy, 01 natural sciences, Conjugated Polyelectrolytes, Polymer solar cell, 0104 chemical sciences, law.invention, chemistry.chemical_compound, chemistry, law, Solar cell, Materials Chemistry, Polythiophene, 0210 nano-technology
Abstract

In the past two decades, bulk heterojunction-organic photovoltaic devices (BHJ-OPVs) have emerged as attractive candidates for solar energy conversion due to their light-weight design and potential for low-cost high-throughput, solution-phase processability. Interfacial engineering is a proven efficient approach to achieve OPVs with high power conversion efficiencies (PCEs). This mini-review provides an overview of the key structural considerations necessary when undertaking the molecular design of conjugated polyelectrolytes (CPEs), for application as interfacial layers (ILs). The different roles of ILs are outlined, together with the advantages and disadvantages of competing classes of IL materials. Particular emphasis is placed on the design and synthesis of water-soluble polythiophene-based IL materials and the influence of their structural characteristics on their performance as a promising class of IL materials. Finally, the challenges and opportunities for polythiophenes as IL materials for OPVs and other solution-processed solar cell technologies (e.g. perovskite solar cells) are discussed.

Published
2017

45. Factors affecting the accuracy of genomic selection for growth and wood quality traits in an advanced-breeding population of black spruce (Picea mariana)

Author

Jean Bousquet, Sébastien Clément, Patrick Lenz, Shawn D. Mansfield, Jean Beaulieu, and Mireille Desponts

Subjects
0301 basic medicine, Linkage disequilibrium, lcsh:QH426-470, Genetic Linkage, lcsh:Biotechnology, Population, Breeding, Biology, Black spruce, 03 medical and health sciences, Gene SNPs, lcsh:TP248.13-248.65, Genetics, Tree improvement and breeding, Picea, education, education.field_of_study, Models, Genetic, Genomic selection, Small number, Genomics, Heritability, Genomic-estimated breeding values, Wood, lcsh:Genetics, Phenotype, 030104 developmental biology, Genetic marker, Trait, Tree breeding, Wood properties, Research Article, Biotechnology
Abstract

Background: Genomic selection (GS) uses information from genomic signatures consisting of thousands of genetic markers to predict complex traits. As such, GS represents a promising approach to accelerate tree breeding, which is especially relevant for the genetic improvement of boreal conifers characterized by long breeding cycles. In the present study, we tested GS in an advanced-breeding population of the boreal black spruce (Picea mariana [Mill.] BSP) for growth and wood quality traits, and concurrently examined factors affecting GS model accuracy. Results: The study relied on 734 25-year-old trees belonging to 34 full-sib families derived from 27 parents and that were established on two contrasting sites. Genomic profiles were obtained from 4993 Single Nucleotide Polymorphisms (SNPs) representative of as many gene loci distributed among the 12 linkage groups common to spruce. GS models were obtained for four growth and wood traits. Validation using independent sets of trees showed that GS model accuracy was high, related to trait heritability and equivalent to that of conventional pedigree-based models. In forward selection, gains per unit of time were three times higher with the GS approach than with conventional selection. In addition, models were also accurate across sites, indicating little genotype-by-environment interaction in the area investigated. Using information from half-sibs instead of full-sibs led to a significant reduction in model accuracy, indicating that the inclusion of relatedness in the model contributed to its higher accuracies. About 500 to 1000 markers were sufficient to obtain GS model accuracy almost equivalent to that obtained with all markers, whether they were well spread across the genome or from a single linkage group, further confirming the implication of relatedness and potential long-range linkage disequilibrium (LD) in the high accuracy estimates obtained. Only slightly higher model accuracy was obtained when using marker subsets that were identified to carry large effects, indicating a minor role for short-range LD in this population. Conclusions: This study supports the integration of GS models in advanced-generation tree breeding programs, given that high genomic prediction accuracy was obtained with a relatively small number of markers due to high relatedness and family structure in the population. In boreal spruce breeding programs and similar ones with long breeding cycles, much larger gain per unit of time can be obtained from genomic selection at an early age than by the conventional approach. GS thus appears highly profitable, especially in the context of forward selection in species which are amenable to mass vegetative propagation of selected stock, such as spruces.

Published
2017

46. High-pressure, high temperature insertion of bismuth in the siliceous zeolite silicalite-1

Author

Romain Viennois, Thomas Hansen, Julien Haines, Patrick Hermet, Jérôme Rouquette, Bruno Alonso, Vasyl Veremeienko, P. Toulemonde, Yixuan Zhao, Arie van der Lee, Sébastien Clément, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Laboratoire Charles Coulomb (L2C), Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Matériaux, Rayonnements, Structure (MRS), Institut Néel (NEEL), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut Laue-Langevin (ILL), ILL, Institut Européen des membranes (IEM), and Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)

Subjects
inorganic chemicals, Materials science, Band gap, Composite number, chemistry.chemical_element, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Bismuth, symbols.namesake, Guest insertion, General Materials Science, Zeolite, business.industry, General Chemistry, Semiconductor, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, equipment and supplies, 0104 chemical sciences, Crystallography, High pressure, chemistry, Silicalite-1, Transmission electron microscopy, symbols, Density functional theory, van der Waals force, 0210 nano-technology, business
Abstract

International audience; A silicalite-1/bismuth composite was synthesized by insertion of liquid bismuth in the 5.5 Å diameter pores of the zeolite under high-pressure, high-temperature conditions. The insertion of bismuth stabilizes the structure with respect to pressure-induced amorphization. Transmission electron microscopy indicated the presence of chains of atoms, which correspond to the 5.5 Å diameter of the host silicalite-1 structure. Neutron powder diffraction also confirmed the insertion of Bi in the pores of silicalite-1. Density functional theory calculations indicate that the insertion of bismuth results in formation of chains with short and long Bi-Bi distances in the pores of the host silicalite-1 linked to the framework by van der Waal's interactions. The material is predicted to be a semiconductor with a band gap of 0.4 eV.

Published
2019

47. Pressure-induced densification of vitreous silica: Insight from elastic properties

Author

Coralie Weigel, René Vacher, Marouane Mebarki, Sébastien Clément, Marie Foret, Benoit Ruffle, Laboratoire Charles Coulomb (L2C), and Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Condensed Matter - Materials Science, Range (particle radiation), Equation of state, Materials science, Coordination number, Materials Science (cond-mat.mtrl-sci), FOS: Physical sciences, Thermodynamics, 02 engineering and technology, 021001 nanoscience & nanotechnology, 01 natural sciences, Light scattering, Brillouin zone, Hysteresis, 0103 physical sciences, Dispersion (optics), [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Compressibility, 010306 general physics, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

\textit{In situ} high-pressure Brillouin light scattering experiments along loading-unloading paths are used to investigate the compressibility of vitreous silica. An accurate equation of state is obtained below \SI{9}{GPa} using sound velocities corrected for dispersion. Conversely, huge inelastic effects are observed in the range \SIrange{10}{60}{GPa}, unveiling the reversible transformation from the fourfold-coordinated structure to the sixfold one. We find that the associated density changes fully correlate with the average Si coordination number. Decompression curves from above \SI{20}{GPa} reveal abrupt backward coordination changes around \SIrange{10}{15}{GPa} and significant hysteresis. Further, contrary to common wisdom, the residual densification of recovered silica samples can be figured out from the pressure cycles., 5 pages, 4 figures, revised version

Published
2019

48. A Cationic Tetraphenylethene as a Light-Up Supramolecular Probe for DNA G-Quadruplexes

Author

Sébastien Ulrich, Mathieu Fossépré, Clément Kotras, Philippe Gerbier, Sébastien Richeter, Mathieu Surin, Virginie Gervais, Sébastien Clément, Maxime Roger, Institut de pharmacologie et de biologie structurale (IPBS), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Laboratory for Chemistry of Novel Materials, University of Mons [Belgium] (UMONS), Université de Mons (UMons), Laboratoire d'Ingénierie des Systèmes Biologiques et des Procédés (LISBP), Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut National de la Recherche Agronomique (INRA), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées, and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Circular dichroism, Molecular model, Supramolecular chemistry, tetraphenylethene, 02 engineering and technology, 010402 general chemistry, G-quadruplex, 01 natural sciences, lcsh:Chemistry, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, Original Research, Chemistry, Isothermal titration calorimetry, General Chemistry, 021001 nanoscience & nanotechnology, G-quadruplexes, Fluorescence, Small molecule, 0104 chemical sciences, Förster resonance energy transfer, lcsh:QD1-999, Biophysics, fluorescence, light-up probe, 0210 nano-technology, supramolecular
Abstract

International audience; Guanine-quadruplexes (G4s) are targets for anticancer therapeutics. In this context, human telomeric DNA (HT-DNA) that can fold into G4s sequences are of particular interest, and their stabilization with small molecules through a visualizable process has become a challenge. As a new type of ligand for HT-G4, we designed a tetraimidazolium tetraphenylethene (TPE-Im) as a water-soluble light-up G4 probe. We study its G4-binding properties with HT-DNA by UV-Visible absorption, circular dichroism and fluorescence spectroscopies, which provide insights into the interactions between TPE-Im and G4-DNA. Remarkably, TPE-Im shows a strong fluorescence enhancement and large shifts upon binding to G4, which is valuable for detecting G4s. The association constants for the TPE-Im/G4 complex were evaluated in different solution conditions via isothermal titration calorimetry (ITC), and its binding modes were explored by molecular modeling showing a groove-binding mechanism. The stabilization of G4 by TPE-Im has been assessed by Fluorescence Resonance Energy Transfer (FRET) melting assays, which show a strong stabilization (1T1/2 around +20◦C), together with a specificity toward G4 with respect to double-stranded DNA.

Published
2019

49. Synthesis and properties of a P3HT-based ABA triblock copolymer containing a perfluoropolyether central segment

Author

Wojciech Zajaczkowski, Ruben Lenaerts, Gérald Lopez, Roberto Lazzaroni, Julien De Winter, Sébastien Clément, Mathieu Surin, Michèle Chevrier, Wojciech Pisula, Bruno Ameduri, Philippe Dubois, Jurgen Kesters, Sébastien Richeter, Wouter Maes, Ahmad Mehdi, Pascal Gerbaux, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Max-Planck-Institut, Hasselt University (UHasselt), Laboratory for Chemistry of Novel Materials, Université de Mons (UMons), Laboratoire de Chimie Organique, Université de Mons-Hainaut, Mass Spectrometry Research Group, and CIRMAP (CIRMAP)

Subjects
Materials science, Absorption spectroscopy, Size-exclusion chromatography, 02 engineering and technology, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Materials Chemistry, Copolymer, [CHIM]Chemical Sciences, Thermal stability, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Mechanical Engineering, Metals and Alloys, Polymer, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, Crystallography, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Mechanics of Materials, Crystallite, Absorption (chemistry), 0210 nano-technology, Glass transition
Abstract

A poly(3-hexylthiophene)-block-perfluoropolyether-block-poly(3-hexylthiophene) (P3HT-b-PFPE-b-P3HT) triblock copolymer was synthesized by copper(I)-catalyzed alkyne–azide cycloaddition (CuAAC) in 95% yield. The copolymer was unequivocally characterized by size exclusion chromatography reaching 27 000 g mol−1 and nuclear magnetic resonance (NMR). As expected, diffusion-ordered spectroscopy NMR experiment revealed a lower diffusion coefficient (2.56 × 10-10 m2 s−1) for the P3HT-b-PFPE-b-P3HT triblock copolymer than the ethynyl end-functionalized P3HT (2.83 × 10-10 m2 s−1). Such a triblock copolymer exhibits i) a good thermal stability with no significant weight loss until 320 °C under air, ii) a glass transition of -50 °C due to the soft PFPE segment and iii) a melting peak arising from P3HT at 236 °C. The UV–vis absorption spectrum exhibits a similar absorption profile to that of pure P3HT with a vibronic structure. Analysis of terpolymer thin films by atomic force microscopy imaging and grazing incidence wide-angle X-ray scattering reveals the formation of P3HT crystallites and an “edge-on” orientation of the polymer chains towards the substrate. Preliminary photovoltaic studies on blends of this triblock copolymer combined with a fullerene derivative indicate that the devices using P3HT-b-PFPE-b-P3HT show an almost similar power conversion efficiency to commercial P3HT.

Published
2019

50. Supramolecular Self‐Assembly of DNA with a Cationic Polythiophene: From Polyplexes to Fibers

Author

Sébastien Clément, Sylvain Gabriele, Laurent Leclercq, Mathieu Surin, Maxime Leclercq, Hervé Cottet, Sébastien Richeter, Jenifer Rubio-Magnieto, Danahe Mohammed, Laboratory for Chemistry of Novel Materials, Université de Mons (UMons), MateriaNova Research Center (MNRS), Université de Mons-Hainaut, Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2), University of Mons [Belgium] (UMONS), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Montpellier (UM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
chemistry.chemical_classification, Hydrodynamic radius, Renewable Energy, Sustainability and the Environment, Oligonucleotide, Biomolecule, [SDV]Life Sciences [q-bio], Supramolecular chemistry, Cationic polymerization, Energy Engineering and Power Technology, 02 engineering and technology, Polymer, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Biomaterials, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical engineering, Materials Chemistry, Polythiophene, Self-assembly, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; Cationic polythiophenes constitute an interesting class of polymers for prospective applications in imaging, gene delivery and biosensing, as they combine solubility in aqueous media and have sensitive optical properties for the detection of biomolecules such as DNA. Here, we study the supramolecular self-assembly of poly[3-(6'-(trimethylphosphonium)hexyl)thiophene-2,5-diyl] (P3HT-PMe3) with different types of DNA, such as single-stranded oligonucleotides or long genomic DNA. Self-assembly in buffered aqueous solution yields polyplexes (polymer/DNA complexes) with hydrodynamic radius ranging from 7 nm to around 25 nm, as observed by Taylor Dispersion Analysis. In these polyplexes, the achiral polymer presents chiroptical signals induced by supramolecular organization along chiral DNA. When the solution of long DNA/P3HT-PMe3 is deposited on surfaces, tens of µm-long fibers are formed by condensation of DNA and compaction of the polyplexes, as evidenced by microscopy techniques.

Published
2019

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