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101. Size-Exclusion Mechanism Driving Host–Guest Interactions between Octahedral Rhenium Clusters and Cyclodextrins

Author

Yann Molard, Clément Falaise, Stéphane Cordier, Anton A. Ivanov, Michael A. Shestopalov, Yuri V. Mironov, Kevin Laouer, Emmanuel Cadot, François Hache, Mohamed Haouas, David Landy, Pascale Changenet, Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Nikolaev Institute of Inorganic Chemistry [Novosibirsk] (NIC), Siberian Branch of the Russian Academy of Sciences (SB RAS), Laboratoire d'Optique et Biosciences (LOB), École polytechnique (X)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Novosibirsk State University (NSU), Unité de Chimie Environnementale et Interactions sur le Vivant (UCEIV), Université du Littoral Côte d'Opale (ULCO), 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), ANR-11-LBX0039-grant, Agence Nationale de la Recherche, 15-15-10006, Russian Science Foundation, Centre National de la Recherche Scientifique, Ministry of Science and Higher Education of the Russian Federation, R?gion Ile de France, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Jonchère, Laurent

Subjects
Circular dichroism, 010405 organic chemistry, Supramolecular chemistry, chemistry.chemical_element, Isothermal titration calorimetry, Crystal structure, Rhenium, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Crystallography, chemistry, [CHIM] Chemical Sciences, Cluster (physics), [CHIM]Chemical Sciences, Molecule, Physical and Theoretical Chemistry, Solvent effects
Abstract

International audience; In aqueous solution, cyclodextrins (CDs) are able to bind strongly either hydrophobic species or also hydrophilic molecules such as octahedral hexametallic cluster. Systematic investigation of the reactivity between native CDs (α- or β-CD) and water-soluble rhenium clusters [ReQ(CN)] with Q = S, Se, and Te were performed, leading to six new crystal structures revealing different types of supramolecular arrangements. Encapsulation of [ReQ(CN)] (Q = S, Se, or Te) within two β-CDs is observed regardless of the cluster size. Interestingly, different assembling scenarios are pointed out depending on the host-guest matching featured by no, partial, or deep inclusion complexes that involved either primary or secondary rim of the CD tori. In the specific case of α-CD, only the smaller cluster [ReS(CN)] is able to form inclusion complex with the tori host. Solution investigations, using a set of complementary techniques including isothermal titration calorimetry, multinuclear NMR methods, cyclic voltammetry, and electrospray ionization mass spectrometry, corroborate nicely conclusions of the solid-state studies. It appears clearly that size-matching supported by solvent effects play key roles in the stability of the host-guest complexes. At last, circular dichroism studies underline that the chirality induction from cyclodextrins to the rhenium cluster depends strongly on the strength of host-guest interactions.

Published
2019
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102. Apical Cyanide Ligand Substitution in Heterometallic Clusters [Re 3 Mo 3 Q 8 (CN) 6 ] n – (Q = S, Se)

Author

Viktoria K. Muravieva, Yakov M. Gayfulin, Vincent Dorcet, Taisiya S. Sukhikh, Maxim R. Ryzhikov, Stéphane Cordier, Nikolay G. Naumov, Tatiana I. Lappi, Yuri V. Mironov, Pierric Lemoine, 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), Nikolaev Institute of Inorganic Chemistry [Novosibirsk] (NIC), Siberian Branch of the Russian Academy of Sciences (SB RAS), Novosibirsk State University (NSU), French Embassy, International Associate Laboratory [1144], Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Molybdenum, Electronic structure, Ligand exchange, 010405 organic chemistry, Chemistry, Substitution (logic), chemistry.chemical_element, Rhenium, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Crystallography, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Cluster compounds, Cyanide ligand
Abstract

International audience; A number of transition metal cluster compounds can be obtained only in the melt of inorganic cyanides and, therefore, contain terminal cyanide ligands. Substitution of these ligands, which is often necessary to change the physicochemical properties of the clusters, is an urgent problem because of their low reactivity in substitution reactions. In this work, a synthetic approach has been developed for the substitution of CN-ligands in the heterometallic cluster anions [Re(3)Mo(3)Q(8)(CN)(6)](n-) (Q = S, n = 6; Q = Se, n = 5) by the 4-tert-butylpyridine (TBP) molecules. Two new compounds, namely [Re3Mo3S8(TBP)(6)] (1) and [Re3Mo3Se8(TBP)(6)] (2), were obtained with high yields and crystallized under solvothermal conditions. It has been shown that compounds 1 and 2 are based on the paramagnetic cluster cores {Re(3)Mo(3)Q(8)}(0) containing 23 cluster valence electrons (CVE). The geometry of the new compounds has been investigated using X-ray structural analysis. The electronic structure has been analyzed using the DFT calculations showing large distortion of M-6 cluster core.

Published
2019
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103. Checklist for the use of potassium concentrations in siliciclastic sediments as paleoenvironmental archives

Author

T. Matys Grygar, Mathieu Martinez, K. Mach, Institute of Inorganic Chemistry, Czech Academy of Sciences [Prague] (CAS), North Bohemian Mines, Géosciences Rennes (GR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers de Rennes (OSUR)-Centre National de la Recherche Scientifique (CNRS), 16-00800S, Grantová Agentura České Republiky, Université de Rennes (UR)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers de Rennes (OSUR), Université de Rennes (UR)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Rennes 2 (UR2)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Rennes 2 (UR2)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Observatoire des Sciences de l'Univers de Rennes (OSUR)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Rennes 1 (UR1), and Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)

Subjects
010506 paleontology, Provenance, Stratigraphy, Geochemistry, Sediment, Geology, Weathering, 010502 geochemistry & geophysics, 01 natural sciences, Lake sediments, Major elements, Past climate, [SDU.STU.GC]Sciences of the Universe [physics]/Earth Sciences/Geochemistry, 13. Climate action, Chemostratigraphy, [SDU.STU.ST]Sciences of the Universe [physics]/Earth Sciences/Stratigraphy, Paleoclimatology, Potassium, Sedimentary rock, Siliciclastic, Parent rock, 0105 earth and related environmental sciences
Abstract

International audience; Weathering indices quantify the release of mobile elements from source units of soils and sediments. They have been employed in geosciences for more than three decades, but their performance in sedimentary archives can still be improved by deciphering other forcing factors than climatic. From the most common alkali and alkaline earth metals included in the weathering indices, K seems to be most suitable for deciphering paleoclimate records of temperate to subtropical non-arid climates, assuming the interpretation respects the complex of controlling factors on sediment geochemistry. As a case study, normalised K concentrations in siliciclastic sediments of the Most Basin (Miocene period, central Europe) are revisited here and variations compared with modern fluvially transported solids. Existing knowledge on manifold controls of K concentrations in sediments is summarised and used to propose list of possible controlling factors, in particular Al/Si and Zr/Rb as grain-size proxies, Ti/Al as provenance proxy relevant for K concentration in parent rocks, and K/Rb as a measure for possible effects of metasomatism. The K/Al or K/Ti element ratios may be efficient in chemostratigraphic correlations in siliciclastic basins and efficient proxies for chemical weathering in the source area. The proposals in this work should stimulate future studies to overcome the underrepresentation of continental sediments in paleoclimate reconstructions.

Published
2019
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104. Influence of Mn/Ca ratio in Mn-Ca coordination clusters: Synthesis, structure, and magnetic characterisation

Author

Anthony J. Fitzpatrick, Annie K. Powell, Grace G. Morgan, Ayuk M. Ako, Anthony B. Carter, Helge Müller-Bunz, Rodolphe Clérac, Christopher E. Anson, Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, School of Chemistry, University College Dublin (UCD), Centre de Recherche Paul Pascal (CRPP), Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), School of Chemistry and Chemical Biology (UCD), University College Dublin [Dublin] (UCD), Department of Biosciences and Chemistry, Institute of Nanotechnology, Karlsruhe Institute of Technology, and DFG (CFN and SPP 1137), the CNRS, the University of Bordeaux, the Région Nouvelle Aquitaine, the GdR MCM-2: Magnétisme & Commutation Moléculaires, and Quantum Matter Bordeaux. Financial support from the Walton Fellowship is also gratefully acknowledged.

Subjects
Manganese, 010405 organic chemistry, Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, Coordination cluster, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, Materials Chemistry, Cluster (physics), Hydroxymethyl, Calcium, Physical and Theoretical Chemistry, Molecular magnetism
Abstract

International audience; Similar reactions of MnCl 2 ⋅4H 2 O and CaCl 2 with 2,6-bis(hydroxymethyl)-4-methylphenol gave heterometallic coordination clusters with very different nuclearities, depending on the Mn:Ca ratio used. With a 1:1 ratio, the hexanuclear cluster [Mn III 3 Ca II 3 (μ 3-Cl(HL Me) 6 (H 2 O) 6 ]Cl 2 ⋅6.74H 2 O (2) with a "triangle-in-triangle" topology was obtained. However, a Mn:Ca ratio of 2:1 resulted in [Mn III 12 Mn II Ca II 6 (μ 4-O) 8 (μ 3-Cl) 3.7 (μ 3-η 1-N 3) 4.3 (HL Me) 12 (-MeCN) 6 ]Cl 2 •15MeOH (3), which corresponds structurally to the replacement by Ca 2+ of six of the seven Mn II centers in our previously-published cluster [Mn III 12 Mn II 7 (μ 4-O) 8 (μ 3-η 1-N 3) 8 (HL Me) 12 (MeCN) 6 ]Cl 2. Magnetic studies showed that the three Mn III centers in 2 are moderately antiferromagnetically coupled, while the results for 3 allowed an experimental estimate of the Mn III-Mn III coupling in the original [Mn 19 ] cluster.

Published
2021
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110. Synthesis, Structure, and Spectroscopic Study of Redox-Active Heterometallic Cluster-Based Complexes [Re(5)MoSe(8)(CN)(6)](n)

Author

Viktoria K. Muravieva, Ivan P. Loginov, Vadim V. Yanshole, Stéphane Cordier, Taisiya S. Sukhikh, Nikolay G. Naumov, Maxim R. Ryzhikov, Vincent Dorcet, Vladimir A. Nadolinny, Siberian Branch of the Russian Academy of Sciences (SB RAS), Nikolaev Institute of Inorganic Chemistry [Novosibirsk] (NIC), Novosibirsk State University (NSU), 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), 20-73-00339, Russian Science Foundation, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Aqueous solution, 010405 organic chemistry, Chemistry, Solvation, 010402 general chemistry, 01 natural sciences, Redox, 0104 chemical sciences, Ion, Inorganic Chemistry, Crystallography, Cluster (physics), [CHIM]Chemical Sciences, Density functional theory, Physical and Theoretical Chemistry, Cyclic voltammetry, Absorption (chemistry)
Abstract

International audience; The heterometallic cluster-based compound K(5)[Re(5)MoSe(8)(CN)(6)] was obtained by high-temperature reaction from a mixture of ReSe(2) and MoSe(2) in molten potassium cyanide. The redox behavior of the [Re(5)MoSe(8)(CN)(6)](5-) cluster anion was studied by cyclic voltammetry in aqueous and organic media showing two reversible one-electron-redox transitions with E(1/2) of -0.462 and 0.357 V versus Ag/AgCl in CH(3)CN. Aqueous media potentials were found to be noticeably shifted to higher values because of solvation. Chemically accessible potentials allowed us to structurally isolate and characterize the [Re(5)MoSe(8)(CN)(6)](n) (n = 3-, 4-, and 5-) cluster complex in several charge states with corresponding cluster skeletal electron (CSE) numbers ranging from 24 to 22. The electronic absorption of the [Re(5)MoSe(8)(CN)(6)](n) cluster complex varies significantly upon a change of the CSE number, especially in the visible and near-IR regions. The local cluster core distortion upon electron removal was confirmed by density functional theory calculation, while the overall geometry of the cluster anion remained practically unaltered.

Published
2021
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111. Nitrosyl linkage photoisomerization in heteroleptic fluoride ruthenium complexes derived from labile nitrate precursors

Author

Denis P. Pishchur, Dominik Schaniel, Artem A. Mikhailov, Gennadiy A. Kostin, Vladislav Yu. Komarov, Nikolaev Institute of Inorganic Chemistry [Novosibirsk] (NIC), Siberian Branch of the Russian Academy of Sciences (SB RAS), Cristallographie, Résonance Magnétique et Modélisations (CRM2), and Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Photoisomerization, 010405 organic chemistry, education, chemistry.chemical_element, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Catalysis, Pyridine ligand, 0104 chemical sciences, Ruthenium, chemistry.chemical_compound, Hydrofluoric acid, chemistry, Nitrate, Materials Chemistry, Thermal stability, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Linkage isomerism, Fluoride
Abstract

Four complexes with trans-ON–Ru–F coordinate were synthesized from the corresponding nitrate precursors. The treatment of fac-[RuNO(NH3)2(NO3)3] with hydrofluoric acid results in the substitution of the labile nitrate ligands by H2O and F−, whereas the treatment of trans-(NO,NO3)-cis-(NH3,NH3)-[RuNO(NH3)2Py2(NO3)](NO3)2·H2O leads to additional pyridine ligand elimination. The structures of the four complexes were characterized by X-ray diffraction: trans(NO,F)-cis(NH3,NH3)-[RuNO(NH3)2(H2O)2F]SiF6 (I), trans(NO,F)-cis(NH3,NH3)-[RuNO(NH3)2Py(NO3)F]2SiF6·H2O (II), trans(NO,F)-cis(NH3,NH3)-[RuNO(NH3)2Py(H2O)F](ClO4)2 (III) and trans(NO,F)-cis(NH3,NH3)-[(RuNOPy(NH3)2F)2(μ-O2H3)](ClO4)3 (IV). Upon light irradiation, complexes I, II and III show reversible formation of metastable linkage isomers MS1 and MS2 with remarkable thermal stability of both isomers. Moreover, complexes I and III show the highest thermal stability of the MS2 isomers, which leads to a higher photogeneration temperature of MS1 via the GS → MS2 → MS1 mechanism. Such excellent properties of the resulting materials can be used in the design of molecular based data storage devices.

Published
2021
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112. Self-assembly of a short amphiphile in water controlled by superchaotropic polyoxometalates: H4SiW12O40 vs. H3PW12O40

Author

Didier Touraud, Olivier Diat, Thomas Buchecker, Philipp Schmid, Ali Khoshsima, Arno Pfitzner, Werner Kunz, Pierre Bauduin, Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Institute of Physical and Theoretical Chemistry [Braunschweig], Technische Universität Braunschweig = Technical University of Braunschweig [Braunschweig], 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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
Cloud point, Materials science, Small-angle X-ray scattering, Ionic bonding, Charge density, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Biomaterials, Colloid, Colloid and Surface Chemistry, Phase (matter), Amphiphile, Physical chemistry, [CHIM]Chemical Sciences, Self-assembly, 0210 nano-technology
Abstract

Nanometric ions, such as polyoxometalates (POMs) or ionic boron clusters, with low charge density have previously shown a strong propensity to bind to macrocycles and to adsorb to neutral surfaces: micellar, surfactant covered water–air and polymer surfaces. These association phenomena were shown to arise from a solvent-mediated effect called the (super-)chaotropic effect. We show here by combining cloud point (CP) measurements, scattering (SAXS/SANS) and spectroscopic techniques (NMR) that Keggin POMs: H4SiW12O40 (SiW) and H3PW12O40 (PW), induce the self-assembly of an organic solvent: dipropylene glycol n-propylether (C3P2), in water. The strong interaction between SiW/PW with C3P2 leads to a drastic increase in the CP, and aqueous solubility, of C3P2, e.g. SiW enables reaching full water-C3P2 co-miscibility at room temperature. At high POM concentrations, SiW leads to a continuous increase of the CP, forming SiW-[C3P2]1-2 complexes, whereas PW produces a decrease in the CP attributed to the formation of nearly “dry” spherical [PW]n[C3P2]m colloids, with n ~ 4 and m ~ 30. At high C3P2/PW contents, the [PW]n[C3P2]m colloids turn into large interconnected structures, delimiting two pseudo-phases: a PW-C3P2-rich phase and a water-rich phase. It is proposed that the stronger electrostatic repulsions between SiW (4−), compared to PW (3−), prevents the formation of mesoscopic colloids.

Published
2021
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113. lamaGOET: an interface for quantum crystallography

Author

Lorraine A. Malaspina, Alessandro Genoni, Simon Grabowsky, Universität Bern [Bern], Institut für Anorganische Chemie und Kristallographie = Institute of Inorganic Chemistry and Crystallography [Universität Bremen], Universität Bremen, Laboratoire de Physique et Chimie Théoriques (LPCT), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), and ANR-17-CE29-0005,QuMacroRef,De nouvelles stratégies efficaces basées sur la mécanique quantique pour l'affinement de structures cristallographiques de macromolécules à haute résolution(2017)

Subjects
Interface (Java), Gaussian, Localized molecular orbitals, 010402 general chemistry, 010403 inorganic & nuclear chemistry, 01 natural sciences, General Biochemistry, Genetics and Molecular Biology, Computer Programs, Condensed Matter::Materials Science, symbols.namesake, Software, 540 Chemistry, [CHIM.CRIS]Chemical Sciences/Cristallography, Wave function, Quantum, business.industry, Atom (order theory), 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, Hirshfeld atom refinement, X-ray constrained wavefunction fitting, symbols, 570 Life sciences, biology, Physics::Accelerator Physics, quantum crystallography, business
Abstract

The program lamaGOET serves as an interface between quantum-mechanical and crystallographic refinement software to enhance the flexibility of the quantum-crystallographic methods Hirshfeld atom refinement and X-ray constrained wavefunction fitting., In quantum crystallography, theoretical calculations and crystallographic refinements are closely intertwined. This means that the employed software must be able to perform both quantum-mechanical calculations and crystallographic least-squares refinements. So far, the program Tonto is the only one able to do that. The lamaGOET interface described herein deals with this issue since it interfaces dedicated quantum-chemical software (the widely used Gaussian package and the specialized ELMOdb program) with the refinement capabilities of Tonto. Three different flavours of quantum-crystallographic refinements of the dipetide glycyl-l-threonine dihydrate are presented to showcase the capabilities of lamaGOET: Hirshfeld atom refinement (HAR), HAR-ELMO, namely HAR coupled with extremely localized molecular orbitals, and X-ray constrained wavefunction fitting.

Published
2021
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114. Algorithmic Learning for Auto-deconvolution of GC-MS Data to Enable Molecular Networking within GNPS

Author

Kelem Gashu, Madeleine Ernst, Mélissa Nothias Esposito, Kirill Veselkov, Michael M. Meijler, Robert A. Quinn, Gaud Dervilly, Audrey Poirier, Katherine N. Maloney, tzhak MizrahiI, Chao Song, Thomas O. Metz, Roman S. Borisov, Rob Knight, Mabel Gonzalez, Roxana Coras, Amina Bouslimani, Chiara Carazzone, Vasilis Vasiliou, Alexander A. Aksenov, Wout Bittremieux, Yann Guitton, Daniel Petras, Zheng Zhang, Larisa N. Kulikova, Robin Schmid, Ilaria Belluomo, James T. Morton, Sneha P. Couvillion, Brooke Anderson, Carrie D. Nicora, Kenneth L. Jones, S. Prévost, Sophie L. F. Doran, Louis-Félix Nothias, Dennis Veselkov, Erika M. Zink, Bruno Le Bizec, Andrea M. Smania, Chris Callewaert, Justin J. J. van der Hooft, Rachel Gregor, Pauline Le Boulch, Alexey V. Melnik, Adolfo Amézquita, Biswapriya B. Misra, Noga Sikron Persi, Mingxun Wang, Raphaël Lugan, Rachel Dutton, Morgan Panitchpakdi, Pieter C. Dorrestein, Meagan C. Burnet, Elizabeth Humston Fulmer, Ivan Laponogov, George B. Hanna, Viatcheslav B. Artaev, Kathleen Dorrestein, Aaron Fait, Andrea Georgina Albarracín Orio, Stav Eyal, Skaggs School of Pharmacy and Pharmaceutical Sciences [San Diego], University of California [San Diego] (UC San Diego), University of California-University of California, Collaborative Mass Spectrometry Innovation Center, Imperial College London, University of California, Wake Forest School of Medicine [Winston-Salem], Wake Forest Baptist Medical Center, Statens Serum Institut [Copenhagen], Wageningen University and Research [Wageningen] (WUR), Universidad de los Andes [Bogota] (UNIANDES), Center for Microbial Ecology and Technology (CMET), Universiteit Gent = Ghent University [Belgium] (UGENT), Michigan State University [East Lansing], Michigan State University System, Universidad Católica de Córdoba, Universidad Nacional de Córdoba [Argentina], Pacific Northwest National Laboratory (PNNL), LECO Corporation, Ben-Gurion University of the Negev (BGU), University of San Diego, Démarche intégrée pour l'obtention d'aliments de qualité (UMR QualiSud), Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad)-Institut de Recherche pour le Développement (IRD)-Avignon Université (AU)-Université de La Réunion (UR)-Université de Montpellier (UM)-Institut national d’études supérieures agronomiques de Montpellier (Montpellier SupAgro), Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro), Laboratoire d'étude des Résidus et Contaminants dans les Aliments (LABERCA), Ecole Nationale Vétérinaire, Agroalimentaire et de l'alimentation Nantes-Atlantique (ONIRIS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), New York University School of Medicine (NYU), New York University School of Medicine, NYU System (NYU)-NYU System (NYU), West Coast Metabolomics Center, University of California [Davis] (UC Davis), Max Planck Institute for Molecular Plant Physiology, Center of Plant Systems Biology and Biotechnology [Plovdiv] (CPSBB), NHS Foundation Trust [London], The Royal Marsden, Yale School of Public Health (YSPH), Institute of Inorganic Chemistry and Analytical Chemistry, A.V. Topchiev Institute of Petrochemical Synthesis (TIPS), Russian Academy of Sciences [Moscow] (RAS), and Peoples Friendship University of Russia [RUDN University] (RUDN)

Subjects
0303 health sciences, 03 medical and health sciences, Computer science, [SDV]Life Sciences [q-bio], 010401 analytical chemistry, Molecular networking, Deconvolution, Gas chromatography–mass spectrometry, 01 natural sciences, Data science, 030304 developmental biology, 0104 chemical sciences
Abstract

Gas chromatography-mass spectrometry (GC-MS) represents an analytical technique with significant practical societal impact. Spectral deconvolution is an essential step for interpreting GC-MS data. No public GC-MS repositories that also enable repository-scale analysis exist, in part because deconvolution requires significant user input. We therefore engineered a scalable machine learning workflow for the Global Natural Product Social Molecular Networking (GNPS) analysis platform to enable the mass spectrometry community to store, process, share, annotate, compare, and perform molecular networking of GC-MS data. The workflow performs auto-deconvolution of compound fragmentation patterns via unsupervised non-negative matrix factorization, using a Fast Fourier Transform-based strategy to overcome scalability limitations. We introduce a “balance score” that quantifies the reproducibility of fragmentation patterns across all samples. We demonstrate the utility of the platform with breathomics analysis applied to the early detection of oesophago-gastric cancer, and by creating the first molecular spatial map of the human volatilome.

Published
2021

115. Host in Host Supramolecular Core-Shell Type Systems Based on Giant Ring-Shaped Polyoxometalates

Author

Pavel A. Abramov, Anton A. Ivanov, Jérôme Marrot, Pierre Bauduin, Emmanuel Cadot, Clément Falaise, Maxim N. Sokolov, Soumaya Khlifi, William Shepard, Stéphane Cordier, Mohamed Haouas, Michael A. Shestopalov, Philipp Schmid, Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ions aux Interfaces Actives (L2IA), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Nikolaev Institute of Inorganic Chemistry [Novosibirsk] (NIC), Siberian Branch of the Russian Academy of Sciences (SB RAS), South Ural State University (SUSU), 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), 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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-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)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Materials science, Aqueous solution, 010405 organic chemistry, Small-angle X-ray scattering, inclusion compounds, Supramolecular chemistry, General Chemistry, General Medicine, Molybdate, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Catalysis, supramolecular chemistry, 0104 chemical sciences, chemistry.chemical_compound, Chaotropic agent, chemistry, cyclodextrin, Chemical physics, Cluster (physics), polyoxometalates (POMs), [CHIM]Chemical Sciences, clusters, Nanoscopic scale
Abstract

International audience; Herein, we show how the chaotropic effect arising from reduced molybdate ions in acidified aqueous solution is able to amplify drastically weak supramolecular interactions. Time-resolved Small Angle X-ray Scattering (SAXS) analysis suggests that molybdenum-blue oligomeric species form huge aggregates in the presence of γ-cyclodextrin (γ-CD) which results in the fast formation of nanoscopic {Mo(154) }-based host-guest species, while X-ray diffraction analysis reveals that the ending-point of the scenario results in an unprecedented three-component well-ordered core-shell-like motif. A similar arrangement was found by using preformed hexarhenium chalcogenide-type cluster [Re(6) Te(8) (CN)(6) ](4-) as exogenous guest. This seminal work brings better understanding of the self-assembly processes in general and gives new opportunities for practical applications in the design of complex multicomponent materials via the simplicity of the non-covalent chemistry.

Published
2021
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130. A complex study of the dependence of the reduced graphite oxide electrochemical behavior on the annealing temperature and the type of electrolyte

Author

S. Ravi P. Silva, Alexey N. Kolodin, Anna A. Iurchenkova, E. O. Fedorovskaya, Egor V. Lobiak, Anna A. Kobets, Ash Stott, Novosibirsk State University, RAS - Nikolaev Institute of Inorganic Chemistry, Siberian Branch, University of Surrey, Department of Chemistry and Materials Science, Aalto-yliopisto, and Aalto University

Subjects
X-ray photoelectron spectroscopy, Materials science, Annealing (metallurgy), General Chemical Engineering, Inorganic chemistry, Graphite oxide, 02 engineering and technology, Thermal treatment, Electrolyte, 010402 general chemistry, Electrochemistry, 01 natural sciences, Redox, chemistry.chemical_compound, supercapacitor, reduced graphite oxide, Fourier transform infrared spectroscopy, Atmospheric temperature range, 021001 nanoscience & nanotechnology, cyclic voltammetry, 0104 chemical sciences, graphite oxide, chemistry, Cyclic voltammetry, 0210 nano-technology
Abstract

In this work we investigate the influence of thermal treatment of reduced graphite oxide (RGO) on its functional composition and electrochemical performance. It is found that carboxyl, carbonyl, hydroxyl and epoxy groups are present on the RGO surface, witch when subject to thermal annealing in the temperature range 230-250°C can be controllably modified. In the process of thermal annealing, we show the formation of quinoid groups due to an increase in the number of defects. Decrease of the number of layers in RGO material and the quantity of oxygen-containing functional groups (OCFG) also occurs. With increase in annealing temperature, sequential removal of OCFG occurs as follows: carboxyl (250°C-600°C), hydroxyl (600°C-800°C), carbonyl and quinoid (700°C-1000°C). Electrochemical measurements over a wide range of pH values of the buffer electrolytes is possible to correlate the peaks in the cyclic voltammogram curves with the redox reactions of oxygen-containing functional groups as a function of applied potential. Peaks correlated with specific redox reactions which are identified as two-electron. The dependence of the specific capacities of materials on the electrolyte type has been studied. Highest capacitance was detected in 1M NaOH at a scan rate 2 mVs−1 and is equal to 210 Fg−1.

Published
2021

131. Photocathodes beyond NiO:charge transfer dynamics in a π‑conjugated polymer functionalized with Ruphotosensitizers

Author

Wahyuono, Ruri A., Seidler, Bianca, Bold, Sébastian, Dellith, Andrea, Dellith, Jan, Ahner, Johannes, Wintergerst, Pascal, Lowe, Grace, Hager, Martin D., Wächtler, Maria, Streb, Carsten, Schubert, Ulrich S., Rau, Sven, Dietzek, Benjamin, Leibniz Institute of Photonic Technology Jena, Department Functional Interfaces, Albert-Einstein-Straße 9, 07745 Jena, Germany, Institute of Physical Chemistry, Department of Engineering Physics, Institut Teknologi Sepuluh, Institute of Inorganic Chemistry I., Solar fuels, hydrogen and catalysis (SolHyCat), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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 Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Institute of Organic Chemistry and Macromolecular Chemistry [Friedrich Schiller University Jena] (IOMC), Friedrich-Schiller-Universität = Friedrich Schiller University Jena [Jena, Germany], Center for Energy and Environmental Chemistry (CEEC Jena), and Laboratory of Organic and Macromolecular Chemistry (IOMC)

Subjects
[CHIM.POLY]Chemical Sciences/Polymers
Abstract

International audience; A conductive polymer (poly(p-phenylenevinylene), PPV) was covalently modified with Ru-II complexes to develop an all-polymer photocathode as a conceptual alternative to dye-sensitized NiO, which is the current state-of-the-art photocathode in solar fuels research. Photocathodes require efficient light-induced charge-transfer processes and we investigated these processes within our photocathodes using spectroscopic and spectro-electrochemical techniques. Ultrafast hole-injection dynamics in the polymer were investigated by transient absorption spectroscopy and charge transfer at the electrode-electrolyte interface was examined with chopped-light chronoamperometry. Light-induced hole injection from the photosensitizers into the PPV backbone was observed within 10 ps and the resulting charge-separated state (CSS) recombined within similar to 5 ns. This is comparable to CSS lifetimes of conventional NiO-photocathodes. Chopped-light chronoamperometry indicates enhanced charge-transfer at the electrode-electrolyte interface upon sensitization of the PPV with the Ru-II complexes and p-type behavior of the photocathode. The results presented here show that the polymer backbone behaves like classical molecularly sensitized NiO photocathodes and operates as a hole accepting semiconductor. This in turn demonstrates the feasibility of all-polymer photocathodes for application in solar energy conversion.

Published
2021
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132. Solution and solid-state light-induced transformations in heterometallic vanadium-ruthenium nitrosyl complex

Author

Artem L. Gushchin, Dominik Schaniel, Vasily Vorobyev, Gennadiy A. Kostin, Natalia V. Kuratieva, Vladimir A. Nadolinny, Iakov S. Fomenko, Artem A. Mikhailov, Nikolaev Institute of Inorganic Chemistry [Novosibirsk] (NIC), Siberian Branch of the Russian Academy of Sciences (SB RAS), Cristallographie, Résonance Magnétique et Modélisations (CRM2), and Centre National de la Recherche Scientifique (CNRS)-Université de Lorraine (UL)

Subjects
General Chemical Engineering, Population, General Physics and Astronomy, Infrared spectroscopy, Quantum yield, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, isomerization, metastable states, [CHIM.COOR]Chemical Sciences/Coordination chemistry, education, ruthenium, education.field_of_study, Photodissociation, General Chemistry, 021001 nanoscience & nanotechnology, Antibonding molecular orbital, oxidovanadium complexes, 0104 chemical sciences, Ruthenium, chemistry, nitrosyl, vanadium, Physical chemistry, 0210 nano-technology, Ground state, [CHIM.OTHE]Chemical Sciences/Other, Single crystal
Abstract

International audience; The work is devoted to the preparation and photochemical investigations of the novel binuclear heterometallic complex [Ru(NO)(NO 2) 2 (μ-NO 2)(μ-CH 3 COO)(μ-O)VO(dbbpy)]. CH 3 CN (dbbpy-4,4'-di-tert-butyl-2,2'-bipyridyl), which is obtained with quantitative yield. The structure of the complex is determined by single crystal X-ray diffraction and by DFT calculations. On the one hand, irradiation at 445 nm of an acetonitrile solution of the complex leads to a NO photo-release reaction. The light excitation induces the charge transfer from NO 2 and dbbpy ligands to the antibonding orbitals of ON-Ru-O-V chain, leading to the NO release, which is confirmed by the DFT. The quantum yield of the Ru-NO photo-cleavage is 0.57±0.05%. The products of the photolysis (NO and paramagnetic Ru III complex) are confirmed by the Griess test and EPR-spectroscopy. On the other hand, the irradiation of the complex in the solid phase at 10 K results in the formation of the metastable bond isomer Ru-ON (MS1), which is detected by the infrared spectroscopy. The stretching vibration of the ν(NO) band of MS1 (1750 cm-1) is shifted by 150 cm-1 to lower energy with respect to the ν(NO) band of the ground state GS (1900 cm-1). The population of the MS1 is about 5%. MS1 thermally decays at 120-140 K back to the GS. Hence, this complex represents a bifunctional platform, which can release nitric oxide in solution and reversibly switch the NO ligand coordination in the solid state. It is shown, that the presence of vanadium strongly influences the photochemical properties of ruthenium nitrosyl both in the solid phase and in solution.

Published
2021
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133. Cationic Zinc Hydride Catalyzed Carbon Dioxide Reduction to Formate: Deciphering Elementary Reactions, Isolation of Intermediates, and Computational Investigations

Author

R. M. Bhargav, Laurent Maron, Ajay Venugopal, Raju Chambenahalli, Alex P. Andrews, Karl N. McCabe, Florian Ritter, Jun Okuda, Indian Institute of Science Education and Research Thiruvananthapuram (IISER TVM), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institute of Inorganic Chemistry [Aachen] (IAC RWTH), Rheinisch-Westfälische Technische Hochschule Aachen University (RWTH), IISER Thiruvananthapuram, and Alexander von Humboldt Foundation

Subjects
carbon dioxide reduction, 010405 organic chemistry, Hydrosilylation, Organic Chemistry, hydrosilylation, chemistry.chemical_element, Zinc hydride, reactive intermediates, General Chemistry, Zinc, Borane, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Hydroboration, chemistry, hydroboration, zinc hydride, Polymer chemistry, Lewis acids and bases, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Electrochemical reduction of carbon dioxide
Abstract

International audience; Zinc has been an element of choice for carbon dioxide reduction in recent years. Zinc compounds have been showcased as catalysts for carbon dioxide hydrosilylation and hydroboration. The extent of carbon dioxide reduction can depend on various factors, including electrophilicity at the zinc center and the denticity of the ancillary ligands. In a few cases, the addition of Lewis acids to zinc hydride catalysts markedly influences carbon dioxide reduction. These factors have been investigated by exploring elementary reactions of carbon dioxide hydrosilylation and hydroboration by using cationic zinc hydrides bearing tetradentate tris[2-(dimethylamino)ethyl]amine and tridentate N,N,N ',N '',N ''-pentamethyldiethylenetriamine in the presence of triphenylborane and tris(pentafluorophenyl)borane.

Published
2021
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134. Dihydrogen cleavage by a dimetalloxycarbene-borane frustrated Lewis pair

Author

Thomas P. Spaniol, Jun Okuda, Christopher C. Cummins, Anh L. P. Nguyen, Laurent Maron, Jared S. Silvia, Albert Paparo, Rhein Westfal TH Aachen, Monash Univ, Dept. mat. Engn, Monash University [Clayton], Massachusetts Institute of Technology (MIT), Institute of Inorganic Chemistry [Aachen] (IAC RWTH), Rheinisch-Westfälische Technische Hochschule Aachen University (RWTH), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Deutsche Forschungsgemeinschaft, Fonds der Chemischen Industrie, and National Science Foundation [CHE-1955612]

Subjects
010405 organic chemistry, chemistry.chemical_element, Borane, 010402 general chemistry, Cleavage (embryo), 01 natural sciences, Medicinal chemistry, Frustrated Lewis pair, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Formate, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Boron
Abstract

Dititanoxycarbene [(TiX3)2(μ-CO2)] (X = N[tBu](3,5-Me2C6H3)) and B(C6F5)3 cleaved dihydrogen under ambient conditions to give the zwitterionic formate [(TiX3)2(μ-OCHO-κO:κO′)(B(C6F5)3)] and the hydrido borate [Ti(N[tBu]Ar)3][HB(C6F5)3].

Published
2021
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135. Reductive elimination of [AlH2](+) from a cationic Ga-Al dihydride

Author

Jun Okuda, Ambre Carpentier, Laurent Maron, Louis J. Morris, Institute of Inorganic Chemistry [Aachen] (IAC RWTH), Rheinisch-Westfälische Technische Hochschule Aachen University (RWTH), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Metals and Alloys, Cationic polymerization, General Chemistry, Medicinal chemistry, Oxidative addition, Catalysis, Reductive elimination, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, chemistry, Covalent bond, Materials Chemistry, Ceramics and Composites, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Carbene, Dissolution
Abstract

International audience; Oxidative addition of TMEDA-supported [AlH2](+) to [{BDI}Ga] (BDI = {HC(C(CH3)N(2,6-iPr(2)-C6H3))(2)}) provides [{BDI}Ga(H)-Al(H)(tmeda)][B(C6H3-3,5-Me-2)(4)] (TMEDA = N,N,N ' N '-tetramethylethylenediamine) with a covalent metal-metal bond. The reaction is readily reversed by substituting TMEDA for an N-heterocyclic carbene or dissolving in THF.

Published
2021
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136. Reduced Arene Complexes of Hafnium Supported by a Triamidoamine Ligand

Author

Priyabrata Ghana, Thomas P. Spaniol, Jun Okuda, Laurent Maron, Ulli Englert, Rajeshkhumar Thayalan, Sebastian Schrader, Institute of Inorganic Chemistry [Aachen] (IAC RWTH), Rheinisch-Westfälische Technische Hochschule Aachen University (RWTH), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Deutsche Forschungsgemeinschaft

Subjects
Nitrile, hafnium, DFT calculation, Protonation, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Catalysis, insertion, chemistry.chemical_compound, Deprotonation, Oxidation state, oxidation state, Research Articles, Coordination Chemistry | Hot Paper, Anthracene, 010405 organic chemistry, Ligand, General Chemistry, 0104 chemical sciences, Benzonitrile, chemistry, Azobenzene, ddc:540, arene ligand, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Research Article
Abstract

A series of hafnium complexes with a reduced arene of the general formula [K(L)][Hf(Xy‐N3N)(arene)] (Xy‐N3N={(3,5‐Me2C6H3)NCH2CH2}3N3−, L=THF, 18‐crown‐6; arene=C10H8 2−, C14H10 2−) mimic the chemistry of hafnium in its formal oxidation state +II. All compounds were obtained upon reduction of the chlorido complex [HfCl(Xy‐N3N)(thf)] with two equivalents of potassium naphthalenide or anthracenide. The reducing nature and the basicity of the reduced anthracene ligand were explored in the reaction of benzonitrile and azobenzene, and by deprotonation of tert‐butylacetylene, respectively. The reduction of benzonitrile provides an initial double nitrile insertion product under kinetic control that rearranges after extrusion of one of the inserted nitriles to a hafnium imido complex as the thermodynamic product. The reduction of azobenzene resulted in a diphenylhydrazido(2−) complex. Treatment of terminal alkynes with the anthracene or diphenylhydrazido(2−) complex led to the selective protonation of the corresponding dianionic ligand., A reduced anthracene complex of hafnium(IV) reacts with two equivalents of benzonitrile to form the hafnium‐bis(iminyl) as the kinetic product that expulses one equivalent of benzonitrile to give an imido complex.

Published
2021
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137. Zinc hydride cation [ZnH](+) supported by TMPDA (TMPDA = N,N,N ',N '-tetramethylpropane-1,3-diamine)

Author

Laurent Maron, Karl N. McCabe, Thomas P. Spaniol, Jun Okuda, Florian Ritter, Institute of Inorganic Chemistry [Aachen] (IAC RWTH), Rheinisch-Westfälische Technische Hochschule Aachen University (RWTH), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Deutsche Forschungsgemeinschaft through the International Research Training Group 'Selectivity in Chemo-and Biocatalysis

Subjects
Dimer, ved/biology.organism_classification_rank.species, chemistry.chemical_element, Zinc hydride, Zinc, Conjugated system, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Inorganic Chemistry, chemistry.chemical_compound, Diamine, Materials Chemistry, Chelation, Physical and Theoretical Chemistry, 3c, Hydride, 010405 organic chemistry, ved/biology, N-donor ligand, 0104 chemical sciences, Chelate, chemistry, 2e bond, Protonolysis, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Conjugate acid
Abstract

International audience; Selective protonolysis of polymeric zinc dihydride [ZnH2](n) by the conjugate acid of the chelating N,N-donor TMPDA (TMPDA = N,N,N',N'-tetramethylpropane-1,3-diamine) [(TMPDA)H)][B(3,5-(CF3)(2)-C6H3)(4)] in THF gave the molecular zinc hydride cation [(TMPDA)ZnH(thf)][B(3,5-(CF3)(2)-C6H3)(4)] that is stable in THF but crystallized as the dimer [(TMPDA)(2)Zn-2(mu-H)(2)][B(3,5-(CF3)(2)-C6H3)(4)](2) from CH2Cl2/n-pentane. The protonolysis with half equivalent of the conjugate acid or the reaction of isolated [(TMPDA)ZnH (thf)][B(3,5-(CF3)(2)-C6H3)(4)] with one equivalent of zinc dihydride in THF gave the molecular dizinc trihydride cation [(TMPDA)(2)Zn2H2(mu-H)][B(3,5-(CF3)(2)-C6H3)(4)]. (C) 2021 Elsevier Ltd. All rights reserved.

Published
2021
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138. Supramolecular frameworks based on rhenium clusters using the synthons approach

Author

Yuri V. Mironov, Racha El Osta, Antoine Demont, Stéphane Cordier, Nikolay G. Naumov, Nathalie Audebrand, 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), Nikolaev Institute of Inorganic Chemistry [Novosibirsk] (NIC), Siberian Branch of the Russian Academy of Sciences (SB RAS), Université de Rennes 1, Centre National de la Recherche Scientifique, CNRS, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
Pyrazine, Supramolecular chemistry, Pharmaceutical Science, chemistry.chemical_element, Crystal engineering, Crystal structure, 010402 general chemistry, 01 natural sciences, Topology, Article, Analytical Chemistry, chemistry.chemical_compound, QD241-441, TheoryofComputation_ANALYSISOFALGORITHMSANDPROBLEMCOMPLEXITY, Drug Discovery, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Supramolecular framework, 010405 organic chemistry, Hydrogen bond, Ligand, Synthon, Organic Chemistry, Rhenium, 0104 chemical sciences, 3. Good health, Crystallography, chemistry, Chemistry (miscellaneous), Rhenium sulfide cluster, Molecular Medicine
Abstract

The reaction of the K4[{Re6Si8}(OH)a6]·8H2O rhenium cluster salt with pyrazine (Pz) in aqueous solutions of alkaline or alkaline earth salts at 4 °C or at room temperature leads to apical ligand exchange and to the formation of five new compounds: [trans-{Re6Si8}(Pz)a2(OH)a2(H2O)a2] (1), [cis-{Re6Si8}(Pz)a2(OH)a2(H2O)a2] (2), (NO3)[cis-{Re6Si8}(Pz)a2(OH)a(H2O)a3](Pz)·3H2O (3), [Mg(H2O)6]0.5[cis-{Re6Si8}(Pz)a2(OH)a3(H2O)a]·8.5H2O (4), and K[cis-{Re6Si8}(Pz)a2(OH)a3(H2O)a]·8H2O (5). Their crystal structures are built up from trans- or cis-[{Re6Si8}(Pz)a2(OH)a4−x(H2O)ax]x−2 cluster units. The cohesions of the 3D supramolecular frameworks are based on stacking and H bonding, as well as on H3O2−bridges in the cases of (1), (2), (4), and (5) compounds, while (3) is built from stacking and H bonding only. This evidences that the nature of the synthons governing the cluster unit assembly is dependent on the hydration rate of the unit.

Published
2021
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139. A new limit for neutrinoless double-beta decay of 100 Mo from the CUPID-Mo experiment (CUPID-Mo Collaboration)

Author

Armengaud, E., Augier, C., Barabash, A.S., Bellini, F, Benato, G, Benoit, Alain, Beretta, M, Bergé, L., Billard, J., Borovlev, Yu, Bourgeois, Ch, Brudanin, V, Camus, P, Cardani, L, Casali, N, Cazes, A., Chapellier, M, Charlieux, F., Chiesa, D, De Combarieu, M, Dafinei, I, Danevich, F, De Jesus, M., Dixon, T, Dumoulin, L, Eitel, K, Ferri, F, Fujikawa, B, Gascon, J., Gironi, L, Giuliani, A, Grigorieva, V, Gros, M, Guerard, E, Helis, D, Huang, H, Huang, R, Johnston, J, Juillard, A., Khalife, H, Kleifges, M, Kobychev, V, Kolomensky, Yu, Konovalov, S, Leder, A, Loaiza, P, Ma, L, Makarov, E, De Marcillac, P, Mariam, R, Marini, L, Marnieros, S, Misiak, D, Navick, X.-F, Nones, C, Norman, E, Novati, V, Olivieri, E, Ouellet, J, Pagnanini, L, Pari, P, Pattavina, L, Paul, B, Pavan, M, PENG, H, Pessina, G, Pirro, S, Poda, D, Polischuk, O, Pozzi, S, Previtali, E, Redon, Th, Rojas, A, Rozov, S, Rusconi, C, Sanglard, V., Scarpaci, J.A., Schäffner, K, Schmidt, B, Shen, Y, Shlegel, V, Siebenborn, B, Singh, V, Tomei, C, Tretyak, V, Umatov, V, Vagneron, L., Velázquez, M, Welliver, B, Winslow, L, Xue, M, Yakushev, E, Zarytskyy, M, Zolotarova, A. S., Institut de Recherches sur les lois Fondamentales de l'Univers (IRFU), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Institut de Physique des 2 Infinis de Lyon (IP2I Lyon), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Hélium : du fondamental aux applications (HELFA), 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), Laboratoire de Physique des 2 Infinis Irène Joliot-Curie (IJCLab), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Cryogénie (Cryo), Laboratoire Souterrain de Modane (LSM - UMR 6417), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3), CUPID, Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Institute of Theoretical and Experimental Physics [Moscow] (ITEP), National Research Center 'Kurchatov Institute' (NRC KI), Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome] (UNIROMA), Laboratori Nazionali di Frascati (INFN), LABORATORY NAZIONALI DI FRASCATI, Hélium : du fondamental aux applications (NEEL - HELFA), University of California [Berkeley] (UC Berkeley), University of California (UC), Nikolaev Institute of Inorganic Chemistry [Novosibirsk] (NIC), Siberian Branch of the Russian Academy of Sciences (SB RAS), Dzhelepov Laboratory of Nuclear Problems [Dubna] (DLNP), Joint Institute for Nuclear Research (JINR), Cryogénie (NEEL - Cryo), Istituto Nazionale di Fisica Nucleare [Sezione di Roma 1] (INFN), Istituto Nazionale di Fisica Nucleare, Università degli Studi di Milano-Bicocca = University of Milano-Bicocca (UNIMIB), Institut Rayonnement Matière de Saclay (IRAMIS), Institute for Nuclear Research of NAS of Ukraine, National Academy of Sciences of Ukraine (NASU), Karlsruhe Institute of Technology (KIT), Université Paris-Saclay, Lawrence Berkeley National Laboratory [Berkeley] (LBNL), Fudan University [Shanghai], Massachusetts Institute of Technology (MIT), Istituto Nazionale di Fisica Nucleare, Sezione di Cagliari (INFN, Sezione di Cagliari), Istituto Nazionale di Fisica Nucleare (INFN), University of Science and Technology of China [Hefei] (USTC), Istituto Nazionale di Fisica Nucleare, Sezione di Milano (INFN), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), University of Southern California (USC), Science et Ingénierie des Matériaux et Procédés (SIMaP), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )

Subjects
[PHYS]Physics [physics], [PHYS.NEXP]Physics [physics]/Nuclear Experiment [nucl-ex], ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2021
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140. Calcium Hydride Catalysts for Olefin Hydrofunctionalization: Ring-Size Effect of Macrocyclic Ligands on Activity

Author

Danny Schuhknecht, Thomas Höllerhage, Laurent Maron, Alisha Mistry, Thomas P. Spaniol, Jun Okuda, Yan Yang, Institute of Inorganic Chemistry [Aachen] (IAC RWTH), Rheinisch-Westfälische Technische Hochschule Aachen University (RWTH), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Deutsche Forschungsgemeinschaft, Chinese Scholarship Council (CSC), and Projekt DEAL

Subjects
calcium hydride, Hydrosilylation, Dimer, chemistry.chemical_element, Calcium, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Catalysis, chemistry.chemical_compound, Pentagonal bipyramidal molecular geometry, Hydrogenolysis, Calcium hydride, 010405 organic chemistry, Hydride, Communication, Organic Chemistry, hydrosilylation, General Chemistry, Communications, 0104 chemical sciences, macrocycles, chemistry, ddc:540, kinetic analysis, Protonolysis, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], hydrogenation
Abstract

The fifteen‐membered NNNNN macrocycle Me5PACP (Me5PACP=1,4,7,10,13‐pentamethyl‐1,4,7,10,13‐pentaazacyclopentadecane) stabilized the [CaH]+ fragment as a dimer with a distorted pentagonal bipyramidal coordination geometry at calcium. The hydride complex was prepared by protonolysis of calcium dibenzyl with the conjugate acid of Me5PACP followed by hydrogenolysis or treating with nOctSiH3 of the intermediate calcium benzyl cation. The calcium hydride catalyzed the hydrogenation and hydrosilylation of unactivated olefins faster than the analogous calcium complex stabilized by the twelve‐membered NNNN macrocycle Me4TACD (Me4TACD=1,4,7,10‐tetramethyl‐1,4,7,10‐tetraazacyclododecane). Kinetic investigations indicate that higher catalytic efficiency for the Me5PACP stabilized calcium hydride is due to easier dissociation of the dimer in solution when compared to the Me4TACD analogue., Macrocyclic ligands recognize ion size, but are rarely used to influence metal‐centered catalytic activity. Calcium hydride cation [CaH]+ supported by the fifteen‐membered NNNNN macrocycle Me5PACP (Me5PACP=1,4,7,10,13‐pentamethyl‐1,4,7,10,13‐pentaazacyclopentadecane) catalyzes hydrogenation and hydrosilylation of unactivated olefins significantly faster than the analogous calcium catalyst containing the twelve‐membered NNNN macrocycle (see figure).

Published
2021
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141. Cationic strontium hydride complexes supported by an NNNN-type macrocycle

Author

Laurent Maron, Ambre Carpentier, Thomas Höllerhage, Ulli Englert, Thomas P. Spaniol, Jun Okuda, Institute of Inorganic Chemistry [Aachen] (IAC RWTH), Rheinisch-Westfälische Technische Hochschule Aachen University (RWTH), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Strontium, Hydride, Metals and Alloys, Cationic polymerization, chemistry.chemical_element, General Chemistry, Calcium, Hydride ligands, Medicinal chemistry, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, Hydrogenolysis, Materials Chemistry, Ceramics and Composites, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract

International audience; A trinuclear strontium hydride [(Me(4)TACD)(3)Sr-3(mu(2)-H)(4)(thf)][B(C6H3-3,5-Me-2)(4)](2) (Me(4)TACD = 1,4,7,10-tetramethyltetraazacyclododecane) and a mixed calcium strontium hydride [(Me(4)TACD)(2)CaSr(mu-H)(2)(thf)][B(C6H3-3,5-Me-2)(4)](2) were isolated by hydrogenolysis of cationic benzyl precursors. A solution of [(Me(4)TACD)(2)CaSr(mu-H)(2)(thf)][B(C6H3-3,5-Me-2)(4)](2) shows hydride ligand exchange between calcium and strontium centers and higher affinity of the hydride ligand toward calcium.

Published
2021
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147. 1,5-Disubstituted 1,2,3-Triazoles as Amide Bond Isosteres Yield Novel Tumor-Targeting Minigastrin Analogs

Author

Roger Schibli, Ibai E. Valverde, Nathalie M. Grob, Martin Béhé, Thomas L. Mindt, Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Paul Scherrer Institute (PSI), 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), Institute of Inorganic Chemistry [University of Vienna], University of Vienna [Vienna], Ludwig Boltzmann Institute Applied Diagnostics [General Hospital of Vienna] (LBI AD), and General Hospital of Vienna

Subjects
Biodistribution, 3-Triazoles, Stereochemistry, Peptidomimetic, media_common.quotation_subject, 01 natural sciences, Biochemistry, Turn (biochemistry), Drug Discovery, [CHIM]Chemical Sciences, Peptide bond, Internalization, Receptor, Cancer, media_common, Tumor Targeting, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, 1,2,3-Triazoles, Peptidomimetics, Structure−activity relationships, Radiopharmaceuticals, Tumor targeting, Structure-Activity Relationships, Organic Chemistry, Biological activity, 0104 chemical sciences, 010404 medicinal & biomolecular chemistry, Yield (chemistry)
Abstract

[Image: see text] 1,5-Disubstituted 1,2,3-triazoles (1,5-Tz) are considered bioisosteres of cis-amide bonds. However, their use for enhancing the pharmacological properties of peptides or proteins is not yet well established. Aiming to illustrate their utility, we chose the peptide conjugate [Nle(15)]MG11 (DOTA-dGlu-Ala-Tyr-Gly-Trp-Nle-Asp-Phe-NH(2)) as a model compound since it is known that the cholecystokinin-2 receptor (CCK2R) is able to accommodate turn conformations. Analogs of [Nle(15)]MG11 incorporating 1,5-Tz in the backbone were synthesized and radiolabeled with lutetium-177, and their pharmacological properties (cell internalization, receptor binding affinity and specificity, plasma stability, and biodistribution) were evaluated and compared with [Nle(15)]MG11 as well as their previously reported analogs bearing 1,4-disubstituted 1,2,3-triazoles. Our investigations led to the discovery of novel triazole-modified analogs of [Nle(15)]MG11 with nanomolar CCK2R-binding affinity and 2-fold increased tumor uptake. This study illustrates that substitution of amides by 1,5-disubstituted 1,2,3-triazoles is an effective strategy to enhance the pharmacological properties of biologically active peptides.

Published
2020
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148. The impact of counterion on the metastable state properties of nitrosyl ruthenium complexes

Author

Artem A. Mikhailov, Gennadiy A. Kostin, Denis P. Pishchur, Dominik Schaniel, Vladislav Yu. Komarov, A. S. Sukhikh, Nikolaev Institute of Inorganic Chemistry [Novosibirsk] (NIC), Siberian Branch of the Russian Academy of Sciences (SB RAS), Cristallographie, Résonance Magnétique et Modélisations (CRM2), and Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, education.field_of_study, 010405 organic chemistry, Population, chemistry.chemical_element, General Chemistry, Activation energy, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Ruthenium, Perchlorate, chemistry.chemical_compound, chemistry, Metastability, Materials Chemistry, Physical chemistry, Thermal stability, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Counterion, education, Palladium
Abstract

International audience; In the present study four new complexes of the trans-[RuNO(NH 3) 4 F] 2+ cation with noble-metal anions [PtCl 6 ] 2-, [PdCl 4 ] 2-and [PtCl 4 ] 2-, and perchlorate anion ClO 4-were synthesized and characterized by spectroscopic (IR, UV/vis), calorimetric (DSC) and single crystal X-Ray diffraction methods. All three complexes with the platinum and palladium cations crystallize in a non-centrosymmetric structure, which is determined by N-H•••Halogen intermolecular interactions. The irradiation of the complexes by light in the spectral range of 300-420 nm induces Ru-ON isomers MS1, and the subsequent irradiation of MS1 in trans-[RuNO(NH 3) 4 F](ClO 4) 2 by 940 nm light results in Ru-(η 2-(NO) isomer MS2 formation, which were detected by IR and UV/vis-spectroscopy. For trans-[RuNO(NH 3) 4 F](ClO 4) 2 and trans-[RuNO(NH 3) 4 F][PdCl 4 ] the activation energy (E a) and frequency factors (lgk 0) of the MS1→GS transformation were determined, which are 104(1) kJ mol-1 and 15.0(2), and 112(6) kJ mol-1 and 16.0(9), respectively. It is shown, that in these complexes the MS1 isomers exhibit excellent thermal stability, trans-[RuNO(NH 3) 4 F][PdCl 4 ] exhibits the highest thermal stability known up to now. The spectroscopic analysis of ground and metastable states allows to underline two important features: i) the absorption of a counterion in the excitation range results in a decreased efficiency of light absorption of the nitrosyl complex cation and consequently leads to a decrease in metastable state population; ii) the interactions with the counterion can influence the position of absorption bands of MS1 and MS2, which requires to change the excitation wavelength for the achievement of the maximum metastable state population. Obtained results can be expanded and applied for other metastable systems, like complexes containing nitrite (NO 2-) or sulfoxide-like (SO) ligands.

Published
2020
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149. Characteristics of hydrate-bound gas retrieved at the Kedr mud volcano (southern Lake Baikal)

Author

Andrey Yu. Manakov, Jeffrey Poort, Alexandr Chenskiy, Hirotsugu Minami, Akihiro Hachikubo, Marc De Batist, Satoshi Yamashita, Gennadiy Kalmychkov, A. V. Khabuev, Oleg Khlystov, Alexey Krylov, Kitami Institute of Technology, Limnological Institute, Siberian Branch of the Russian Academy of Sciences (SB RAS), Saint Petersburg State University (SPBU), A.P. Vinogradov Institute of Geochemistry, Institut des Sciences de la Terre de Paris (iSTeP), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Institut national des sciences de l'Univers (INSU - CNRS), Renard Centre of Marine Geology (RCMG), Universiteit Gent = Ghent University [Belgium] (UGENT), Irkutsk State University (ISU), and Nikolaev Institute of Inorganic Chemistry [Novosibirsk] (NIC)

Subjects
ANOMALIES, GULF, 010504 meteorology & atmospheric sciences, Hydrogen, Energy science and technology, Clathrate hydrate, chemistry.chemical_element, lcsh:Medicine, 010502 geochemistry & geophysics, 01 natural sciences, Methane, Article, MEXICO, chemistry.chemical_compound, METHANE, Propane, GLOBAL DATASET, [SDU.STU.VO]Sciences of the Universe [physics]/Earth Sciences/Volcanology, ISOTOPIC COMPOSITION, lcsh:Science, 0105 earth and related environmental sciences, BASIN, Multidisciplinary, Chemistry, lcsh:R, Sediment, Biogeochemistry, HYDROGEN, Environmental sciences, Neopentane, 13. Climate action, Environmental chemistry, Earth and Environmental Sciences, lcsh:Q, Hydrate, SEDIMENTS, Mud volcano, ETHANE
Abstract

We reported the characteristics of hydrate-bound hydrocarbons in lake-bottom sediments at the Kedr mud volcano in Lake Baikal. Twenty hydrate-bearing sediment cores were retrieved, and methane-stable isotopes of hydrate-bound gases (δ13C and δ2H of − 47.8‰ to − 44.0‰ V-PDB and − 280.5‰ to − 272.8‰ V-SMOW, respectively) indicated their thermogenic origin accompanied with secondary microbial methane. Powder X-ray diffraction patterns of the crystals and molecular composition of the hydrate-bound gases suggested that structure II crystals showed a high concentration of ethane (around 14% of hydrate-bound hydrocarbons), whereas structure I crystals showed a relatively low concentration of ethane (2–5% of hydrate-bound hydrocarbons). These different crystallographic structures comprised complicated layers in the sub-lacustrine sediment, suggesting that the gas hydrates partly dissociate, concentrate ethane and form structure II crystals. We concluded that a high concentration of thermogenic ethane primarily controls the crystallographic structure of gas hydrates and that propane, iso-butane (2-methylpropane) and neopentane (2,2-dimethylpropane) are encaged into crystals in the re-crystallisation process.

Published
2020
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150. Dynamic Features of Transition States for β-Scission Reactions of Alkenes over Acid Zeolites Revealed by AIMD Simulations

Author

Charles Bignaud, Céline Chizallet, Pascal Raybaud, Jérôme Rey, Tomáš Bučko, IFP Energies nouvelles (IFPEN), École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL), Department of Biochemistry, Faculty of Natural Sciences, Comenius University in Bratislava, Comenius University in Bratislava, Institute of Inorganic Chemistry of the Czech Academy of Sciences (UACH / CAS), and Czech Academy of Sciences [Prague] (CAS)

Subjects
Carbonium Ions, Zeolithes, 010402 general chemistry, 01 natural sciences, Catalysis, Reaction rate constant, Computational chemistry, [CHIM]Chemical Sciences, Zeolite, β-scissions, chemistry.chemical_classification, AIMD Simulations, Alkene, 010405 organic chemistry, Acidity, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, General Medicine, Transition state, 0104 chemical sciences, Cracking, chemistry, [SDE]Environmental Sciences, Density functional theory, Transition path sampling, Isomerization
Abstract

International audience; Zeolite‐catalyzed alkene cracking is key to optimize the size of hydrocarbons. The nature and stability of intermediates and transition states (TS) are, however, still debated. We combine transition path sampling and blue moon ensemble density functional theory simulations to unravel the behavior of C7 alkenes in CHA zeolite. Free energy profiles are determined, linking π‐complexes, alkoxides and carbenium ions, for B1 (secondary to tertiary) and B2 (tertiary to secondary) β‐scissions. B1 is found to be easier than B2. The TS for B1 occurs at the breaking of the C−C bond, while for B2 it is the proton transfer from propenium to the zeolite. We highlight the dynamic behaviors of the various intermediates along both pathways, which reduce activation energies with respect to those previously evaluated by static approaches. We finally revisit the ranking of isomerization and cracking rate constants, which are crucial for future kinetic studies.

Published
2020
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