Article
Chemistry, Multidisciplinary
Mathis J. Benedikter, Janis V. Musso, Wolfgang Frey, Roman Schowner, Michael R. Buchmeiser
Summary: Despite their excellent selectivities and activities, Mo- and W-based catalysts for olefin metathesis have not been widely used due to their air sensitivity. The synthesized cationic-at-metal molybdenum and tungsten imido alkylidene NHC nitrile complexes are stable in air and can catalyze olefin metathesis reactions without prior activation. The presence of a nitrile ligand is crucial for their stability, while variations in imido and anionic ligands affect reactivities and stability.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Monica Martinez-Junquera, Elena Lalinde, M. Teresa Moreno, Elvira Alfaro-Arnedo, Iciar P. Lopez, Ignacio M. Larrayoz, Jose G. Pichel
Summary: This study synthesized four new cyclometalated Pt(ii) complexes bearing acyclic diaminocarbene (ADC) ligands and investigated their photophysical properties and antiproliferative properties through various experiments and analyses. The complexes exhibit green or orange phosphorescence and show aggregation induced emission in certain fluid solutions. Cytotoxicity studies also revealed good activity for these complexes, particularly in affecting DNA electrophoretic mobility.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Nadine Weyer, Myron Heinz, Julia I. Schweizer, Clemens Bruhn, Max C. Holthausen, Ulrich Siemeling
Summary: The N-heterocyclic silylene shows a remarkable combination of thermal stability and reactivity towards small molecules, producing different follow-up products in reactions with CO2, N2O, H2O, NH3, and FcPH(2). Unexpectedly, the reaction with H3BNH3 results in B-H activation instead of N-H activation. DFT results suggest dramatically different mechanisms for these H-X insertions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemical Research Methods
Fady Nahra, Nikolaos Tzouras, Alba Collado, Steven P. Nolan
Summary: N-heterocyclic carbene gold(I) chloride and hydroxide complexes are commonly used as synthetic reagents and efficient catalysts. This study describes a straightforward and practical method for synthesizing mononuclear gold complexes with high yields, as well as the synthesis of a mononuclear gold(I) hydroxide complex and an improved synthesis method for a dinuclear gold(I) hydroxide complex. This methodology offers advantages such as the use of sustainable reaction solvents and commercially available starting materials.
Article
Biochemistry & Molecular Biology
Mirko Ruamps, Stephanie Bastin, Lionel Rechignat, Alix Sournia-Saquet, Laure Vendier, Noel Lugan, Jean-Marie Mouesca, Dmitry A. Valyaev, Vincent Maurel, Vincent Cesar
Summary: The coordination chemistry of the N-heterocyclic carbene ligand IMes((NMe2)2), and its interaction with transition metal centers, was investigated. The redox behavior of the resulting organometallic complexes was studied, revealing the different oxidation states and their effects on the donating properties of the ligand.
Article
Chemistry, Physical
Sebastien Le Roux, Guido Ori, Stephane Bellemin-Laponnaz, Mauro Boero
Summary: Metal carbene complexes are a common class of compounds in organometallic chemistry that can catalyze various reactions. The nature of the metallic ion has little impact on the structure of the ligand, but removing an electron can affect the ligand conformation and subsequently influence the catalytic properties of the complex.
CHEMICAL PHYSICS LETTERS
(2021)
Article
Chemistry, Inorganic & Nuclear
David Dunlop, Milos Vecera, Robert Gyepes, Pavel Kubat, Kamil Lang, Michal Horacek, Jiri Pinkas, Ludmila Simkova, Alan Liska, Martin Lamac
Summary: The paper investigates the preparation, solid-state structures, electrochemical behavior, and luminescent properties of cationic group 4 metallocene complexes with pendant imine and pyridine donor groups. The solid state structures were determined by X-ray diffraction analysis and their electrochemical behavior was studied through cyclic voltammetry. DFT calculations were performed to explain the properties of the complexes.
INORGANIC CHEMISTRY
(2021)
Article
Oncology
Lara Massai, Luigi Messori, Andrea Carpentieri, Angela Amoresano, Chiara Melchiorre, Tania Fiaschi, Alessandra Modesti, Tania Gamberi, Francesca Magherini
Summary: In this study, the mode of action of Au(NHC) and Au(NHC)(2)PF6 was investigated, identifying common cellular targets while confirming their different influence on mitochondrial function.
CANCER CHEMOTHERAPY AND PHARMACOLOGY
(2022)
Article
Multidisciplinary Sciences
Jun Choi, Kyungkon Kim, Sung-Jin Kim
Summary: Luminescent solar concentrators (LSCs) are solar light-harvesting devices that focus light on photovoltaic cells to generate electricity. Research has shown that using zinc-doped quantum dots as energy transferring donors can significantly improve the performance of LSCs.
SCIENTIFIC REPORTS
(2021)
Article
Chemistry, Applied
Vanessa Vethacke, Vanessa Claus, Martin C. Dietl, Daniel Ehjeij, Arne Meister, Jonas F. Huber, Leon K. Paschai Darian, Matthias Rudolph, Frank Rominger, A. Stephen K. Hashmi
Summary: A variety of unsymmetric diaryl gold N-acyclic carbene (NAC) complexes were successfully synthesized by three different methods, allowing access to new complexes and overcoming previous limitations in the isonitrile route. These new complexes also proved to be successful as pre-catalysts in gold-catalyzed phenol synthesis.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Inorganic & Nuclear
Despoina Varna, Elena Geromichalou, Antonios G. Hatzidimitriou, Rigini Papi, George Psomas, Panagiotis Dalezis, Paraskevas Aslanidis, Theodora Choli-Papadopoulou, Dimitrios T. Trafalis, Panagiotis A. Angaridis
Summary: In recent years, there has been increasing interest in studying Ag(I) coordination compounds as effective antibacterial and anticancer agents. This study synthesized a series of Ag(I) complexes with phosphines and heterocyclic thioamide ligands, and evaluated their antibacterial and anticancer properties. The results showed that some of these complexes exhibited potent activity against bacteria and cancer cells, with certain selectivity towards normal cells.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Paul Zaby, Jan Blasius, Anna K. Mueller, Steven P. Nolan, Oldamur Holloczki
Summary: The formation mechanism of metal-N-heterocyclic carbene (NHC) complexes from imidazolium salts in the presence of weak bases was investigated through theoretical methods. Quantum chemical calculations revealed that both sodium acetate and trimethylamine facilitate complex formation. Molecular dynamics simulations showed that the ionic nature of the [AuCl2](-) and imidazolium ions, as well as the sodium acetate base, keep these species associated in the reaction mixture through ion pairing. The neutral amine, however, remains mostly separated from the other reaction partners, making it a significantly less effective base.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Clemens Kaussler, Darren Wragg, Claudia Schmidt, Guillermo Moreno-Alcantar, Christian Jandl, Johannes Stephan, Roland A. Fischer, Stefano Leoni, Angela Casini, Riccardo Bonsignore
Summary: This study focuses on improving the design of metal complexes as stabilizers of noncanonical DNA secondary structures. A series of cyclic dinuclear Au(I) N-heterocyclic carbene complexes based on xanthine and benzimidazole ligands have been synthesized and characterized. The compounds show stabilization properties towards G-quadruplexes (G4s) and moderate antiproliferative activity in human cancer cells. The binding modes and free energy landscape of the most active compound have been studied using metadynamics.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Armands Ruduss, Zanis Sisojevs, Sergey Belyakov, Kaspars Traskovskis
Summary: This study provides detailed synthetic procedures for accessing mesyl and triflyl functionalized derivatives of 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene (SIPr). New luminescent carbene-metal-amide (CMA) Cu(I) complexes based on acceptor group functionalized SIPr have been prepared. The effect of the LUMO energy in the sulfonyl functionalized N-heterocyclic carbene (NHC) series on the emissive properties of the CMAs has been investigated.
Article
Chemistry, Multidisciplinary
Ichraf Slimani, Serap Sahin-Bolukbasi, Mustafa Ulu, Enes Evren, Nevin Gurbuz, Ilknur Ozdemir, Naceur Hamdi, Ismail Ozdemir
Summary: A series of rhodium(i) complexes with N-heterocyclic carbene ligands showed high in vitro cytotoxic activity against human cancer cells, with complex 2b exhibiting the most selective cytotoxic activity. These complexes demonstrated greater cytotoxicity against cancer cells compared to established anticancer agents cisplatin and 5-fluorouracil.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
Yannick Geiger, Stephane Bellemin-Laponnaz
Summary: Non-linear effects between enantiomeric excesses of ligand and product are common in asymmetric catalysis, and they are useful tools for mechanistic investigations. This study shows that catalyst precipitation affects the shape and amplitude of non-linear effects curves, and it also observes several peculiar features. Overall, this research provides a better understanding of chiral catalytic systems.
Article
Chemistry, Physical
Anna Bonfiglio, Pei-Wan Hsiao, Yin Chen, Christophe Gourlaouen, Quentin Marchand, Vincent Cesar, Stephane Bellemin-Laponnaz, Yun-Xin Wang, Chin-Wei Lu, Chantal Daniel, Federico Polo, Hai-Ching Su, Matteo Mauro
Summary: This study presents a class of bright heterobimetallic emitters with enhanced fluorescence efficiency and radiative rate constant. The application of these bimetallic complexes in light-emitting electrochemical cells achieves high external quantum efficiency.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Inorganic & Nuclear
Refka Guermazi, David Specklin, Christophe Gourlaouen, Pierre Fremont, Samuel Dagorne
Summary: This study reports on the synthesis, structure, and use of new [(IPrCl)Zn-R](+) and [((IBu)-Bu-t)Zn-R](+) cations in alkyne hydroboration catalysis. The results show that [(IPrCl)Zn-C6F5](+) cation exhibits the highest catalytic activity.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Julien Egly, Weighang Chen, Aline Maisse-Francois, Stephane Bellemin-Laponnaz, Thierry Achard
Summary: Amide synthesis is a crucial transformation in chemistry and biology. N-heterocyclic carbene-based ruthenium catalyst systems have been proven to be active for direct synthesis of amides. In this study, a series of Ru complexes with thioether-functionalized N-heterocyclic carbene ligands were prepared and applied to the amidation reaction, resulting in high conversions but moderate yields.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Damien Bissessar, Julien Egly, Thierry Achard, Pascal Steffanut, Matteo Mauro, Stephane Bellemin-Laponnaz
Summary: A tetranuclear copper-iodide cluster has been identified as a stable precursor for further post-functionalization, allowing the direct functionalization of alkenes and providing access to a wide range of luminescent copper cubane complexes, including the first example of water-soluble luminescent cubane copper iodide.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Thibault Thierry, Yannick Geiger, Stephane Bellemin-Laponnaz
Summary: Phenomena related to asymmetric amplification are crucial for understanding the emergence of homochirality in life. This study focuses on asymmetric catalysis and investigates non-linear effects in chiral amplification. The authors provide experimental evidence of a new nonlinear hyperpositive effect in enantioselective zinc-catalyzed alkylation. Their research also reveals a mechanism involving both monomeric and dimeric complexes that contribute to different enantioselectivities.
Article
Chemistry, Physical
Yuri C. A. Sokolovicz, Antonio Buonerba, Carmine Capacchione, Samuel Dagorne, Alfonso Grassi
Summary: The zinc complex demonstrates high catalytic activity and selectivity in the polymerization of cyclohexene oxide (CHO), producing poly(cyclohexene oxide) (PCHO) with remarkable TOF values at room temperature. The complex also catalyzes the ring-opening copolymerization of CO2 with CHO, yielding poly(cyclohexene carbonate) (PCHC) with high polydispersity index values. The formation of dinuclear species during the reaction highlights potential new zinc catalysts that impact the polymerization process.
Article
Oncology
Conor McCartin, Candice Dussouillez, Chloe Bernhard, Eric Mathieu, Juliette Blumberger, Monique Dontenwill, Christel Herold-Mende, Ahmed Idbaih, Philippe Lavalle, Stephane Bellemin-Laponnaz, Antoine Kichler, Sylvie Fournel
Summary: The resistance and recurrence of tumors pose major challenges for cancer patient survival. Research has identified a subset of stem-cell-like cells in tumors that contribute to this problem. Developing new chemotherapeutic compounds to target these cells is of great interest for more effective cancer treatments.
Article
Engineering, Biomedical
Conor McCartin, Juliette Blumberger, Candice Dussouillez, Patricia Fernandez de Larrinoa, Monique Dontenwill, Christel Herold-Mende, Philippe Lavalle, Beatrice Heurtault, Stephane Bellemin-Laponnaz, Sylvie Fournel, Antoine Kichler
Summary: Cationic polymers like polyethylenimine (PEI) have been widely used as gene delivery agents and drug delivery agents. Recent studies have shown that certain polycations have higher toxicity towards cancer stem cells (CSCs) than differentiated tumor cells. Since CSCs play a critical role in cancer drug resistance, tumor recurrence, and poor clinical prognosis, it is important to investigate compounds that can target and eliminate these cells.
JOURNAL OF FUNCTIONAL BIOMATERIALS
(2023)
Article
Chemistry, Inorganic & Nuclear
Salvatore Impemba, Irene Tozio, Giuseppina Roviello, Samir Mameri, Samuel Dagorne, Stefano Milione
Summary: Mono- and bimetallic aluminum complexes with bidentate NS or tetradentate NSSN ligands were synthesized and characterized. The aluminum centers in these complexes have tetrahedral coordination geometries surrounded by anionic nitrogen and neutral sulfur atoms. X-ray diffraction studies confirmed the structure of the complexes with thioethyl or thiopropyl bridge. Both mono- and bimetallic aluminum complexes showed fluxional behaviors in solution. The bimetallic complex with the shortest bridge (ethyl bridge) exhibited the highest activity in the ring opening polymerization of L-lactide.
Article
Chemistry, Physical
Jordi Vila, Miquel Sola, Thierry Achard, Stephane Bellemin-Laponnaz, Anna Pla-Quintana, Anna Roglans
Summary: This article describes the [2 + 2 + 2] cycloaddition of 1,5-bisallenes and alkynes under the catalysis of Rh(I) with hemilabile thioether-functionalized N-heterocyclic carbene ligands. This method effectively provides access to different trans-5,6-fused bicyclic systems with two exocyclic double bonds in the cyclohexene ring. The complete mechanism of this transformation as well as the preference for the trans-fusion over the cis-fusion has been rationalized by density functional theory calculations.
Article
Multidisciplinary Sciences
Damien Bissessar, Thibault Thierry, Julien Egly, Valerio Giuso, Thierry Achard, Pascal Steffanut, Matteo Mauro, Stephane Bellemin-Laponnaz
Summary: We synthesized and studied three new copper halide derivatives 2a-c, which are tetranuclear copper-iodide clusters consisting of a cubane-like {Cu4I4} motif and phosphine ligands P. They differ in the type of phosphines used as ligands: a monophosphine with a single pendant ester unit (2a), two pendant ester units (2b), and a diphosphine containing two esters in the linker (2c). The complexes displayed intense and long-lived photoluminescence in the orange region with PLQY values of 0.43-0.84 at room temperature, mainly associated with a (CC)-C-3 excited state with mixed (XMCT)-X-3 character.
Article
Chemistry, Physical
Gael Printz, Dmytro Ryzhakov, Christophe Gourlaouen, Beatrice Jacques, Samir Messaoudi, Francoise Dumas, Franck Le Bideau, Samuel Dagorne
Summary: We report the first use of thiosquaramides as polymerization catalysts, showing their effectiveness for controlled ring-opening polymerization of lactide in the presence of an alcohol source and NEt3. Comparison with less acidic squaramides reveals the importance of a balanced NH Brönsted acidity for optimal catalytic performance. Surprisingly, DFT-supported calculations demonstrate that secondary interactions between thiosquaramide N-substituents and the incoming lactide are crucial for catalytic activity, which is rarely observed in the field of organo-catalyzed polymerizations. Such findings suggest the significance of catalyst substituent/substrate interactions in various other systems.
Article
Chemistry, Inorganic & Nuclear
Xuejuan Xu, Christophe Gourlaouen, Beatrice Jacques, Samuel Dagorne
Summary: This study reports the synthesis and characterization of novel Zn(II)-based organocations and their application in catalytic reactions. The results demonstrate that these cations exhibit good performance in catalyzing hydrosilylation reactions.
Article
Radiology, Nuclear Medicine & Medical Imaging
T. Thibault, M. Gurung, C. Leuvrey, A. Boos, P. Ronot, I. El Masoudi, P. Hoerner, S. Bellemin-Laponnaz
Summary: This study found that lead-containing gloves may present a risk of metal leaching when in contact with sweat, and the level of lead leaching depends on the acidity of the sweat and the duration of contact. Gloves with a protective lining reduce the transfer of lead into sweat, but significant levels of lead are still present.