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  • H. Amouri, « Luminescent Complexes of Platinum, Iridium, and Coinage Metals Containing N-Heterocyclic Carbene Ligands: Design, Structural Diversity, and Photophysical Properties », Chemical Reviews, vol. 123, nᵒ 1, p. 230-270, janv. 2023.
    Résumé : The employment of N-heterocyclic carbenes (NHCs) to design luminescent metal compounds has been the focus of recent intense investigations because of the strong σ-donor properties, which bring stability to the whole system and tend to push the d–d dark states so high in energy that they are rendered thermally inaccessible, thereby generating highly emissive complexes for useful applications such as organic light-emitting diodes (OLEDs), or featuring chiroptical properties, a field that is still in its infancy. Among the NHC complexes, those containing organic chromophores such as naphthalimide, pyrene, and carbazole exhibit rich emission behavior and thus have attracted extensive interest in the past five years, especially carbene coinage metal complexes with carbazolate ligands. In this review, the design strategies of NHC-based luminescent platinum and iridium complexes with large spin–orbit-coupling (SOC) are described first. Subsequent paragraphs illustrate the recent advances of luminescent coinage metal complexes with nucleophilic- and electrophilic-based carbenes based on silver, gold, and copper metal complexes that have the ability to display rich excited state emissions in particular via thermally activated delayed fluorescence (TADF). The luminescence mechanism and excited state dynamics are also described. We then summarize the advance of NHC–metal complexes in the aforementioned fields in recent years. Finally, we propose the development trend of this fast-growing field of luminescent NHC–metal complexes.
    Mots-clés : ARC.

  • M. Balas, A. Mayoufi, R. Villanneau, et F. Launay, « Revisiting the Mukaiyama-type epoxidation for the conversion of styrene into styrene carbonate in the presence of O <sub>2</sub> and CO <sub>2</sub> », Reaction Chemistry & Engineering, p. 10.1039.D2RE00330A, 2023.
    Résumé : Alkene epoxidation using the Mukaiyama process involving O 2 and a sacrificial aldehyde, as the first step of the global alkene oxidative carboxylation, does not necessarily require a metal catalyst. , Since its first report in the early 1990s, Mukaiyama-type aerobic epoxidation involving the presence of an aldehyde as an electron donor is considered as an interesting oxidation reaction. Among the various metal catalysts efficient for this process, salen-type complexes have many advantages: i) cheap Schiff-base ligands can be easily synthesized and functionalized, ii) their metal complexes are described with most transition metals from the periodic table and iii) these compounds are also efficient for the catalytic formation of cyclic carbonates from epoxides and CO 2 , which makes them ideal candidates for the oxidative carboxylation of alkenes. The present work aimed at revisiting the aerobic oxidation of styrene using Cr( iii ) and Mn( iii ) salen complexes in the presence of isobutyraldehyde with the idea to further use these complexes (without any work-up), as co-catalysts for the formation of styrene carbonate under CO 2 pressure. However, contrary to what is often described in the literature, the present study showed that the introduction of a metal catalyst is not necessary for the epoxidation of styrene at 80 °C in benzonitrile. In our hands, yields of ca. 15% of styrene carbonate were obtained from styrene using O 2 (3.5 bar) and CO 2 (11 bar) as reagents in the presence of isobutyraldehyde (2.5 eq), tetrabutylammonium bromide ( ca. 2 mol%) and the Cr( iii ) salen complex ( ca. 1 mol%). Apparently, the oxidation of Cr( iii ) to Cr( vi ) species in the presence of O 2 and isobutyraldehyde is detrimental to the kinetics of the tetrabutylammonium bromide-catalyzed cycloaddition of CO 2 to styrene oxide.
    Mots-clés : E-POM, POLE 2.

  • F. Banchini, B. Leroux, E. Le Gall, M. Presset, O. Jackowski, F. Chemla, et A. Perez-Luna, « Enantioselective Sequential Catalytic Arylation-Fukuyama Cross-coupling of 1,1-Biszincioalkane Linchpins », Chemistry – A European Journal, vol. n/a, nᵒ n/a, p. e202301084, 2023.
    Résumé : 1,1-Bis(iodozincio)alkanes are used as dinucleophilic linchpins in an enantioselective double cross-coupling reaction sequence involving aryl iodides and then thioesters. The two catalytic C−C bond-forming reactions are achieved in the same pot through two distinct palladium-based catalytic systems: a first non-enantioselective one delivering configurationally labile secondary benzylzinc species from an achiral precursor, and a second enantioconvergent one that operates a highly efficient dynamic kinetic resolution of the racemic intermediates. This strategy, new in the area of asymmetric synthesis through two consecutive electrophilic substitution reactions of geminated C(sp3)-organodimetallics, provides useful methodology to access in a modular fashion acyclic α-disubstituted ketone products with very high enantiomeric purity.
    Mots-clés : bimetallics, cross-coupling, enantioselectivity, POLE 1, ROCS, tandem reactions, zinc.

  • M. Barbazanges, Y. Gimbert, et L. Fensterbank, « Gold-Catalyzed Addition of Propargyl Acetates to Olefins via O-Acyl Migration/Cyclopropanation Sequence: Insight into the Diastereoselective Formation of the Alkene », The Journal of Organic Chemistry, vol. 88, nᵒ 5, p. 3297-3302, mars 2023.
    Résumé : This article discloses a study on the well-known addition of propargyl acetates to olefins via an O-acyl migration/cyclopropanation sequence. Herein, we show that the stereochemical outcome of the olefin is strongly dependent on the gold catalyst and reaction parameters (concentration, temperature, and alkene partner equivalents); the E- and Z-isomers can be selectively formed by the judicious choice of reaction conditions.
    Mots-clés : CSOB, MACO, POLE 1, POLE 3.

  • A. Beghennou, G. Gontard, H. Dossmann, K. Passador, S. Thorimbert, V. Corcé, et C. Botuha, « 1,6-Naphthyridin-7(6H)-ones: synthesis and optical properties », Organic & Biomolecular Chemistry, vol. 21, p. 2976-2982, mars 2023.
    Résumé : Efficient synthesis of original 1,6-naphthyridin-7(6H)-ones and their optical properties are described. Their powerful fluorescence properties including dual fluorescence, solvatochromism, acidochromism, large Stokes shifts and high quantum yields, suitable for biological applications or as luminescent devices in materials science, are evidenced.
    Mots-clés : CHEMBIO, CSOB, POLE 3.

  • C. C. Bories, G. Gontard, M. Barbazanges, E. Derat, et M. Petit, « Hydrido-Cobalt Complexes for the Chemo- and Regioselective 1,2-Silylative Dearomatization of N-Heteroarenes », Organic Letters, vol. 25, nᵒ 5, p. 843-848, févr. 2023.
    Résumé : We describe an efficient regio- and chemoselective dearomatization of N-heteroarenes using hydrido-cobalt catalysts. Reactions were performed under mild conditions on a wide range of N-heteroarenes leading exclusively to the silyl-1,2-dihydroheteroarene. Various quinolines and pyridines bearing electron-donating and electron-withdrawing substituents are compatible with this methodology. DFT calculations, NMR spectroscopic studies, and X-ray diffraction analysis underlined the importance of a second silane for the final step of the reaction.
    Mots-clés : MACO, POLE 1.

  • C. Debrie, N. Coudert, J. - M. Guigner, T. Nicolai, F. Stoffelbach, O. Colombani, et J. Rieger, « Unimer Exchange Is not Necessary for Morphological Transitions in Polymerization-Induced Self-Assembly », Angewandte Chemie International Edition, vol. 62, nᵒ 8, p. e202215134, 2023.
    Résumé : Polymerization-induced self-assembly (PISA) has established itself as a powerful and straightforward method to produce polymeric nano-objects of various morphologies in (aqueous) solution. Generally, spheres are formed in the early stages of polymerization that may evolve to higher order morphologies (worms or vesicles), as the solvophobic block grows during polymerization. Hitherto, the mechanisms involved in these morphological transitions during PISA are still not well understood. Combining a systematic study of a representative PISA system with rheological measurements, we demonstrate that—unexpectedly—unimer exchange is not necessary to form higher order morphologies during radical RAFT-mediated PISA. Instead, in the investigated aqueous PISA, the monomer present in the polymerization medium is responsible for the morphological transitions, even though it slows down unimer exchange.
    Mots-clés : Block Copolymers, Micelles, PISA, POLYMERES, Rheology, Vesicles.

  • G. Delecourt, L. Plet, Y. L. Guen, O. Tezgel, G. Tresset, P. Midoux, T. Montier, V. Bennevault, et P. Guégan, « Synthesis of Double Hydrophilic Block Copolymers Poly(2-isopropyl-2-oxazoline-b-ethylenimine) and their DNA Transfection Efficiency », Macromolecular Bioscience, vol. 23, nᵒ 1, p. 2200296, 2023.
    Résumé : Gene delivery is now a part of the therapeutic

    arsenal for vaccination and treatments of inherited or acquired diseases. Polymers represent an opportunity to develop new synthetic vectors for gene transfer, with a prerequisite of improved delivery and reduced toxicity compared to existing polymers. Here, the synthesis in a two-step's procedure of linear poly(ethylenimine-b-2-isopropyl-2-oxazoline) block copolymers with the linear polyethylenimine (lPEI) block of various molar masses is reported; the molar mass of the poly(2-isopropyl-2-oxazoline) (PiPrOx) block has been set to 7 kg mol−1. Plasmid DNA condensation is successfully achieved, and in vitro transfection efficiency of the copolymers is at least comparable to that obtained with the lPEI of same molar mass. lPEI-b-PiPrOx block copolymers are however less cytotoxic than their linear counterparts. PiPrOx can be a good alternative to PEG which is often used in drug delivery systems. The grafting of histidine moieties on the lPEI block of lPEI-b-PiPrOx does not provide any real improvement of the transfection efficiency. A weak DNA condensation is observed, due to increased steric hindrance along the lPEI backbone. The low cytotoxicity of lPEI-b-PiPrOx makes this family a good candidate for future gene delivery developments.
    Mots-clés : gene therapy, oxazoline, PEGylation alternative, PEI, POLYMERES.

  • J. Glatz, M. Donnart, G. Gontard, Y. Li, et R. Lescouëzec, « Design of Redox-Active Cs⊂{Fe4Ni4} Cyanide-Bridged Cage Complexes Bearing Monodentate Ligands: Synthesis, Structure, and Electronic Properties », Crystal Growth & Design, vol. 23, nᵒ 3, p. 1709-1717, mars 2023.
    Résumé : In recent years, strong efforts have been devoted to the design and crystallization of molecular models of the cyanido-bridged inorganic polymers known as “Prussian Blue Analogues” (PBA). In this work, we more specifically focus on soluble octametallic complexes that represent an elemental unit of the PBA cubic network. The self-assembly of tris-cyanido, the fac-[FeIII(Tp)(CN)3]− (Tp = hydro-tris(pyrazol-1-yl-borate) complex, and Ni(II) salts is shown to lead to {[Fe(Tp)(CN)3]4[Ni(S)3]4} procubes, where the Ni(II) ions are coordinated to labile solvent molecules (S: DMF or CH3CN). 1H and 133Cs paramagnetic NMR studies show that (i) the cubic complex is relatively stable during several days in solution, in particular in acetonitrile and (ii) a Cs+ ion can be inserted inside the cubic cavity as revealed by the presence of a strongly shifted 133Cs paramagnetic signal near −800 ppm at 300 K. The resulting Cs⊂{[Fe(Tp)(CN)3]4[Ni(S)3]4}5+ procube shows an enhanced stability as shown by time dependent 1H and 133Cs paramagnetic NMR spectra collected during several weeks. FT-IR spectra confirm the expected Fe(III) and Ni(II) redox states, with the occurrence of a single characteristic cyanide stretching vibration near 2170 cm–1. The Fe(III) redox state is also confirmed by cyclic voltammetry experiments in acetonitrile, with the occurrence of four pseudoreversible reduction events that can be assigned to the successive reduction of the FeIII ions in the Cs procube. Although these procubes could not be isolated as single crystals, the substitution of the labile coordinated solvent of the Cs-containing procube by N-donor imidazole monodentate ligands allows the crystallization of the novel Cs⊂{[Fe(Tp)(CN)3]4-[NiII(Im)3]4}Cl3 (Im = 1H imidazole) cubic complex by slow diffusion of ether into a DMF mother solution. The analyses of this cube demonstrate that in solution in ambient condition, Fe(III) centers are gradually reduced to Fe(II). The presence of three chlorides as counterions suggests that the cube can be isolated in the FeII2FeIII2NiII4 redox state. The presence of at least two Fe(II) ions is actually confirmed by cyclic voltammetry experiment in DMF and FT-IR spectroscopy. An intermediate state FeIIFeIII3NiII4 can be isolated by isolating fresh crystals (ca. 72 h) as demonstrated by FT-IR, cyclic voltammetry, and the magnetic measurements, that also reveal the presence of paramagnetic ferromagnetic interactions between the low-spin FeIII and NiII ions.
    Mots-clés : ERMMES, POLE 2.

  • P. Idlas, E. Lepeltier, G. Bastiat, P. Pigeon, M. J. McGlinchey, N. Lautram, A. Vessières, G. Jaouen, et C. Passirani, « Physicochemical Characterization of Ferrocifen Lipid Nanocapsules: Customized Drug Delivery Systems Guided by the Molecular Structure », Langmuir, vol. 39, nᵒ 5, p. 1885-1896, janv. 2023.
    Résumé : Ferrocifens, lipophilic organometallic complexes, comprise a biologically active redox motif [ferrocenyl-ene-p-phenol] which confers very interesting cytotoxic properties to this family. However, because of their highly lipophilic nature, a formulation stage is required before being administered in vivo. In recent decades, ferrocifen lipid nanocapsules (LNCs) have been successfully formulated and have demonstrated anticancer activity on multidrug-resistant cancers in several mice and rat models (glioblastoma, breast cancer, and metastatic melanoma). A recent family of ferrocifens (succinimidoalkyl-ferrociphenols, including P722) appears to be most efficacious on several resistant cancer cell lines, with IC50 values in the nanomolar range together with promising in vivo results on murine ovarian cancer models. As LNCs are composed of an oily core (caprylic/capric triglycerides), modulation of the succinimido-ferrociphenol lipophilicity could be a valuable approach toward improving the drug loading in LNCs. As the drug loading of the diphenol P722 in LNCs was low, it was structurally modified to increase its lipophilicity and thereby the payload in LNCs. Chemical modification led to a series of five succinimido-ferrocifens. Results confirmed that these slight structural modifications led to increased drug loading in LNCs for all ferrocifens, with no reduction of their cytotoxicity on the SKOV3 ovarian cancer cell line. Interestingly, encapsulation of two of the ferrocifens, diester P769 and monophenolic ester (E)-P998, led to the formation of a gel. This was unprecedented behavior, a phenomenon that could be rationalized in terms of the positioning of ferrocifens in LNCs as shown by the decrease of interfacial tension measurements at the water/oil interface. Moreover, these results highlighted the importance of obtaining a gel of this particular motif, in which the acetylated phenolic ring and the succinimidoalkyl moieties are mutually cis relative to the central double bond. Promising perspectives to use these ferrocifen-loaded LNCs to treat glioblastoma could be readily envisaged by local application of the gel in the cavity after tumor resection.
    Mots-clés : CHEMBIO, POLE 3.

  • S. Kassamba, M. Reboli, A. Perez-Luna, F. Ferreira, et M. Durandetti, « Synthesis of 6-membered germacycles by intramolecular germylzincation of alkynes », Organic Chemistry Frontiers, juin 2023.
    Résumé : Intramolecular addition of Ge–H bonds across internal alkynes was performed in excellent yields (from 78 to 94% according to the structures) for the first time in one operation with high regio- and stereoselectivities. The key step consists in intramolecular germylzincation of arylgermane cores bearing C–C triple bonds. We first studied the reactivity of dialkylzincs towards Ge–H bonds using hexane as solvent at 80 °C. The E configuration of the products suggested that the reaction proceeds following a syn addition to the alkyne. Tetrasubstituted vinylgermanes can be obtained in one pot, with retention of the C–C double bond geometry, through Cu-catalyzed electrophilic substitution of the C(sp2)–Zn bond of the vinylzinc intermediates. In contrast, when the reaction was performed under radical conditions (AIBN), the Z isomer were obtained, and no further cross-coupling occurred.
    Mots-clés : POLE 1, ROCS.

  • G. K. Kinkutu, C. Louis, M. Roy, J. Blanchard, et J. Oble, « C3-Alkylation of furfural derivatives by continuous flow homogeneous catalysis », Beilstein Journal of Organic Chemistry, vol. 19, nᵒ 1, p. 582-592, mai 2023.
    Résumé : Beilstein Journal of Organic Chemistry
    Mots-clés : Pole 1, ROCS.

  • E. Liu, S. Cherraben, L. Boulo, C. Troufflard, B. Hasenknopf, G. Vives, et M. Sollogoub, « A molecular information ratchet using a cone-shaped macrocycle », Chem, p. S245192942200660X, 2023.

  • H. Madec, F. Figueiredo, K. Cariou, S. Roland, M. Sollogoub, et G. Gasser, « Metal complexes for catalytic and photocatalytic reactions in living cells and organisms », Chemical Science, vol. 14, nᵒ 3, p. 409-442, 2023.
    Résumé : This review presents discrete metal complexes that catalyse or photocatalyse reactions within living cells or living organisms. , The development of organometallic catalysis has greatly expanded the synthetic chemist toolbox compared to only exploiting “classical” organic chemistry. Although more widely used in organic solvents, metal-based catalysts have also emerged as efficient tools for developing organic transformations in water, thus paving the way for further development of bio-compatible reactions. However, performing metal-catalysed reactions within living cells or organisms induces additional constraints to the design of reactions and catalysts. In particular, metal complexes must exhibit good efficiency in complex aqueous media at low concentrations, good cell specificity, good cellular uptake and low toxicity. In this review, we focus on the presentation of discrete metal complexes that catalyse or photocatalyse reactions within living cells or living organisms. We describe the different reaction designs that have proved to be successful under these conditions, which involve very few metals (Ir, Pd, Ru, Pt, Cu, Au, and Fe) and range from in cellulo deprotection/decaging/activation of fluorophores, drugs, proteins and DNA to in cellulo synthesis of active molecules, and protein and organelle labelling. We also present developments in bio-compatible photo-activatable catalysts, which represent a very recent emerging area of research and some prospects in the field.
    Mots-clés : GOBS, POLE 3.

  • A. Mamontov, L. Chang, H. Dossmann, B. Bertrand, L. Dechoux, et S. Thorimbert, « Iron Catalyzed Dearomatization of Pyridines into Annelated Azepine Derivatives in a One-Step, Three-Component Reaction », Organic Letters, vol. 25, nᵒ 1, p. 256-260, 2023.
    Résumé : Commercially available Fe(TTP)Cl catalyzes three-component dearomative formal cycloaddition reactions between pyridines, diazo compounds, and coumalates. Diversely substituted annelated seven-membered N-heterocycles could be generated in less than 10 min in one step at room temperature. The reaction is compatible to gram scale. The extension to benzimidazoles in place of pyridines has been successfully demonstrated. The mechanism of this reaction has been carefully examined by computational studies that corroborate the observed regioselectivities.
    Mots-clés : CHEMBIO, CSOB, POLE 3.

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  • A. Mascherpa, N. Ishii, A. Tayagui, J. Liu, M. Sollogoub, et A. J. Fairbanks, « Lysosomal Targeting of β‐Cyclodextrin », Chemistry – A European Journal, vol. 29, nᵒ 4, p. e202203252, janv. 2023.

  • V. Pellas, F. Sallem, J. Blanchard, A. Miche, S. M. Concheso, C. Méthivier, M. Salmain, et S. Boujday, « Silica-coated gold nanorods biofunctionalization for localized surface plasmon resonance (LSPR) biosensing », Talanta, vol. 255, p. 124245, avr. 2023.
    Résumé : We introduce here the engineering of nanobiosensors designed from gold nanorods coated with an ultrathin layer of silica (AuNR@SiO2) and biofunctionalized with antibodies for the Localized Surface Plasmon Resonance (LSPR) biosensing of proteins. Despite the outstanding properties of AuNRs, their use for LSPR biosensing is limited due to the presence of the surfactant cetyltrimethylammonium bromide (CTAB) – mandatory for their synthesis - which forms a strongly-bounded and positively-charged bilayer at their surface and significantly complicates their bio-functionalization. When coated with a thin layer of silica, these nanomaterials exhibit an improved sensitivity to refractive index change which augurs for better analytical performances. Here, we undertook an in-depth investigation of the biofunctionalization of AuNR@SiO2 via three different routes to design and test a label-free LSPR biosensor operating in solution. In the first route, we took advantage of the negatively charged external silica shell to immobilize anti-rabbit IgG antibody by electrostatic physisorption. In the second and third routes, the silica surface was reacted with thiol or aldehyde terminated silanes, subsequently utilized to covalently attach anti-rabbit IgG antibody to the surface. The resulting nanoprobes were characterized by a wide range of physical methods (TEM, XPS, DLS, ELS and UV-Visible spectroscopy) then tested for the biosensing of rabbit-IgG. The three nanobiosensors maintain an excellent colloidal stability after analyte recognition and exhibit extremely high analytical performances in terms of specificity and dynamic range, with an LoD down to 12 ng/mL.
    Mots-clés : CHEMBIO, Core−Shell, Gold nanorods, Immunosensing, LSPR, POLE 3, Silica coating, Surface chemistry.

  • A. Vessières et M. J. McGlinchey, « Bioorganometallic chemistry – the early years », Journal of Organometallic Chemistry, vol. 987-988, p. 122623, avr. 2023.
    Résumé : Bioorganometallic chemistry is now a maturing field attracting researchers around the world, and also across the Periodic Table. It has found applications in a broad range of areas such as drug discovery, biocatalysis and imaging. We review here the first experiments carried out in the early 1980′s at the Ecole Nationale Supérieure de Chimie de Paris under the leadership of Gérard Jaouen, a key figure and visionary in the development of this theme. However, they also required important contributions from Canadian collaborators with expertise in NMR and IR spectroscopy, together with the availability of more powerful and versatile instrumentation. This collaboration found its fulfillment in the demonstration of the use of metal carbonyl complexes (exemplified by an estradiol derivative labeled by a Cr(CO)3 unit) as non-isotopic tracers allowing the detection of estradiol receptors, an essential marker for setting up a targeted therapy for breast cancer. This approach was based on the premise that the intense metal carbonyl stretching vibrations are found in a window (2100–1850 cm−1) where the protein itself does not absorb. The field was extended to the arena of non-isotopic immunoassays, including the simultaneous detection of multiple antiepileptic drugs bearing metal carbonyl labels. More recently, taking advantage of the new technique of atomic force microscopy-infrared spectroscopy (AFM-IR) it has been possible to accomplish direct tracing of these complexes in cells. The contributions of the original group of workers in the field are highlighted, and placed in the perspective of today's subsequent emphasis on the management of previously untreatable cancers.
    Mots-clés : 2D NMR, CHEMBIO, Estrogen receptor, FT-IR spectroscopy, Immunoassay, Metal carbonyls, Organometallic tracers, POLE 3.

  • J. Yang, V. Giuso, M. - C. Hou, E. Remadna, J. Forté, H. - C. Su, C. Gourlaouen, M. Mauro, et B. Bertrand, « Biphenyl Au(III) Complexes with Phosphine Ancillary Ligands: Synthesis, Optical Properties, and Electroluminescence in Light-Emitting Electrochemical Cells », Inorganic Chemistry, mars 2023.
    Résumé : A series of ten cationic complexes of the general formula [(C^C)Au(P^P)]X, where C^C = 4,4′-di-tert-butyl-1,1′-biphenyl, P^P is a diphosphine ligand, and X is a noncoordinating counteranion, have been synthesized and fully characterized by means of chemical and X-ray structural methods. All the complexes display a remarkable switch-on of the emission properties when going from a fluid solution to a solid state. In the latter, long-lived emission with lifetime τ = 1.8–83.0 μs and maximum in the green-yellow region is achieved with moderate to high photoluminescence quantum yield (PLQY). This emission is ascribed to an excited state with a mainly triplet ligand-centered (3LC) nature. This effect strongly indicates that rigidification of the environment helps to suppress nonradiative decay, which is mainly attributed to the large molecular distortion in the excited state, as supported by density functional theory (DFT) and time-dependent DFT (TD-DFT) computation. In addition, quenching intermolecular interactions of the emitter are avoided thanks to the steric hindrance of the substituents. Emissive properties are therefore restored efficiently. The influence of both diphosphine and anion has been investigated and rationalized as well. Using two complexes as examples and owing to their enhanced optical properties in the solid state, the first proof-of-concept of the use of gold(III) complexes as electroactive materials for the fabrication of light-emitting electrochemical cell (LEC) devices is herein demonstrated. The LECs achieve peak external quantum efficiency, current efficiency, and power efficiency up to ca. 1%, 2.6 cd A–1, and 1.1 lm W–1 for complex 1PF6 and 0.9%, 2.5 cd A–1, and 0.7 lm W–1 for complex 3, showing the potential use of these novel emitters as electroactive compounds in LEC devices.
    Mots-clés : CHEMBIO, POLE 3.
  • 2022

    • « Boron, silicon, nitrogen and sulfur-based contemporary precursors for the generation of alkyl radicals by single electron transfer and their synthetic utilization - Chemical Society Reviews (RSC Publishing) », 2022. [Online]. Available: [Accessed: 31-janv.-2023].
      Mots-clés : CHEMBIO, MACO, POLE 1, POLE 3.

    • P. Aoun, A. Hammoud, M. A. Martínez-Aguirre, L. Bouteiller, et M. Raynal, « Asymmetric hydroamination with far fewer chiral species than copper centers achieved by tuning the structure of supramolecular helical catalysts », Catalysis Science & Technology, vol. 12, nᵒ 3, p. 834-842, févr. 2022.
      Résumé : The incorporation of a few chiral monomers (the “sergeants”) in a backbone composed of a majority of achiral monomers (the “soldiers”) is a well-established strategy to control the handedness of helical polymers. However, the implementation of this “sergeants-and-soldiers” effect in asymmetric catalysis is still at its infancy, with only limited examples for which the sergeant amount is actually in lower amount than the (metal) catalytic unit. Herein, supramolecular co-polymers composed of a benzene-1,3,5-tricarboxamide (BTA) phosphine soldier and a catalytically-inactive BTA sergeant were evaluated in the copper-catalysed hydroamination of styrene. Screening of various BTA ligands revealed the marked influence of substituents on the aryl group of the BTA phosphine ligand, the 3,5-bis-CF3-substituted ligand providing the highest rate and enantioselectivity. Thorough optimization of the reaction parameters led to a robust protocol for the generation of the amine product in high yield (82 ± 4%) and moderate e.e. (68 ± 6%). Addition of an achiral BTA additive was found to be beneficial for improving the yield (80–99%), enantioselectivity (up to 81% e.e.) and “sergeants-and-soldiers” effect displayed by the supramolecular helical catalyst. Consequently, an enantio-enriched product (75% e.e.) was afforded with as low as 0.51 mol% of sergeant in the catalytic mixture, i.e. one chiral molecule for 10 copper centers.
      Mots-clés : POLYMERES.

    • E. Atrián-Blasco, L. de Cremoux, X. Lin, R. Mitchell-Heggs, L. Sabater, S. Blanchard, et C. Hureau, « Keggin-type polyoxometalates as Cu( <span style="font-variant:small-caps;">ii</span> ) chelators in the context of Alzheimer's disease », Chemical Communications, vol. 58, nᵒ 14, p. 2367-2370, 2022.
      Résumé : Keggin-type POMs extract Cu( ii ) from the Alzheimer's-related amyloid-β peptide. They prevent Cu(Aβ) ROS production, while ill-defined Cu(Aβ) aggregates are switched to fibrils due to Cu(POM) modulation of the apo-Aβ's assembly. , Two Keggin polyoxometalates were used as new copper ligands to counteract the effects of Cu II (Amyloid-β) interaction. Their ability to remove Cu II from Cu II (Amyloid-β), to stop Cu II (Amyloid-β) induced formation of reactive oxygen species and to restore apo-like self-assembly of Cu II (Amyloid-β) was shown.
      Mots-clés : E-POM, POLE 2.

    • X. Bai, A. Al

      i, N. Wang, Z. Liu, Z. Lv, Z. Zhang, X. Zhao, H. Hao, Y. Zhang, et F. - U. Rahman, « Inhibition of SREBP-mediated lipid biosynthesis and activation of multiple anticancer mechanisms by platinum complexes: Ascribe possibilities of new antitumor strategies », European Journal of Medicinal Chemistry, vol. 227, p. 113920, 2022.

    • M. Balas, R. Villanneau, et F. Launay, « Bibliographic survey of the strategies implemented for the one-pot synthesis of cyclic carbonates from styrene and other alkenes using CO2 and green oxidants », Journal of CO2 Utilization, vol. 65, p. 102215, 2022.

    • S. Bassoli, A. Schallmey, J. Oble, G. Poli, et A. Pradal, « Short Hydroacylation-Based Synthesis of Four Aryl-3-hydroxypropanones, Predictable Biomass-Derived C9 Platform Molecules », Catalysis Research, vol. 02, nᵒ 04, p. 036, oct. 2022.
      Résumé : A two-step protocol for the synthesis of aryl-3-hydroxypropanones, which were regarded as lignin degradation products, was proposed herein. This protocol provided a more rapid and easier access to aryl-3-hydroxypropanones, and aryl-3-hydroxypropanones were expected to be ideal platform molecules for the synthesis of more complex value-added targets.
      Mots-clés : POLE 1, ROCS.

    • P. Bayat, D. Gatineau, D. Lesage, A. Martinez, et R. B. Cole, « Benchmarking higher energy collision dissociation (HCD) by investigation of binding energies of gas‐phase host–guest complexes of hemicryptophane cages », Journal of Mass Spectrometry, vol. 57, nᵒ 9, p. e4879, 2022.

    • K. A. Bhullar, M. I. M. Horgan, A. Le, D. Fania, R. Wuhrer, V. Razmovski-Naumovski, K. Chan, P. Castignolles, et M. Gaborieau, « Assessing the quantification of acetylation in konjac glucomannan via ATR-FTIR and solid-state NMR spectroscopy », Carbohydrate Polymers, vol. 291, p. 119659, sept. 2022.
      Résumé : Dietary fiber like konjac glucomannan (KGM) is important in maintaining good human health. There is no established method for quantifying the average degree of acetylation DA of this polysaccharide. Polysaccharides are notoriously difficult to dissolve. In this study, KGM could not be fully dissolved in common solvents and was characterized in the solid state. ATR-FTIR spectroscopy enabled a fast qualitative assessment of acetylation, selective to the outer layer of KGM particles, and identifying excipients like magnesium stearate. Average DA was quantified for the first time with solid-state 13C NMR in KGM: semi-quantitative measurements on the same arbitrary scale by cross polarization (1 to 2 days) were calibrated with a few longer single-pulse excitation measurements (approximately 1 week). DA values ranged from 4 to 8% of the hexoses in the backbone, in agreement with previously reported values. This method could be used for quality control and standardization of KGM products.
      Mots-clés : ATR-FTIR spectroscopy, Degree of acetylation, Konjac glucomannan, pole 4, POLYMERES, Quantification, Solid-state NMR spectroscopy, Solubility.

    • F. Bigi, D. Cauzzi, N. Della Ca’, M. Malacria, R. Maggi, E. Motti, Y. Wang, et G. Maestri, « Evolution of Triangular All-Metal Aromatic Complexes from Bonding Quandaries to Powerful Catalytic Platforms », ACS Organic & Inorganic Au, vol. 2, nᵒ 5, p. 373-385, oct. 2022.
      Résumé : This manuscript describes an overview on the literature detailing the observation of trinuclear complexes that present delocalized metal–metal bonds similar to those of regular aromatics, which are formed combining main group elements. A particular emphasis is given to the structural and electronic features of aromatic clusters that are sufficiently stable to allow their isolation. In parallel to the description of their key bonding properties, the work presents reported catalytic applications of these complexes, which already span from elaborated C–C-forming cascades to highly efficient cross-coupling methods. These examples present peculiar aspects of the unique reactivity exerted by all-metal aromatic complexes, which can often be superior to their established, popular mononuclear peers in terms of chemoselectivity and chemical robustness.
      Mots-clés : MACO, POLE 1.

    • F. Bouihi, B. Schmaltz, F. Mathevet, D. Kreher, J. Faure-Vincent, C. Yildirim, A. Elhakmaoui, J. Bouclé, M. Akssira, F. Tran-Van, et M. Abarbri, « D-π-A-Type Pyrazolo[1,5-a]pyrimidine-Based Hole-Transporting Materials for Perovskite Solar Cells: Effect of the Functionalization Position », Materials, vol. 15, nᵒ 22, p. 7992, janv. 2022.
      Résumé : Donor–acceptor (D–A) small molecules are regarded as promising hole-transporting materials for perovskite solar cells (PSCs) due to their tunable optoelectronic properties. This paper reports the design, synthesis and characterization of three novel isomeric D-π-A small molecules PY1, PY2 and PY3. The chemical structures of the molecules consist of a pyrazolo[1,5-a]pyrimidine acceptor core functionalized with one 3,6-bis(4,4′-dimethoxydiphenylamino)carbazole (3,6-CzDMPA) donor moiety via a phenyl π-spacer at the 3, 5 and 7 positions, respectively. The isolated compounds possess suitable energy levels, sufficient thermal stability (Td > 400 °C), molecular glass behavior with Tg values in the range of 127–136 °C slightly higher than that of the reference material Spiro-OMeTAD (126 °C) and acceptable hydrophobicity. Undoped PY1 demonstrates the highest hole mobility (3 × 10−6 cm2 V−1 s−1) compared to PY2 and PY3 (1.3 × 10−6 cm2 V−1 s−1). The whole isomers were incorporated as doped HTMs in planar n-i-p PSCs based on double cation perovskite FA0.85Cs0.15Pb(I0.85Br0.15)3. The non-optimized device fabricated using PY1 exhibited a power conversion efficiency (PCE) of 12.41%, similar to that obtained using the reference, Spiro-OMeTAD, which demonstrated a maximum PCE of 12.58% under the same conditions. The PY2 and PY3 materials demonstrated slightly lower performance in device configuration, with relatively moderate PCEs of 10.21% and 10.82%, respectively, and slight hysteresis behavior (−0.01 and 0.02). The preliminary stability testing of PSCs is also described. The PY1-based device exhibited better stability than the device using Spiro-OMeTAD, which could be related to its slightly superior hydrophobic character preventing water diffusion into the perovskite layer.
      Mots-clés : 3, 5-a]pyrimidine, 6-CzDMPA, D-π-A, hole-transporting materials, perovskite solar cells, POLYMERES, pyrazolo[1.

    • N. A. Burger, G. Meier, L. Bouteiller, B. Loppinet, et D. Vlassopoulos, « Dynamics and Rheology of Supramolecular Assemblies at Elevated Pressures », The Journal of Physical Chemistry B, vol. 126, nᵒ 35, p. 6713-6724, sept. 2022.
      Résumé : A methodology to investigate the linear viscoelastic properties of complex fluids at elevated pressures (up to 120 MPa) is presented. It is based on a dynamic light scattering (DLS) setup coupled with a stainless steel chamber, where the test sample is pressurized by means of an inert gas. The viscoelastic spectra are extracted through passive microrheology. We discuss an application to hydrogen-bonding motif 2,4-bis(2-ethylhexylureido)toluene (EHUT), which self-assembles into supramolecular structures (tubes and filaments) in apolar solvents dodecane and cyclohexane. High levels of pressure (roughly above 20 MPa) are found to slow down the terminal relaxation process; however, the increases in the entanglement plateau modulus and the associated persistence length are not significant. The concentration dependence of the plateau modulus, relaxation times (fast and slow), and correlation length is practically the same for all pressures and exhibits distinct power-law behavior in different regimes. Within the tube phase in dodecane, the relative viscosity increment is weakly enhanced with increasing pressure and reaches a plateau at about 60 MPa. In fact, depending on concentration, the application of pressure in the tube regime may lead to a transition from a viscous (unentangled) to a viscoelastic (partially entangled to well-entangled) solution. For well-entangled, long tubes, the extent of the plateau regime (ratio of high- to low-moduli crossover frequencies) increases with pressure. The collective information from these observations is summarized in a temperature–pressure state diagram. These findings provide ingredients for the formulation of a solid theoretical framework to better understand and exploit the role of pressure in the structure and dynamics of supramolecular polymers.
      Mots-clés : POLYMERES.

    • N. A. Burger, G. Pembouong, L. Bouteiller, D. Vlassopoulos, et B. Loppinet, « Complete Dynamic Phase Diagram of a Supramolecular Polymer », Macromolecules, vol. 55, nᵒ 7, p. 2609-2614, avr. 2022.
      Résumé : We revisit the equilibrium phase diagram of the much-studied model supramolecular polymer, 2,4-bis(2-ethylhexylureido)toluene (EHUT) in nonpolar solvents and provide unambiguous evidence of a much richer behavior, characterized by four distinct regimes. Typically, two types of self-assembled structures are formed: tubes (filaments) at higher (lower) concentrations and lower (higher) temperatures. The tube structure forms viscoelastic solutions that had been characterized by rheology, however, without detailed analysis of the experimental signals. Here, we combine rheology and microrheology to establish the complete dynamic phase diagram of EHUT in dodecane. It still comprises two structures, tubes and filaments, with the transition temperature being almost constant over the examined wide concentration range, as confirmed with the help of complementary differential scanning calorimetry measurements. The tubes are found to exist in three dynamic states with increasing concentration, unentangled, partially entangled, and well entangled, which are separated by isolength lines. We present criteria for unambiguously identifying these phases and discuss their distinct concentration and temperature dependencies. The new, complete phase diagram may serve as a guide for investigating other supramolecular polymers with tunable rheology and, more importantly, providing insights into a universal description of one-dimensional self-assembled structures by linking this class of materials with the classic wormlike surfactant micelles, for which the partially and well-entangled regimes were recently elucidated.
      Mots-clés : POLYMERES.

    • A. I. Carbajo‐Gordillo, J. López‐Fernández, J. M. Benito, J. L. Jiménez Blanco, M. L. Santana‐Armas, G. Marcelo, C. Di Giorgio, C. Przybylski, C. Ortiz Mellet, C. Tros de Ilarduya, F. Mendicuti, et J. M. García Fernández, « Enhanced Gene Delivery Triggered by Dual pH/Redox Responsive Host‐Guest Dimerization of Cyclooligosaccharide Star Polycations », Macromolecular Rapid Communications, vol. 43, nᵒ 11, p. 2200145, 2022.

    • F. Célerse, T. J. Inizan, L. Lagardère, O. Adjoua, P. Monmarché, Y. Miao, E. Derat, et J. - P. Piquemal, « An Efficient Gaussian-Accelerated Molecular Dynamics (GaMD) Multilevel Enhanced Sampling Strategy: Application to Polarizable Force Fields Simulations of Large Biological Systems », Journal of Chemical Theory and Computation, vol. 18, nᵒ 2, p. 968-977, févr. 2022.
      Résumé : We introduce a novel multilevel enhanced sampling strategy grounded on Gaussian-accelerated Molecular Dynamics (GaMD). First, we propose a GaMD multi-GPUs-accelerated implementation within the Tinker-HP molecular dynamics package. We introduce the new “dual-water” mode and its use with the flexible AMOEBA polarizable force field. By adding harmonic boosts to the water stretching and bonding terms, it accelerates the solvent–solute interactions while enabling speedups, thanks to the use of fast multiple–time step integrators. To further reduce the time-to-solution, we couple GaMD to Umbrella Sampling (US). The GaMD─US/dual-water approach is tested on the 1D Potential of Mean Force (PMF) of the solvated CD2–CD58 system (168 000 atoms), allowing the AMOEBA PMF to converge within 1 kcal/mol of the experimental value. Finally, Adaptive Sampling (AS) is added, enabling AS–GaMD capabilities but also the introduction of the new Adaptive Sampling–US–GaMD (ASUS–GaMD) scheme. The highly parallel ASUS–GaMD setup decreases time to convergence by, respectively, 10 and 20 times, compared to GaMD–US and US. Overall, beside the acceleration of PMF computations, Tinker-HP now allows for the simultaneous use of Adaptive Sampling and GaMD-”dual water” enhanced sampling approaches increasing the applicability of polarizable force fields to large-scale simulations of biological systems.
      Mots-clés : MACO, POLE 1.

    • L. Chazot-Franguiadakis, J. Eid, M. Socol, B. Molcrette, P. Guégan, M. Mougel, A. Salvetti, et F. Montel, « Optical Quantification by Nanopores of Viruses, Extracellular Vesicles, and Nanoparticles », Nano Letters, vol. 22, nᵒ 9, p. 3651-3658, mai 2022.
      Résumé : Nanopores combined with optical approaches can be used to detect viral particles. In this work, we demonstrate the ability of hydrodynamical driving and optical sensing to identify and quantify viral particles in a biological sample. We have developed a simple and rapid method which requires only fluorescent labeling of the particles and can therefore be applied to a wide range of virus type. The system operates in real time and at the single particle level while providing a low error on concentration (4%) and a low limit of detection of 105 particles/mL for an acquisition time of 60 s with the ability to increase the acquisition time to achieve a lower limit.
      Mots-clés : POLYMERES.

    • Y. Chen, X. Wang, X. Ma, S. Liang, Q. Gao, E. V. Tretyakova, Y. Zhang, D. Zhou, et S. Xiao, « Facial Synthesis and Bioevaluation of Well-Defined OEGylated Betulinic Acid-Cyclodextrin Conjugates for Inhibition of Influenza Infection », Molecules, vol. 27, nᵒ 4, p. 1163, févr. 2022.
      Résumé : Betulinic acid (BA) and its derivatives exhibit a variety of biological activities, especially their anti-HIV-1 activity, but generally have only modest inhibitory potency against influenza virus. The entry of influenza virus into host cells can be competitively inhibited by multivalent derivatives targeting hemagglutinin. In this study, a series of hexa-, hepta- and octavalent BA derivatives based on α-, β- and γ-cyclodextrin scaffolds, respectively, with varying lengths of flexible oligo(ethylene glycol) linkers was designed and synthesized using a microwave-assisted copper-catalyzed 1,3-dipolar cycloaddition reaction. The generated BA-cyclodextrin conjugates were tested for their in vitro activity against influenza A/WSN/33 (H1N1) virus and cytotoxicity. Among the tested compounds, 58, 80 and 82 showed slight cytotoxicity to Madin-Darby canine kidney cells with viabilities ranging from 64 to 68% at a high concentration of 100 μM. Four conjugates 51 and 69–71 showed significant inhibitory effects on influenza infection with half maximal inhibitory concentration values of 5.20, 9.82, 7.48 and 7.59 μM, respectively. The structure-activity relationships of multivalent BA-cyclodextrin conjugates were discussed, highlighting that multivalent BA derivatives may be potential antiviral agents against influenza infection.
      Mots-clés : GOBS, POLE 3.

    • V. Corcé, C. Ollivier, et L. Fensterbank, « Boron, silicon, nitrogen and sulfur-based contemporary precursors for the generation of alkyl radicals by single electron transfer and their synthetic utilization », Chemical Society Reviews, vol. 51, nᵒ 4, p. 1470-1510, févr. 2022.
      Résumé : Recent developments in the use of boron, silicon, nitrogen and sulfur derivatives in single-electron transfer reactions for the generation of alkyl radicals are described. Photoredox catalyzed, electrochemistry promoted or thermally-induced oxidative and reductive processes are discussed highlighting their synthetic scope and discussing their mechanistic pathways.
      Mots-clés : CHEMBIO, MACO, POLE 1, POLE 3.

    • S. Curpanen, G. Poli, A. Perez-Luna, et J. Oble, « C3−H Silylation of Furfurylimines: Direct Access to a Novel Biobased Versatile Synthetic Platform Derived from Furfural », Asian Journal of Organic Chemistry, vol. 11, nᵒ 7, p. e202200199, 2022.
      Résumé : Herein we report directed iridium-catalyzed C3−H silylation of furfuryl imines, which grants access to versatile synthetic platforms. This transformation was developed on furfuryl derivatives, using imines as directing groups, and trialkylsilanes or bis(trimethylsilyl)methylsilane as silylating agents, in the presence of a hydride scavenger. Subsequently, fluoride-mediated activation strategies were applied to the C3−SiMe(OSiMe3)2 furfural derivatives to achieve a wide range of transformations of the C3−Si bond. Arylation, alkenylation, alkynylation, allylation and alkylation, as well as halogenation and trifluoromethylation were achieved in modest to high yields. A variety of high value-added products were thus easily obtained from the same common C3-silylated furfural-based platform.
      Mots-clés : Biomass, Fluoride, Furfural, Iridium, POLE 1, ROCS, Silicon.

    • S. Curpanen, P. Reichert, G. Lupidi, G. Poli, J. Oble, et A. Perez-Luna, « Modular synthesis of 2-furyl carbinols from 3-benzyldimethylsilylfurfural platforms relying on oxygen-assisted C–Si bond functionalization », Beilstein Journal of Organic Chemistry, vol. 18, nᵒ 1, p. 1256-1263, sept. 2022.
      Résumé : Beilstein Journal of Organic Chemistry
      Mots-clés : POLE 1, ROCS.

    • S. De, A. Flambard, B. Xu, L. ‐M. Chamoreau, G. Gontard, L. Lisnard, Y. Li, M. ‐L. Boillot, et R. Lescouëzec, « Molecular Magnetic Materials Based on {Co <sup>III</sup> (Tp*)(CN) <sub>3</sub> } <sup>−</sup> Cyanidometallate: Combined Magnetic, Structural and <sup>59</sup> Co NMR Study », Chemistry – A European Journal, vol. 28, nᵒ 50, p. e202200783, sept. 2022.

    • T. Deis, J. Forte, L. Fensterbank, et G. Lemière, « Synthesis and Reactivity of Martin’s Spirosilane-Derived Chloromethylsilicate », Molecules, vol. 27, nᵒ 6, p. 1767, janv. 2022.
      Résumé : Pentacoordinate silicon derivatives with a chloromethyl ligand are versatile compounds that are usually obtained from the corresponding tetravalent trialkoxy- or trihalogeno(chloromethyl)silane. We describe herein the synthesis of a chloromethylsilicate bearing two Martin’s ligands readily obtained by addition of in situ generated chloromethyllithium to a spirosilane. The reactivity of this new species was evaluated and it has been established that the chloride is displaced by strong nucleophiles such as alkyllithiums and (hetero)aryllithiums. In Lewis acidic conditions, the pentacoordinate silicon species rearranges through a formal insertion of a methylene into one Si–C bond, to form a new tetravalent spirosilane with a six-membered ring. The same kind of rearrangement can be triggered also by addition of a Lewis base. The mechanism of the rearrangement in both conditions has been studied by means of DFT calculations.
      Mots-clés : DFT calculations, MACO, pentacoordination, POLE 1, Sila-Matteson rearrangement, silicon, spirosilane.

    • T. Deis, J. Maury, F. Medici, M. Jean, J. Forte, N. Vanthuyne, L. Fensterbank, et G. Lemière, « Synthesis and Optical Resolution of Configurationally Stable Zwitterionic Pentacoordinate Silicon Derivatives », Angewandte Chemie International Edition, vol. 61, nᵒ 3, p. e202113836, 2022.
      Résumé : Stereogenic silicon centres in functionalised tetracoordinated organosilanes generally exhibit very high configurational stability under neutral conditions. This stability drops completely when higher coordination states of the silicon centre are reached due to rapid substituent exchange. Herein we describe the synthesis of chiral and neutral pentacoordinate silicon derivatives with high configurational stability. The zwitterionic nature of these air- and water-tolerant species allows for the first time their direct and efficient optical resolution using chiral HPLC techniques. By means of this method, pentacoordinate silicon compounds exhibiting high Si-inversion have been obtained as single enantiomers. A rationalisation of the enantiomerisation pathways has been also carried out using DFT calculations.
      Mots-clés : Chiral HPLC, Chirality, MACO, Optical resolution, POLE 1, Silicon, Zwitterion.

    • A. Delvaux, E. Rathahao-Paris, et S. Alves, « Different ion mobility-mass spectrometry coupling techniques to promote metabolomics », Mass Spectrometry Reviews, vol. 41, nᵒ 5, p. 695-721, 2022.
      Résumé : Metabolomics has become increasingly popular in recent years for many applications ranging from clinical diagnosis, human health to biotechnological questioning. Despite technological advances, metabolomic studies are still currently limited by the difficulty of identifying all metabolites, a class of compounds with great chemical diversity. Although lengthy chromatographic analyses are often used to obtain comprehensive data, many isobar and isomer metabolites still remain unresolved, which is a critical point for the compound identification. Currently, ion mobility spectrometry is being explored in metabolomics as a way to improve metabolome coverage, analysis throughput and isomer separation. In this review, all the steps of a typical workflow for untargeted metabolomics are discussed considering the use of an ion mobility instrument. An overview of metabolomics is first presented followed by a brief description of ion mobility instrumentation. The ion mobility potential for complex mixture analysis is discussed regarding its coupling with a mass spectrometer alone, providing gas-phase separation before mass analysis as well as its combination with different separation platforms (conventional hyphenation but also multidimensional ion mobility couplings), offering multidimensional separation. Various instrumental and analytical conditions for improving the ion mobility separation are also described. Finally, data mining, including software packages and visualization approaches, as well as the construction of ion mobility databases for the metabolite identification are examined.
      Mots-clés : CSOB, hyphenated method, Ion mobility-mass spectrometry, metabolomics, multidimensional data, POLE 3.

    • P. Dong, S. Cheng, Y. Wang, H. Gao, Y. Zhang, T. Zhu, P. Yu, et X. Meng, « A self-adjuvanting anti-tumor nanoliposomal vaccine based on fluorine-substituted MUC1 glycopeptide », Chemical Communications, vol. 58, nᵒ 62, p. 8642-8645, 2022.
      Résumé : Both the tumor-associated antigen and the mode of its presentation affect the immune response for antitumor vaccines. , Herein, a self-adjuvanting fluorinated MUC1-based nanoliposomal antitumor vaccine was constructed for the first time. Both the tumor-associated antigen and the mode of its presentation affect the immune response for antitumor vaccines.
      Mots-clés : GOBS, POLE 3.

    • L. J. P. Dufour, A. M. Herrmann, J. Leloup, C. Przybylski, L. Foti, L. Abbadie, et N. Nunan, « Potential energetic return on investment positively correlated with overall soil microbial activity », Soil Biology and Biochemistry, vol. 173, p. 108800, 2022.

    • C. Fayolle, P. Pigeon, N. Fischer-Durand, M. Salmain, O. Buriez, A. Vessières, et E. Labbé, « Synthesis, Electrochemical and Fluorescence Properties of the First Fluorescent Member of the Ferrocifen Family and of Its Oxidized Derivatives », Molecules, vol. 27, nᵒ 19, p. 6690, 2022.
      Résumé : The first fluorescent ferrociphenol derivative (P797) has been synthesized via McMurry cross-coupling followed by copper-catalyzed [3 + 2] azide-alkyne cycloaddition of the fluorescent group coumarin. Cyclic voltammograms of P797 exhibit either a monoelectronic oxidation wave ascribed to the ferrocene Fe(II) → Fe(III) conversion or a three-electron oxidation process in the presence of a base, leading to a Fe(III) quinone methide adduct. This general sequence is consistent with those previously described for non-fluorescent ferrociphenols. Furthermore, the fluorescence properties of P797 and its oxidized intermediates appear to strongly depend on the redox state of the ferrocene group. Indeed, electrochemical generation of Fe(III) (ferrocenium) states markedly increases the fluorescence emission intensity. In contrast, the emission of the Fe(II) (ferrocene) states is partially quenched by photoinduced electron transfer (PET) from the Fe(II) donor to the coumarin acceptor and by concentration-dependent self-quenching. Owing to its switchable fluorescence properties, complex P797 could represent an innovative and useful tool to study the biodistribution and the redox state of ferrocifens in cancer cells.
      Mots-clés : CHEMBIO, coumarin, ferrocene, fluorescence switching, PET, POLE 3, redox state.
      Note Note

    • S. Gahlot, A. Gradone, M. Roy, M. Giorgi, S. Conti, P. Ceroni, M. Villa, et M. Gingras, « Persulfurated Benzene-Cored Asterisks with π-Extended ThioNaphthyl Arms: Synthesis, Structural, Photophysical and Covalent Dynamic Properties », Chemistry – A European Journal, vol. 28, nᵒ 46, p. e202200797, 2022.
      Résumé : The synthesis of regioisomeric asterisks (5) and (6) incorporating a benzene core with six 1-naphthylthio or six 2-naphthylthio arms are reported in search for new materials with optoelectronic properties. The consequences on the extension of a π system surrounding a persulfurated benzene core provide a new avenue to study the structural, photophysical, and chemical properties of such family of all-organic phosphors. It also diverts the persulfuration mechanism after two radical cyclizations for making a [5]dithiohelicene by-product (7) and favors dynamic sulfur component exchange reactions surrounding the core. These exchanges convert asterisks (5) and (6), non-phosphorescent at 20 °C to the highly phosphorescent (4) (ϕ ∼100 %, solid state at 20 °C). For asterisks (5) and (6), the absence of the typical phosphorescence of the per(phenylthio)benzene core in the solid state at 20 °C and the presence of a weak naphthalene-based phosphorescence at 77 K is attributed to an energy transfer from the triplet state of the persulfurated benzene core to the outer naphthalene moieties, resulting in an antenna system.
      Mots-clés : arenes, aromatic substitution, materials science, photophysics, POLE 1, ROCS, sulfur, supramolecular chemistry.

    • J. Glatz, J. - R. Jiménez, L. Godeffroy, H. J. von Bardeleben, L. Fillaud, E. Maisonhaute, Y. Li, L. - M. Chamoreau, et R. Lescouëzec, « Enlightening the Alkali Ion Role in the Photomagnetic Effect of FeCo Prussian Blue Analogues », Journal of the American Chemical Society, vol. 144, nᵒ 24, p. 10888-10901, juin 2022.

    • A. Groué, J. - P. Tranchier, G. Gontard, M. Jean, N. Vanthuyne, et H. Amouri, « Enantiopure Cyclometalated Rh(III) and Ir(III) Complexes Displaying Rigid Configuration at Metal Center: Design, Structures, Chiroptical Properties and Role of the Iodide Ligand », Chemistry, vol. 4, nᵒ 1, p. 156-167, mars 2022.
      Résumé : Enantiopure N-heterocyclic carbene half-sandwich metal complexes of the general formula [Cp*M(C^C:)I] (M = Rh, Ir; C^C: = NI-NHC; NI-H = Naphthalimide; NHC = N-heterocyclic carbene) are reported. The rhodium compound was obtained as a single isomer displaying six membered metallacycle and was resolved on chiral column chromatography to the corresponding enantiomers (S)-[Cp*Rh(C^C:)I] (S)-2 and (R)-[Cp*Rh(C^C:)I] (R)-2. The iridium congener, however, furnishes a pair of regioisomers, which were resolved into (S)-[Cp*Ir(C^C:)I] (S)-3 and (R)-[Cp*Ir(C^C:)I] (R)-3 and (S)-[Cp*Ir(C^C:)I] (S)-4 and (R)-[Cp*Ir(C^C:)I] (R)-4. These regioisomers differ from each other, only by the size of the metallacycle; five-membered for 3 and six-membered for 4. The molecular structures of (S)-2 and (S)-4 are reported. Moreover, the chiroptical properties of these compounds are presented and discussed. These compounds display exceptional stable configurations at the metal center in solution with enantiomerization barrier ΔG≠ up to 124 kJ/mol. This is because the nature of the naphthalimide-NHC clamp ligand and the iodide ligand contribute to their configuration’s robustness. In contrast to related complexes reported in the literature, which are often labile in solution.
      Mots-clés : ARC, chiral resolution, circular dichroism, configurational stability, enantiopure.

    • M. S. M. Holmsen, C. Blons, A. Amgoune, M. Regnacq, D. Lesage, E. D. Sosa Carrizo, P. Lavedan, Y. Gimbert, K. Miqueu, et D. Bourissou, « Mechanism of Alkyne Hydroarylation Catalyzed by (P,C)-Cyclometalated Au(III) Complexes », Journal of the American Chemical Society, vol. 144, nᵒ 49, p. 22722-22733, déc. 2022.

    • A. Hueber, Y. Gimbert, G. Langevin, J. - M. Galano, A. Guy, T. Durand, N. Cenac, J. Bertrand-Michel, et J. - C. Tabet, « Identification of bacterial lipo-amino acids: origin of regenerated fatty acid carboxylate from dissociation of lipo-glutamate anion », Amino Acids, vol. 54, nᵒ 2, p. 241-250, 2022.
      Résumé : Abstract The identification of bacterial metabolites produced by the microbiota is a key point to understand its role in human health. Among them, lipo-amino acids (LpAA), which are able to cross the epithelial barrier and to act on the host, are poorly identified. Structural elucidation of few of them was performed by high-resolution tandem mass spectrometry based on electrospray combined with selective ion dissociations reach by collision-induced dissociation (CID). The negative ions were used for their advantages of yielding only few fragment ions sufficient to specify each part of LpAA with sensitivity. To find specific processes that help structural assignment, the negative ion dissociations have been scrutinized for an LpAA: the N -palmitoyl acyl group linked to glutamic acid (C16Glu). The singular behavior of [C16Glu-H]¯ towards CID showed tenth product ions, eight were described by expected fragment ions. In contrast, instead of the expected product ions due to CONH-CH bond cleavage, an abundant complementary dehydrated glutamic acid and fatty acid anion pair were observed. Specific to glutamic moiety, they were formed by a stepwise dissociation via molecular isomerization through ion–dipole formation prior to dissociation. This complex dissociated by partner splitting either directly or after inter-partner proton transfer. By this pathway, surprising regeneration of deprotonated fatty acid takes place. Such regeneration is comparable to that occurred from dissociation to peptides containing acid amino-acid. Modeling allow to confirm the proposed mechanisms explaining the unexpected behavior of this glutamate conjugate.
      Mots-clés : CSOB, POLE 3.
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