Nos tutelles

CNRS

Rechercher





Accueil > Publications

publications

publié le , mis à jour le

2023



  • 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.


  • 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.


  • 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, p. 122623, janv. 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, estrogen receptor, FT-IR spectroscopy, immunoassay, Metal carbonyls, organometallic tracers, POLE 3.

2022



  • 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.


  • 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, 2022.


  • 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.


  • 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.


  • 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 CoIII(Tp*)(CN)3− Cyanidometallate: Combined Magnetic, Structural and 59Co NMR Study », Chemistry – A European Journal, vol. 28, nᵒ 50, p. e202200783, 2022.
    Résumé : The cyanidocobaltate of formula fac-PPh4[CoIII(Me2Tp)(CN)3] ⋅ CH3CN (1) has been used as a metalloligand to prepare polynuclear magnetic complexes (Me2Tp=hydrotris(3,5-dimethylpyrazol-1-yl)borate). The association of 1 with in situ prepared [FeII(bik)2(MeCN)2](OTf)2 (bik=bis(1-methylimidazol-2-yl)ketone) leads to a molecular square of formula [CoIII(Me2Tp)(CN)3]2[FeII(bik)2]2(OTf)2 ⋅ 4MeCN ⋅ 2H2O (2), whereas the self-assembly of 1 with preformed cluster [CoII2(OH2)(piv)4(Hpiv)4] in MeCN leads to the two-dimensional network of formula [CoII2(piv)3]2[CoIII(Me2Tp)(CN)3]2 ⋅ 2CH3CN∞ (3). These compounds were structurally characterized via single crystal X-ray analysis and their spectroscopic (FTIR, UV-Vis and 59Co NMR) properties and magnetic behaviours were also investigated. Bulk magnetic susceptibility measurements reveal that 1 is diamagnetic and 3 is paramagnetic throughout the explored temperature range, whereas 2 exhibits sharp spin transition centered at ca. 292 K. Compound 2 also exhibits photomagnetic effects at low temperature, selective light irradiations allowing to promote reversibly and repeatedly low-spin⇔high-spin conversion. Besides, the diamagnetic nature of the Co(III) building block allows us studying these compounds by means of 59Co NMR spectroscopy. Herein, a 59Co chemical shift has been used as a magnetic probe to corroborate experimental magnetic data obtained from bulk magnetic susceptibility measurements. An influence of the magnetic state of the neighbouring atoms is observed on the 59Co NMR signals. Moreover, for the very first time, 59Co NMR technique has been successfully introduced to investigate molecular materials with distinct magnetic properties.
    Mots-clés : ERMMES, POLE 2.


  • 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, sept. 2022.


  • L. J. P. Dufour, A. M. Herrmann, J. Leloup, C. Przybylski, L. Foti, L. Abbadie, et N. Nunan, « Energetic Return on Investment Determines Overall Soil Microbial Activity », SSRN Electronic Journal, 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.


  • 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.


  • A. Hueber, M. Green, J. Ujma, K. Richardson, Y. Gimbert, N. Cenac, J. Bertrand-Michel, et J. - C. Tabet, « Energy-Resolved Ion Mobility Spectrometry: Composite Breakdown Curves for Distinguishing Isomeric Product Ions », Journal of the American Society for Mass Spectrometry, p. jasms.2c00233, déc. 2022.


  • A. Hueber, C. Petitfils, P. Le Faouder, G. Langevin, A. Guy, J. - M. Galano, T. Durand, J. - F. Martin, J. - C. Tabet, N. Cenac, et J. Bertrand-Michel, « Discovery and quantification of lipoamino acids in bacteria », Analytica Chimica Acta, vol. 1193, p. 339316, 2022.


  • C. Huez, D. Guérin, S. Lenfant, F. Volatron, M. Calame, M. L. Perrin, A. Proust, et D. Vuillaume, « Redox-controlled conductance of polyoxometalate molecular junctions », Nanoscale, vol. 14, nᵒ 37, p. 13790-13800, sept. 2022.
    Résumé : We demonstrate the reversible in situ photoreduction of molecular junctions of a phosphomolybdate [PMo12O40]3− monolayer self-assembled on flat gold electrodes, connected by the tip of a conductive atomic force microscope. The conductance of the one electron reduced [PMo12O40]4− molecular junction is increased by ∼10, and this open-shell state is stable in the junction in air at room temperature. The analysis of a large current–voltage dataset by unsupervised machine learning and clustering algorithms reveals that the electron transport in the pristine phosphomolybdate junctions leads to symmetric current–voltage curves, controlled by the lowest unoccupied molecular orbital (LUMO) at 0.6–0.7 eV above the Fermi energy with ∼25% of the junctions having a better electronic coupling to the electrodes than the main part of the dataset. This analysis also shows that a small fraction (∼18% of the dataset) of the molecules is already reduced. The UV light in situ photoreduced phosphomolybdate junctions systematically feature slightly asymmetric current–voltage behaviors, which is ascribed to the electron transport mediated by the single occupied molecular orbital (SOMO) nearly at resonance with the Fermi energy of the electrodes and by a closely located single unoccupied molecular orbital (SUMO) at ∼0.3 eV above the SOMO with a weak electronic coupling to the electrodes (∼50% of the dataset) or at ∼0.4 eV but with a better electrode coupling (∼50% of the dataset). These results shed light on the electronic properties of reversible switchable redox polyoxometalates, a key point for potential applications in nanoelectronic devices.
    Mots-clés : E-POM, POLE 2.


  • S. Hupin, V. Tognetti, F. Rosu, S. Renaudineau, A. Proust, G. Izzet, V. Gabelica, C. Afonso, et H. Lavanant, « Lennard-Jones interaction parameters of Mo and W in He and N2 from collision cross-sections of Lindqvist and Keggin polyoxometalate anions », Physical Chemistry Chemical Physics, vol. 24, nᵒ 26, p. 16156-16166, juill. 2022.
    Résumé : Drift tube ion mobility spectrometry (DTIMS) coupled with mass spectrometry was used to determine the collision cross-sections (DTCCS) of polyoxometalate anions in helium and nitrogen. As the geometry of the ion, more than its mass, determines the collision cross-section with a given drift gas molecule, we found that both Lindqvist ions Mo6O192− and W6O192− had a DTCCSHe value of 103 ± 2 Å2, and both Keggin ions PMo12O403− and PW12O403− had a DTCCSHe value of 170 ± 2 Å2. Similarly, ion mobility experiments in N2 led to DTCCSN2 values of 223 ± 2 Å2 and 339 ± 4 Å2 for Lindqvist and Keggin anions, respectively. Using optimized structures and partial charges determined from density functional theory calculations, followed by CCS calculations via the trajectory method, we determined Lennard-Jones 6-12 potential parameters ε, σ of 5.60 meV, 3.50 Å and 3.75 meV, 4.40 Å for both Mo and W atoms interacting with He and N2, respectively. These parameters reproduced the CCS of polyoxometalates within 2% accuracy.
    Mots-clés : E-POM, POLE 2.


  • P. Idlas, A. Ladaycia, F. Némati, E. Lepeltier, P. Pigeon, G. Jaouen, D. Decaudin, et C. Passirani, « Ferrocifen stealth LNCs and conventional chemotherapy: a promising combination against multidrug-resistant ovarian adenocarcinoma », International Journal of Pharmaceutics, p. 122164, sept. 2022.
    Résumé : Ovarian cancer is one of the deadliest epithelial malignancies in women, owing to the multidrug resistance that restricts the success of conventional chemotherapy, carboplatin and paclitaxel. High grade serous ovarian carcinoma can be classified into two subtypes, the chemosensitive High OXPHOS and the Low OXPHOS tumour, less sensitive to chemotherapy. This difference of treatment efficacy could be explained by the redox status of these tumours, High OXPHOS exhibiting a chronic oxidative stress and an accumulation of reactive oxygen species. Ferrocifens, bio-organometallic compounds, are believed to be ROS producers with a good cytotoxicity on ovarian cancer cell lines. The aim of this study was to evaluate the in vivo efficacy of ferrocifen stealth lipid nanocapsules on High and Low OXPHOS ovarian Patient-Derived Xenograft models, alone or in combination to standard chemotherapy. Accordingly, two ferrocifens, P53 and P722, were encapsulated in stealth LNCs. The treatment by stealth P722-LNCs in combination with standard chemotherapy induced, with a concentration eight time lower than in stealth P53-LNCs, similar tumour reduction on a Low OXPHOS model, allowing us to conclude that P722 could be a leading ferrocifen to treat ovarian cancer. This combination of treatments may represent a promising synergistic approach to treat resistant ovarian adenocarcinoma.
    Mots-clés : CHEMBIO, Multidrug resistance, Nanoparticle, Organometallic compound, Ovarian cancer, Patient-Derived Xenograft model, POLE 3, ROS producer molecule.


  • O. Jackowski et A. Perez-Luna, « 4.4.38.14 Propargylsilanes (Update 2022) », in Science of Synthesis, 2022/3: Knowledge Updates 2022/3, 1st editionᵉʳ éd., Thieme Verlag, 2022.
    Résumé : Thieme E-Books & E-Journals
    Mots-clés : POLE 1, ROCS.


  • L. K/Bidi, A. Desjonquères, G. Izzet, et G. Guillemot, « H<sub>2</sub> Evolution at a Reduced Hybrid Polyoxometalate and Its Vanadium-Oxo Derivative Used as Molecular Models for Reducible Metal Oxides », Inorganic Chemistry, p. acs.inorgchem.2c01741, juill. 2022.


  • P. Kumar, A. Swain, J. Acharya, Y. Li, V. Kumar, G. Rajaraman, E. Colacio, et V. Chandrasekhar, « Synthesis, Structure, and Zero-Field SMM Behavior of Homometallic Dy2, Dy4, and Dy6 Complexes », Inorganic Chemistry, vol. 61, nᵒ 30, p. 11600-11621, août 2022.
    Résumé :

    ng> The synthesis, structure, and magnetic properties of three DyIII complexes of different nuclearity, [Dy2(H2L)2(NO3)] [NO3]·2H2O·CH3OH (1), [Dy4(HL)2(piv)4(OH)2] (2), and [Dy6(H2L)3(μ3–OH)(μ3–CO3)3(CH3OH)4(H2O)8] 5Cl·3H2O (3) [(H4L) = 6-((bis(2-hydroxyethyl)amino)-N′-(2-hydroxybenzylidene)picolinohydrazide)], are described. This variety of complexes with the same ligand could be obtained by playing with the metal-to-ligand molar ratio, the type of DyIII salt, the kind of base, and the presence/absence of coligand. 1 is a dinuclear complex, while 2 is a tetranuclear assembly with a butterfly-shaped topology. 3 is a homometallic hexanuclear complex that exhibits a propeller-shaped topology. Interestingly, in this complex 3, three atmospheric carbon dioxide molecules are trapped in the form of carbonate ions, which assist in holding the hexanuclear complex together. All of the complexes reveal a slow relaxation of magnetization even in zero applied field. Complex 1 is a zero-field SMM with an effective energy barrier (Ueff) of magnetization reversal equal to 87(1) K and a relaxation time of τ0 = 6.4(3) × 10–9 s. Under an applied magnetic field of 0.1 T, these parameters change to Ueff = 101(3) K, τ0 = 2.5(1) × 10–9 s. Complex 2 shows zero-field SMM behavior with Ueff = 31(2) K, τ0 = 4.2(1) × 10–7 s or τ01 = 2(1) × 10–7 s, Ueff1 = 37(8) K, τ02 = 5(6) × 10–5 s, and Ueff2 = 8(4) by considering two Orbach relaxation processes, while 3, also a zero-field SMM, shows a double relaxation of magnetization [Ueff1 = 62.4(3) K, τ01 = 4.6(3) × 10–8 s, and Ueff1 = 2(1) K, τ02 = 4.6(2) × 10–5 s]. The ab initio calculations indicated that in these complexes, the Kramer’s ground doublet is characterized by an axial g-tensor with the prevalence of the mJ = ±15/2 component, as well as that due to the weak magnetic coupling between the metal centers, the magnetic relaxation, which is dominated by the single DyIII centers rather than by the exchange-coupled states, takes place via Raman/Orbach or TA-QTM. Moreover, theoretical calculations support a toroidal magnetic state for complex 2.
    Mots-clés : ERMMES, POLE 2.


  • M. Laurans, M. Mattera, R. Salles, L. K’Bidi, P. Gouzerh, S. Renaudineau, F. Volatron, G. Guillemot, S. Blanchard, G. Izzet, A. Solé-Daura, J. M. Poblet, et A. Proust, « When Identification of the Reduction Sites in Mixed Molybdenum/Tungsten Keggin-Type Polyoxometalate Hybrids Turns Out Tricky », Inorganic Chemistry, vol. 61, nᵒ 20, p. 7700-7709, mai 2022.


  • P. Le Bellec, P. Midoux, H. Cheradame, V. Bennevault, et P. Guégan, « Tuneable thermal properties of PTHF-based copolymers by incorporation of epoxide units », European Polymer Journal, vol. 168, p. 111096, avr. 2022.
    Résumé : In order to decrease the crystallinity of polytetrahydrofuran (PTHF), statistical copolymerizations with 1,2-butylene oxide (BO) and 3,3-dimethyl-1,2-butylene oxide (DMBO) epoxides as comonomer were investigated in a process compatible with an easy scaling up. Difunctionnal poly(tetrahydrofuran-stat-1,2-butylene oxide)s (PTHF-stat-PBO) and poly(tetrahydrofuran-stat-3,3-dimethyl-1,2-butylene oxide)s (PTHF-stat-PDMBO) were synthesized in the range of 0–20 °C using different operating conditions. The reactivity ratios showed a homogeneous distribution of the epoxide units all along the copolymer chains by using BO, while an alternation of several THF and DMBO monomer units sequences was obtained in the DMBO-based copolymers. Still, both copolymerizations fit well with an ideal copolymerization behavior. A slow addition of BO during the propagation step or the introduction of BO or DMBO at the beginning of the polymerization were investigated. Whatever the comonomer used, its insertion in the polymer chain reduced the melting temperature of the copolymers and the impact of the THF polymerization equilibrium on the yields. As a consequence, higher polymerization yields were obtained. A fairly good control of the polymer molar masses was observed, although elimination reactions were highlighted. However, operating conditions were determined to limit the content of the resulting alkene chain ends to about 10%, providing guaranties for further macromolecular architectures developments.
    Mots-clés : 2-Butylene oxide, 2-Butylene oxide3, 3-Dimethyl-1, Cationic ring-opening polymerization, Equilibrium, POLYMERES, Reactivity ratio, Tetrahydrofuran1, Thermal properties.


  • S. Le Luyer, P. Guégan, et N. Illy, « Episulfide Anionic Ring-Opening Polymerization Initiated by Alcohols and Primary Amines in the Presence of γ-Thiolactones », Macromolecules, vol. 55, nᵒ 13, p. 5430-5440, juill. 2022.
    Résumé : Among the sulfur-containing polymers, polythioethers remain very attractive structures due to their high sulfur atom content, making them interesting candidates for various industrial applications, for example, in the fields of energy storage or biomedical applications. Although anionic ring-opening polymerization of episulfides is known since decades, only a limited number of efficient initiating systems enable the synthesis of well-defined polymer chains. In this work, a one-pot, two-step method was developed in order to efficiently initiate the anionic ring-opening polymerization of propylene sulfide with alcohol or amine moieties using the latent thiol functionality of γ-thiolactones. First, the ring opening of γ-thiolactones with alcohols or amines was investigated in the presence of various bases (2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 4-dimethylaminopyridine, tBuP1, and tBuP4). Then, the polymerization conditions were optimized, allowing the synthesis of well-defined α,ω-heterotelechelic poly(propylene sulfide)s with controlled molar mass up to 10 kg·mol–1 as evidenced by size-exclusion chromatography, 1H, 13C, and 2D NMR, and matrix-assisted laser desorption and ionization time-of-flight mass spectrometry. Depending on the initiating function (alcohol or amine), the initiator and the polythioether chains are connected either by an ester or by an amide bond. The stability of these bonds was studied under basic conditions.
    Mots-clés : POLYMERES.


  • A. Li, L. - M. Chamoreau, B. Baptiste, L. Delbes, Y. Li, F. Lloret, Y. Journaux, et L. Lisnard, « Solvothermal Synthesis, Temperature-Dependent Structural Study, and Magnetic Characterization of a Multipolydentate Oxamate-Based 2D Coordination Network », Crystal Growth & Design, vol. 22, nᵒ 12, p. 7518-7526, déc. 2022.
    Résumé : A multipolydentate N-substituted oxamate ligand bearing an additional carboxylato group has been successfully reacted in solvothermal conditions to form the 2D coordination network (TMA)3[CuMn(paba)2(OAc)]·8H2O (1). This coordination network displays a brick-wall type morphology with, thanks to the augmented connectivity of the ligand, a lower than usual metal ion nuclearity for the building subunit. Temperature-dependent structural studies indicate that the layered structure undergoes dehydration at 90 °C and remains stable up to 200 °C. Magnetic characterizations show that 1 behaves as a ferrimagnet, with a Curie temperature of 2.8 K.
    Mots-clés : ERMMES, POLE 2.


  • C. Loro, J. Oble, F. Foschi, M. Papis, E. M. Beccalli, S. Giofrè, G. Poli, et G. Broggini, « Acid-mediated decarboxylative C–H coupling between arenes and O-allyl carbamates », Organic Chemistry Frontiers, vol. 9, nᵒ 6, p. 1711-1718, mars 2022.
    Résumé : Treatment of O-allyl N-tosyl carbamates with aromatic compounds in the presence of Cu(OTf)2 or TMSOTf as promoters affords N-substituted 1-arylpropan-2-amines, 1,2-diarylpropanes, 1,1-diarylpropanes, or indanes, depending on the nature of the promoter and of the aryl substrates. A full mechanistic rational allowing appreciation of the outcome of these novel C–H based cascades is proposed. An initial acid promoted decarboxylative/deamidative Friedel–Crafts allylation takes place. After protonation of the allylated arene, evolution of the resulting cation may follow different paths depending on the nature of the arene partner and of the allyl moiety in the carbamate.
    Mots-clés : POLE 1, ROCS.


  • S. Mabrouk, H. Rinnert, L. Balan, J. Jasniewski, S. Blanchard, G. Medjahdi, R. Ben Chaabane, et R. Schneider, « Highly Luminescent and Photostable Core/Shell/Shell ZnSeS/Cu:ZnS/ZnS Quantum Dots Prepared via a Mild Aqueous Route », Nanomaterials, vol. 12, nᵒ 18, p. 3254, sept. 2022.
    Résumé : An aqueous-phase synthesis of 3-mercaptopropionic acid (3-MPA)-capped core/shell/shell ZnSeS/Cu:ZnS/ZnS QDs was developed. The influence of the Cu-dopant location on the photoluminescence (PL) emission intensity was investigated, and the results show that the introduction of the Cu dopant in the first ZnS shell leads to QDs exhibiting the highest PL quantum yield (25%). The influence of the Cu-loading in the dots on the PL emission was also studied, and a shift from blue–green to green was observed with the increase of the Cu doping from 1.25 to 7.5%. ZnSeS/Cu:ZnS/ZnS QDs exhibit an average diameter of 2.1 ± 0.3 nm and are stable for weeks in aqueous solution. Moreover, the dots were found to be photostable under the continuous illumination of an Hg–Xe lamp and in the presence of oxygen, indicating their high potential for applications such as sensing or bio-imaging.
    Mots-clés : E-POM, POLE 2.


  • 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, déc. 2022.
    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.

    trong>Mots-clés :
    CHEMBIO, CSOB, POLE 3.


  • C. Mathonière, D. Mitcov, E. Koumousi, D. Amorin-Rosario, P. Dechambenoit, S. Fatima Jafri, P. Sainctavit, C. Cartier dit Moulin, L. Toupet, E. Trzop, E. Collet, M. - A. Arrio, A. Rogalev, F. Wilhelm, et R. Clérac, « Metal-to-metal electron transfer in a cyanido-bridged {Fe <sub>2</sub> Co <sub>2</sub> } square complex followed by X-ray diffraction and absorption techniques », Chemical Communications, vol. 58, nᵒ 86, p. 12098-12101, 2022.
    Résumé : Combining X-ray diffraction and absorption spectroscopy, a full picture of the thermal-, light- and X-ray-induced metal-to-metal electron transfer in a cyanido-bridged molecular Fe/Co square is obtained, demonstrating the concerted and concomitant role played by the Fe and Co sites. , The switching properties of a cyanido-bridged Fe/Co square molecule were investigated by single-crystal X-ray diffraction and X-ray absorption spectroscopy at both Fe and Co K-edges. Combining these two techniques, a complete picture of the thermal-, light- and X-ray-induced metal-to-metal electron transfer is obtained, illustrating the concerted role played by the Fe and Co sites.
    Mots-clés : ERMMES, POLE 2.


  • Y. Mazouzi, F. Sallem, F. Farina, A. Loiseau, N. R. Tartaglia, M. Fontaine, A. Parikh, M. Salmain, C. Neri, et S. Boujday, « Biosensing Extracellular Vesicle Subpopulations in Neurodegenerative Disease Conditions », ACS Sensors, vol. 7, nᵒ 6, p. 1657-1665, juin 2022.
    Résumé : Extracellular vesicles (EVs) are secreted nanoparticles that are involved in intercellular communication and that modulate a wide range of biological processes in normal and disease conditions. However, EVs are highly heterogeneous in terms of origin in the cell, size, and density. As a result, complex protocols are required to identify and characterize specific EV subpopulations, limiting biomedical applications, notably in diagnostics. Here, we show that combining quartz crystal microbalance with dissipation (QCM-D) and nanoplasmonic sensing (NPS) provides a facile method to track the viscoelastic properties of small EVs. We applied this multisensing strategy to analyze small EVs isolated by differential ultracentrifugation from knock-in mouse striatal cells expressing either a mutated allele or wild-type allele of huntingtin (Htt), the Huntington’s disease gene. Our results validate the sensing strategy coupling QCM-D and NPS and suggest that the mass and viscoelastic dissipation of EVs can serve as potent biomarkers for sensing the intercellular changes associated with the neurodegenerative condition.
    Mots-clés : CHEMBIO, POLE 3.


  • A. Mori, S. Curpanen, C. Pezzetta, A. Perez-Luna, G. Poli, et J. Oble, « C−H Activation Based Functionalization of Furfural Derivatives », European Journal of Organic Chemistry, vol. n/a, nᵒ n/a, p. e202200727, 2022.
    Résumé : Furfural and related compounds are building blocks of industrial interest, obtained from raw biomass. Their use as precursors of basic and fine chemicals has gained increasing attention as a green alternative to petroleum-derived compounds. Several works have reported the functionalization of furfurals to obtain a wider range of chemicals, opening up new synthetic possibilities and applications, ranging from biofuels to pharmaceuticals. Among these works, processes based on C−H activation are the most attractive ones for their atom economy and the possibility to use non-activated substrates. This minireview summarizes the reported methods of direct C−H functionalization of furfurals without prior modification of the redox state of the aldehyde function. In particular, the transition metal catalyzed functionalization of each bond of the heteroaromatic nucleus of these molecules is systematically discussed, as well as examples of C−H transformations of the aldehyde function.
    Mots-clés : Biomass, Catalysis, C−H Activation, Furfural, POLE 1, ROCS, Transition metal.


  • F. Najlaoui, B. Busser, G. S. Taïwe, P. Pigeon, N. Sturm, D. Giovannini, N. Marrakchi, A. Rhouma, G. Jaouen, S. Gibaud, et M. De Waard, « Succinimido–Ferrocidiphenol Complexed with Cyclodextrins Inhibits Glioblastoma Tumor Growth In Vitro and In Vivo without Noticeable Adverse Toxicity », Molecules, vol. 27, nᵒ 14, p. 4651, 2022.
    Résumé : SuccFerr (N-[4-ferrocenyl,5-5-bis (4-hydroxyphenyl)-pent-4-enyl]-succinimide) has remarkable antiproliferative effects in vitro, attributed to the formation of a stabilized quinone methide. The present article reports in vivo results for a possible preclinical study. SuccFerr is lipophilic and insoluble in water, so the development of a formulation to obviate this inconvenience was necessary. This was achieved by complexation with randomly methylated cyclodextrins (RAMEßCDs). This supramolecular water-soluble system allowed the in vivo experiments below to proceed. Application of SuccFerr on the glioblastoma cancer cell line U87 indicates that it affects the cellular cycle by inducing a blockade at G0/G1 phase, linked to apoptosis, and another one at the S phase, associated with senescence. Using healthy Fischer rats, we show that both intravenous and subcutaneous SuccFerr: RAMEßCD administration at 5 mg/kg lacks toxic effects on several organs. To reach lethality, doses higher than 200 mg/kg need to be administered. These results prompted us to perform an ectopic in vivo study at 1 mg/kg i.v. ferrocidiphenol SuccFerr using F98 cells xenografted in rats. Halting of cancer progression was observed after six days of injection, associated with an immunological defense response linked to the active principle. These results demonstrate that the properties of the selected ferrocidiphenol SuccFerr transfer successfully to in vivo conditions, leading to interesting therapeutic perspectives based on this chemistry.
    Mots-clés : anticancer drug, CHEMBIO, cyclodextrin, ferrocenyl tamoxifen derivatives, glioblastoma, POLE 3.


  • M. Ndour, J. - P. Bonnet, S. Cavalaglio, T. Lombard, M. Courty, L. Aymard, C. Przybylski, et V. Bonnet, « The formulation of a CMC binder/silicon composite anode for Li-ion batteries: from molecular effects of ball milling on polymer chains to consequences on electrochemical performances », Materials Advances, vol. 3, nᵒ 23, p. 8522-8533, 2022.
    Résumé : The semi-synthetic polysaccharide carboxymethylcellulose (CMC) is one of the most studied and effective polymer binders for silicon-based anodes in Li-ion batteries. , The semi-synthetic polysaccharide carboxymethylcellulose (CMC) is one of the most studied and effective polymer binders for silicon-based anodes in Li-ion batteries. The formulation of the corresponding composite negative electrode with an appropriate mixture of electroactive silicon, a CMC binder and a carbon additive is mandatory to ensure a good electrical conductivity. Blending is commonly realized by a highly energetic ball milling treatment of these three aforementioned components. This type of mixing reduces the size of the obtained particles and can also potentially agglomerate them. Morever, it allows the formation of a nanostructured mixture which is essential for both the silicon activation and to achieve good electrochemical performance. However, such strong treatment can also cause a significant degradation of the polymer chains, as we have recently demonstrated for polyacrylic acid (PAA). In the present work, the structural and chemical effects of this mechanical grinding on three commercial CMCs ranging from 90 to 700 kg mol −1 were investigated. All the polymers were characterized using SEC-MALLS, FTIR spectroscopy, MALDI-TOF mass spectrometry and TGA-MS thermal analysis. In all cases, a huge average molecular weight decrease was noticed, leading to the appearance of a bimodal distribution with low (52–72 kg mol −1 ) to very low molecular weight populations (1–1.8 kg mol −1 ). From these results, two formulations of a negative electrode were compared, one with ball milling of the three compounds and another one including only ball milling steps for silicon and carbon. After the correlation of the characteristics of this negative electrode composite with the electrochemical results, it was demonstrated that a high number of functions for supramolecular or covalent linkages are keypoints of the herein anode performance. Low molecular weight CMC derivatives (about 64 kg mol −1 ) obtained by ball milling treatment led to higher stability of the electrode.
    Mots-clés : CSOB, POLE 3.


  • M. Nicolas, B. Beito, M. Oliveira, M. Tudela Martins, B. Gallas, M. Salmain, S. Boujday, et V. Humblot, « Strategies for Antimicrobial Peptides Immobilization on Surfaces to Prevent Biofilm Growth on Biomedical Devices », Antibiotics, vol. 11, nᵒ 1, p. 13, 2022.
    Résumé : Nosocomial and medical device-induced biofilm infections affect millions of lives and urgently require innovative preventive approaches. These pathologies have led to the development of numerous antimicrobial strategies, an emergent topic involving both natural and synthetic routes, among which some are currently under testing for clinical approval and use. Antimicrobial peptides (AMPs) are ideal candidates for this fight. Therefore, the strategies involving surface functionalization with AMPs to prevent bacterial attachment/biofilms formation have experienced a tremendous development over the last decade. In this review, we describe the different mechanisms of action by which AMPs prevent bacterial adhesion and/or biofilm formation to better address their potential as anti-infective agents. We additionally analyze AMP immobilization techniques on a variety of materials, with a focus on biomedical applications. Furthermore, we summarize the advances made to date regarding the immobilization strategies of AMPs on various surfaces and their ability to prevent the adhesion of various microorganisms. Progress toward the clinical approval of AMPs in antibiotherapy is also reviewed.
    Mots-clés : AMP, antimicrobial, biofilms, biofunctionalization, CHEMBIO, immobilization, peptide, POLE 3.


  • N. Paulhe, C. Canlet, A. Damont, L. Peyriga, S. Durand, C. Deborde, S. Alves, S. Bernillon, T. Berton, R. Bir, A. Bouville, E. Cahoreau, D. Centeno, R. Costantino, L. Debrauwer, A. Delabrière, C. Duperier, S. Emery, A. Flandin, U. Hohenester, D. Jacob, C. Joly, C. Jousse, M. Lagree, N. Lamari, M. Lefebvre, C. Lopez-Piffet, B. Lyan, M. Maucourt, C. Migne, M. - F. Olivier, E. Rathahao-Paris, P. Petriacq, J. Pinelli, L. Roch, P. Roger, S. Roques, J. - C. Tabet, M. Tremblay-Franco, M. Traïkia, A. Warnet, V. Zhendre, D. Rolin, F. Jourdan, E. Thévenot, A. Moing, E. Jamin, F. Fenaille, C. Junot, E. Pujos-Guillot, et F. Giacomoni, « PeakForest: a multi-platform digital infrastructure for interoperable metabolite spectral data and metadata management », Metabolomics, vol. 18, nᵒ 6, p. 40, 2022.
    Résumé : Abstract Introduction Accuracy of feature annotation and metabolite identification in biological samples is a key element in metabolomics research. However, the annotation process is often hampered by the lack of spectral reference data in experimental conditions, as well as logistical difficulties in the spectral data management and exchange of annotations between laboratories. Objectives To design an open-source infrastructure allowing hosting both nuclear magnetic resonance (NMR) and mass spectra (MS), with an ergonomic Web interface and Web services to support metabolite annotation and laboratory data management. Methods We developed the PeakForest infrastru

    cture, an open-source Java tool with automatic programming interfaces that can be deployed locally to organize spectral data for metabolome annotation in laboratories. Standardized operating procedures and formats were included to ensure data quality and interoperability, in line with international recommendations and FAIR principles. Results PeakForest is able to capture and store experimental spectral MS and NMR metadata as well as collect and display signal annotations. This modular system provides a structured database with inbuilt tools to curate information, browse and reuse spectral information in data treatment. PeakForest offers data formalization and centralization at the laboratory level, facilitating shared spectral data across laboratories and integration into public databases. Conclusion PeakForest is a comprehensive resource which addresses a technical bottleneck, namely large-scale spectral data annotation and metabolite identification for metabolomics laboratories with multiple instruments. PeakForest databases can be used in conjunction with bespoke data analysis pipelines in the Galaxy environment, offering the opportunity to meet the evolving needs of metabolomics research. Developed and tested by the French metabolomics community, PeakForest is freely-available at https://github.com/peakforest .
    Mots-clés : CSOB, POLE 3.


  • P. Pigeon, M. Gaschard, M. Othman, M. Salmain, et G. Jaouen, « α-Hydroxylactams as Efficient Entries to Diversely Functionalized Ferrociphenols: Synthesis and Antiproliferative Activity Studies », Molecules, vol. 27, nᵒ 14, p. 4549, 2022.
    Résumé : The [ferrocene-ene-phenol] motif has been identified as the pharmacophore responsible for the anticancer activity of the family of ferrocene-based molecules coined ferrocifens, owing to its unique redox properties. The addition of imide entities to the historical ferrociphenol scaffold tremendously enhanced the cytotoxic activity of a large panel of cancer cell cultures and preliminary studies showed that the reduction of one of the carbonyl groups of the imide groups to the corresponding α-hydroxylactams only slightly affected the antiproliferative activity. As a continuation to these studies, we took advantage of the facile conversion of α-hydroxylactams to highly electrophilic N-acyliminium ions to graft various substituents to the imide motif of phthalimido ferrocidiphenol. Cell viability studies showed that the newly synthesized compounds showed diverse cytotoxic activities on two breast cancer cell lines, while only one compound was significantly less active on the non-tumorigenic cell line hTERT-RPE1.
    Mots-clés : <i>N</i>-acyliminium ion, anticancer activity, CHEMBIO, ferrocene, ferrocifen, hydroxylactam, POLE 3.


  • A. Pradal, « 2.15 - Four-Membered Rings With Two Oxygen Atoms », in Comprehensive Heterocyclic Chemistry IV, D. S. C. Black, J. Cossy, et C. V. Stevens, Éd. Oxford: Elsevier, 2022, p. 507-537.
    Résumé : This chapter is dealing with the chemistry about 1,2- and 1,3-dioxetanes, even if most of what is reported concerns 1,2-dioxetane derivatives. These derivatives are becoming more and more important since their chemiluminescent properties are of great interest for imaging and detection applications. After a description of the theoretical studies made for a better understanding of the decomposition mechanism, some new data dealing with analytics and synthesis are given. This chapter ends with new updates about applications of the chemistry of 1,2-dioxetanes.
    Mots-clés : Chemiluminescence, Decomposition, Dioxetanes, Firefly dioxetanone, Light emission, POLE 1, ROCS.


  • C. Przybylski et V. Bonnet, « Probing topology of supramolecular complexes between cyclodextrins and alkali metals by ion mobility-mass spectrometry », Carbohydrate Polymers, vol. 297, p. 120019, 2022.


  • E. Rathahao‐Paris, A. Delvaux, M. Li, B. Guillon, E. Venot, F. Fenaille, K. Adel‐Patient, et S. Alves, « Rapid structural characterization of human milk oligosaccharides and distinction of their isomers using trapped ion mobility spectrometry time‐of‐flight mass spectrometry », Journal of Mass Spectrometry, vol. 57, nᵒ 10, 2022.
--- Exporter la sélection au format