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  • 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.

  • 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, 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.

  • 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, janv. 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

  • 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.

  • 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.

  • 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.

  • 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.

  • 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, janv. 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.

  • 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.

  • J. Sanz Garcia, M. Gaschard, I. Navizet, M. Sahihi, S. Top, Y. Wang, P. Pigeon, A. Vessières, M. Salmain, et G. Jaouen, « Inhibition of cathepsin B by ferrocenyl indenes highlights a new pharmacological facet of ferrocifens », European Journal of Inorganic Chemistry, vol. 2022, nᵒ 9, janv. 2022.
    Résumé : The family of ferrocifens initially built up from the anti-estrogen tamoxifen shows a broad antitumor activity both  in vitro  and  in vivo . Their mechanism of action relies on the presence of the redox motif [ferrocene-ene-phenol] that, under oxidative conditions, generates reactive oxygen species (ROS) and affords electrophilic quinone methides (QMs) having the ability to alkylate biological nucleophiles and in turn elicit a strong antiproliferative activity. In this context, the cysteine protease cathepsin B was initially presumed to be a target for ferrocenyl QMs.  In vitro  enzymatic assays ruled out this hypothesis but unexpectedly revealed that other ferrocifen metabolites, i.e. ferrocenyl indenes, acted as moderate inhibitors of cathepsin B. These experimental results were nicely confirmed by molecular docking calculations, that showed that the monophenol ferrocenyl indene and to a lower extent the diphenol interacted with the active site of cathepsin B, making it an unanticipated target of ferrocifens.
    Mots-clés : antitumor agent, bioorganometallic chemistry, CHEMBIO, computational chemistry, cysteine protease, docking, POLE 3.

  • M. Soroush, W. Ait Mammar, A. Wilson, H. Ghourchian, M. Salmain, et S. Boujday, « Design and Optimization of a Magneto-Plasmonic Sandwich Biosensor for Integration within Microfluidic Devices », Biosensors, vol. 12, nᵒ 10, p. 799, oct. 2022.
    Résumé : We designed a magneto-plasmonic biosensor for the immunodetection of antigens in minute sample volume. Both spherical gold nanoparticles (AuNP) and magnetic beads (MB) were conjugated to goat anti-rabbit IgG antibody (Ab) capable of recognizing a model target, rabbit IgG (rIgG). The AuNP bioconjugate was used as the optical detection probe while the MB one was used as the capture probe. Addition of the target analyte followed by detection probe resulted in the formation of a sandwich immunocomplex which was separated from the unbound AuNP-Ab conjugate by application of an external magnetic field. The readout was executed either in a direct or in indirect way by measuring the UV–Visible spectrum of each fraction in a specially designed microcell. Dose–response curves were established from the optical signal of the immunocomplex and unbound AuNP-Ab conjugate fractions. Finally, the assay was transposed to a microfluidic cell specially designed to enable easy separation of the immunocomplex and AuNP-Ab conjugate fractions and subsequent analysis of the latter fraction and achieve the quantification of the analyte in the ng/mL concentration range.
    Mots-clés : CHEMBIO, gold nanoparticles, immunosensor, magnetic beads, microfluidic chip, optical transduction, POLE 3.

  • F. Zhao, M. Abdellaoui, W. Hagui, M. Ballarin-Marion, J. Berthet, V. Corcé, S. Delbaere, H. Dossmann, A. Espagne, J. Forté, L. Jullien, T. Le Saux, V. Mouriès-Mansuy, C. Ollivier, et L. Fensterbank, « Reactant-induced photoactivation of in situ generated organogold intermediates leading to alkynylated indoles via Csp2-Csp cross-coupling », Nature Communications, vol. 13, nᵒ 1, p. 2295, avr. 2022.
    Résumé : Photosensitization of organogold intermediates is an emerging field in catalysis. In this context, an access to 2,3-disubstituted indoles from o-alkynyl aniline and iodoalkyne derivatives via a gold-catalyzed sequence under visible-light irradiation and in the absence of an exogenous photocatalyst was uncovered. A wide scope of the process is observed. Of note, 2-iodo-ynamides can be used as electrophiles in this cross-coupling reaction. The resulting N-alkynyl indoles lend themselves to post-functionalization affording valuable scaffolds, notably benzo[a]carbazoles. Mechanistic studies converge on the fact that a potassium sulfonyl amide generates emissive aggregates in the reaction medium. Static quenching of these aggregates by a vinylgold(I) intermediate yields to an excited state of the latter, which can react with an electrophile via oxidative addition and reductive elimination to forge the key C-C bond. This reactant-induced photoactivation of an organogold intermediate opens rich perspectives in the field of cross-coupling reactions.
    Mots-clés : CHEMBIO, CSOB, Photocatalysis, POLE 1, POLE 3, Reaction mechanisms.


  • L. Chang, N. Fischer-Durand, G. Gontard, B. Bertrand, S. Thorimbert, et L. Dechoux, « A solvent-free, catalyst-free formal [3+3] cycloaddition dearomatization strategy: towards new fluorophores for biomolecules labelling », ChemSusChem, vol. 14, nᵒ 8, p. 1821-1824, 2021.
    Résumé : A general, sustainable dearomatization reaction for nitrogen-containing heterocycles was developed. Under solvent free conditions and without catalyst, the biorenewable methyl coumalate ( MC ) reacts as an efficient C3 partner to convert eleven types of basic aromatic rings into their pyrido[1,2-a] fused derivatives in good to excellent yields. The fluorescence properties of some of the products were harnessed to conjugate fluorescent tags to BSA and immunoglobulin G.
    Mots-clés : CHEMBIO, dearomatization reaction, fluorescent probes, methyl coumalate, Michael addition, Nitrogen heterocycles, POLE 3.

  • J. - R. Jiménez, B. Xu, H. E. Said, Y. Li, J. von Bardeleben, L. - M. Chamoreau, R. Lescouëzec, S. Shova, D. Visinescu, M. - G. Alexandru, J. Cano, et M. Julve, « Field-induced single ion magnet behaviour of discrete and one-dimensional complexes containing [bis(1-methylimidazol-2-yl)ketone]-cobalt(II) building units », Dalton Transactions, vol. 50, nᵒ 44, p. 16353-16363, nov. 2021.
    Résumé : We describe herein the first examples of six-coordinate CoII single-ion magnets (SIMs) based on the β-diimine Mebik ligand [Mebik = bis(1-methylimidazol-2-yl)ketone]: two mononuclear [CoII(Rbik)2L2] complexes and one mixed-valence {CoIII2CoII}n chain of formulas [CoII(Mebik)(H2O)(dmso)(μ-NC)2CoIII2(μ-2,5-dpp)(CN)6]n·1.4nH2O (3) [L = NCS (1), NCSe (2) and 2,5-dpp = 2,5-bis(2-pyridyl)pyrazine (3)]. Two bidentate Mebik molecules plus two monodentate N-coordinated pseudohalide groups in cis positions build somewhat distorted octahedral surroundings around the high-spin cobalt(II) ions in 1 and 2. The diamagnetic [CoIII2(μ-2,5-dpp)(CN)8]2− metalloligand coordinates the paramagnetic [CoII(Mebik)(H2O)(dmso)]2+ complex cations in a bis-monodentate fashion to afford neutral zigzag heterobimetallic chains in 3. Ab initio calculations, and cryomagnetic dc (2.0–300 K) and ac (2.0–12 K) measurements as well as EPR spectroscopy for 1–3 show the existence of magnetically isolated high-spin cobalt(II) ions with D values of 59.84–89.90 (1), 66.32–93.90 (2) and 70.40–127.20 cm−1 (3) and field-induced slow relaxation of the magnetization, being thus new examples of SIMs with transversal magnetic anisotropy. The analysis of their relaxation dynamics reveals that the relaxation of the magnetization occurs by the Raman (with values of the n parameter covering the range 6.0–6.8) and direct spin-phonon processes.
    Mots-clés : ERMMES, POLE 2.

  • S. Khodjoyan, E. Remadna, H. Dossmann, D. Lesage, G. Gontard, J. Forté, H. Hoffmeister, U. Basu, I. Ott, P. Spence, Z. Waller, M. Salmain, et B. Bertrand, « [(C^C)Au(N^N)]+ complexes as a new family of anticancer candidates: synthesis, characterization and exploration of the antiproliferative properties », Chemistry – A European Journal, vol. 27, nᵒ 63, p. 15773-15785, 2021.
    Résumé : A library of eleven cationic gold(III) complexes of the general formula [(C^C)Au(N^N)] + when C^C is either biphenyl or 4,4’-ditertbutyldiphenyl and N^N is a bipyridine, phenanthroline or dipyridylamine derivative have been synthesized and characterized. Contrasting effects on the viability of the triple negative breast cancer cells MDA-MB-231 was observed from a preliminary screening. The antiproliferative activity of the seven most active complexes were further assayed on a larger panel of human cancer cells as well as on non-cancerous cells for comparison. Two complexes stood out for being either highly active or highly selective. Eventually, reactivity studies with biologically meaningful amino acids, glutathione, higher order DNA structures and thioredoxin reductase (TrxR) revealed a markedly different behavior from that of the well-known coordinatively isomeric [(C^N^C)Au(NHC)] + structure. This makes the [(C^C)Au(N^N)] + complexes a new class of organogold compounds with an original mode of action.
    Mots-clés : Bioorganometallics, Biphenyl, Cancer, Chelate, CHEMBIO, CSOB, Gold, POLE 3.

  • E. Levernier, K. Jaouadi, H. - R. Zhang, V. Corcé, A. Bernard, G. Gontard, C. Troufflard, L. Grimaud, E. Derat, C. Ollivier, et L. Fensterbank, « Phenyl Silicates with Substituted Catecholate Ligands: Synthesis, Structural Studies and Reactivity », Chemistry – A European Journal, vol. 27, nᵒ 34, p. 8782-8790, 2021.
    Résumé : While the generation of aryl radicals by photoredox catalysis under reductive conditions is well documented, it has remained challenging under an oxidative pathway. Because of the easy photo-oxidation of alkyl bis-catecholato silicates, a general study of phenyl silicates bearing substituted catecholate ligands has been achieved. The newly synthesized phenyl silicates have been fully characterized, and their reactivity has been explored. It was found that, thanks to the substitution of the catecholate moiety, notably with the 4-cyanocatecholato ligand, the phenyl radical could be generated and trapped. Computational studies provided a rationale for these findings.
    Mots-clés : aryl radicals, CHEMBIO, MACO, oxidation, photoredox catalysis, POLE 1, POLE 3, silicates.

  • A. Li, L. - M. Chamoreau, B. Baptiste, Y. Li, Y. Journaux, et L. Lisnard, « Solvothermal synthesis, structure and magnetic properties of heterometallic coordination polymers based on a phenolato-oxamato co-bidentate-tridentate ligand », Dalton Transactions, vol. 50, nᵒ 2, p. 681-688, janv. 2021.
    Résumé : The use of solvothermal conditions has succesfully led to the preparation of heterometallic 1D coordination polymers from a co-bidentate-tridentate phenolato-oxamato ligand. The reaction of the N-(2-hydoxyphenyl)oxamic acid (ohpma) with acetate salts of transition metal ions at 80 °C has yielded the heterobimetallic [Cu(ohpma)M(OAc)(DMF)2] (M = Co (1); Mn (2)) and the heterotrimetallic [Cu(ohpma)Co0.57Mn0.43(OAc)(DMF)2] (3) chain compounds. Single-crystal and powder diffraction studies show that the polymers are isostructural. Magnetic studies suggest the existence of an inter-chain two-dimensional antiferromagnetic interaction taking place in compounds 1–3.
    Mots-clés : ERMMES, POLE 2.

  • B. Neil, F. Lucien, L. Fensterbank, et C. Chauvier, « Transition-Metal-Free Silylation of Unactivated C(sp2)–H Bonds with tert-Butyl-Substituted Silyldiazenes », ACS Catalysis, vol. 11, nᵒ 21, p. 13085-13090, nov. 2021.
    Résumé : Aromatic organosilanes bearing C(sp2)–Si bonds have found increasing applications across the chemical science, yet are mostly produced by atom-uneconomical stoichiometric procedures. Catalytic alternatives using hydrosilanes as silicon sources have also been described, but they display unfavorable thermodynamics and are mostly based on expensive catalytic systems, often derived from noble metals, or lack generality. Herein, we describe the use of an alternative silicon source, namely the tert-butyl-substituted silyldiazenes (tBu–N═N–SiR3), that are readily accessible from commercially available precursors and whose structure enables the C(sp2)–H bond silylation of unactivated heteroaryl and aryl compounds under ambient, transition-metal-free catalytic conditions.
    Mots-clés : MACO, POLE 1.


  • Abdmouleh, Fatma, El Arbi, Mehdi, Hajer, Ben Saad, Jellali, Karim, Etata, Emna, Amara, Ibtissem Ben, Pigeon, Pascal, Hanen, Ben Hassen, Top, Siden, Jaouen, Gérard, Hammami, Riadh, Mamdouh, Ben Ali, et Gupta, Girish Kumar, « Antimicrobial, Antitumor and Side Effects Assessment of a Newly Synthesized Tamoxifen Analog », Current Topics in Medicinal Chemistry, vol. 20, nᵒ 25, p. 2281-2288, sept. 2020.
    Résumé : Background: Tamoxifen citrate is a very prevalent drug marketed under several trade names like Apo-Tamox, Nolvadex, Tamec, Tamizam, and Tamoplex. This molecule is approved by the FDA for breast cancer treatment. Some studies have shown that tamoxifen has anti-tuberculosis and antiparasitic activities. Like any drug, tamoxifen possesses side effects, more or less dangerous. Aims: Basically, this work is a comparative study that aims to: primarily compare the antimicrobial and antitumor activities of tamoxifen and a newly synthesized tamoxifen analog; and to determine the molecule with lesser side effects. Methods: Three groups of mice were injected with tamoxifen citrate and compound 2(1,1-bis[4-(3- dimethylaminopropoxy)phenyl]-2-phenyl-but-1-ene dihydrochloride) at doses corresponding to C1 (1/10), C2 (1/50), and C3 (1/100) to compound 2 lethal dose (LD50 = 75 mg/kg) administered to adult mice. A group of noninjected mice served as a study control. Results: Experimental results suggest that compound 2 has better antitumor and antimicrobial activity than tamoxifen citrate besides its lower toxicity effects. Conclusion: The results obtained from the present study confirmed the antitumor and antimicrobial effect of tamoxifen citrate and its hematological side effects. Compound 2 seems to be more effective than tamoxifen citrate for antitumor and antimicrobial treatment while having less hematological side effects and less disruption of the blood biochemical parameters. These findings encourage us to perform further studies on compound 2 and test it for other therapeutic uses for which tamoxifen was found effective.
    Mots-clés : CHEMBIO, POLE 3.

  • A. Benchohra, C. Méthivier, J. Landoulsi, D. Kreher, et R. Lescouëzec, « Electrospray ionization: an efficient approach to deposit polymetallic molecular switches onto gold surfaces », Chemical Communications, vol. 56, nᵒ 48, p. 6587-6589, 2020.
    Résumé : Electrospray ionization (EI) deposition is proven efficient in obtaining monolayers of a polymetallic charge transfer complex on gold surfaces. , Electrospray ionization (EI) deposition is proven efficient in obtaining monolayers of a polymetallic charge transfer complex on gold surfaces. The molecule's integrity is monitored by using PM-IRRAS and XPS. This approach broadens the perspective of molecular magnetic switch deposition, which is currently dominated by the thermal evaporation of monometallic spin crossover (SCO) complexes.
    Mots-clés : ERMMES, POLE 2.

  • J. ‐R. Jiménez, J. Glatz, A. Benchohra, G. Gontard, L. ‐M. Chamoreau, J. ‐F. Meunier, A. Bousseksou, et R. Lescouëzec, « Electron Transfer in the Cs⊂{Mn <sub>4</sub> Fe <sub>4</sub> } Cubic Switch: A Soluble Molecular Model of the MnFe Prussian‐Blue Analogues », Angewandte Chemie International Edition, vol. 59, nᵒ 21, p. 8089-8093, mai 2020.

  • Z. Li, T. Bavaro, S. Tengattini, R. Bernardini, M. Mattei, F. Annunziata, R. B. Cole, C. Zheng, M. Sollogoub, L. Tamborini, M. Terreni, et Y. Zhang, « Chemoenzymatic synthesis of arabinomannan (AM) glycoconjugates as potential vaccines for tuberculosis », European Journal of Medicinal Chemistry, vol. 204, p. 112578, 2020.

  • Y. Liu, J. Oble, A. Pradal, et G. Poli, « Catalytic Domino Annulations through η3-Allylpalladium Chemistry: A Never-Ending Story », European Journal of Inorganic Chemistry, vol. 2020, nᵒ 11-12, p. 942-961, 2020.
    Résumé : Annulative η3-allylpalladium chemistry has been a longstanding trending research topic since the 80's. Nowadays, this research area is still providing challenges to the catalysis community leading to the development original and brand-new transformations. Several reaction partners have been used as precursors for η3-allylpalladium species, namely allyl diacetates, allyl monoacetates, 3-acetoxy-2-trimethylsilylmethyl-1-propene (ASMP), alkylidene cyclopropanes (ACPs), vinyl cyclopropanes (VCPs), vinyl aziridines, and vinyl epoxides. This minireview is intended to show the recent developments in the field of annulative η3-allylpalladium chemistry with emphasis on new reactivity, enantioselective transformations as well as potential applications in total synthesis.
    Mots-clés : POLE 1, ROCS.

  • S. Nasri, M. Hajji, M. Guergueb, S. Dhifaoui, V. Marvaud, F. Loiseau, F. Molton, T. Roisnel, T. Guerfel, et H. Nasri, « Spectroscopic, Electrochemical, Magnetic and Structural Characterization of an Hexamethylenetetramine Co(II) Porphyrin Complex – Application in the Catalytic Degradation of Vat Yellow 1 dye », Journal of Molecular Structure, p. 129676, nov. 2020.
    Résumé : In this study, a new cobaltous-(hexamethylenetetramine) [meso-tetra(para-methoxyphenyl)porphyrin complex with the formula [CoII(TMPP)(HMTA)] (I) was synthesized. The molecular structure was confirmed in solution by 1H NMR spectroscopy and mass spectrometry methods, and the single crystal X-ray diffraction structure of (I) was determined at both room temperature and low temperature. This species was further characterized by infrared, UV-visible and fluorescence spectroscopies, magnetic susceptibility measurements and cyclic voltammetry. The chemical reactivity behavior was also assessed theoretically through Density Functional Theory (DFT) approach. Magnetic investigation indicates that the Co(II)-HMTA porphyrin (I) species at low temperature is a cobaltous low-spin (S = 1/2) species while at high temperature complex (I) exhibits a spin-crossover low-spin (S = 1/2) ↔ high-spin (S = 3/2). The adsorption kinetic of the “vat yellow 1 dye” was carried out in aqueous solution at pH = 6. The experimental results are better fitted using the pseudo second order model. Furthermore, complex (I) was tested as catalyst in the degradation of the vat yellow 1 dye using an aqueous H2O2 solution and by photodegradation under solar light.
    Mots-clés : E-POM, POLE 2.

  • Y. Ren, J. Forte, K. Cheaib, N. Vanthuyne, L. Fensterbank, H. Vezin, M. Orio, S. Blanchard, et M. Desage-El Murr, « Optimizing Group Transfer Catalysis by Copper Complex with Redox-Active Ligand in an Entatic State », Iscience, vol. 23, nᵒ 3, p. UNSP 100955, mars 2020.
    Résumé : Metalloenzymes use earth-abundant non-noble metals to perform high-fidelity transformations in the biological world. To ensure chemical efficiency, metalloenzymes have acquired evolutionary reactivity-enhancing tools. Among these, the entatic state model states that a strongly distorted geometry induced by ligands around a metal center gives rise to an energized structure called entatic state, strongly improving the reactivity. However, the original definition refers both to the transfer of electrons or chemical groups, whereas the chemical application of this concept in synthetic systems has mostly focused on electron transfer, therefore eluding chemical transformations. Here we report that a highly strained redox-active ligand enables a copper complex to perform catalytic nitrogen- and carbon-group transfer in as fast as 2 min, thus exhibiting a strong increase in reactivity compared with its unstrained analogue. This report combines two reactivity-enhancing features from metalloenzymes, entasis and redox cofactors, applied to group-transfer catalysis.
    Mots-clés : aziridination, cu, E-POM, galactose-oxidase, generation, MACO, metal-complexes, models, oxidation, POLE 1, POLE 2, radicals, reactivity, site.


  • S. De, A. Flambard, D. Garnier, P. Herson, F. H. Köhler, A. Mondal, K. Costuas, B. Gillon, R. Lescouëzec, B. Le Guennic, et F. Gendron, « Probing the Local Magnetic Structure of the [FeIII(Tp)(CN)3]− Building Block Via Solid-State NMR Spectroscopy, Polarized Neutron Diffraction, and First-Principle Calculations », Chemistry – A European Journal, vol. 25, nᵒ 52, p. 12120-12136, 2019.
    Résumé : Abstract The local magnetic structure in the [FeIII(Tp)(CN)3]− building block was investigated by combining paramagnetic Nuclear Magnetic Resonance (pNMR) spectroscopy and polarized neutron diffraction (PND) with first-principle calculations. The use of the pNMR and PND experimental techniques revealed the extension of spin-density from the metal to the ligands, as well as the different spin mechanisms that take place in the cyanido ligands: Spin-polarization on the carbon atoms and spin-delocalization on the nitrogen atoms. The results of our combined density functional theory (DFT) and multireference calculations were found in good agreement with the PND results and the experimental NMR chemical shifts. Moreover, the ab-initio calculations allowed us to connect the experimental spin-density map characterized by PND and the suggested distribution of the spin-density on the ligands observed by NMR spectroscopy. Interestingly, significant differences were observed between the pseudo-contact contributions of the chemical shifts obtained by theoretical calculations and the values derived from NMR spectroscopy using a simple point-dipole model. These discrepancies underline the limitation of the point-dipole model and the need for more elaborate approaches to break down the experimental pNMR chemical shifts into contact and pseudo-contact contributions.
    Mots-clés : ERMMES, POLE 2.

  • M. Okubo, J. Long, D. R. Talham, et R. Lescouëzec, « Solid-state electrochemistry of metal cyanides », Comptes Rendus Chimie, vol. 22, nᵒ 6, p. 483 - 489, 2019.
    Résumé : Efficient energy storage in the form of batteries contributes to building sustainable society. As advanced batteries need positive electrode materials capable of larger capacity, higher voltage, and lower cost, it is important to search for novel electrode materials. Among various inorganic/organic materials, cyanido-bridged coordination compounds are promising candidates for battery electrodes due to their ability to undergo solid-state redox reaction associated with ion (de)intercalation. In this review, recent results about the thermodynamic and kinetic aspects of the solid-state electrochemistry of cyanido-bridged coordination compounds are summarized, providing a fundamental basis toward developing cyanide electrodes for advanced batteries. Résumé Le stockage de l’énergie dans des batteries performantes est un élément clé pour le développement des énergies renouvelables et d'un modèle de société durable. Un des défis pour construire de nouvelles batteries plus performantes est le développement de matériaux d'intercalation pour cathode présentant de plus grandes capacités, de plus grands voltages et des coûts réduits. Parmi les divers matériaux organiques et inorganiques explorés, les polymères de coordination à pont cyanure sont des candidats prometteurs. Ceux ci peuvent s'oxyder et se réduire à l’état solide en (dés)intercalant des ions. Dans cette revue, quelques résultats récents sur les aspects thermodynamiques et cinétiques des propriétés électrochimiques des polymères de coordination à pont cyanure sont résumés, démontrant leur potentiel intérêt comme életcrodes dans de nouvelles batteries.
    Mots-clés : ERMMES, POLE 2.


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