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Productions scientifiques

2019, ICR-2010-2019.

ACL - Articles dans des revues à comité de lecture

33 références.

  • Abdallah, M.; Hijazi, A.; Graff, B.; Fouassier, J. - P.; Rodeghiero, G.; Gualandi, A.; Dumur, F.; Cozzi, P. G.; Lalevee, J. Polymer Chemistry 2019, 10 (7), 872-884.
    Résumé : The goal of this paper concerns the first evaluation of two recently reported coumarins to initiate photopolymerization reactions. These two compounds (CoumA and CoumB) are proposed as high performance visible light photoinitiators and evaluated as photoredox catalysts (PCs), in the presence of an iodonium salt or with an amine, for both the free radical polymerization (FRP) of (meth) acrylates and the cationic polymerization (CP) of epoxides upon visible light exposure using an LED at 405 nm. These coumarin derivatives showed a high photoinitiation ability i. e. excellent polymerization rates and high final monomer conversions were obtained. The photophysical and photochemical properties of the coumarin derivatives were studied in terms of absorption, steady state photolysis and fluorescence spectroscopy. The photoinitiation mechanisms of the coumarin derivatives were discussed from fluorescence quenching, redox behavior and cyclic voltammetry experiments. A full picture of the involved photochemical mechanisms is provided. Coumarin-based systems are high performance photoinitiators, and their use in new photosensitive 3D printing resins will also be presented. Remarkably, CoumB is also found to be very efficient for the preparation of hydrogels under mild conditions due to its high solubility in water i. e. CoumB corresponds to a high-performance water soluble photoinitiator. Finally, the usage of the new coumarin derivatives for photocomposite synthesis with glass fibers (thick samples with a good depth of cure) using a near-UV conveyor (LED @ 395 nm) is particularly outlined.

  • Audran, G.; Marque, S. R. A.; Santelli, M. Journal of Physical Chemistry A 2019, 123 (7), 1380-1388.
    Résumé : After quantum calculations of absolute free energies of polyatomic sulfur derivatives or hydrocarbon oligomer compounds, we have studied the variations of G(n) as a function of the number of repeating units n (sulfur atoms or hydrocarbon units, G(n) = 2 to about 60), and observed that these values can be correlated by (a) a nearly perfect linear relationship, Gn = An + B (A and B, constants), with a high accuracy which enables an extrapolation for higher values of n, and (b) a power law:, delta G = G(n)/n - G((n-1)) /(n-1) = C/n(d) (C and d, constants). From comparison of variations of the C-C bond lengths, we show that the conjugation of trans-polyenes (up to C60H62) is more important than for polyynes (up to C60H2).

  • Bahramian, A.; Eyraud, M.; Maria, S.; Vacandio, F.; Djenizian, T.; Knauth, P. Corrosion Science 2019, 149, 75-86.
    Résumé : Cu/Ni-P/Au multi-layer systems are employed as electrical contacts. The Au top-layer is thin and porous. These pores deliver the corrosive media to the under-layer, which induces the corrosion by a galvanic coupling mechanism. Therefore, filling these pores is essential to improve the lifetime of electronic devices. The pores can be sealed by the electrodeposition of poly(methyl methacrylate) that decreased the porosity index (about 97%) and increased the corrosion resistance (about

  • Bai, S.; Barbatti, M. Journal of chemical theory and computation 2019, 15 (3), 1503-1513.
    Résumé : Spin-exchange internal conversion (SEIC) is a general class of reactions having singlet fission and triplet fusion as particular cases. Based on a charge transfer (CT) mediated mechanism and analytical derivation with a model Hamiltonian, we propose proxies for estimating the coupling strength in both diabatic and adiabatic pictures for general SEIC reactions. In the diabatic picture, we demonstrated the existence of a bilinear relationship between the coupling strength and molecular orbital overlap, which provides a practical way to predict diabatic couplings. In the adiabatic picture, we showed that nonadiabatic couplings can be approximated by simple functions of the wave function

  • Bailey, D. M.; Brugniaux, J. V.; Filipponi, T.; Marley, C. J.; Stacey, B.; Soria, R.; Rimoldi, S. F.; Cerny, D.; Rexhaj, E.; Pratali, L.; Salinas Salmon, C.; Murillo Jauregui, C.; Villena, M.; Smirl, J. D.; Ogoh, S.; Pietri, S.; Scherrer, U.; Sartori, C. Journal of Physiology-London 2019, 597 (2), 611-629.
    Résumé : Chronic mountain sickness (CMS) is a maladaptation syndrome encountered at high altitude (HA) characterised by severe hypoxaemia that carries a higher risk of stroke and migraine and is associated with increased morbidity and mortality. The present cross-sectional study examined to what extent exaggerated systemic oxidative-inflammatory-nitrosative stress (OXINOS), defined by an increase in free radical formation and corresponding decrease in vascular nitric oxide (NO) bioavailability, is associated with impaired cerebrovascular function, accelerated cognitive decline and depression in CMS. Venous blood was obtained from healthy male lowlanders (80 m, n = 17), and age- and gender- matched HA dwellers born and bred in La Paz, Bolivia (3600 m) with (CMS+, n= 23) and without (CMS-, n= 14) CMS. We sampled blood for oxidative (electron paramagnetic resonance spectroscopy, HPLC), nitrosative (ozone-based chemiluminescence) and inflammatory (fluorescence) biomarkers. We employed transcranial Doppler ultrasound to measure cerebral blood flow (CBF) and reactivity. We utilised psychometric tests and validated questionnaires to assess cognition and depression. Highlanders exhibited elevated systemic OXINOS (P< 0.05vs. lowlanders) that was especially exaggerated in the more hypoxaemic CMS+ patients (P< 0.05 vs. CMS-). OXINOS was associated with blunted cerebral perfusion and vasoreactivity to hypercapnia, impaired cognition and, in CMS+, symptoms of depression. Collectively, these findings are the first to suggest that a physiological continuum exists for hypoxaemia-induced OXINOS in HA dwellers that when excessive is associated with accelerated cognitive decline and depression, helping identify those in need of specialist neurological assessment and support.

  • Capozzi, A.; Patel, S.; Gunnarsson, C. P.; Marco-Rius, I.; Comment, A.; Karlsson, M.; Lerche, M. H.; Ouari, O.; Ardenkjaer-Larsen, J. H. Angewandte Chemie-International Edition 2019, 58 (5), 1334-1339.
    Résumé : Free radicals generated by UV-light irradiation of a frozen solution containing a fraction of pyruvic acid (PA) have demonstrated their dissolution dynamic nuclear polarization (dDNP) potential, providing up to 30% [1-C-13] PA liquid-state polarization. Moreover, their labile nature has proven to pave a way to nuclear polarization storage and transport. Herein, differently from the case of PA, the issue of providing dDNP UV-radical precursors (trimethylpyruvic acid and its methyl-deuterated form) not involved in any metabolic pathway was investigated. The C-13 dDNP performance was evaluated for hyperpolarization of [U-C-13(6),1,2,3,4,5,6,6-d(7)]-D-glucose. The generated UV-radicals proved to be versatile and highly efficient polarizing agents, providing, after dissolution and transfer (10 s), a C-13 liquid-state polarization of up to 32%.

  • Combes, S.; Tran, K. T.; Ayhan, M. M.; Karoui, H.; Rockenbauer, A.; Tonetto, A.; Monnier, V.; Charles, L.; Rosas, R.; Viel, S.; Siri, D.; Tordo, P.; Clair, S.; Wang, R.; Bardelang, D.; Ouari, O. Journal of the American Chemical Society 2019.
    Résumé : Triangular shapes have inspired scientists over time and are common in nature, such as the flower petals of oxalis triangularis, the triangular faces of tetrahedrite crystals, and the icosahedron faces of virus capsids. Supramolecular chemistry has enabled the construction of triangular assemblies, many of which possess functional features. Among these structures, cucurbiturils have been used to build supramolecular triangles, and we recently reported paramagnetic cucurbit[8]uril (CB[8]) triangles, but the reasons for their formation remain unclear. Several parameters have now been identified to explain their formation. At first sight, the radical nature of the guest was of prime importance in obtaining the triangles, and we focused on extending this concept to biradicals to get supramolecular hexaradicals. Two sodium ions were systematically observed by ESI-MS in trimer structures, and the presence of Na+ triggered or strengthened the triangulation of CB[8]/guest 1:1 complexes in solution. X-ray crystallography and molecular modeling have allowed the proposal of two plausible sites of residence for the two sodium cations. We then found that a diamagnetic guest with an H-bond acceptor function is equally good at forming CB[8] triangles. Hence, a guest molecule containing a ketone function has been precisely triangulated thanks to CB[8] and sodium cations as determined by DOSY-NMR and DLS. A binding constant for the triangulation of 1:1 to 3:3 complexes is proposed. This concept has finally been extended to the triangulation of ditopic guests toward network formation by the reticulation of CB[8] triangles using dinitroxide biradicals.
  • Delmotte, N.; Roche, M.; Giraud, R.; Roche, M.; Falaise, C.; Chambost, H.; Gensollen, S. Haemophilia 2019, 25, 102-102.

  • Edeleva, M.; Audran, G.; Marque, S.; Bagryanskaya, E. Materials (Basel, Switzerland) 2019, 12 (5).
    Résumé : Because alkoxyamines are employed in a number of important applications, such as nitroxide-mediated polymerization, radical chemistry, redox chemistry, and catalysis, research into their reactivity is especially important. Typically, the rate of alkoxyamine homolysis is strongly dependent on temperature. Nonetheless, thermal regulation of such reactions is not always optimal. This review describes various ways to reversibly change the rate of C⁻ON bond homolysis of alkoxyamines at constant temperature. The major methods influencing C⁻ON bond homolysis without alteration of temperature are protonation of functional groups in an alkoxyamine, formation of metal⁻alkoxyamine complexes, and chemical transformation of alkoxyamines. Depending on the structure of an alkoxyamine, these approaches can have a significant effect on the homolysis rate constant, by a factor of up to 30, and can shorten the half-lifetime from days to seconds. These methods open new prospects for the application of alkoxyamines in biology and increase the safety of (and control over) the nitroxide-mediated polymerization method.

  • Fersing, C.; Basmaciyan, L.; Boudot, C.; Pedron, J.; Hatter, S.; Cohen, A.; Castera-Ducros, C.; Primas, N.; Laget, M.; Casanova, M.; Bourgeade-Delmas, S.; Piednoel, M.; Sournia-Saquet, A.; Mbou, V. B.; Courtioux, B.; Boutet-Robinet, E.; Since, M.; Milne, R.; Wyllie, S.; Fairlamb, A. H.; Valentin, A.; Rathelot, P.; Verhaeghe, P.; Vanelle, P.; Azas, N. Acs Medicinal Chemistry Letters 2019, 10 (1), 34-39.
    Résumé : Twenty nine original 3-nitroimidazo[1,2-a]pyridine derivatives, bearing a phenylthio (or benzylthio) moiety at position 8 of the scaffold, were synthesized. In vitro evaluation highlighted compound 5 as an antiparasitic hit molecule displaying low cytotoxicity for the human HepG2 cell line (CC50 > 100 mu M) alongside good antileishmanial activities (IC50 = 1-2.1 mu M) against L. donovani, L. infantum, and L. major; and good antitrypanosomal activities (IC50 = 1.3-2.2 mu M) against T. brucei brucei and T. cruzi, in comparison to several reference drugs such as miltefosine, fexinidazole, eflornithine, and benznidazole (IC50 = 0.6 to 13.3 mu M). Molecule 5, presenting a low reduction potential (E degrees = -0.63 V), was shown to be selectively bioactivated by the L. donovani type 1 nitroreductase (NTR1). Importantly, molecule 5 was neither mutagenic (negative Ames test), nor genotoxic (negative comet assay), in contrast to many other nitroaromatics. Molecule 5 showed poor microsomal stability; however, its main metabolite (sulfoxide) remained both active and nonmutagenic, making 5 a good candidate for further in vivo studies.

  • Guerineau, V.; Rollet, M.; Viel, S.; Lepoittevin, B.; Costa, L.; Saint-Aguet, P.; Laurent, R.; Roger, P.; Gigmes, D.; Martini, C.; Huc, V. Nature Communications 2019, 10, 113.
    Résumé : Calixarenes are cyclic oligomers obtained by condensation of suitable p-functionalised phenols with formaldehyde, usually allowing for the synthesis of the well known small calixarenes (including up to eight phenolic subunits). We report here the discovery of much larger members of this family, exhibiting sizes up to 90 phenolic subunits: the giant calixarenes. These macrocycles are obtained according to simple, easily scalable processes, in yields up to 65%. We show that the formation of these giant macrocycles is favored by an oxygencontaining-group at the para-position of the starting phenol, high concentrations of heavy alkaline bases (rubidium or cesium hydroxides) and long reaction times. A mechanism is proposed to rationalize these observations. These giant macrocycles can also be obtained in the quasi-solid state, opening interesting perspectives in the field of calixarenes chemistry. Along with their intrinsic fundamental interest, these objects are also opening interesting applicative potentialities.

  • Le, D.; Dilger, M.; Pertici, V.; Diabate, S.; Gigmes, D.; Weiss, C.; Delaittre, G. Angewandte Chemie (International ed. in English) 2019, 58 (14), 4725-4731.
    Résumé : We report the straightforward, time-efficient synthesis of radical core-shell nanoparticles (NPs) by polymerization-induced self-assembly. A nitroxide-containing hydrophilic macromolecular precursor was prepared by ring-opening metathesis copolymerization of norbornenyl derivatives of TEMPO and oligoethylene glycol and was chain-extended in situ with norbornene in ethanolic solution, leading to simultaneous amphiphilic block copolymer formation and self-assembly. Without any intermediate purification from the monomers to the block copolymers, radical NPs with tunable diameters ranging from 10 to 110 nm are obtained within minutes at room temperature. The high activity of the radical NPs as chemoselective and homogeneous, yet readily recyclable catalysts is demonstrated through oxidation of a variety of alcohols and recovery by simple centrifugation. Furthermore, the NPs show biocompatibility and antioxidant activity in vitro.

  • Liu, R.; Gao, X.; Barbatti, M.; Jiang, J.; Zhang, G. The journal of physical chemistry letters 2019, 10 (6), 1388-1393.
    Résumé : Pure light-atom organic phosphorescent molecules have been under scientific scrutiny because they are inexpensive, flexible, and environment friendly. The development of such materials, however, faces a bottleneck problem of intrinsically small spin-orbit couplings, which can be addressed by seeking a proper balance between intersystem crossing (ISC) and fluorescence rates. Using N-substituted naphthalimides as the prototype molecule, we applied chemical modifications with several electrophilic and nucleophilic functional groups, to approach the goal. The selected electron donating groups actively restrain the fluorescence, enabling an efficient ISC to the triplet manifold. Electron withdrawing groups do not change the luminescent properties of the parent species. The changes in ISC and fluorescence rates are related to the nature of the lowest singlet state, which changes from localized excitation into charge-transfer excitation upon configuration change of excited molecules. This finding opens an alternative strategy for designing pure light-atom organic phosphorescent molecules for emerging luminescent materials applications.

  • Lo Presti, C.; Curti, C.; Montana, M.; Bornet, C.; Vanelle, P. Medecine Et Maladies Infectieuses 2019, 49 (1), 1-8.
    Résumé : Despite its benign characteristics, chickenpox is a childhood disease responsible for complications and deaths, particularly in the high-risk population. VariZIG (R), not commercialized in France, is a good alternative for seronegative individuals exposed to the virus and not eligible for vaccination. The efficacy of routine vaccination has been demonstrated with a decrease in chickenpox incidence and with the development of herd immunity. Over time, the protective antibody titer of vaccinated people decreases and can be maintained by two doses of the vaccine. A tetravalent measles-mumps-rubella-chickenpox vaccine, used in the United States, has a good tolerability in spite of the occurrence of fever and febrile seizures. Routine vaccination would contribute to make savings in France, by reducing direct and indirect costs of chickenpox. (C) 2018 Elsevier Masson SAS. All rights reserved.

  • Luconi, L.; Garino, C.; Vioglio, P. C.; Gobetto, R.; Chierotti, M. R.; Yakhvarov, D.; Gafurov, Z. N.; Morozov, V.; Sakhapov, I. 'yas; Rossin, A.; Giambastiani, G. Acs Omega 2019, 4 (1), 1118-1129.
    Résumé : Four metal halides of the ((PCN)-P-tBu) NiX family [X = F (1), Cl (2), Br (3), or I (4); PCN = 1-[3-[(di-tert-butylphosphino) methyl] phenyl]-1H-pyrazole] have been prepared through a direct reaction of the corresponding anhydrous NiX2 salts and the unsymmetrical PCN pincer ligand. Structural information from single-crystal X-ray data, F-19 solution nuclear magnetic resonance, and combined electrochemical results [cyclic voltammetry (CV) and in situ electron paramagnetic resonance spectro-electrochemistry] reveal that the fluoride complex 1 is different from the other halides 2-4 in terms of electro-oxidation behavior (presence of three anodic peaks instead of one in the CV profile). 1 is also different from its symmetrical analogue ((PCP)-P-tBu) NiF in terms of halogen-bonding capability toward the halogen-bond donor, iodopentafluorobenzene (C6F5I, IPFB). The positive Delta S degrees value for the formation of the 1...IPFB adduct inferred from the van't Hoff plots is in agreement with the existence of (1.H2O) aggregates in solution, not present in 2-4. The high nucleophilicity of the fluoride ligand and the simultaneous presence of electrophilic (acidic) protons on the sidearm of the pyrazole ligand are at the origin of the observed phenomena.

  • Marin, A. C.; Culcasi, M.; Cassien, M.; Stocker, P.; Thetiot-Laurent, S.; Robillard, B.; Chinnici, F.; Pietri, S. Food Chemistry 2019, 285, 67-76.
    Résumé : The efficacy against oxidative degradation in model and sulphite-free white wines of two commercial, insoluble chitosans (one being approved for winemaking) were investigated by electron paramagnetic resonance (EPR). Both compounds at various doses significantly inhibited the formation of alpha-(4-pyridyl-1-oxide)-N-t-butylnitrone (4-POBN)-1-hydroxyethyl adducts under normal wine storage conditions. Pre-incubation with 2 g/L chitosan followed by filtration had a better effect than adding 50 mg/L sulphur dioxide to the experimental Chardonnay wine on the release of 4-POBN adducts after 6 days of incubation with 100 mu M iron(II). In a relevant photo-oxidative system acetaldehyde formation was significantly reduced after 6 days of incubation. Parallel EPR tests were performed to assess the importance of metal chelation (iron and copper) versus direct scavenging of hydroxyl radicals on the effect of chitosan. The present data support the potentiality of using biocompatible chitosan as a healthier complement and/or alternative to sulphur dioxide against white wine oxidative spoilage.

  • Mathias, F.; Curti, C.; Montana, M.; Bornet, C.; Vanelle, P. European Journal of Clinical Microbiology & Infectious Diseases 2019, 38 (2), 209-231.
    Résumé : Clostridium difficile infections (CDI) dramatically increased during the last decade and cause a major public health problem. Current treatments are limited by the high disease recurrence rate, severity of clinical forms, disruption of the gut microbiota, and colonization by vancomycin-resistant enterococci (VRE). In this review, we resumed current treatment options from official recommendation to promising alternatives available in the management of adult CDI, with regard to severity and recurring or non-recurring character of the infection. Vancomycin remains the first-line antibiotic in the management of mild to severe CDI. The use of metronidazole is discussed following the latest US recommendations that replaced it by fidaxomicin as first-line treatment of an initial episode of non-severe CDI. Fidaxomicin, the most recent antibiotic approved for CDI in adults, has several advantages compared to vancomycin and metronidazole, but its efficacy seems limited in cases of multiple recurrences. Innovative therapies such as fecal microbiota transplantation (FMT) and antitoxin antibodies were developed to limit the occurrence of recurrence of CDI. Research is therefore very active, and new antibiotics are being studied as surotomycin, cadazolid, and rinidazole.

  • Montana, M.; Mathias, F.; Terme, T.; Vanelle, P. European Journal of Medicinal Chemistry 2019, 163, 136-147.
    Résumé : Cancer is a leading cause of death and a major health problem worldwide. While many effective anticancer agents are available, the majority of drugs currently on the market are not specific, raising issues like the common side effects of chemotherapy. However, recent research hold promise for the development of more efficient and safer anticancer drugs. Quinoxaline and its derivatives are becoming recognized as a novel class of chemotherapeutic agents with activity against different tumors. The present review compiles and discusses studies concerning the therapeutic potential of the anticancer activity of quinoxaline derivatives, covering articles published between July 2013 and July 2018. (C) 2018 Elsevier Masson SAS. All rights reserved.

  • Oswald, L.; Al Ouahabi, A.; Laure, C.; Amalian, J. - A.; Charles, L.; Lutz, J. - F. Journal of Polymer Science Part a-Polymer Chemistry 2019, 57 (3), 403-410.
    Résumé : Soluble supports, with optimal molecular structures for iterative oligomer synthesis, were prepared by atom transfer radical copolymerization of styrene with Fmoc-amino ethyl methacrylate. Size exclusion chromatography and nuclear magnetic resonance indicated formation of copolymers with controlled chain lengths, chain ends, dispersity, and comonomer compositions. These polymers were afterward subjected to two subsequent modifications steps: (a) the debromination of their omega-chain ends via a tributyltin hydride treatment and (b) the removal of the Fmoc-protecting groups in acidic conditions, thus leading to bromine-free copolymers with a precise primary amine loading capacity. These universal amine-containing precursors were then derived into a variety of functional supports. A glycine-loaded Wang-type soluble polystyrene support was prepared in two steps and tested for peptide synthesis as well as for the preparation of digital oligo(alkoxyamine amide)s. In both cases, it was possible to obtain uniform sequence-defined oligomers as evidenced by electrospray ionization tandem mass spectrometry. However, each type of oligomer required specific experimental conditions and therefore soluble supports with an adapted loading capacity for optimal synthesis. Furthermore, the amine-containing universal precursors were also transformed into soluble supports for iterative phosphoramidite chemistry. A support was specifically conceived for the iterative synthesis of abiotic digital oligo(phosphodiester)s and another one was designed for oligonucleotide synthesis. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 403-410

  • Pereira Rodrigues, G.; Lopes de Lima, T. M.; de Andrade, R. B.; Ventura, E.; do Monte, S. A.; Barbatti, M. The journal of physical chemistry. A 2019, 123 (10), 1953-1961.
    Résumé : High-level multireference electronic structure calculations have been performed to study the Cl- yield from photoexcited CF3CH2Cl (HCFC-133a). The analysis of this process tells that it relates to an electron transfer from the carbon to the Cl atom, forming a highly polar contact ion-pair complex, CF3HCH+···Cl-, in the excited (S3) state. This complex has a strong binding energy of 3.53 eV, from which 0.47 eV is due to an underlying hydrogen bond. Through comparison with the results obtained for the prototype CH3Cl system, where a similar ion-pair state associated with Cl- formation has also been observed, it is suggested that photodissociation of HCFC-133a can also yield Cl- through an analogous process. This hypothesis is further supported by nonadiabatic dynamics simulations, which shows formation of the ion-pair complex in the subpicosecond time scale.

  • Pertici, V.; Pin-Barre, C.; Rivera, C.; Pellegrino, C.; Laurin, J.; Gigmes, D.; Trimaille, T. Biomacromolecules 2019, 20 (1), 149-163.
    Résumé : Injectable hydrogels are promising platforms for tissue engineering and local drug delivery as they allow minimal invasiveness. We have here developed an injectable and biodegradable hydrogel based on an amphiphilic PNIPAAm-b-PLA-b-PEG-b-PLA-b-PNIPAAm pentablock copolymer synthesized by ring-opening polymerization/nitroxide-mediated polymerization (ROP/NMP) combination. The hydrogel formation at around

  • Phan, T. N. T.; Issa, S.; Gigmes, D. Polymer International 2019, 68 (1), 7-13.
    Résumé : Nanostructured block copolymer electrolytes (BCEs) based on poly(ethylene oxide) (PEO) are considered as promising candidates for solid-state electrolytes in high energy density lithium metal batteries (LMBs). Because of their self-assembly properties, they confer on electrolytes both high mechanical strength and sufficient ionic conductivity, which linear PEO cannot provide. Two types of PEO-based BCEs are commonly known. There are the traditional ones, also called dual-ion conducting BCEs, which are a mixture of block copolymer chains and lithium salts. In these systems, the cations and anions participate in the conduction, inducing a concentration polarization in the electrolyte, thus leading to poor performances of LMBs. The second family of BCEs are single-lithium-ion conducting BCEs (SIC-BCEs), which consist of anions being covalently grafted to the polymer backbone, therefore involving conduction by lithium ions only. SIC-BCEs have marked advantages over dual-ion conducting BCEs due to a high lithium ion transference number, absence of anion concentration gradients as well as low rate of lithium dendrite growth. This review focuses on the recent developments in BCEs for applications in LMBs with particular emphasis on the physicochemical and electrochemical properties of these materials. (c) 2018 Society of Chemical Industry

  • Pigot, C.; Dumur, F. Materials 2019, 12 (4), 662.
    Résumé : The fabrication of macromolecular organic structures on surfaces is one major concern in materials science. Nanoribbons, linear polymers, and porous nanostructures have gained a lot of interest due to their possible applications ranging from nanotemplates, catalysis, optoelectronics, sensors, or data storage. During decades, supramolecular chemistry has constituted an unavoidable approach for the design of well-organized structures on surfaces displaying a long-range order. Following these initial works, an important milestone has been established with the formation of covalent bonds between molecules. Resulting from this unprecedented approach, various nanostructures of improved thermal and chemical stability compared to those obtained by supramolecular chemistry and displaying unique and unprecedented properties have been developed. However, a major challenge exists: the growth control is very delicate and a thorough understanding of the complex mechanisms governing the on-surface chemistry is still needed. Recently, a new approach consisting in elaborating macromolecular structures by combining consecutive steps has been identified as a promising strategy to elaborate organic structures on surface. By designing precursors with a preprogrammed sequence of reactivity, a hierarchical or a sequential growth of 1D and 2D structures can be realized. In this review, the different reaction combinations used for the design of 1D and 2D structures are reported. To date, eight different sequences of reactions have been examined since 2008, evidencing the intense research activity existing in this field.

  • Poyer, S.; Chendo, C.; Laure, C.; Lutz, J. - F.; Siri, D.; Charles, L. International Journal of Mass Spectrometry 2019, 438, 29-35.
    Résumé : Information could be stored in the backbone of sequence-defined oligo(alkoxyamine amide)s based on coded amide moieties, and further retrieved by MS/MS sequencing since their collision-induced dissociation only proceeded via competitive homolysis of alkoxyamine linkages. However, when occurring at chain ends, C-ON bond homolysis did not yield the set of complementary product ions expected from such a charge-remote reaction. The actual role of the adducted proton on the dissociation mechanism was then investigated. Using a set of tri(alkoxyamine amide)s that each contained two C-ON bonds, theoretical calculations first showed that protonation most favorably occurred at nitroxide moieties or at the central amide group compared to terminal amides. This result explained why the fragment at the left-hand side of the first C-ON bond was always released as a radical and never detected as a charged product. These calculations also showed that tri(alkoxyamine amide)s would exist as different protomers that could be experimentally evidenced for some of the studied species by traveling wave ion mobility spectrometry (TWIMS). TWIMS-MS/MS experiments were then performed for individual study of the IMS-resolved protomer. So-obtained data suggested that C-ON bond cleavage did not occur when the nitroxide nitrogen was protonated. However, calculations performed on optimized structures evidenced that, prior to alkoxyamine homolysis, the proton adducted to the nitroxide could be transferred onto the nearby amide oxygen atom, hence permitting to rationalize TWIMS-MS/MS data. (C) 2018 Elsevier B.V. All rights reserved.

  • Rolere, S.; Monge, S.; Rakotonirina, M. D.; Guillaneuf, Y.; Gigmes, D.; Robin, J. - J. Journal of Polymer Science Part a-Polymer Chemistry 2019, 57 (2), 120-129.
    Résumé : Chemical modification of poly(lactic acid) (PLA) with N-acetoxy-phthalimide (NAPI) was performed in the melt by reactive extrusion, without using any peroxide initiator. The aminyl and nitroxide radicals produced from the NAPI thermal degradation, were, respectively, used (a) to create PLA macroradicals, and (b) to functionalize the PLA samples through nitroxide radical coupling. Depending on the extrusion temperature and the initial NAPI concentration, grafting rates up to 0.24 mol % were measured, modifying the PLA optical properties. This study represents an original new way of modification of PLA without the use of conventional peroxide initiators. Indeed, the undesirable side reactions (PLA branching or crosslinking) usually observed when using peroxides to initiate the radical grafting of PLA were avoided when using NAPI. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 120-129

  • Rolere, S.; Monge, S.; Rakotonirina, M. D.; Guillaneuf, Y.; Gigmes, D.; Robin, J. - J. Journal of Polymer Science Part a-Polymer Chemistry 2019, 57 (8), 917-928.
    Résumé : Radical grafting of poly(lactide) (PLA) during postpolymerization reactive extrusion is usually done with peroxide initiation, leading to undesirable side reactions (branching or crosslinking) and to difficulties to control the process parameters as well as the final macromolecular structure. The use of N-acetoxy-phthalimide (NAPI) was investigated as an alternative to peroxides for the functionalization in the melt of PLA with N-phenylmaleimide (PhM) monomer. The use of NAPI was found to lead to similar grafting rates in comparison to peroxides, with a better control of the PLA macromolecular structure, due to the formation of nitroxide radicals that combine with the produced macroradicals. Also, the grafting site on PLA backbone was identified after hydrolysis of grafted PLA. Above an optimal PhM concentration, homopolymerization of the monomer was also highlighted. (c) 2019 Wiley Periodicals, Inc.

  • Spitz, C.; Mathias, F.; Pechine, S.; Doan, T. H. D.; Innocent, J.; Pellissier, S.; Di Giorgio, C.; Crozet, M. D.; Janoir, C.; Vanelle, P. Chemmedchem 2019, 14 (5), 561-569.
    Résumé : Metronidazole is one of the first-line treatments for non-severe Clostridium difficile infections (CDI). However, resistance limits its use in cases of severe and complicated CDI. Structure-activity relationships previously described for the 5-nitroimidazole series have shown that functionalization at the 2- and 4-positions can impart better activity against parasites and anaerobic bacteria than metronidazole. Herein we report the synthesis of new 2,4-disubstituted 5-nitroimidazole compounds that show potent antibacterial activity against C. difficile. We used a vicarious nucleophilic substitution of hydrogen (VNS) reaction to introduce a phenylmethylsulfone at the 4-position and a unimolecular radical nucleophilic substitution (S(RN)1) reaction to introduce an ethylenic function at the 2-position of the 5-nitroimidazole scaffold.

  • Tesfaye, A. T.; Dumur, F.; Gigmes, D.; Maria, S.; Monconduit, L.; Djenizian, T. Scientific Reports 2019, 9, 4301.
    Résumé : The high failure strain of thermoplastic elastomers (TPEs) is a very desirable feature for rechargeable Li-ion batteries by improving the lifetime of high specific capacity anode materials that undergo mechanical fractures induced by large volume variations. In this work, poly(styrene-b-2-hydroxyethyl acrylate) called PS-b-PH EA was synthesized by a nitroxide meditated polymerization method. Owing to the use of a specific polystyrene macroinitiator (SG1), a suitable TPE copolymer with long hydroxyethyl acrylate blocks to ensure good mechanical properties is obtained for the first time. We show that the electrochemical properties of the PS-b-PHEA-coated SnSb anode are drastically improved by suppressing the crack formation at the surface of the electrode. Indeed, electrochemical characterization revealed that a high and stable gravimetric capacity over 100 cycles could be achieved. Moreover, excellent capacity reversibility was achieved when cycled at multiple C-rates and fast kinetics confirming the strong protection role of the polymer. The advanced chemical and mechanical properties of PS-b-PHEA open up promising perspectives to significantly improve the electrochemical performance of all electrodes that are known to suffer from large volume variations.

  • Thureau, P.; Juramy, M.; Ziarelli, F.; Viel, S.; Mollica, G. Solid state nuclear magnetic resonance 2019, 99, 15-19.
    Résumé : A method based on highly concentrated radical solutions is investigated for the suppression of the NMR signals arising from solvents that are usually used for dynamic nuclear polarization experiments. The presented method is suitable in the case of powders, which are impregnated with a radical-containing solution. It is also demonstrated that the intensity and the resolution of the signals due to the sample of interest is not affected by the high concentration of radicals. The method proposed here is therefore valuable when sensitivity is of the utmost importance, namely samples at natural isotopic abundance.

  • Thureau, P.; Sturniolo, S.; Zilka, M.; Ziarelli, F.; Viel, S.; Yates, J. R.; Mollica, G. Magnetic resonance in chemistry : MRC 2019.
    Résumé : Structure determination of functional organic compounds remains a formidable challenge when the sample exists as a powder. Nuclear magnetic resonance crystallography approaches based on the comparison of experimental and Density Functional Theory (DFT)-computed 1 H chemical shifts have already demonstrated great potential for structure determination of organic powders, but limitations still persist. In this study, we discuss the possibility of using 13 C-13 C dipolar couplings quantified on powdered theophylline at natural isotopic abundance with the help of dynamic nuclear polarization, to realize a DFT-free, rapid screening of a pool of structures predicted by ab initio random structure search. We show that although 13 C-13 C dipolar couplings can identify structures possessing long range structural motifs and unit cell parameters close to those of the true structure, it must be complemented with other data to recover information about the presence and the chemical nature of the supramolecular interactions.

  • Tran, J.; Pesenti, T.; Cressonnier, J.; Lefay, C.; Gigmes, D.; Guillaneuf, Y.; Nicolas, J. Biomacromolecules 2019, 20 (1), 305-317.
    Résumé : 2-Methylene-1,3-dioxepane (MDO) and different vinyl ether (VE) monomers were successfully copolymerized by free-radical radical ring-opening copolymerization (rROP) to yield P(MDO-co-VE) copolymers with M-n = 7 000-13 000 g.mol(-1) and high molar fractions of MDO (F-MDO = 0.7-0.9). By using VE derivatives of different aqueous solubilities or by grafting PEG chains onto the copolymers by "click" chemistry via azide-containing

  • Vinciguerra, D.; Jacobs, M.; Denis, S.; Mougin, J.; Guillaneuf, Y.; Lazzari, G.; Zhu, C.; Mura, S.; Couvreur, P.; Nicolas, J. Journal of Controlled Release 2019, 295, 223-236.
    Résumé : Well-defined, heterotelechelic polymer prodrugs for combination therapy were synthesized by using a combination of the "drug-initiated" nitroxide-mediated polymerization from a gemcitabine-alkoxyamine initiator and the nitroxide exchange reaction using TEMPO-bearing drugs to end-cap the drug-polymer chain-end by a second drug. This methodology was successfully applied to two different clinically relevant combinations, gemcitabine/doxorubicin (Gem/Dox) and gemcitabine/lapatinib (Gem/Lap), showing a certain degree of universality of the synthetic methodology. It also represented the first nanocarrier for the co-delivery of Gem and Lap ever reported. Well-controlled, low molar mass heterotelechelic polymers (M-n = 2100-4090 g.mol(-1), D = 1.18-1.38) with similar to 1:1 drug ratios and high overall drug loadings up to 40 wt% were obtained. They were formulated into nanoparticles by nanoprecipitation and exhibited average diameters in the 34-154 nm range, with narrow particle size distributions (PSD= 0.01-0.22) and excellent colloidal stability over time. Their biological evaluation in terms of drug release and cytotoxicity was performed and compared to that of different monofunctional polymer prodrug formulations. We showed that heterobifunctional polymer prodrugs induced cytotoxicity to MCF-7 cells, with IC50 values in the 120-300 nM range depending on the combination tested. Interestingly, whereas Gem/Dox combination did not lead to noticeable improvement over monofunctional therapies, co-nanoprecipitation of Gem/Lap prodrugs led to synergistic effect.

  • Vioglio, P. C.; Thureau, P.; Juramy, M.; Ziarelli, F.; Viel, S.; Williams, P. A.; Hughes, C. E.; Harris, K. D. M.; Mollica, G. The journal of physical chemistry letters 2019, 1505-1510.
    Résumé : Crystallization plays an important role in many areas, and to derive a fundamental understanding of crystallization processes, it is essential to understand the sequence of solid phases produced as a function of time. Here, we introduce a new NMR strategy for studying the time evolution of crystallization processes, in which the crystallizing system is quenched rapidly to low temperature at specific time points during crystallization. The crystallized phase present within the resultant "frozen solution" may be investigated in detail using a range of sophisticated NMR techniques. The low temperatures involved allow dynamic nuclear polarization (DNP) to be exploited to enhance the signal intensity in the solid-state NMR measurements, which is advantageous for detection and structural characterization of transient forms that are present only in small quantities. This work opens up the prospect of studying the very early stages of crystallization, at which the amount of solid phase present is intrinsically low.