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Your search keyword '"François, Jérôme"' showing total 188 results
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188 results on '"François, Jérôme"'

1. Hydrogenation of Xylose to Xylitol in the Presence of Bimetallic Nanoparticles Ni3Fe Catalyst in the Presence of Choline Chloride

Author

Naseeb Ullah, François Jérôme, and Karine De Oliveira Vigier

Subjects
hydrogenation, sugars, deep eutectic solvents, Chemical technology, TP1-1185, Chemistry, QD1-999
Abstract

Hydrogenation of sugars to sugars alcohols is of prime interest for food applications for instance. Xylose obtained from the hemicellulose fraction of lignocellulosic biomass can be hydrogenated to xylitol. Herein, we conducted catalytic hydrogenation reactions in a non-conventional media approach by using choline chloride, a non-toxic naturally occurring organic compound that can form a deep eutectic solvent with xylose. Acknowledging the benefits of cost-effective transition metal-based alloys, Ni3Fe1 bimetallic nanoparticles were utilized as a hetero-catalyst. Under optimized reaction conditions (110 °C, 3 h and 30 bar H2), a highly concentrated feed of xylose (76 wt.%) was converted to 80% of xylitol, showing the benefit of using choline chloride. Overall, the catalytic conversion activity and the product selectivity in the substrate-assisted DES media are relatively high but, the recyclability of the catalyst should be improved in the presence of such media.

Published
2022
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2. Mechanocatalytic Depolymerization of Cellulose With Perfluorinated Sulfonic Acid Ionomers

Author

Ayman Karam, Prince N. Amaniampong, José M. García Fernández, Claudio Oldani, Sinisa Marinkovic, Boris Estrine, Karine De Oliveira Vigier, and François Jérôme

Subjects
cellulose, depolymerization, mechanocatalysis, Aquivion, biomass, Chemistry, QD1-999
Abstract

Here, we investigated that the mechanocatalytic depolymerization of cellulose in the presence of Aquivion, a sulfonated perfluorinated ionomer. Under optimized conditions, yields of water soluble sugars of 90–97% were obtained using Aquivion PW98 and PW66, respectively, as a solid acid catalyst. The detailed characterization of the water soluble fraction revealed (i) the selective formation of oligosaccharides with a DP up to 11 and (ii) that depolymerization and reversion reactions concomitantly occurred during the mechanocatalytic process, although the first largely predominated. More importantly, we discussed on the critical role of water contained in Aquivion and cellulose on the efficiency of the mechanocatalytic process.

Published
2018
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3. Conversion of Ammonia to Hydrazine Induced by High‐Frequency Ultrasound

Author

François Jérôme, Karine De Oliveira Vigier, Anaelle Humblot, Stéphane Streiff, Laurie Grimaud, Audrey Allavena, Prince Nana Amaniampong, Tony Chave, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire Interfaces et Surfaces d'Oxydes (LISO), Service de physique de l'état condensé (SPEC - UMR3680), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Eco-Efficient Products & Processes Laboratory (E2P2L), and RHODIA-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Work (thermodynamics), Materials science, Aqueous solution, Radical, Hydrazine, General Chemistry, 02 engineering and technology, General Medicine, Photochemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Catalysis, 0104 chemical sciences, Ammonia, chemistry.chemical_compound, chemistry, Degradation (geology), [CHIM]Chemical Sciences, Organic synthesis, 0210 nano-technology
Abstract

International audience; Hydrazine is a chemical of outmost importance in our society, either for organic synthesis or energy purpose. The direct conversion of NH3 to hydrazine is highly appealing but it remains a very difficult task because the degradation of hydrazine is thermodynamically more feasible than the cleavage of the N-H bond of NH3. As a result, any catalyst capable of activating NH3 will thus unavoidably decompose N2H4. Here we show that cavitation bubbles, created by ultrasonic irradiation of aqueous NH3 at a high frequency, act as micro-reactors to activate and convert NH3 to NH species, without assistance of any catalyst, yielding hydrazine at the bubble-liquid interface. The compartmentation of in situ produced hydrazine in the bulk solution, which is maintained close to 30°C, advantageously prevents its thermal degradation, a recurrent problem faced by previous technologies. This work also points towards a path to scavenge •OH radicals by adjusting the NH3 concentration.

Published
2021

4. Hydroamination of non-activated alkenes with ammonia: a holy grail in catalysis

Author

Stéphane Streiff, François Jérôme, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Eco-Efficient Products &Processes Laboratory (E2PL2), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-RHODIA

Subjects
chemistry.chemical_classification, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Radical, Multiple applications, Regioselectivity, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Catalysis, Ammonia, chemistry.chemical_compound, chemistry, Amine gas treating, Hydroamination, Alkyl
Abstract

International audience; Alkyl amines represent an important class of chemicals with multiple applications in our daily life. Among the different routes to alkyl amines, the catalytic hydroamination of alkenes with amines is of high interest mainly because it occurs in a 100% atom-economical fashion. To circumvent thermodynamic limitations, activated alkenes or activated amines are essentially employed in such reactions. To date, the catalytic hydroamination of cheap and abundant non-activated (linear) alkenes with ammonia, the simplest amine, remains an unsolved reaction by catalysis. This tutorial review covers the advances reported so far in the intermolecular hydroamination of non-activated linear alkenes with simple alkyl amines, with special interest in ammonia. Focusing on thermodynamics, catalysis and emerging technologies, we aim at providing new perspectives to look at this challenging reaction from a different point of view. In particular, we highlight that the generation of amino radicals from NH3 using “physics activation” is a potential source of inspiration to (i) reduce energy barriers and (ii) reverse the regioselectivity to complete anti-Markovnikov addition

Published
2021

5. Glycerol in energy transportation: a state-of-the-art review

Author

Yanlong Gu, Tianjian Zhang, François Jérôme, and Changhui Liu

Subjects
Solvent system, chemistry.chemical_compound, Materials science, chemistry, Heat transfer, Chemical conversion, Glycerol, Environmental Chemistry, State of the art review, Biochemical engineering, Raw material, Pollution, Energy (signal processing)
Abstract

Glycerol, which bears green, low-cost, and good miscibility features, provides a variety of solvent portfolios to satisfy the complex market demands. Owing to its abundant feedstock and unique properties, glycerol is a good candidate in catalysis, high-value-added chemical conversion, and solvents. It can also be used as an energy transportation medium attributed to its high boiling temperature, promising thermal stability, and fertile hydrogen bond. Despite the great potential of glycerol in energy transportation, a review paper that summarizes and discusses its recent advances is blank to date. In this review paper, recent advances in the utilization of glycerol and glycerol-based mixture solvent systems in energy transportation were summarized. Thermophysical properties of glycerol-containing fluids, including their performance in various heat transfer occasions, and principles of related energy transportation were comprehensively introduced and discussed. Applications of these fluids in industrial processes were also discussed systematically. Furthermore, advantages and drawbacks of glycerol in energy transportation were concluded. It opens an important avenue to alleviate the backlog of glycerol production by means of valuable applications.

Published
2021

6. Formaldehyde in multicomponent reactions

Author

Changhui Liu, François Jérôme, Wenbo Huang, Yanlong Gu, Jiahao Zhang, and Zhonghao Rao

Subjects
Flexibility (engineering), chemistry.chemical_compound, Organic reaction, Chemistry, Waste production, Formaldehyde, Environmental Chemistry, Molecule, Reactivity (chemistry), Organic synthesis, Biochemical engineering, Raw material, Pollution
Abstract

Acting as a C1 building block, formaldehyde is of great significance in organic synthesis. It is also a key feedstock in several industries, such as resins, polymers, adhesives, and paints. Multicomponent reactions (MCRs) have emerged as applicable tools in organic reactions because efficient MCRs allow the creation of several chemical bonds in one sequence without labor-consuming reaction condition optimization and work-up procedures, thus minimizing waste production, cost, and labor consumption. In this review, we mainly focus on the recent advances in the contribution of formaldehyde, which was herein used as a versatile C1 building block to produce either acyclic or heterocyclic molecules via MCRs with the potential to be more sustainable than lengthier alternatives and used as a divergent chemical thanks to its excellent reactivity, flexibility, and hydrophilicity.

Published
2021

7. Direct Catalytic Conversion of Furfural to Furan‐derived Amines in the Presence of Ru‐based Catalyst

Author

Wahiba Ramdani, Karine De Oliveira Vigiera, Marc Pera-Titus, Changru Ma, Eric Muller, François Jérôme, Shi Jiang, and Centre National de la Recherche Scientifique (CNRS)

Subjects
Tandem, General Chemical Engineering, [CHIM.CATA]Chemical Sciences/Catalysis, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Furfural, 01 natural sciences, 0104 chemical sciences, Catalysis, Methyl isobutyl ketone, chemistry.chemical_compound, General Energy, chemistry, Furan, Yield (chemistry), Environmental Chemistry, Organic chemistry, General Materials Science, Amine gas treating, Direct reaction, 0210 nano-technology
Abstract

International audience; The production of amine intermediates from biomass is capturing increasing attention. Herein we report simple and efficient preparation of l furan-derived amines (for instance 1-(furan-2-yl)-4-methylpentan-2-amine) with high yield (up to 95%) from (E)-1-(furan-2-yl)-5-methylhex-1-en-3-one. The catalyst used was Ru/C and it was recyclable up to 4th cycle. To further realize cost-efficiency, one-reactor tandem concept was attempted. To this aim direct reaction from furfural was investigated. A high yield (74%) towards 1-(furan-2-yl)-4-methylpentan-2-amine could be achieved starting directly from furfural in the presence of methylisobutyl ketone, NH3, H2 and Ru/C catalyst.

Published
2020

8. Selective Acid-Catalyzed Hydroarylation of Nonactivated Alkenes with Aniline Assisted by Hexafluoroisopropanol

Author

Karine De Oliveira Vigier, Anaelle Humblot, Fan Jiang, François Jérôme, Marc Pera-Titus, Raphael Wischert, and Gongming Peng

Subjects
chemistry.chemical_compound, Aniline, Chemistry, Acid catalyzed, Organic Chemistry, Reactivity (chemistry), Hydroamination, Selectivity, Combinatorial chemistry, Trifluoromethanesulfonate, Ring strain, Catalysis
Abstract

The catalytic hydroarylation of nonactivated alkenes with aniline is a reaction of high interest, aiming at providing C-functionalized aniline derivatives that are important precursors for the fabrication of polyurethanes. However, this reaction remains a longstanding goal of catalysis, as it requires one to simultaneously address two important goals: (1) the very low reactivity of nonactivated alkenes and (2) control of the hydroarylation/hydroamination selectivity. As a result, the hydroarylation of aniline is mostly restricted to activated alkenes (i.e., featuring ring strain, conjugation, or activation with electron-donating or -withdrawing groups). Here we show that the combination of bismuth triflate and hexafluoroisopropanol (HFIP) leads to the formation of highly active catalytic species capable of promoting the hydroarylation of various nonactivated alkenes, such as 1-octene, 1-heptene, and 1-undecene, among others, with aniline with high selectivity (71-92%). Through a combined experimental and computational investigation, we propose a reaction pathway where HFIP stabilizes the rate-determining transition state through a H-bond interaction with the triflate anion, thus assisting the acid catalyst in the hydroarylation of nonactivated alkenes. From a practical point of view, this work opens a catalytic access to C-functionalized aniline derivatives from two cheap and abundant feedstocks in a 100% atom-economical fashion.

Published
2021

9. Pivotal role of H2 in the isomerisation of isosorbide over a Ru/C catalyst

Author

Marc Pera-Titus, François Jérôme, K. de Olivera Vigier, A. Ramzan, Carine Michel, Raphael Wischert, H. Hu, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Eco-Efficient Products &Processes Laboratory (E2PL2), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-RHODIA, Solvay, ENS de Lyon, École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Eco-Efficient Products & Processes Laboratory (E2P2L), RHODIA-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and ANR-16-IDEX-0005,IDEXLYON,IDEXLYON(2016)

Subjects
Isosorbide, Hydrogen, 010405 organic chemistry, chemistry.chemical_element, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Solvent, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, medicine, Solubility, Inert gas, Isomerization, Stoichiometry, medicine.drug
Abstract

International audience; Isosorbide isomerisation is a known reaction that can proceed over Ru and Ni-based heterogeneous catalysts. As a rule, an exogenous H2 pressure (40–100 bar) is required, even though H2 does not participate stoichiometrically in the reaction. By marrying experiments with DFT computations, we ascribe the role of H2 in isosorbide isomerisation to a coverage effect on the catalyst surface. We demonstrate the possibility of conducting the reaction at a low H2 pressure either in the presence of an inert gas to increase H2 solubility in an underlying solvent or using 2-propanol as a hydrogen donor. This might benefit the economy and safety of a potential industrial process.

Published
2021

10. Hydrogenation of Sugars to Sugar Alcohols in the Presence of a Recyclable Ru/Al 2 O 3 Catalyst Commercially Available

Author

Thierry Tassaing, Isaline Bonnin, François Jérôme, Karine De Oliveira Vigier, Raphaël Méreau, Institut des Sciences Moléculaires (ISM), and Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Renewable Energy, Sustainability and the Environment, Chemistry, General Chemical Engineering, General Chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Catalysis, Environmental Chemistry, Organic chemistry, [CHIM]Chemical Sciences, Sugar, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2021

11. Synthesis and Properties

Author

François Jérôme and Karine De Oliveira Vigier

Subjects
Surface tension, Viscosity, Chemistry, Thermodynamics, Freezing point
Published
2019

12. Synergistic Effect of High-Frequency Ultrasound with Cupric Oxide Catalyst Resulting in a Selectivity Switch in Glucose Oxidation under Argon

Author

Yingqiao Wang, Ngoc Han Tran, Duy Quang Dao, Prince Nana Amaniampong, Matthew Sherburne, François Jérôme, Karine De Oliveira Vigier, Quang Thang Trinh, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Fédération de recherche INCREASE (INCREASE), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-LIttoral ENvironnement et Sociétés (LIENSs), La Rochelle Université (ULR)-Centre National de la Recherche Scientifique (CNRS)-La Rochelle Université (ULR)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Centre National de la Recherche Scientifique (CNRS)-Laboratoire de Chimie des Polymères Organiques (LCPO), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Centre National de la Recherche Scientifique (CNRS)-Laboratoire de Génie Chimique (LGC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centre de recherche sur l'intégration économique et financière (CRIEF), Université de Poitiers-Université de Poitiers, Nanyang Technological University [Singapour], Physicochimie de la Combustion (PC2), Physicochimie des Processus de Combustion et de l’Atmosphère - UMR 8522 (PC2A), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), National Research Foundation Singapore, Centre National de la Recherche Scientifique, R?gion Nouvelle-Aquitaine, ANR-16-CE07-0003,CELLOPLASM,Clivage de la liaison béta-1,4 glycosidique de la cellulose par plasma atmospherique non-thermique: mécanisme et application pour la production d'alkylglycosides(2016), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre de Recherche sur l'Intégration Economique et Financière (CRIEF), Université de Poitiers-Université de Poitiers-LIttoral ENvironnement et Sociétés - UMRi 7266 (LIENSs), Université de La Rochelle (ULR)-Centre National de la Recherche Scientifique (CNRS)-Université de La Rochelle (ULR)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Laboratoire de Génie Chimique (LGC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), and Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)

Subjects
Radical, Inorganic chemistry, Oxide, 010402 general chemistry, DFT, 01 natural sciences, 7. Clean energy, Biochemistry, Catalysis, Sonochemistry, Metal, chemistry.chemical_compound, Colloid and Surface Chemistry, Oxidation, Copper oxide, glucuronic acid, ultrasound, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Glucuronic acid, 0104 chemical sciences, chemistry, visual_art, Gluconic acid, visual_art.visual_art_medium, Selectivity
Abstract

We report here, and rationalize, a synergistic effect between a non-noble metal oxide catalyst (CuO) and high-frequency ultrasound (HFUS) on glucose oxidation. While CuO and HFUS are able to independently oxidize glucose to gluconic acid, the combination of CuO with HFUS led to a dramatic change of the reaction selectivity, with glucuronic acid being formed as the major product. By means of density functional theory (DFT) calculations, we show that, under ultrasonic irradiation of water at 550 kHz, the surface lattice oxygen of a CuO catalyst traps H· radicals stemming from the sonolysis of water, making the ring-opening of glucose energetically unfavorable and leaving a high coverage of ·OH radical on the CuO surface, which selectively oxidizes glucose to glucuronic acid. This work also points toward a path to optimize the size of the catalyst particle for an ultrasonic frequency that minimizes the damage to the catalyst, resulting in its successful reuse.

Published
2019

13. Selective Synthesis of THF-Derived Amines from Biomass-Derived Carbonyl Compounds

Author

Changru Ma, Marc Pera-Titus, Eric Muller, François Jérôme, Shi Jiang, Karine De Oliveira Vigier, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Eco-Efficient Products &Processes Laboratory (E2PL2), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-RHODIA, and Solvay (France)

Subjects
010405 organic chemistry, Biomass, chemistry.chemical_element, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 010402 general chemistry, Furfural, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Transformation (genetics), chemistry, Organic chemistry, Aldol condensation, ComputingMilieux_MISCELLANEOUS, Amination, Palladium
Abstract

Selective transformation of biomass or biomass-based feedstocks into value-added amines is highly desirable and constitutes one of the most important challenges in catalysis. As of today, only few ...

Published
2019

14. Catalytic glycosylation of glucose with alkyl alcohols over sulfonated mesoporous carbons

Author

Sébastien Rio, Karine De Oliveira Vigier, Anne Ponchel, Wahiba Ramdani, Ayman Karam, François Jérôme, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), UCCS Équipe Catalyse Supramoléculaire, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille-Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Glycosylation, 010405 organic chemistry, Chemistry, Process Chemistry and Technology, Glycoside, chemistry.chemical_element, [CHIM.CATA]Chemical Sciences/Catalysis, Solid acid, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Yield (chemistry), [CHIM]Chemical Sciences, Organic chemistry, Physical and Theoretical Chemistry, Mesoporous material, Carbon, ComputingMilieux_MISCELLANEOUS, Alkyl
Abstract

Herein we investigated the catalytic performances of sulfonated mesoporous carbons in the glycosylation of carbohydrates with alkyl alcohols. Catalytic performances were compared to common solid acid catalysts previously reported for this reaction. Under optimized conditions, the targeted alkyl glycosides were obtained in 85% yield, together with a turn over frequency and a space time yield higher than those of the best heterogeneous catalysts reported so far in such reaction. Furthermore, the presence of mesoporous channels significantly lowered the deactivation rate of the catalyst in comparison to a non-porous sulfonated carbon.

Published
2019

15. Synthesis of functionalized tetrahydrofuran derivatives from 2,5-dimethylfuran through cascade reactions

Author

Marc Pera-Titus, K. De Oliveira Vigier, François Jérôme, J. Li, Eric Muller, Eco-Efficient Products &Processes Laboratory (E2PL2), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-RHODIA, Solvay (France), Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), and Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Condensation, 2,5-Dimethylfuran, [CHIM.CATA]Chemical Sciences/Catalysis, Alkylation, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Pollution, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Polymer chemistry, Environmental Chemistry, Aldol condensation, ComputingMilieux_MISCELLANEOUS, Tetrahydrofuran, Methyl group
Abstract

A three-step strategy is proposed for the functionalization of the methyl group of 2,5-dimethylfuran, encompassing the ring opening of 2,5-dimethylfuran to 2,5-hexanedione, its further aldol condensation with aldehydes, and hydrogenation–cyclization of the condensation intermediate to generate alkylated tetrahydrofuran. Active and selective catalysts could be identified for the aldol condensation and hydrogenation–cyclization reactions.

Published
2019

16. Catalytic Conversion of Carbohydrates to Furanic Derivatives in the Presence of Choline Chloride

Author

François Jérôme and Karine De Oliveira Vigier

Subjects
carbohydrates, furanic derivatives, choline chloride, low melting mixture, deep eutectic solvent, Chemical technology, TP1-1185, Chemistry, QD1-999
Abstract

The synthesis of furanic derivatives (5-hydroxymethylfurfural (HMF), furfural…) from carbohydrates is of high interest for a wide range of applications. These reactions are carried out in the presence of various solvents, and among them choline chloride can be used. It is a salt that can form a low melting mixture with a carbohydrate (fructose, glucose…) or a deep eutectic mixture with carboxylic acid. A review of the studies performed in the conversion of carbohydrates to furanic derivatives in the presence of choline chloride is presented here with the advantages and drawbacks of this solvent. Choline chloride can enhance the selectivity to HMF by stabilizing effect and allows the conversion of highly concentrated feed. However, the extraction of the products from these solvents still needs improvement.

Published
2017
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17. Supercritical Carbon Dioxide Extraction of Value-Added Products and Thermochemical Synthesis of Platform Chemicals from Food Waste

Author

Iris K.M. Yu, Yong Sik Ok, Thomas M. Attard, Season S. Chen, François Jérôme, Daniel C.W. Tsang, Chi Sun Poon, and Andrew J. Hunt

Subjects
chemistry.chemical_classification, Wax, Renewable Energy, Sustainability and the Environment, General Chemical Engineering, Extraction (chemistry), Biomass, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Supercritical fluid, 0104 chemical sciences, chemistry.chemical_compound, Food waste, chemistry, visual_art, visual_art.visual_art_medium, Levulinic acid, Environmental Chemistry, Food science, 0210 nano-technology, Hydroxymethylfurfural, Polyunsaturated fatty acid
Abstract

Immense global generation of food waste calls for advanced technologies to maximize the use of such renewable carbon-based resources. In this study, corn, taro, lettuce, and bean sprout, were valorized for the production of value-added chemicals via sequential supercritical CO2 (scCO2) extraction and thermochemical conversion. The scCO2 extraction was performed at 350 bar and 50 °C for 60 min. The extracts of the lettuce contained sterols (764 μg g–1) that have potential anticancer properties. While bean sprout extracts had a higher content of saturated fatty acids (641 μg g–1), corn extracts comprised polyunsaturated fatty acids (405 μg g–1) as one of the major compounds, which are beneficial to cholesterol control. There were also notable amounts of wax esters (75–774 μg g–1) in these food waste extracts. Taro extracts were rich in both saturated (2313 μg g–1) and unsaturated fatty acids (1605 μg g–1) and, in particular, contained difatty acids that exhibit pharmaceutical activities. Moreover, the solid residues after scCO2 extraction served as the substrates for platform chemical production. The starch-rich substrates, i.e., taro and corn, resulted in 11–20% hydroxymethylfurfural (HMF) after microwave heating at 140 °C for 5–10 min using SnCl4 catalyst. In comparison, due to the high fiber content, lettuce and bean sprout required a higher temperature of 170–190 °C for chemical decomposition over H2SO4, generating a levulinic acid yield of ∼7%, in company with glucose and fructose as the coproducts. This study on the combined technologies suggested good compatibility between scCO2 extraction and subsequent thermochemical conversion, producing a wide spectrum of value-added chemicals from biomass waste. We herein highlight the vast potential of integrated technologies for food waste valorization in achieving sustainable and carbon-efficient biorefineries.

Published
2018

18. Organic Acid-Regulated Lewis Acidity for Selective Catalytic Hydroxymethylfurfural Production from Rice Waste: An Experimental–Computational Study

Author

Iris K.M. Yu, Karine De Oliveira Vigier, Zhishan Su, Chi Sun Poon, Yong Sik Ok, François Jérôme, Alex C.K. Yip, Daniel C.W. Tsang, Department of Civil and Environmental Engineering [Hong Kong] (CEE), The Hong Kong Polytechnic University [Hong Kong] (POLYU), University of Canterbury [Christchurch], Sichuan University [Chengdu] (SCU), Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Poitiers-Institut de Chimie du CNRS (INC), Korea University [Seoul], and Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Maleic acid, Renewable Energy, Sustainability and the Environment, General Chemical Engineering, Oxalic acid, [CHIM.CATA]Chemical Sciences/Catalysis, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Oxalate, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Succinic acid, Environmental Chemistry, Malic acid, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS, Hydroxymethylfurfural, Organic acid, Nuclear chemistry
Abstract

A series of organic acids, including maleic acid (maleicA), malic acid (malicA), succinic acid (SA), and oxalic acid (OA)/oxalate, was evaluated as green additives to promote the selective Al(III)-catalyzed production of hydroxymethylfurfural (HMF) from food waste. The roles of Al(III)–organic acid interactions in altering the catalytic functions were elucidated on the basis of experimental and computational evidence. The catalytic results showed that the Al/OA and Al/oxalate systems gave the slowest glucose conversion among the studied systems. OA/oxalate had such a high affinity for Al(III), that the Lewis acidity of Al(III) (i.e., ability to accept electron pairs) was unfavorably reduced, which was supported by the theoretical calculations of Gibbs free energies considering the Al(III)–OA complexes the most thermodynamically feasible. When rice waste was used as the substrate, which is rich in glucose-based starch, the addition of maleicA to the Al(III) system enhanced the HMF selectivity. The Lewis ac...

Published
2018

19. Sequential acid-catalyzed alkyl glycosylation and oligomerization of unprotected carbohydrates

Author

Lea Spitzer, Henri Cramail, Sébastien Lecommandoux, François Jérôme, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Fédération de recherche INCREASE (INCREASE), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-LIttoral ENvironnement et Sociétés (LIENSs), La Rochelle Université (ULR)-Centre National de la Recherche Scientifique (CNRS)-La Rochelle Université (ULR)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Centre National de la Recherche Scientifique (CNRS)-Laboratoire de Chimie des Polymères Organiques (LCPO), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Centre National de la Recherche Scientifique (CNRS)-Laboratoire de Génie Chimique (LGC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centre de recherche sur l'intégration économique et financière (CRIEF), Université de Poitiers-Université de Poitiers, Laboratoire de Chimie des Polymères Organiques (LCPO), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Team 2 LCPO : Biopolymers & Bio-sourced Polymers, Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Team 3 LCPO : Polymer Self-Assembly & Life Sciences, Centre National de la Recherche Scientifique, Conseil Régional Aquitaine, Université de Bordeaux, Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre de Recherche sur l'Intégration Economique et Financière (CRIEF), Université de Poitiers-Université de Poitiers-LIttoral ENvironnement et Sociétés - UMRi 7266 (LIENSs), Université de La Rochelle (ULR)-Centre National de la Recherche Scientifique (CNRS)-Université de La Rochelle (ULR)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Laboratoire de Génie Chimique (LGC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)

Subjects
chemistry.chemical_classification, Anomer, Glycosylation, 010405 organic chemistry, Glycosyl acceptor, Mannose, Alkyne, Alcohol, [CHIM.CATA]Chemical Sciences/Catalysis, Propargyl alcohol, 010402 general chemistry, 01 natural sciences, Pollution, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Environmental Chemistry, Monosaccharide, Organic chemistry
Abstract

An efficient method has been developed to synthesize end-functionalized oligosaccharides from unprotected monosaccharides in a one-pot/two-step approach. In the first step, mannose (and glucose) was functionalized with an alkyne group at the anomeric position through the Fisher-glycosylation reaction with propargyl alcohol as a glycosyl acceptor. In the second step, the functionalized monosaccharides were oligomerized and the experimental conditions were optimized by varying the temperature, time and the molar ratio between alcohol and sugar to reach a up to 8. The obtained oligosaccharides showed complete propargylation at their reducing chain-end and were successfully coupled to oleic acid via the Huisgen reaction, affording bio-based surfactants.

Published
2021

20. A Combined Experimental-Theoretical Study on Diels-Alder Reaction with Bio-Based Furfural: Towards Renewable Aromatics

Author

Changru Ma, Eric Muller, Karine De Oliveira Vigier, Raphael Wischert, Frédéric Guégan, I van Scodeller, François Jérôme, and Centre National de la Recherche Scientifique (CNRS)

Subjects
Steric effects, Chemistry, General Chemical Engineering, Aromatization, 02 engineering and technology, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 021001 nanoscience & nanotechnology, Furfural, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, General Energy, Computational chemistry, Reagent, Electrophile, Environmental Chemistry, General Materials Science, Chemical equilibrium, 0210 nano-technology, Selectivity, ComputingMilieux_MISCELLANEOUS, Diels–Alder reaction
Abstract

The synthesis of relevant renewable aromatics from bio-based furfural derivatives and cheap alkenes is carried out by using a Diels-Alder/aromatization sequence. The prediction and the control of the ortho/meta selectivity in the Diels-Alder step is an important issue to pave the way to a wide range of renewable aromatics, but it remains a challenging task. A combined experimental-theoretical approach reveals that, as a general trend, ortho and meta cycloadducts are the kinetic and thermodynamic products, respectively. The nature of substituents, both on the dienes and dienophiles, significantly impacts the feasibility of the reaction, through a modulation on the nucleo- and electrophilicity of the reagents, as well as the ortho/meta ratio. We show that the ortho/meta selectivity at the reaction equilibrium stems from a subtle interplay between charge interactions, favoring the ortho products, and steric interactions, favoring the meta isomers. This work also points towards a path to optimize the aromatization step.

Published
2020

21. Selective dihydroxylation of methyl oleate to methyl-9,10-dihydroxystearate in the presence of a recyclable tungsten based catalyst and hydrogen peroxide

Author

François Jérôme, Nahla Araji, Audrey Moores, Gregory Chatel, Karine De Oliveira Vigier, and Centre National de la Recherche Scientifique (CNRS)

Subjects
Methyl oleate, 010405 organic chemistry, chemistry.chemical_element, 02 engineering and technology, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Tungsten, 021001 nanoscience & nanotechnology, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Transfer agent, Dihydroxylation, Phase (matter), Yield (chemistry), Materials Chemistry, Organic chemistry, 0210 nano-technology, Hydrogen peroxide
Abstract

International audience; The dihydroxylation of fatty methyl esters is of prime importance for the synthesis of surfactants and lubricants. The conversion of methyl oleate (MO) to 98% yield of methyl-9,10-dihydroxysterate (MDHS) was performed in the presence of H2O2 and H3PW12O40 catalyst in absence of a phase transfer agent. The study of the effect of hydrogen peroxide concentration revealed that significant catalytic activity was only achieved for an optimal amount of H2O2. A mechanism for this reaction was proposed where hydrogen peroxide reacts with H3PW12O40 to produce peroxo-phosphotungstate anions, which directly dihydroxylate MO. The recyclability of the catalyst was also studied. To this aim, a recyclable form of the heteropolyacid was synthesized using Cs cations (Cs2.3H0.7PW12O40). This catalyst was recycled up to three cycles without significant loss in catalytic performances.

Published
2020

23. Modeling of Ethylene Glycol Production from Glucose in a Semi‐Continuous Reactor

Author

Ghislain Irakoze, François Jérôme, Yolande Pérès, Michel Delmas, Patrick Cognet, Karine De Oliveira Vigier, Martine Urrutigoïty, Carlos Murillo, Laboratoire de Génie Chimique (LGC), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), and INCREASE CNRS federation

Subjects
Process modeling, 010405 organic chemistry, Chemistry, General Chemical Engineering, Continuous reactor, 02 engineering and technology, General Chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 7. Clean energy, Industrial and Manufacturing Engineering, 0104 chemical sciences, Catalysis, modelling, chemistry.chemical_compound, Chemical engineering, semi-continuous reaction, reaction kinetics, [CHIM.COOR]Chemical Sciences/Coordination chemistry, glucose, 0210 nano-technology, Ethylene glycol
Abstract

International audience; A numerical study describes the catalytic conversion of glucose into ethylene glycol (EG) in a semi-batch reactor. This analysis couples a set of power law models (homogeneous reactions) and Langmuir-Hinshelwood-Hougen-Watson (LHHW) equations (hydrogenations). For this purpose, the kinetic parameters of the LHHW expressions are estimated for the reaction conditions. Then, the kinetic model evaluates the influence of the H2 pressure and the catalyst concentrations on the selectivity. The results indicate that the EG yield is increased by setting the temperature and the H2 pressure. In this manner, the process reduces the hexitols and methane production and increases the EG yield. The originality of the work is based on the influence of the H2 pressure and the catalyst concentrations in the model.

Published
2020

24. Selective Hydrogenation of Xylose to Xylitol over Co/SiO 2 Catalysts

Author

Karine De Oliveira Vigier, Sébastien Royer, Andreea Raluca Ifrim, Adrian Ungureanu, Wahiba Ramdani, François Jérôme, Maïté Audemar, Tang Junhui, and Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Organic Chemistry, chemistry.chemical_element, [CHIM.CATA]Chemical Sciences/Catalysis, Xylose, 010402 general chemistry, Xylitol, 7. Clean energy, 01 natural sciences, Catalysis, 12. Responsible consumption, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, 13. Climate action, Organic chemistry, Physical and Theoretical Chemistry, Cobalt
Abstract

International audience; Xylose can be selectively converted to xylitol in water, with an optimized yield of 98%, in the presence of a simple silica supported metallic cobalt-Co/SiO2-catalyst. This catalyst displays initial outstanding catalytic properties in proper solvent, the best one being pure water. Recyclability studies show a moderate deactivation of the catalyst, while selectivity to xylitol remains almost unchanged after 4 cycles, confirming the promising character of this catalyst formulation for the xylitol production process. Xylose is a product issued from the hydrolysis of beechwood hemicelluloses. Different routes exists for the valorisation of xylose, amongst the selective hydrogenation to xylitol (scheme 1). Xylitol is an extensively used molecule in food, cosmetics, and pharmaceutical industry[1-4]. Xylitol has then been identified as one of the top-twelve value added chemicals that can be obtained from biomass [5]. As an example, xylitol is a valuable water soluble sweetener due to its atypical properties amongst, compared to sucrose, a higher sweetness strength and a lower energy capacity. Today, xylitol is widely incorporated in daily consumed products (chewing gums, chocolates, toothpastes, etc.) [6]. With an estimated market of 340 M$, xylitol is becoming the most popular "natural" sweeteners [7]. Industrial production of xylitol by selective catalytic hydrogenation appears as an economically viable approach. Scheme 1. Hydrogenation of xylose to xylitol. Xylitol can be produced by catalytic hydrogenation in the presence of RANEY® nickel. Reaction is performed in liquid phase, under high hydrogen pressure and temperature in batch-type reactors [8]. Selectivity above 90%, at high conversion degree can be obtained at 80-130°C under 40-70 bar of H2 (5 wt.% catalyst of the xylose mass present at 40-60 wt.% in water) in the presence of RANEY® nickel. Despite the high selectivity and activity reached using this catalyst, with economic advantages related to the use of noble metal free catalysts for the reaction, the intrinsic properties of the nickel, amongst toxicity and limited stability,[8-9] makes the research of efficient catalyst substitutes. Indeed, the use of xylitol for food applications imply the absence of any trace of nickel in final product, nickel being recognized as a carcinogen compound. Most of recent studies were devoted to the study of supported noble metals, such as Ru, Rh and Pd, in monometallic or bimetallic catalytic systems, with the possible adding of dopants as Sn [8-15] Ru appeared as the most efficient. Hernandez-Mejia et al.[16] reported that xylose can be selectively converted to xylitol in the presence of rutile phase TiO2 supported Ru (1 wt.%), despite the low surface area displayed by the rutile support. Authors then reported xylose yields higher than 90%, for a reaction performed in water at

Published
2020

25. An efficient hydrogenation catalytic model hosted in a stable hyper-crosslinked porous-organic-polymer: from fatty acid to bio-based alkane diesel synthesis

Author

Nguyen Thanh Binh, Ramana Singuru, François Jérôme, Subhash Chandra Shit, Asmaa Drif, Jihyeon Lee, Quang Thang Trinh, Quyet Van Le, Prince Nana Amaniampong, Dai-Viet N. Vo, John Mondal, Pham Thanh Huyen, Kwangjin An, Thi To Nga Phan, Dang Nam Nguyen, Matthew Sherburne, Chitra Sarkar, Ngoc Han Tran, Duy Quang Dao, and Centre National de la Recherche Scientifique (CNRS)

Subjects
Alkane, chemistry.chemical_classification, food.ingredient, Chemistry, Decarbonylation, Vegetable oil refining, 02 engineering and technology, [CHIM.CATA]Chemical Sciences/Catalysis, Alkylation, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Pollution, Soybean oil, 0104 chemical sciences, Catalysis, Diesel fuel, food, Chemical engineering, Environmental Chemistry, 0210 nano-technology, Hydrodeoxygenation
Abstract

International audience; In this study, Pd-based catalytic model hosted over nitrogen enriched fibrous Porous-Organic-Polymer (POP) is established to execute hydrodeoxygenation of various vegetable oils in producing potential large-scale renewable diesel. Here we report a cost effective synthesis strategy of a new microporous hypercrosslinked POP through the FeCl3 assisted Friedel-Crafts alkylation reaction, followed by fabrication of Pd 0-NPs (2-3 nm) with solid gas phase hydrogenation route to deliver a novel catalytic system. This catalyst (called Pd@PPN) exhibits versatile catalytic performance for different types of vegetable oils including palm oil, soybean oil, sunflower oil and rapeseed oil to furnish long chain diesel range alkanes. The catalyst is comprehensively characterized by various spectroscopic tools and shows high stability during five runs of recycling without the leaching of Pd occuring. Our results further reveal that direct decarbonylation (DCN) pathway of fatty acid to produce alkanes with one carbon less is the dominated mechanism. At optimized conditions, using stearic acid to represent the long linear carboxylic acids in the vegetable oils, up to 90 % conversion with 83 % selectivity of C17-alkane has been achieved on our fabricated catalyst. Density functional theory (DFT) calculations are performed to provide insights into the electronic properties of the catalyst, the mechanistic reaction pathway, the crucial role of catalyst surface and the product selectivity trend. The strong interaction between corrugated polymer-frame-structure and the Pd-NPs suggests there is the presence of high density step sites on the fabricated Pd-NP anchored within the cage of polymer structure. DFT calcualtions also reveal the strong promotional effect of step sites and charge transfer in facilitating rate-limiting steps during the decarbonylation (DCN) pathway and removal of strongly bound intermediates formed during the process, therefore explain the high activity of the fabricated Pd@PPN catayst for the hydrodeoxygenation (HDO) conversion to produce bio-based alkanes diesel.

Published
2020

26. Conversion of furfural to tetrahydrofuran-derived secondary amines under mild conditions

Author

Karine De Oliveira Vigier, Eric Muller, François Jérôme, Shi Jiang, Marc Pera-Titus, Centre National de la Recherche Scientifique (CNRS), Eco-Efficient Products &Processes Laboratory (E2PL2), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-RHODIA

Subjects
010405 organic chemistry, Biomass, chemistry.chemical_element, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, Furfural, 01 natural sciences, Pollution, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Bioenergy, Environmental Chemistry, Organic chemistry, [CHIM]Chemical Sciences, Tetrahydrofuran, ComputingMilieux_MISCELLANEOUS, Palladium
Abstract

International audience; The production of amino-containing compounds from biomass is an important goal of research programs. Starting from carbohydrate-based furfural, a simple and highly efficient system was developed for producing a library of secondary and tertiary tetrahydrofurfurylamines under mild conditions (25 °C/1 bar H2) with excellent yields (>90%). Commercially available Pd/Al2O3 proved to be a suitable catalyst and exhibited outstanding performance.

Published
2020

27. Synthesis of Furfuryl Alcohol from Furfural: A Comparison between Batch and Continuous Flow Reactors

Author

Christophe Len, Yantao Wang, Deyang Zhao, Karine De Oliveira Vigier, Sébastien Royer, Maïté Audemar, François Jérôme, and Centre National de la Recherche Scientifique (CNRS)

Subjects
Control and Optimization, batch reactor, Batch reactor, Energy Engineering and Power Technology, 010402 general chemistry, Furfural, furfuryl alcohol, 01 natural sciences, 7. Clean energy, lcsh:Technology, Catalysis, Furfuryl alcohol, chemistry.chemical_compound, continuous flow, Hemicellulose, Electrical and Electronic Engineering, Engineering (miscellaneous), ComputingMilieux_MISCELLANEOUS, 010405 organic chemistry, Renewable Energy, Sustainability and the Environment, Chemistry, lcsh:T, furfural, [CHIM.CATA]Chemical Sciences/Catalysis, 0104 chemical sciences, Chemical engineering, Yield (chemistry), Batch processing, hydrogenation, Selectivity, Energy (miscellaneous)
Abstract

Furfural is a platform molecule obtained from hemicellulose. Among the products that can be produced from furfural, furfuryl alcohol is one of the most extensively studied. It is synthesized at an industrial scale in the presence of CuCr catalyst, but this process suffers from an environmental negative impact. Here, we demonstrate that a non-noble metal catalyst (Co/SiO2) was active (100% conversion of furfural) and selective (100% selectivity to furfuryl alcohol) in the hydrogenation of furfural to furfuryl alcohol at 150 °C under 20 bar of hydrogen. This catalyst was recyclable up to 3 cycles, and then the activity decreased. Thus, a comparison between batch and continuous flow reactors shows that changing the reactor type helps to increase the stability of the catalyst and the space-time yield. This study shows that using a continuous flow reactor can be a solution to the catalyst suffering from a lack of stability in the batch process.

Published
2020

28. Selective radical depolymerization of cellulose to glucose induced by high frequency ultrasound

Author

Isabelle Capron, Jonathan Clarhaut, Karine De Oliveira Vigier, Ayman Karam, Tony Chave, Somia Haouache, François Jérôme, Prince Nana Amaniampong, José M. García Fernández, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Physiopathologie des Adaptations Nutritionnelles (PhAN), Université de Nantes - UFR de Médecine et des Techniques Médicales (UFR MEDECINE), Université de Nantes (UN)-Université de Nantes (UN)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Sonochimie dans les Fluides Complexes (LSFC), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), University of Sevilla, Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Universidad de Sevilla / University of Sevilla, ANR-16-CE07-0003,CELLOPLASM,Clivage de la liaison béta-1,4 glycosidique de la cellulose par plasma atmospherique non-thermique: mécanisme et application pour la production d'alkylglycosides(2016), and Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Poitiers-Institut de Chimie du CNRS (INC)

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Depolymerization, Radical, Glycosidic bond, General Chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, 0104 chemical sciences, Homolysis, Catalysis, chemistry.chemical_compound, Chemistry, chemistry, Degradation (geology), [CHIM]Chemical Sciences, Cellulose, Selectivity
Abstract

The depolymerization of cellulose to glucose is a challenging reaction and often constitutes a scientific obstacle in the synthesis of downstream bio-based products. Here, we show that cellulose can be selectively depolymerized to glucose by ultrasonic irradiation in water at a high frequency (525 kHz). The concept of this work is based on the generation of H˙ and ˙OH radicals, formed by homolytic dissociation of water inside the cavitation bubbles, which induce the cleavage of the glycosidic bonds. The transfer of radicals on the cellulose particle surfaces prevents the side degradation of released glucose into the bulk solution, allowing maintaining the selectivity to glucose close to 100%. This work is distinguished from previous technologies in that (i) no catalyst is needed, (ii) no external source of heating is required, and (iii) the complete depolymerization of cellulose is achieved in a selective fashion. The addition of specific radical scavengers coupled to different gaseous atmospheres and ˙OH radical dosimetry experiments suggested that H˙ radicals are more likely to be responsible for the depolymerisation of cellulose., Ultrasonic irradiation of cellulose at a high frequency induces its selective depolymerization to glucose at room temperature and atmospheric pressure within only a few minutes.

Published
2020

29. Hydroconversion of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran and 2,5‐Dimethyltetrahydrofuran over Non‐promoted Ni/SBA‐15

Author

Eric Marceau, Sébastien Royer, Robert Wojcieszak, Franck Dumeignil, Shuo Chen, François Jérôme, Karine De Oliveira Vigier, Carmen Ciotonea, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-17-CE07-0022,NobleFreeCat,Nanoparticules bimétalliques sans métal noble pour l'hydrogénation des sucres(2017), Université de Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS], and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, 2,5-Dimethylfuran, chemistry.chemical_element, 02 engineering and technology, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Catalysis, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Nickel, chemistry, Biofuel, 5-hydroxymethylfurfural, Organic chemistry, HMF, hydroconversion, nickel, biofuels, incipient wetness impregnation, Physical and Theoretical Chemistry, 0210 nano-technology, Incipient wetness impregnation, Hydroxymethylfurfural
Abstract

The selective hydroconversion of 5‐hydroxymethylfurfural (HMF) to biofuels is currently highly sought‐for. While the literature has demonstrated that this reaction is possible on promoted Ni catalysts, we show here that a monometallic, non‐promoted Ni/SBA‐15 catalyst, prepared by incipient wetness impregnation, can convert HMF to 2,5‐dimethylfuran (DMF) and to 2,5‐dimethyltetrahydrofuran (DMTHF) at 180 °C, in a consecutive way. Through a control over reaction time, high yields to DMF (71 %, at conversion of 93 %) or DMTHF (97 %, at conversion of 100 %) can be achieved. Kinetic modelling suggests a preferential route to DMF via 5‐methylfurfural (MFFR) as intermediate, though the route via 2,5‐bis(hydroxylmethyl)furan (BHMF) is also present. The favored route in the experimental conditions involves the hydrogenolysis of the hydroxyl group of HMF as first step, followed by the hydrogenation of the aldehyde function, to methylfurfuryl alcohol (MFOL). It is suggested a higher reaction rate of hydrogenation or hydrogenolysis of the side group is linked to the presence of a methyl group in the molecule. No hydrogenation of the furan ring is detected on the intermediates. 12;7

Published
2020

30. Synergistic Application of XPS and DFT to Investigate Metal Oxide Surface Catalysis

Author

Quang Thang Trinh, François Jérôme, Kartavya Bhola, Prince Nana Amaniampong, Samir H. Mushrif, Nanyang Technological University [Singapour], Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), and Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Surface (mathematics), Materials science, Oxide, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, Metal, Condensed Matter::Materials Science, chemistry.chemical_compound, X-ray photoelectron spectroscopy, Physics::Chemical Physics, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, [CHIM.CATA]Chemical Sciences/Catalysis, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, General Energy, Chemical engineering, chemistry, visual_art, visual_art.visual_art_medium, Condensed Matter::Strongly Correlated Electrons, Density functional theory, 0210 nano-technology
Abstract

To investigate metal oxide surface catalysis, determining an appropriate Hubbard U-correction term is a challenge for the density functional theory (DFT) community and identifying realistic reactio...

Published
2018

31. Catalyst‐Free Synthesis of Alkylpolyglycosides Induced by High‐Frequency Ultrasound

Author

Yves Blériot, José M. García Fernández, Carmen Ortiz Mellet, Jean-Louis Clément, Prince Nana Amaniampong, Karine De Oliveira Vigier, François Jérôme, Gregory Chatel, Didier Gigmes, Centre National de la Recherche Scientifique (France), Université de Poitiers, Junta de Andalucía, European Commission, Conseil régional d'Aquitaine, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Fédération de recherche INCREASE (INCREASE), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre de Recherche sur l'Intégration Economique et Financière (CRIEF), Université de Poitiers-Université de Poitiers-LIttoral ENvironnement et Sociétés - UMRi 7266 (LIENSs), Université de La Rochelle (ULR)-Centre National de la Recherche Scientifique (CNRS)-Université de La Rochelle (ULR)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Laboratoire de Génie Chimique (LGC), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Instituto de Investigaciones Químicas (IIQ), Universidad de Sevilla-Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Laboratoire de Chimie Moléculaire et Environnement (LCME), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry]), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-LIttoral ENvironnement et Sociétés (LIENSs), La Rochelle Université (ULR)-Centre National de la Recherche Scientifique (CNRS)-La Rochelle Université (ULR)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Centre National de la Recherche Scientifique (CNRS)-Laboratoire de Chimie des Polymères Organiques (LCPO), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Centre National de la Recherche Scientifique (CNRS)-Laboratoire de Génie Chimique (LGC), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centre de recherche sur l'intégration économique et financière (CRIEF), Université de Poitiers-Université de Poitiers, Universidad de Sevilla / University of Sevilla-Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), INCREASE, Region Nouvelle Aquitaine, and ANR-16-CE07-0003,CELLOPLASM,Clivage de la liaison béta-1,4 glycosidique de la cellulose par plasma atmospherique non-thermique: mécanisme et application pour la production d'alkylglycosides(2016)

Subjects
Glycosylation, Surfactants, General Chemical Engineering, Carbohydrates, Degree of polymerization, 010402 general chemistry, 01 natural sciences, Catalysis, symbols.namesake, chemistry.chemical_compound, Ultrasound, [CHIM]Chemical Sciences, Environmental Chemistry, General Materials Science, ComputingMilieux_MISCELLANEOUS, Alkyl, chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Glycoside, Combinatorial chemistry, 3. Good health, 0104 chemical sciences, General Energy, Alkylpolyglycosides, symbols, Degradation (geology), Fischer glycosidation, High frequency ultrasound
Abstract

The irradiation of concentrated feeds of carbohydrates in alcoholic solution by high-frequency ultrasound (550 kHz) induces the formation of alkylpolyglycosides (APGs). This work is distinct from previous reports in that it does not involve any (bio)catalyst or activating agent, it takes place at only 40 °C, thus avoiding degradation of carbohydrates, and it selectively yields APGs with a degree of polymerization in a window of 2¿7, an important limitation of the popular Fischer glycosylation. This ultrasound-based technology proved successful with a range of different valuable carbohydrates and alkyl alcohols. The elucidation of the structure of all the produced glycosides strongly suggests that 1,6-anhydrosugars formed in situ are key intermediate species., Authors are grateful to the CNRS, the University of Poitiers, the Ministry of Research, the Région Nouvelle Aquitaine, the MINECO (contract nos. SAF2016‐76083‐R and CTQ2015‐64425‐C2‐1‐R), the Junta de Andalucía (contract no. FQM2012‐1467) and the European Community (FEDER) for their financial supports.

Published
2018

32. Transglycosylation: A Key Reaction to Access Alkylpolyglycosides from Lignocellulosic Biomass

Author

Sinisa Marinkovic, Boris Estrine, François Jérôme, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and ARD Agroind Rech & Dev, Green Chem Dept

Subjects
010405 organic chemistry, Chemistry, General Chemical Engineering, Lignocellulosic biomass, Context (language use), [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Product distribution, 0104 chemical sciences, chemistry.chemical_compound, General Energy, Yield (chemistry), Environmental Chemistry, Organic chemistry, General Materials Science, Hemicellulose, Cellulose, ComputingMilieux_MISCELLANEOUS
Abstract

An overview is provided on the recent advances in transglycosylation of cellulose and hemicellulose with either short-chain or long-chain alkyl alcohols. Catalytic processes are compared in terms of yield, selectivity and space-time yield, with a view to identifying the most promising pathways for future developments. In this context, the synthesis of alkylpolyglycosides directly from lignocellulosic biomass is discussed while keeping in mind the impact of the botanical origin on the transglycosylation reaction and the product distribution. A section dedicated to the physicochemical properties and ecological footprint of alkylpolyglycosides is also included.

Published
2018

33. Critical analysis of reference studies on the toxicokinetics of aluminum-based adjuvants

Author

Romain K. Gherardi, Jean-Daniel Masson, Guillemette Crépeaux, François-Jérôme Authier, and Christopher Exley

Subjects
Adult, 0301 basic medicine, Adolescent, medicine.medical_treatment, Population, Urine, Pharmacology, Biochemistry, Inorganic Chemistry, 03 medical and health sciences, Adjuvants, Immunologic, Coordination Complexes, Toxicity Tests, medicine, Animals, Humans, Toxicokinetics, Aluminum Compounds, Child, education, Vaccines, education.field_of_study, Minimal risk, Chemistry, Potential risk, QH, Age Factors, Infant, Aluminum salts, Absorption, Physiological, Renal Elimination, 030104 developmental biology, Animal studies, Adjuvant, Aluminum
Abstract

We reviewed the three toxicokinetic reference studies commonly used to suggest that aluminum (Al)-based adjuvants are innocuous. A single experimental study was carried out using isotopic 26Al (Flarend et al., Vaccine, 1997). This study used aluminum salts resembling those used in vaccines but ignored adjuvant uptake by cells that was not fully documented at the time. It was conducted over a short period of time (28 days) and used only two rabbits per adjuvant. At the endpoint, Al elimination in the urine accounted for 6% for Al hydroxide and 22% for Al phosphate, both results being incompatible with rapid elimination of vaccine-derived Al in urine. Two theoretical studies have evaluated the potential risk of vaccine Al in infants, by reference to an oral "minimal risk level" (MRL) extrapolated from animal studies. Keith et al. (Vaccine, 2002) used a high MRL (2 mg/kg/d), an erroneous model of 100% immediate absorption of vaccine Al, and did not consider renal and blood-brain barrier immaturity. Mitkus et al. (Vaccine, 2011) only considered solubilized Al, with erroneous calculations of absorption duration. Systemic Al particle diffusion and neuro-inflammatory potential were omitted. The MRL they used was both inappropriate (oral Al vs. injected adjuvant) and still too high (1 mg/kg/d) regarding recent animal studies. Both paucity and serious weaknesses of reference studies strongly suggest that novel experimental studies of Al adjuvants toxicokinetics should be performed on the long-term, including both neonatal and adult exposures, to ensure their safety and restore population confidence in Al-containing vaccines.

Published
2018

34. Cognitive dysfunction associated with aluminum hydroxide-induced macrophagic myofasciitis: A reappraisal of neuropsychological profile

Author

Paul Kauv, François-Jérôme Authier, Romain K. Gherardi, Anaïs Charles-Nelson, Paul Blanc-Durand, Anne-Catherine Bachoud-Lévi, Axel Van Der Gucht, Mehdi Aoun Sebaiti, and Emmanuel Itti

Subjects
Male, 0301 basic medicine, medicine.medical_specialty, Memory, Episodic, Aluminum Hydroxide, Neuroimaging, Neuropsychological Tests, Audiology, Hospitals, Special, Biochemistry, Dichotic Listening Tests, Cohort Studies, Diagnosis, Differential, Hospitals, University, Inorganic Chemistry, Executive Function, 03 medical and health sciences, 0302 clinical medicine, Adjuvants, Immunologic, Visual memory, medicine, Humans, Attention, Cognitive Dysfunction, Fasciitis, Episodic memory, Cognitive deficit, Retrospective Studies, Dysexecutive syndrome, Myositis, Verbal Behavior, Chemistry, Cognitive disorder, Cognition, Executive functions, medicine.disease, Magnetic Resonance Imaging, 030104 developmental biology, Asymptomatic Diseases, Female, Neurotoxicity Syndromes, France, medicine.symptom, Verbal memory, 030217 neurology & neurosurgery
Abstract

Patients with macrophagic myofasciitis (MMF) present with diffuse arthromyalgias, chronic fatigue, and cognitive disorder. Representative features of MMF-associated cognitive dysfunction include attentional dysfunction, dysexecutive syndrome, visual memory deficit and left ear extinction. Our study aims to reevaluate the neuropsychological profile of MMF. 105 unselected consecutive MMF patients were subjected to a neuropsychological battery of screen short term and long-term memory, executive functions, attentional abilities, instrumental functions and dichotic listening. From these results, patients were classified in four different groups: Subsymptomatic patients (n=41) with performance above pathological threshold (-1.65 SD) in all tests; Fronto-subcortical patients (n=31) who showed pathological results at executive functions and selective attention tests; Papezian patients (n=24) who showed pathological results in storage, recognition and consolidation functions for episodic verbal memory, in addition to fronto-subcortical dysfunction; and Extinction patients (n=9) who had a left ear extinction at dichotic listening test in association to fronto-subcortical and papezian dysfunction. In addition, inter-test analysis showed that patients with apparently normal cognitive functions (Subsymptomatic group) performed significantly worse to attention tests compared to others. In conclusion, our study shows that (i) most patients have specific cognitive deficits; (ii) all patients with cognitive deficit have impairment of executive functions and selective attention; (iii) patients without measurable cognitive deficits display significant weakness in attention; (iv) episodic memory impairment affects verbal, but not visual, memory; (v) none of the patients show an instrumental dysfunction.

Published
2018

35. Selective Conversion of Concentrated Feeds of Furfuryl Alcohol to Alkyl Levulinates Catalyzed by Metal Triflates

Author

Bertrand Doumert, Alban Chappaz, Matthieu Corbet, Karine De Oliveira Vigier, Raphael Wischert, Didier Morvan, Jonathan Lai, Armin T. Liebens, François Jérôme, Xavier Trivelli, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Poitiers-Institut de Chimie du CNRS (INC), Eco-Efficient Products &Processes Laboratory (E2PL2), RHODIA-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Solvay, Institut Michel Eugène Chevreul - FR 2638 (IMEC), Université d'Artois (UA)-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centrale Lille Institut (CLIL), Unité de Glycobiologie Structurale et Fonctionnelle UMR 8576 (UGSF), Institut National de la Recherche Agronomique (INRA)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), CNRS, French Ministry of research, SOLVAY, Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Eco-Efficient Products & Processes Laboratory (E2P2L), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université de Poitiers-Centre National de la Recherche Scientifique (CNRS), Eco-Efficient Products and Processes Laboratory (E2P2L), Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Solvay, Fédération M.E. Chevreul, Université de Lille, Sciences et Technologies, Unité de Glycobiologie Structurale et Fonctionnelle - UMR 8576 (UGSF), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-RHODIA

Subjects
General Chemical Engineering, 02 engineering and technology, 01 natural sciences, 7. Clean energy, Furfuryl alcohol, Catalysis, Alkyl levulinate, Metal, chemistry.chemical_compound, Environmental Chemistry, Organic chemistry, Biomass, Metal triflates, ComputingMilieux_MISCELLANEOUS, Alkyl, chemistry.chemical_classification, 010405 organic chemistry, Renewable Energy, Sustainability and the Environment, Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 021001 nanoscience & nanotechnology, Concenterd feed, 0104 chemical sciences, Acid catalysis, visual_art, visual_art.visual_art_medium, 0210 nano-technology
Abstract

International audience; Herein, we describe an efficient and recyclable catalytic system based on metal triflates capable of converting highly concentrated feeds of furfuryl alcohol (30-40 wt %) to alkyl levulinates in excellent yields (>90%). This constitutes a unique and important advance in the field. Indeed, the dilution of feedstocks represent one of the major bottlenecks in catalysis for the industrial deployment of biobased fuels and chemicals in our society. The impact of water in the metal triflates catalytic performances is also discussed. A comparison with a commercialized process (SFOS) shows that this catalytic route is in line with industrial requirements in terms of yield, selectivity, reactor productivity, and capacity. In particular, unprecedented space time yields up to 200 kg m(-3) h(-1) were obtained.

Published
2018

36. Valorization of lignocellulosic fibres of paper waste into levulinic acid using solid and aqueous Brønsted acid

Author

François Jérôme, Shicheng Zhang, Lei Wang, Season S. Chen, Chi Sun Poon, Andrew J. Hunt, Iris K.M. Yu, Daniel C.W. Tsang, Yong Sik Ok, Nanayang Technological University (NTU), Nanayang Technological University, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), and Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Environmental Engineering, Bioengineering, 02 engineering and technology, 01 natural sciences, 7. Clean energy, chemistry.chemical_compound, medicine, Levulinic acid, Organic chemistry, Dehydration, Cellulose, Ion-exchange resin, Waste Management and Disposal, ComputingMilieux_MISCELLANEOUS, Aqueous solution, 010405 organic chemistry, Renewable Energy, Sustainability and the Environment, Chemistry, Temperature, Water, [CHIM.CATA]Chemical Sciences/Catalysis, General Medicine, 021001 nanoscience & nanotechnology, medicine.disease, Biorefinery, Levulinic Acids, 0104 chemical sciences, Yield (chemistry), 0210 nano-technology, Brønsted–Lowry acid–base theory, Acids, Nuclear chemistry
Abstract

This study aims to produce levulinic acid (LA) from paper towel waste in environment-friendly and economically feasible conditions, and evaluate the difference using solid and aqueous Bronsted acids. Direct dehydration of glucose to LA required sufficiently strong Bronsted acidity, where Amberlyst 36 demonstrated rapid production of approximately 30Cmol% of LA in 20min. However, the maximum yield of LA was limited by mass transfer. In contrast, the yield of LA gradually increased to over 40Cmol% in 1M H2SO4 at 150°C in 60min. The SEM images revealed the conversion in dilute acids under microwave at 150°C resulting in swelling structures of cellulose, which were similar to the pre-treatment process with concentrated acids. Further increase in reaction temperature to 200°C significantly shortened the reaction time from 60 to 2.5min, which saved the energy cost as revealed in preliminary cost analysis.

Published
2018

37. Cover Picture: Conversion of Ammonia to Hydrazine Induced by High‐Frequency Ultrasound (Angew. Chem. Int. Ed. 48/2021)

Author

Anaelle Humblot, Prince Nana Amaniampong, Laurie Grimaud, Audrey Allavena, Tony Chave, François Jérôme, Karine De Oliveira Vigier, and Stéphane Streiff

Subjects
Materials science, business.industry, Ultrasound, Hydrazine, INT, General Chemistry, Catalysis, Ammonia, chemistry.chemical_compound, chemistry, Cover (algebra), business, Nuclear chemistry, High frequency ultrasound
Published
2021

39. Non-linear dose-response of aluminium hydroxide adjuvant particles: Selective low dose neurotoxicity

Author

Yasmine Baba-Amer, Josette Cadusseau, Christopher A. Shaw, Housam Eidi, Bruno Giros, Marie-Odile David, Christopher Exley, Guillemette Crépeaux, François-Jérôme Authier, Eleni T. Tzavara, Romain K. Gherardi, Institut Mondor de Recherche Biomédicale (IMRB), Institut National de la Santé et de la Recherche Médicale (INSERM)-IFR10-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12), École nationale vétérinaire d'Alfort (ENVA), Structure et activité des biomolécules normales et pathologiques (SABNP), Université d'Évry-Val-d'Essonne (UEVE)-Institut National de la Santé et de la Recherche Médicale (INSERM), Neurosciences Paris Seine (NPS), Sorbonne Université (SU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Biologie Paris Seine (IBPS), Sorbonne Université (SU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), The Birchall Centre, Keele University-Lennard-Jones Laboratories, University of British Columbia (UBC), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12), École nationale vétérinaire - Alfort (ENVA), Neuroscience Paris Seine (NPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Biologie Paris Seine (IBPS), and Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
0301 basic medicine, myalgia, particle, [SDV]Life Sciences [q-bio], medicine.medical_treatment, Aluminium oxyhydroxide, Aluminum Hydroxide, Pharmacology, Toxicology, Mice, 03 medical and health sciences, 0302 clinical medicine, Immune system, Adjuvants, Immunologic, adjuvant, Tibialis anterior muscle, neurotoxicity, medicine, Animals, Humans, Dose-Response Relationship, Drug, non-monotonous dose response, Chemistry, Macrophagic myofasciitis, Neurotoxicity, Brain, macrophagic myofasciitis, medicine.disease, R1, QR, 3. Good health, 030104 developmental biology, Lymphatic system, Nonlinear Dynamics, Immunology, Forebrain, Nanoparticles, Female, medicine.symptom, Adjuvant, Locomotion, 030217 neurology & neurosurgery
Abstract

Aluminium (Al) oxyhydroxide (Alhydrogel®), the main adjuvant licensed for human and animal vaccines, consists of primary nanoparticles that spontaneously agglomerate. Concerns about its safety emerged following recognition of its unexpectedly long-lasting biopersistence within immune cells in some individuals, and reports of chronic fatigue syndrome, cognitive dysfunction, myalgia, dysautonomia and autoimmune/inflammatory features temporally linked to multiple Al-containing vaccine administrations. Mouse experiments have documented its capture and slow transportation by monocyte-lineage cells from the injected muscle to lymphoid organs and eventually the brain. The present study aimed at evaluating mouse brain function and Al concentration 180 days after injection of various doses of Alhydrogel® (200, 400 and 800 μg Al/kg of body weight) in the tibialis anterior muscle in adult female CD1 mice. Cognitive and motor performances were assessed by 8 validated tests, microglial activation by Iba-1 immunohistochemistry, and Al level by graphite furnace atomic absorption spectroscopy. An unusual neuro-toxicological pattern limited to a low dose of Alhydrogel® was observed. Neurobehavioural changes, including decreased activity levels and altered anxiety-like behaviour, were observed compared to controls in animals exposed to 200 μg Al/kg but not at 400 and 800 μg Al/kg. Consistently, microglial number appeared increased in the ventral forebrain of the 200 μg Al/kg group. Cerebral Al levels were selectively increased in animals exposed to the lowest dose, while muscle granulomas had almost completely disappeared at 6 months in these animals. We conclude that Alhydrogel® injected at low dose in mouse muscle may selectively induce long-term Al cerebral accumulation and neurotoxic effects. To explain this unexpected result, an avenue that could be explored in the future relates to the adjuvant size since the injected suspensions corresponding to the lowest dose, but not to the highest doses, exclusively contained small agglomerates in the bacteria-size range known to favour capture and, presumably, transportation by monocyte-lineage cells. In any event, the view that Alhydrogel® neurotoxicity obeys “the dose makes the poison” rule of classical chemical toxicity appears overly simplistic.\ud Abbreviations Al, Aluminium; dLNs, draining lymph nodes; im, intra-muscular; MMF, macrophagic myofasciitis; NOR, novel object recognition test; PFA, paraformaldehyde

Published
2017

40. Elucidation of the role of betaine hydrochloride in glycerol esterification: towards bio-based ionic building blocks

Author

Christian Bachmann, C. Journoux-Lapp, K. De Oliveira Vigier, Sinisa Marinkovic, Boris Estrine, François Jérôme, Gilles Frapper, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Agro-Industrie Recherches et Développements, Green Chemistry Department, and Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Poitiers-Institut de Chimie du CNRS (INC)

Subjects
Green chemistry, Nucleophilic addition, Betaine Hydrochloride, 010405 organic chemistry, Chemistry, Ionic bonding, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Pollution, 0104 chemical sciences, Catalysis, Solvent, chemistry.chemical_compound, Betaine, Yield (chemistry), Environmental Chemistry, Organic chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

The mechanism of bio-based betaine hydrochloride esterification with glycerol has been studied through DFT modelling and experimental approaches. Interestingly, our proposed mechanism differs from the classical Watson and Ingold ones. In particular, we found that the glycine betaine hydrochloride cluster contains a non-dissociated HCl molecule in its structure. This trapped HCl acted as a proton relay to favor the formation of unconstrained six-membered ring transition state structures both in nucleophilic addition (C–O bond coupling) and H2O elimination pathways. These findings led us to optimize this reaction. In particular, glyceryl betaine esters were produced in a yield up to 90% and with a space time yield up to 670 kg m−3 h−1 unreported to date. The absence of an external catalyst and solvent, as well as the use of a stoichiometric mixture of acidified glycine betaine and glycerol, two co-products of the sugar beet and vegetable oil industries, respectively, represent notable advantages within the framework of sustainable chemistry. This work opens a straightforward route to bio-based and valuable ionic building blocks which are of high interest for the synthesis of ionic surfactants or liquids. Furthermore, the results reported in this work also rationalize the high catalytic performances of glycine betaine hydrochloride recently reported in acid-catalyzed reactions.

Published
2017

42. Catalytic oxidative dehydrogenation of malic acid to oxaloacetic acid

Author

Virginie Belliere-Baca, Antonio Pineda, Didier Morvan, Karine De Oliveira Vigier, François Jérôme, Asmaa Drif, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Adisseo France S.A.S

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Decarboxylation, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Pollution, 0104 chemical sciences, Catalysis, Amino acid, chemistry.chemical_compound, chemistry, Oxaloacetic acid, Yield (chemistry), Environmental Chemistry, Organic chemistry, Dehydrogenation, Malic acid, Pyruvic acid, ComputingMilieux_MISCELLANEOUS
Abstract

Here we report the oxidative dehydrogenation of malic acid to oxaloacetic acid, a key precursor in the fabrication of amino acids, over Pt–Bi/C catalysts. Under optimized conditions, we discovered that OAA was selectively produced with up to 60% conversion (i.e. 60% yield). The recurrent unwanted decarboxylation of OAA to pyruvic acid was circumvented by successfully conducting the catalytic reaction at 25 °C. A comparison with the classical Fenton oxidation reaction is discussed.

Published
2019

43. Eco-efficient synthesis of 2-quinaldic acids from furfural

Author

François Jérôme, Dong Xiaohan, Na Zhang, Minghao Li, Yanlong Gu, Beijing University of Agriculture, Interdisciplinary Centre for Security, Reliability and Trust [Luxembourg] (SnT), Université du Luxembourg (Uni.lu), and Huazhong Univ Sci & Technol, Sch Chem & Chem Engn, Wuhan (Huazhong Univ Sci & Technol, Sch Chem & Chem Engn, Wuhan)

Subjects
Green chemistry, Reissert reaction, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Potassium cyanide, 010402 general chemistry, Furfural, 01 natural sciences, Pollution, 0104 chemical sciences, chemistry.chemical_compound, Hydrolysis, Aniline, chemistry, Scientific method, Yield (chemistry), Environmental Chemistry, Organic chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

Quinaldic acids are important fine chemicals. Nowadays, industrial methods to synthesize quinaldic acids rely heavily on a three-step process established based on the Reissert reaction, which involves however the use of highly toxic potassium cyanide. In this paper, a novel cyclization of aniline with ethyl 4,4-diethoxycrotonate was realized, which offered ethyl quinaldate in good yield. Based on this reaction, an eco-efficient method to prepare quinaldic acids was developed, which involves the following three steps: (i) synthesis of ethyl 4,4-diethoxycrotonate through photooxidation of furfural and a consecutive ring-opening alcoholysis; (ii) cyclization of ethyl 4,4-diethoxycrotonate with aniline, and (iii) hydrolysis of the generated ethyl quinaldate. This new method not only avoids the use of toxic potassium cyanide but also meets many salient features of green chemistry, such as the use of bio-based feedstocks, environmentally benign metal-free conditions and good reaction yields.

Published
2019

44. Synthesis of Alkyl Polyglycosides From Glucose and Xylose for Biobased Surfactants: Synthesis, Properties, and Applications

Author

François Jérôme, Sinisa Marinkovic, and Boris Estrine

Subjects
chemistry.chemical_classification, Glycoside, Pentose, Lignocellulosic biomass, Xylose, Polysaccharide, symbols.namesake, chemistry.chemical_compound, Monomer, chemistry, symbols, Organic chemistry, lipids (amino acids, peptides, and proteins), Fischer glycosidation, Alkyl
Abstract

This review is dedicated to lignocellulosic biomass and its two main components d -xylose and d -glucose as raw materials for the production of alkyl polyglycosides. Alkyl polyglucoside surfactants have been industrially developed since the late 1980s, and recent developments in the field of alkyl polyglycosides have focused on d -xylose-based equivalent molecules. Applications of alkyl polyglycosides and the preparation of glucose and/or pentose-based surfactants are discussed. The recent progresses on Fischer glycosylation and on the conversion of lignocellulosic polysaccharides into various alkyl glycosides are addressed. This paper provides also a discussion of various surfactant properties and their relationship to the process and the sugar-based material (xylans, lignocellulosic biomass, and d -xylose and d -glucose monomers). The application fields and the ecological profile of the alkyl polyglycosides are discussed.

Published
2019

45. Utilization of bio-based glycolaldehyde aqueous solution in organic synthesis: application to the synthesis of 2,3-dihydrofurans

Author

Yanlong Gu, François Jérôme, Yves Queneau, Wenbo Huang, Rongxian Bai, Jing Xu, Huazhong University of Science and Technology [Wuhan] (HUST), Chimie Organique et Bioorganique (COB), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), and Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Glycolaldehyde, Aqueous solution, Nitromethane, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Acetal, 010402 general chemistry, 01 natural sciences, Pollution, 0104 chemical sciences, Deep eutectic solvent, chemistry.chemical_compound, chemistry, Environmental Chemistry, Organic chemistry, Organic synthesis, Cellulose, Acetonitrile
Abstract

International audience; Glycolaldehyde is a biomass-derived chemical compound available from cellulose or glucose. Until now, little attention has been devoted to its use towards value-added chemicals. To explore novel transformations of glycolaldehyde, in this work, a three-component reaction of glycolaldehyde, indole and a 1,3-dicarbonyl compound was developed to synthesize a class of 3-(indol-3-yl)-2,3-dihydrofurans. Using glycolaldehyde diethyl acetal as a glycolaldehyde source, the reaction can be performed in organic solvents, and two catalytic systems were proved to be effective: (a) Sc(OTf) 3 /nitromethane and (b) Ni(ClO 4) 2 ·6H 2 O/ acetonitrile. However, these conditions applied to the direct use of the bio-based glycolaldehyde aqueous solution did not provide the dihydrofurans efficiently. To enable the use of an aqueous solution of glycolaldehyde, a hitherto unreported deep eutectic solvent (DES) was developed by using FeCl 3 ·6H 2 O and meglumine (N-methylglucamine) as precursors. The FeCl 3 ·6H 2 O/meglumine DES was characterized by FTIR, TGA and DSC, and the obtained results demonstrated unambiguously the formation of a DES. This DES was found to be an efficient and water-compatible promoting medium for the abovementioned three-component reaction. A variety of 3-(indol-3-yl)-2,3-dihydrofurans were synthesized in good yields. The FeCl 3 ·6H 2 O/meglumine DES system can also be recycled without significant loss of activity.

Published
2019

46. Front Cover: A Combined Experimental–Theoretical Study on Diels‐Alder Reaction with Bio‐Based Furfural: Towards Renewable Aromatics (ChemSusChem 1/2021)

Author

Changru Ma, Karine De Oliveira Vigier, I van Scodeller, Eric Muller, Frédéric Guégan, François Jérôme, and Raphael Wischert

Subjects
Materials science, business.industry, General Chemical Engineering, Biomass, Bio based, Furfural, Renewable energy, chemistry.chemical_compound, General Energy, Front cover, chemistry, Diels alder, Environmental Chemistry, Organic chemistry, General Materials Science, business, Diels–Alder reaction
Published
2020

47. Heterogeneously-acid catalyzed oligomerization of glycerol over recyclable superacid Aquivion ® PFSA

Author

Karine De Oliveira Vigier, Armin T. Liebens, Nassim Sayoud, Jonathan Lai, François Jérôme, Claudio Oldani, and Ayman Karam

Subjects
010405 organic chemistry, Process Chemistry and Technology, Regioselectivity, Context (language use), 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Hammett acidity function, chemistry, Nafion, Glycerol, Organic chemistry, Superacid, Physical and Theoretical Chemistry, Selectivity
Abstract

This manuscript explores the catalytic activity, selectivity and stability of Aquivion ® PFSA PW98 in the oligomerization of glycerol. Aquivion ® PFSA PW98 is a solid superacid catalyst with a Hammett acidity function of −12. Furthermore, the perfluorinated structure allows this polymer to stand quite high operating temperature (up to 150–160 °C) without loss in mechanical and chemical integrity which is of huge interest for glycerol conversion. In this context, we discovered that Aquivion ® PFSA PW98 was nearly fully selective to oligoglycerols up to 80% conversion of glycerol. The oligomerization degree of oligoglycerol and the regioselectivity of the reaction (linear vs branched and cyclic isomers) were fully analyzed by means of GC and SEC chromatographies. In contrast to conventional solid acid catalysts, Aquivion ® PFSA PW98 was found highly robust in glycerol and was sucessfully recycled at least 10 times without apparent decrease in activity or selectivity. A comparison with Nafion NR 50 is also included to shed light on the potential of Aquivion ® PFSA PW98 for acid-catalyzed conversion of glycerol.

Published
2016

48. Impact of Nonthermal Atmospheric Plasma on the Structure of Cellulose: Access to Soluble Branched Glucans

Author

Cédric Gaillard, Elodie Fourré, José M. García Fernández, Carmen Ortiz Mellet, Abdellatif Barakat, Joakim Delaux, Jean-Michel Tatibouët, Christine Canaff, François Jérôme, Ingénierie des Agro-polymères et Technologies Émergentes (UMR IATE), Institut national d’études supérieures agronomiques de Montpellier (Montpellier SupAgro), Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad)-Centre international d'études supérieures en sciences agronomiques (Montpellier SupAgro)-Université Montpellier 2 - Sciences et Techniques (UM2)-Université de Montpellier (UM)-Institut National de la Recherche Agronomique (INRA), Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universidad de Sevilla, Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de la Recherche Agronomique (INRA), Instituto de Investigaciones Químicas (IIQ), and Consejo Superior de Investigaciones Científicas [Madrid] (CSIC)-Universidad de Sevilla

Subjects
Plasma Gases, 010402 general chemistry, Cleavage (embryo), Polysaccharide, 01 natural sciences, Catalysis, chemistry.chemical_compound, Polysaccharides, [SDV.IDA]Life Sciences [q-bio]/Food engineering, Dextrins, Organic chemistry, Biomass, Cellulose, Glucans, chemistry.chemical_classification, Downstream processing, 010405 organic chemistry, Organic Chemistry, Non-thermal atmospheric plasma, Glycosidic bond, General Chemistry, 0104 chemical sciences, Microcrystalline cellulose, Solvent, Solubility, chemistry
Abstract

We have investigated the effect of non-thermal atmospheric plasma (NTAP) on the structure of microcrystalline cellulose. In particular, by means of different characterization methods, we demonstrate that NTAP promotes the partial cleavage of the β-1,4 glycosidic bond of cellulose leading to the release of short-chain cellodextrins that are reassembled in situ, preferentially at the C6 position, to form branched glucans with either a glucosyl or anhydroglucosyl terminal residue. The ramification of cellulosic chain induced by NTAP yields branched glucans that are soluble in DMSO or in water, thus opening a straightforward access to processable glucans from cellulose. Importantly, the absence of solvent and catalyst considerably facilitates downstream processing as compared to (bio)catalytic processes which typically occur in diluted conditions.

Published
2016

49. Depolymerization of cellulose to processable glucans by non-thermal technologies

Author

K. De Oliveira Vigier, François Jérôme, Gregory Chatel, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), and Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Poitiers-Institut de Chimie du CNRS (INC)

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Depolymerization, Glycosidic bond, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Pollution, 0104 chemical sciences, Catalysis, Sonochemistry, chemistry.chemical_compound, chemistry, Chemical engineering, Polymerization, [CHIM]Chemical Sciences, Environmental Chemistry, Surface modification, Organic chemistry, Cellulose, Macromolecule
Abstract

International audience; In this review, we discuss the recent progress made in the field of non-thermal technologies for the selective depolymerization of cellulose to processable glucans. The synergy of these technologies with catalysis, their impact on the cellulose structure and reactivity are discussed. Particularly, we highlight that these non-thermal technologies not only induce a fast cleavage of the β-1,4 glycosidic bond of cellulose but also promote random re-polymerization reactions yielding glucans with different types of glycosidic linkages (α/β-1,4, -1,3, -1,6, -1,2) and degrees of polymerization. Remarkably, these technologies are capable of converting cellulose to soluble glucans at low temperature (

Published
2016

50. Fast and solvent free polymerization of carbohydrates induced by non-thermal atmospheric plasma

Author

Karine De Oliveira Vigier, Michaël Nigen, Jean-Michel Tatibouët, Abdellatif Barakat, Joakim Delaux, Elodie Fourré, Loyda Atencio, José M. García Fernández, François Jérôme, Ingénierie des Agro-polymères et Technologies Émergentes (UMR IATE), Institut national d’études supérieures agronomiques de Montpellier (Montpellier SupAgro), Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad)-Centre international d'études supérieures en sciences agronomiques (Montpellier SupAgro)-Université Montpellier 2 - Sciences et Techniques (UM2)-Université de Montpellier (UM)-Institut National de la Recherche Agronomique (INRA), Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), IIQ Instituto de Investigaciones Quimicas, Spanish National Research Council (CSIC), Institut national d’études supérieures agronomiques de Montpellier (Montpellier SupAgro)-Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad)-Centre international d'études supérieures en sciences agronomiques (Montpellier SupAgro)-Université Montpellier 2 - Sciences et Techniques (UM2)-Université de Montpellier (UM)-Institut National de la Recherche Agronomique (INRA), Université de Poitiers-Centre National de la Recherche Scientifique (CNRS), Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad)-Institut National de la Recherche Agronomique (INRA)-Université Montpellier 2 - Sciences et Techniques (UM2)-Centre international d'études supérieures en sciences agronomiques (Montpellier SupAgro)-Université de Montpellier (UM)-Institut national d’études supérieures agronomiques de Montpellier (Montpellier SupAgro), Institut National de la Recherche Agronomique (France), Ministerio de Economía y Competitividad (España), Junta de Andalucía, European Commission, Universidad de Sevilla, and Centre National de la Recherche Scientifique (France)

Subjects
Molar mass, Hydrodynamic radius, Aqueous solution, 010405 organic chemistry, Chemistry, 02 engineering and technology, 021001 nanoscience & nanotechnology, 01 natural sciences, Pollution, 0104 chemical sciences, 12. Responsible consumption, Catalysis, Solvent, Chemical engineering, Polymerization, Yield (chemistry), Environmental Chemistry, Organic chemistry, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, 0210 nano-technology, Chemical decomposition
Abstract

Non-thermal atmospheric plasma (NTAP) is a physical technology that has been previously employed for surface treatment (cleaning, coating, erosion, etc.) and water or air depollution. We show here that, beyond surface effects, NTAP is capable of enabling the complete and fast polymerization of various mono- and disaccharides in the solid state within only a few minutes and at low temperature (40-80 °C). NTAP-induced polymerization involves a radical mechanism and yields water soluble polysaccharides with a mean molar mass of up to 100000 g mol and a mean hydrodynamic radius of 3 nm. Although polymerization reactions promoted by NTAP occurs in a random manner, the α-1,6 and β-1,6 linkages are however dominant. Furthermore, we discovered that NTAP is highly selective, strongly favoring glycosylation over other chemical transformations in the bulk. Under our working conditions, glycosyl units are preserved that constitute the repeating units of the polysaccharide product. No chemical degradation (e.g. intramolecular dehydration reactions) was observed, allowing a white powder to be recovered with a yield higher than 93 wt%. From a practical point of view, NTAP has great potential for breakthrough in the production of polysaccharides, notably because it does not require the use of a solvent or catalyst, thus by-passing the traditional post-treatment of aqueous effluents and catalyst recycling characteristic of biotechnological polysaccharide production. Its efficiency at low temperature also prevents carbohydrates from degradation. Finally, NTAP proceeds on an on/off switch basis, allowing the polymerization reaction to be started and stopped quasi instantaneously., This study was funded by the CNRS, INRA and the French Ministry of Research, including the PhD grant of J. Delaux. This study was also supported by the Spanish Ministerio de Economía y Competitividad (contract numbers SAF2013-44021-R and CTQ2010-15848), the Junta de Andalucía (contract number FQM2012-1467) and the European Regional Development Funds (FEDER and FSE). The authors are grateful to the technical assistance from the research support services of the University of Sevilla (CITIUS), INRA-NANTES and IC2MP. The authors also expressed their sincere thanks to members of the FR CNRS INCREASE 3707 consortium for fruitful discussions and scientific advices.

Published
2016

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