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1. Galf-Specific Neolectins: Towards Promising Diagnostic Tools

Author

Mateja Seničar, Benoît Roubinet, Pierre Lafite, Laurent Legentil, Vincent Ferrières, Ludovic Landemarre, and Richard Daniellou

Subjects
galactofuranosidase, neolectin bioengineering, site-directed mutagenesis, neoglycoprotein, Biology (General), QH301-705.5, Chemistry, QD1-999
Abstract

In the absence of naturally available galactofuranose-specific lectin, we report herein the bioengineering of GalfNeoLect, from the first cloned wild-type galactofuranosidase (Streptomyces sp. strain JHA19), which recognises and binds a single monosaccharide that is only related to nonmammalian species, usually pathogenic microorganisms. We kinetically characterised the GalfNeoLect to confirm attenuation of hydrolytic activity and used competitive inhibition assay, with close structural analogues of Galf, to show that it conserved interaction with its original substrate. We synthetised the bovine serum albumin-based neoglycoprotein (GalfNGP), carrying the multivalent Galf units, as a suitable ligand and high-avidity system for the recognition of GalfNeoLect which we successfully tested directly with the galactomannan spores of Aspergillus brasiliensis (ATCC 16404). Altogether, our results indicate that GalfNeoLect has the necessary versatility and plasticity to be used in both research and diagnostic lectin-based applications.

Published
2024
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2. Strategies to access the [5-8] bicyclic core encountered in the sesquiterpene, diterpene and sesterterpene series

Author

Cécile Alleman, Charlène Gadais, Laurent Legentil, and François-Hugues Porée

Subjects
5-8 bicycle, cyclization strategies, terpenes, Science, Organic chemistry, QD241-441
Abstract

Terpene compounds probably represent the most diversified class of secondary metabolites. Some classes of terpenes, mainly diterpenes (C20) and sesterterpenes (C25) and to a lesser extent sesquiterpenes (C15), share a common bicyclo[3.6.0]undecane core which is characterized by the presence of a cyclooctane ring fused to a cyclopentane ring, i.e., a [5-8] bicyclic ring system. This review focuses on the different strategies elaborated to construct this [5-8] bicyclic ring system and their application in the total synthesis of terpenes over the last two decades. The overall approaches involve the construction of the 8-membered ring from an appropriate cyclopentane precursor. The proposed strategies include metathesis, Nozaki–Hiyama–Kishi (NHK) cyclization, Pd-mediated cyclization, radical cyclization, Pauson–Khand reaction, Lewis acid-promoted cyclization, rearrangement, cycloaddition and biocatalysis.

Published
2023
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3. In vitro and in vivo immunomodulatory properties of octyl-β-d-galactofuranoside during Leishmania donovani infection

Author

Hélène Guegan, Kevin Ory, Sorya Belaz, Aurélien Jan, Sarah Dion, Laurent Legentil, Christelle Manuel, Loïc Lemiègre, Thomas Vives, Vincent Ferrières, Jean-Pierre Gangneux, and Florence Robert-Gangneux

Subjects
Visceral leishmaniasis, Leishmania donovani, Immunostimulation treatment, Galactofuranose, Furanoside, Macrophage polarization, Infectious and parasitic diseases, RC109-216
Abstract

Abstract Background The chemotherapeutic arsenal available to treat visceral leishmaniasis is currently limited, in view of many drawbacks such as high cost, toxicity or emerging resistance. New therapeutic strategies are particularly needed to improve the management and the outcome in immunosuppressed patients. The combination of an immunomodulatory drug to a conventional anti-Leishmania treatment is an emerging concept to reverse the immune bias from Th2 to Th1 response to boost healing and prevent relapses. Methods Here, immunostimulating and leishmanicidal properties of octyl-β-d-galactofuranose (Galf) were assessed in human monocyte-derived macrophages (HM) and in a murine model, after challenge with Leishmania donovani promastigotes. We recorded parasite loads and expression of various cytokines and immune effectors in HM and mouse organs (liver, spleen, bone marrow), following treatment with free (Galf) and liposomal (L-Galf) formulations. Results Both treatments significantly reduced parasite proliferation in HM, as well as liver parasite burden in vivo (Galf, P

Published
2019
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4. Molecular Interactions of β-(1→3)-Glucans with Their Receptors

Author

Laurent Legentil, Franck Paris, Caroline Ballet, Sophie Trouvelot, Xavier Daire, Vaclav Vetvicka, and Vincent Ferrières

Subjects
β-(1→3)-glucans, Dectin-1, CR3, glycolipids, langerin, CBM, Organic chemistry, QD241-441
Abstract

β-(1→3)-Glucans can be found as structural polysaccharides in cereals, in algae or as exo-polysaccharides secreted on the surfaces of mushrooms or fungi. Research has now established that β-(1→3)-glucans can trigger different immune responses and act as efficient immunostimulating agents. They constitute prevalent sources of carbons for microorganisms after subsequent recognition by digesting enzymes. Nevertheless, mechanisms associated with both roles are not yet clearly understood. This review focuses on the variety of elucidated molecular interactions that involve these natural or synthetic polysaccharides and their receptors, i.e., Dectin-1, CR3, glycolipids, langerin and carbohydrate-binding modules.

Published
2015
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5. Identification of Three Elicitins and a Galactan-Based Complex Polysaccharide from a Concentrated Culture Filtrate of Phytophthora infestans Efficient against Pectobacterium atrosepticum

Author

Guillaume Saubeau, Fanny Gaillard, Laurent Legentil, Caroline Nugier-Chauvin, Vincent Ferrières, Didier Andrivon, and Florence Val

Subjects
elicitin, GC-MS, MALDI TOF, PAMPs-triggered immunity, phenylalanine ammonialyase, polysaccharide, plant defense responses, Solanum tuberosum, Organic chemistry, QD241-441
Abstract

The induction of plant immunity by Pathogen Associated Molecular Patterns (PAMPs) constitutes a powerful strategy for crop protection. PAMPs indeed induce general defense responses in plants and thus increase plant resistance to pathogens. Phytophthora infestans culture filtrates (CCFs) are known to induce defense responses and decrease the severity of soft rot due to Pectobacterium atrosepticum in potato tubers. The aim of this study was to identify and characterize the active compounds from P. infestans filtrate. The filtrate was fractionated by gel filtration, and the protection effects against P. atrosepticum and the ability to induce PAL activity were tested for each fraction. The fraction active in protection (F1) also induced PAL activity, as did the whole filtrate. Three elicitins (INF1, INF4 and INF5) were identified in F1b, subfraction of F1, by MALDI-TOF-MS and MS/MS analyses. However, deproteinized F1b still showed biological activity against the bacterium, revealing the presence of an additional active compound. GC-MS analyses of the deproteinized fraction highlighted the presence of a galactan-based complex polysaccharide. These experiments demonstrate that the biological activity of the CCF against P. atrosepticum results from a combined action of three elicitins and a complex polysaccharide, probably through the activation of general defense responses.

Published
2014
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6. Multiple-stage Precursor Ion Separation and High Resolution Mass Spectrometry toward Structural Characterization of 2,3-Diacyltrehalose Family from Mycobacterium tuberculosis

Author

Cheryl Frankfater, Robert B. Abramovitch, Georgiana E. Purdy, John Turk, Laurent Legentil, Loïc Lemiègre, and Fong-Fu Hsu

Subjects
tandem mass spectrometry, linear ion trap, glycolipid, diacyltrehalose, Mycobacterium tuberculosis, Physics, QC1-999, Chemistry, QD1-999
Abstract

Mass spectrometry (MS)-based precursor ion isolation, collision-induced dissociation (CID) fragmentation, and detection using linear ion-trap multiple-stage mass spectrometry (LIT MSn) in combination with high resolution mass spectrometry (HRMS) provides a unique tool for structural characterization of complex mixture without chromatographic separation. This approach permits not only separation of various lipid families and their subfamilies, but also stereoisomers, thereby, revealing the structural details. In this report, we describe the LIT MSn approach to unveil the structures of a 2,3-diacyl trehalose (DAT) family isolated from the cell envelope of Mycobacterium tuberculosis, in which more than 30 molecular species, and each species consisting of up to six isomeric structures were found. LIT MSn performed on both [M + Na]+ and [M + HCO2]− ions of DAT yield complimentary structural information for near complete characterization of the molecules, including the location of the fatty acyl substituents on the trehalose backbone. This latter information is based on the findings of the differential losses of the two fatty acyl chains in the MS2 and MS3 spectra; while the product ion spectra from higher stage LIT MSn permit confirmation of the structural assignment.

Published
2019
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8. Distinguishing Galactoside Isomers with Mass Spectrometry and Gas-Phase Infrared Spectroscopy

Author

Isabelle Compagnon, Laura L. Kiessling, Baptiste Schindler, Vincent Ferrieres, Jordan Ho, Oznur Yeni, Laurent Legentil, Amira Gharbi, Richard Brédy, Massachusetts Institute of Technology (MIT), École normale supérieure - Lyon (ENS Lyon), Institut Lumière Matière [Villeurbanne] (ILM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-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)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Centre National de la Recherche Scientifique (CNRS), This work was supported by ANR ALGAIMS (grant ANR-18-CE29-0006-03 to IC) and the National Institute of Allergy and Infectious Disease (Al-126592 to LLK) and the NIH Common Fund (U01GM125288 to LLK)., ANR-18-CE29-0006,ALGAIMS,Analyses de polysaccharides comportant des unités Galf par IRMPD et MS-mobilité ionique(2018), Structure et dynamique multi-échelle des édifices moléculaires (DYNAMO), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon, 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), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
Glycan, Anomer, Spectrophotometry, Infrared, Stereochemistry, Adducts, Carbohydrates, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Mass Spectrometry, Article, chemistry.chemical_compound, Colloid and Surface Chemistry, Carbohydrate Conformation, Monosaccharide, [CHIM]Chemical Sciences, Infrared multiphoton dissociation, chemistry.chemical_classification, Ions, biology, 010405 organic chemistry, Chemistry, Galactosides, Stereoisomerism, General Chemistry, Mycobacterium tuberculosis, Furanose, Galactoside, Chemical biology, 0104 chemical sciences, Klebsiella pneumoniae, Pyranose, Galactose, biology.protein, Molecular structure
Abstract

International audience; Sequencing glycans is demanding due to their structural diversity. Compared to mammalian glycans, bacterial glycans pose a steeper challenge because they are constructed from a larger pool of monosaccharide building blocks, including pyranose and furanose isomers. Though mammalian glycans incorporate only the pyranose form of galactose (Galp), many pathogens, including Mycobacterium tuberculosis and Klebsiella pneumoniae, contain galactofuranose (Galf) residues in their cell envelope. Thus, glycan sequencing would benefit from methods to distinguish between pyranose and furanose isomers of different anomeric configurations. We used infrared multiple photon dissociation (IRMPD) spectroscopy with mass spectrometry (MS-IR) to differentiate between pyranose- and furanose-linked galactose residues. These targets pose a challenge for MS-IR because the saccharides lack basic groups, and galactofuranose residues are highly flexible. We postulated cationic groups that could complex through hydrogen bonding would offer a solution. Here, we present the first MS-IR analysis of hexose ammonium adducts. We compared their IR fingerprints with those of lithium adducts. We determined the diagnostic MS-IR signatures of the α- and β-anomers of galactose in furanose and pyranose forms. We also showed these signatures could be applied to disaccharides to assign galactose ring size. Our findings highlight the utility of MS-IR for analyzing the unique substructures that occur in bacterial glycans.

Published
2021

9. Synthesis of an Exhaustive Library of Naturally Occurring Gal

Author

Bénédicte, Favreau, Oznur, Yeni, Simon, Ollivier, Joël, Boustie, Françoise Le, Dévéhat, Jean-Paul, Guégan, Mathieu, Fanuel, Hélène, Rogniaux, Richard, Brédy, Isabelle, Compagnon, David, Ropartz, Laurent, Legentil, and Vincent, Ferrières

Subjects
Galactose, Glycosides, Disaccharides, Mannose, Mass Spectrometry
Abstract

Nature offers a huge diversity of glycosidic derivatives. Among numerous structural modulations, the nature of the ring size of hexosides may induce significant differences on both biological and physicochemical properties of the glycoconjugate of interest. On this assumption, we expect that small disaccharides bearing either a furanosyl entity or a pyranosyl residue would give a specific signature, even in the gas phase. On the basis of the scope of mass spectrometry, two analytical techniques to register those signatures were considered, i.e., the ion mobility (IM) and the infrared multiple photon dissociation (IRMPD), in order to build up cross-linked databases. d-Galactose occurs in natural products in both tautomeric forms and presents all possible regioisomers when linked to d-mannose. Consequently, the four reducing Gal

Published
2021

10. Synthesis of an Exhaustive Library of Naturally Occurring Galf-Manp and Galp-Manp Disaccharides. Toward Fingerprinting According to Ring Size by Advanced Mass Spectrometry-Based IM-MS and IRMPD

Author

Hélène Rogniaux, Oznur Yeni, Jean-Paul Guégan, Richard Brédy, Françoise Le Dévéhat, Bénédicte Favreau, Simon Ollivier, David Ropartz, Laurent Legentil, Vincent Ferrières, Joël Boustie, Isabelle Compagnon, Mathieu Fanuel, 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), Structure et dynamique multi-échelle des édifices moléculaires (DYNAMO), Institut Lumière Matière [Villeurbanne] (ILM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Unité de recherche sur les Biopolymères, Interactions Assemblages (BIA), Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), The authors thank the Agence Nationale de la Recherche (ANR) for financially supporting the ALGAIM-MS project (ANR-18-CE29-0006-02, https://algaims-35.webself.net/accueil). The NMR platform PRISM (Université de Rennes 1, https://biosit.univ-rennes1.fr/prism-plate-forme-rennaise-dimagerie-et-spectroscopie-multimodales) is also acknowledged for recording 1H and 13C spectra at 500 and 125 MHz, respectively., ANR-18-CE29-0006,ALGAIMS,Analyses de polysaccharides comportant des unités Galf par IRMPD et MS-mobilité ionique(2018), 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 Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon, INRA Plateforme BIBS, Unité de Recherche Biopolymères, Interactions, Assemblages, Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-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)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Centre National de la Recherche Scientifique (CNRS), BioInformatique et BioStatistiques (2-BIBS), Centre International de Recherche en Infectiologie - UMR (CIRI), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Stereochemistry, Organic Chemistry, Glycosidic bond, 010402 general chemistry, Mass spectrometry, 01 natural sciences, Tautomer, 0104 chemical sciences, Ring size, Residue (chemistry), chemistry.chemical_compound, Structural isomer, [CHIM]Chemical Sciences, Glycosyl, Infrared multiphoton dissociation
Abstract

International audience; Nature offers a huge diversity of glycosidic derivatives. Among numerous structural modulations, the nature of the ring size of hexosides may induce significant differences on both biological and physicochemical properties of the glycoconjugate of interest. On this assumption, we expect that small disaccharides bearing either a furanosyl entity or a pyranosyl residue would give a specific signature, even in the gas phase. On the basis of the scope of mass spectrometry, two analytical techniques to register those signatures were considered, i.e., the ion mobility (IM) and the infrared multiple photon dissociation (IRMPD), in order to build up cross-linked databases. d-Galactose occurs in natural products in both tautomeric forms and presents all possible regioisomers when linked to d-mannose. Consequently, the four reducing Galf-Manp disaccharides as well as the four Galp-Manp counterparts were first synthesized according to a highly convergent approach, and IM-MS and IRMPD-MS data were second collected. Both techniques used afforded signatures, specific to the nature of the connectivity between the two glycosyl entities.

Published
2021

11. Improvement of the versatility of an arabinofuranosidase against galactofuranose for the synthesis of galactofuranoconjugates

Author

Olivier Tasseau, Aline Pillot, Laurent Legentil, Quentin Pavic, Sylvain Tranchimand, 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, Ministère de l'Enseignement supérieur, de la Recherche et de l'Innovation, ANR-15-CE07-0009-01, Agence Nationale de la Recherche, Région Bretagne, Conseil Régional des Pays de la Loire, ANR-15-CE07-0009,C-linkAse,Nouveau biocatalyseurs pour la C-glycosylation: mutation d'hydrolases pour l'obtention de C-glycosides modulables à fort potentiel industriel(2015), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
Models, Molecular, 0301 basic medicine, Glycoside Hydrolases, Mutant, Kinetics, Mutagenesis (molecular biology technique), 01 natural sciences, Biochemistry, Acylation, 03 medical and health sciences, chemistry.chemical_compound, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, chemistry.chemical_classification, Molecular Structure, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Aryl, Organic Chemistry, Wild type, Galactose, Substrate (chemistry), Combinatorial chemistry, 0104 chemical sciences, 030104 developmental biology, Enzyme, chemistry, Mutation, Glycoconjugates
Abstract

International audience; Galactofuranoconjugates are rare compounds with interesting biological properties. Their syntheses by traditional approaches are however tedious. Glycosidases are nowadays often used to simplify such syntheses but the use of galactofuranosidase has not been described yet for the synthesis of galactofuranoconjugates. Interestingly CtAraf51, an α-l-arabinofuranosidase from Ruminiclostridium thermocellum, is able to use aryl- or alkyl-β-d-galactofuranosides as the substrate but with very low efficiency. To allow its use as a synthesis tool, we decided to improve the efficiency of this enzyme toward these non-natural substrates. First, we identified three residues that can contribute to unfavorable interactions with the p-nitrophenyl-β-d-galactofuranoside. After mutagenesis, two mutants have shown a catalytic efficiency four- and threefold higher than that of the wild type, respectively. These two mutants were then evaluated in the transglycosylation reaction using ethanol as a model acceptor substrate. Under these conditions one mutant was much more efficient 50% conversion was reached ten times faster than with the WT. Finally both mutants were converted into thioglycoligases in the thioligation reaction, the reaction was two times faster than with the E173A single mutant, and in the acylation reaction a fourfold increase in the initial velocity was found. The synthetic potential of the resulting mutants to synthesize various O-, S- and acyl galactofuranoconjugates was further evaluated and yields up to 82% were obtained for the synthesis of ethyl- or thiophenyl galactofuranosides and methoxybenzoic galactofuranose.

Published
2019

12. Synthesis of an Exhaustive Library of Naturally Occurring Galf-Manp and Galp-Manp Disaccharides. Towards Fingerprinting According to the Ring Size by Advanced Mass Spectrometry-Based IM-MS and IRMPD

Author

Bénédicte Favreau, Hélène Rogniaux, Laurent Legentil, Isabelle Compagnon, Richard Brédy, Vincent Ferrieres, Mathieu Fanuel, Simon Ollivier, Joël Boustie, David Ropartz, Jean-Paul Guégan, Oznur Yeni, and Françoise Le Dévéhat

Subjects
chemistry.chemical_classification, Ring size, chemistry.chemical_compound, Residue (chemistry), chemistry, Stereochemistry, Structural isomer, Glycosyl, Glycosidic bond, Infrared multiphoton dissociation, Mass spectrometry, Tautomer
Abstract

Nature offers a huge diversity of glycosidic derivatives. Amongst numerous structural modulations, the nature of the ring size of hexosides may induce significant differences on both biological and physicochemical properties of the glycoconjugate of interest. On this assumption, we expect that small disaccharides bearing either a furanosyl entity or a pyranosyl residue would give a specific signature, even in the gas phase. On the basis of the scope of mass spectrometry, two analytical techniques to register those signatures were considered, i.e. the ion-mobility (IM) and the infra-red multiple photon dissociation (IRMPD), in order to build up cross-linked databases. D-Galactose occurs in natural products in both tautomeric forms and presents all possible regioisomers when linked to D-mannose. Consequently, the four reducing Galf-Manp disaccharides as well as the four Galp-Manp counterparts were firstly synthesized according to a highly convergent approach, and IM-MS and IRMPD-MS data were secondly collected. Both techniques used afforded signatures, specific to the nature of the connectivity between the two glycosyl entities.

Published
2021

13. 6-Deoxy-6-fluoro galactofuranosides: regioselective glycosylation, unexpected reactivity, and anti-leishmanial activity

Author

Thierry Benvegnu, Jeane Vaugenot, Laurent Legentil, Rémi Marchal, Vincent Ferrieres, Olivier Tasseau, Abderrafek El Harras, Boris Le Guennic, 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, 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)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
Glycosylation, Stereochemistry, Antiprotozoal Agents, chemistry.chemical_element, Stereoisomerism, 010402 general chemistry, 01 natural sciences, Biochemistry, chemistry.chemical_compound, Parasitic Sensitivity Tests, Carbohydrate Conformation, [CHIM]Chemical Sciences, Reactivity (chemistry), Physical and Theoretical Chemistry, Furans, Leishmania, biology, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Regioselectivity, Galactosides, biology.organism_classification, Acceptor, 0104 chemical sciences, chemistry, Fluorine, Carbohydrate conformation
Abstract

International audience; Selective glycosylation of the C-6 fluorinated galactofuranosyl acceptor 2 was studied with four galactofuranosyl donors. It was highlighted that this electron-withdrawing atom strongly impacted the behavior of the acceptor, thus leading to unprecedented glycosylation pathways. Competition between expected glycosylation of 2, ring expansion of this acceptor and furanosylation, and intermolecular aglycon transfer was observed. Further investigation of the fluorinated synthetic compounds showed that the presence of fluorine atom contributed to increase the inhibition of the growth of Leishmania tarentolae, a non-pathogenic strain of Leishmania.

Published
2020

14. Identification and Quantification of Any Isoforms of Carbohydrates by 2D UV-MS Fingerprinting of Cold Ions

Author

Erik Saparbaev, Viktoriia Aladinskaia, Vincent Ferrieres, Laurent Legentil, Oleg V. Boyarkin, Vladimir Kopysov, Ecole Polytechnique Fédérale de Lausanne (EPFL), 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), 200020_172522, Swiss National Science Foundation (grant 200020_172522), Novartis Foundation, 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), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Gene isoform, Aromatic compounds, Chromatography, Chemistry, Ultraviolet Rays, 010401 analytical chemistry, Carbohydrates, 010402 general chemistry, Mass spectrometry, 01 natural sciences, Chemical biology, Mass Spectrometry, 0104 chemical sciences, Analytical Chemistry, Ion, Cold Temperature, Fragmentation (mass spectrometry), Isomerism, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Mixtures, Molecule, [CHIM]Chemical Sciences, Molecular structure
Abstract

International audience; Biological functionality of isomeric carbohydrates may differ drastically, making their identifications indispensable in many applications of life science. Because of the large number of isoforms, structural assignment of saccharides is challenging and often requires a use of different orthogonal analytical techniques. We demonstrate that isomeric carbohydrates of any isoforms can be distinguished and quantified using solely the library-based method of 2D ultraviolet fragmentation spectroscopy-mass spectrometry (2D UV-MS) of cold ions. The two-dimensional "fingerprint" identities of UV transparent saccharides were revealed by photofragmentation of their noncovalent complexes with aromatic molecules. We assess the accuracy of the method by comparing the known relative concentrations of isomeric carbohydrates mixed in solution with the concentrations that were mathematically determined from the measured in the gas-phase fingerprints of the complexes. For the tested sets with up to five isomers of di- to heptasaccharides, the root-mean-square deviation of 3-5% was typically achieved. This indicates the expected level of accuracy in analysis of unknown mixtures for isomeric carbohydrates of similar complexity.

Published
2020

15. A fully enzymatic esterification/transesterification sequence for the preparation of symmetrical and unsymmetrical trehalose diacyl conjugates

Author

Vincent Ferrières, Thierry Benvegnu, Sunchu Prabhakar, Thomas Vives, Loïc Lemiègre, Laurent Legentil, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-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)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), IFCPAR/CEFIPRA organization [5105-1], CNRS, Ministere de l'Enseignement Superieur et de la Recherche, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
Reaction conditions, chemistry.chemical_classification, 010405 organic chemistry, technology, industry, and agriculture, Disaccharide, Sequence (biology), Transesterification, 010402 general chemistry, 01 natural sciences, Pollution, Trehalose, 0104 chemical sciences, chemistry.chemical_compound, Enzyme, chemistry, Environmental Chemistry, Organic chemistry, lipids (amino acids, peptides, and proteins), [CHIM.OTHE]Chemical Sciences/Other, Conjugate
Abstract

International audience; Monoacyl and diacyl trehalose were synthesized in two steps from trehalose and carboxylic acids. The carboxylic acids were converted first into the corresponding 2,2,2-trifluoroethyl esters through a biocatalyzed esterification. The acyl donor was then transferred to the disaccharide through biocatalyzed transesterification. Thanks to microwave reaction conditions the transesterification proceeded selectively to the monoacyl trehalose or to the diacyl counterparts depending on the sole amount of the acyl donor. These reaction conditions were also applied for the preparation of unsymmetrical diacyl trehalose in a fully enzymatic sequence.

Published
2017

16. Efficient isomerization of methyl arabinofuranosides into corresponding arabinopyranosides in presence of pyridine

Author

Srinivas Hotha, Thierry Benvegnu, Vincent Ferrières, Laurent Legentil, Sunchu Prabhakar, Loïc Lemiègre, 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), CNRS, Ministère de l’Enseignement Supérieur et de la Recherche, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
Arabinose, Isomerization, Glycosylation, Pyridines, Lyxose, Ribose, Pentoses, 010402 general chemistry, 01 natural sciences, Biochemistry, Analytical Chemistry, chemistry.chemical_compound, Isomerism, Nucleophile, Pyridine, [CHIM]Chemical Sciences, Organic chemistry, Glycosides, Alkyl, chemistry.chemical_classification, Xylose, Molecular Structure, 010405 organic chemistry, Methanol, Organic Chemistry, General Medicine, 0104 chemical sciences, chemistry, Methyl pentosides, Fisher glycosylation, Selectivity
Abstract

International audience; Fisher glycosylation, the oldest but efficient reaction towards alkyl glycosides, suffers nonetheless from lack of selectivity, especially when dealing with pentoses. In this case, a mixture of the four isomers, namely the furanosides and the pyranosides, is formed. According to previous studies, the rate and selectivity of the reaction depend greatly on the reaction time and the temperature. In this report, another factor was evaluated, the introduction of a weak nucleophilic base. Interestingly, addition of pyridine few hours after the reaction has started allowed rapid isomerization of the methyl pentofuranosides into its pyranoside counterparts. The reaction proceeds with great diastereoselectivity using arabinose, ribose, xylose and lyxose as starting pentoses. Corresponding methyl pyranosides were obtained as the sole isomers with yields ranging from 65% to 75%. © 2016 Elsevier Ltd

Published
2016

17. Hydrophobized laminarans as new biocompatible anti-oomycete compounds for grapevine protection

Author

Annick Chiltz, Sophie Trouvelot, Franck Paris, Vincent Ferrieres, Manon Jubien, Grégory Lecollinet, Jean-Marie Joubert, Jonathan Negrel, Xavier Daire, Marielle Adrian, Laurent Legentil, Marie-Claire Héloir, 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), GOEMAR, Agroécologie [Dijon], Université de Bourgogne (UB)-Institut National de la Recherche Agronomique (INRA)-Université Bourgogne Franche-Comté [COMUE] (UBFC)-AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement, Region Bretagne, 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)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Institut National de la Recherche Agronomique (INRA)-Université de Bourgogne (UB)-AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement-Université Bourgogne Franche-Comté [COMUE] (UBFC), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
Polymers and Plastics, Acylation, Context (language use), 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Sulfation, Anti-Infective Agents, Laminaran, Materials Chemistry, Plant defense against herbivory, [CHIM]Chemical Sciences, Vitis, Glucans, Disease Resistance, Plant Diseases, biology, Chemistry, Organic Chemistry, food and beverages, Induced resistance, 021001 nanoscience & nanotechnology, biology.organism_classification, Antimicrobial, 0104 chemical sciences, Elicitor, Biochemistry, Oomycetes, Plasmopara viticola, +3%29-Glucans%22">beta-(1 -> 3)-Glucans, Downy mildew, Grapevine, Laminaria, 0210 nano-technology, β-(1→3)-Glucans
Abstract

International audience; Laminaran, a beta-(1 -> 3)-glucan extracted from Laminaria digitata, is a known elicitor of plant defenses, but provides only low level of disease control in vineyard trials. In this context, laminaran was partly hydrophobized by grafting from 1.6 to 7.6 lauryl chains to the native saccharidic chain and the impact of sulfation of the hydrophobized glucans was studied. The activity of the different synthesized laminaran derivatives as antimicrobial agents against Plasmopara viticola, the causal agent of grape downy mildew, and as elicitors of defense reactions in planta, was evaluated. Our results showed that acylation imparts an antimicrobial activity to laminaran which is related to the degree of acylation, AL3, with 7.6 lauryl chains, being the most effective derivative. Sulfation of the acylated laminarans did not further increase the antimicrobial activity. Our results also demonstrated that the efficacy of AL3 against Plasmopara viticola was most likely due to the direct antimicrobial activity of the lauryl chains rather than to an elicitation of plant defenses.

Published
2019

18. Protecting Group Strategies Toward Glycofuranoses

Author

Laurent Legentil, Vincent Ferrières, Loïc Lemiègre, 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), and Sébastien Vidal (éd)

Subjects
chemistry.chemical_compound, Glycosylation, chemistry, Silylation, Stereochemistry, Acetylation, [CHIM]Chemical Sciences, Protecting group
Abstract

International audience; This chapter focuses on protecting group strategies used for furanoses and furanosides. It describes the first reactions that allow the synthesis of five-membered rings and then the main acyl, acetal, and silyl protections. Regioselective protection and deprotection are also addressed, according to chemical or chemoenzymatic approaches.

Published
2019

19. Multiple-stage Precursor Ion Separation and High Resolution Mass Spectrometry toward Structural Characterization of 2,3-Diacyltrehalose Family from Mycobacterium tuberculosis

Author

Fong-Fu Hsu, John Turk, Robert B. Abramovitch, Laurent Legentil, Loïc Lemiègre, Georgiana E. Purdy, Cheryl Frankfater, Washington University School of Medicine in St. Louis, Washington University in Saint Louis (WUSTL), Michigan State University [East Lansing], Michigan State University System, Oregon Health and Science University [Portland] (OHSU), 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), R21AI128427, Foundation for the National Institutes of Health, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
Stereochemistry, Filtration and Separation, Tandem mass spectrometry, Mass spectrometry, Dissociation (chemistry), Analytical Chemistry, Ion, lcsh:Chemistry, 03 medical and health sciences, chemistry.chemical_compound, Fragmentation (mass spectrometry), linear ion trap, tandem mass spectrometry, Molecule, Quadrupole ion trap, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Mycobacterium tuberculosis, 030304 developmental biology, 0303 health sciences, Chemistry, 030302 biochemistry & molecular biology, Trehalose, [SDV.MP.BAC]Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology, lcsh:QC1-999, 3. Good health, lcsh:QD1-999, diacyltrehalose, glycolipid, lcsh:Physics
Abstract

Mass spectrometry (MS)-based precursor ion isolation, collision-induced dissociation (CID) fragmentation, and detection using linear ion-trap multiple-stage mass spectrometry (LIT MSn) in combination with high resolution mass spectrometry (HRMS) provides a unique tool for structural characterization of complex mixture without chromatographic separation. This approach permits not only separation of various lipid families and their subfamilies, but also stereoisomers, thereby, revealing the structural details. In this report, we describe the LIT MSn approach to unveil the structures of a 2,3-diacyl trehalose (DAT) family isolated from the cell envelope of Mycobacterium tuberculosis, in which more than 30 molecular species, and each species consisting of up to six isomeric structures were found. LIT MSn performed on both [M + Na]+ and [M + HCO2]&minus, ions of DAT yield complimentary structural information for near complete characterization of the molecules, including the location of the fatty acyl substituents on the trehalose backbone. This latter information is based on the findings of the differential losses of the two fatty acyl chains in the MS2 and MS3 spectra, while the product ion spectra from higher stage LIT MSn permit confirmation of the structural assignment.

Published
2019

20. Spectroscopic diagnostic for the ring-size of carbohydrates in the gas phase: furanose and pyranose forms of GalNAc

Author

Laurent Legentil, Isabelle Compagnon, Vincent Ferrieres, Baptiste Schindler, Abdul-Rhaman Allouche, Structure et dynamique multi-échelle des édifices moléculaires (DYNAMO), Institut Lumière Matière [Villeurbanne] (ILM), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon, 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), Physico-chimie théorique (THEOCHEM), Institut Universitaire de France, ANR-16-CE30-0012, Agence Nationale de la Recherche, ANR-16-CE30-0012,CIRCE,Dynamique de relaxation induite par la correlation dans les molecules complexes excitées par UVX(2016), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
chemistry.chemical_classification, General Physics and Astronomy, Protonation, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Furanose, 01 natural sciences, Dissociation (chemistry), 0104 chemical sciences, 3. Good health, Ring size, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Pyranose, chemistry, Computational chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Ion trap, Infrared multiphoton dissociation, Physical and Theoretical Chemistry, 0210 nano-technology, Spectroscopy
Abstract

International audience; Hexoses are mainly found in nature in the pyranose form (6-membered ring). Yet, furanose forms (5-membered ring) are observed in some rare polysaccharides. Using IRMPD spectroscopy (InfraRed Multiple Photon Dissociation), we propose a straightforward diagnostic of the ring-size of N-acetyl galactosamine ions. The furanose form of N-acetyl galactosamine was synthesized and its protonated ion was isolated in an ion trap to measure its gas phase vibrational spectrum by IRMPD. Comparison with the IRMPD spectrum of its pyranose counterpart reveals that they have distinctive optical fingerprints. This new MS-based diagnostic opens the way to facile identification of the ring-size in oligosaccharides. Our experimental data also provide new insights to support the theoretical description of the conformational behavior of the furanose ring, which is notoriously more flexible than the pyranose form but remains difficult to assess.

Published
2019

21. Galactofuranosidase from JHA 19 Streptomyces sp:. subcloning and biochemical characterization

Author

Svetlana V. Eliseeva, Kaoru Takegawa, Mateja Seničar, Vincent Ferrieres, Laurent Legentil, Richard Daniellou, Pierre Lafite, Stéphane Petoud, Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut de Chimie Organique et Analytique (ICOA), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM), 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), Kyushu University [Fukuoka], APR IR NeoLect project from the Region Centre-Val de Loire, France, La Ligue Regionale contre le Cancet, Institut National de la Sante et de la Recherche Medicale (INSERM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-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)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Kyushu University, and Jonchère, Laurent

Subjects
[SDV.BIO]Life Sciences [q-bio]/Biotechnology, Glycoside Hydrolases, beta-D-galactofuranosidase, 010402 general chemistry, 01 natural sciences, Biochemistry, Streptomyces, Substrate Specificity, Analytical Chemistry, law.invention, Thio-beta-D-galactofuranoside inhibition, law, Enzyme Stability, Hydrolase, Glycoside hydrolase, Cloning, Molecular, chemistry.chemical_classification, biology, 010405 organic chemistry, Chemistry, Organic Chemistry, Temperature, General Medicine, Metabolism, Subcloning, Hydrogen-Ion Concentration, biology.organism_classification, [SDV.BIO] Life Sciences [q-bio]/Biotechnology, 0104 chemical sciences, Kinetics, Enzyme, Biocatalysis, Recombinant DNA
Abstract

International audience; Despite the crucial role of the rare galactofuranose (Galf) in many pathogenic micro-organisms and our increased knowledge of its metabolism, there is still a lack of recombinant and efficient galactofuranoside hydrolase available for chemo-enzymatic synthetic purposes of specific galactofuranosyl-conjugates. Subcloning of the Galf-ase from JHA 19 Streptomyces sp. and its further overexpression lead us to the production of this enzyme with a yield of 0.5 mg/L of culture. It exhibits substrate specificity exclusively towards pNP beta-D-Galf, giving a K-M value of 250 mu M, and the highest enzymatic efficiency ever observed of 14 mM(-1) s(-1). It proved to be stable to temperature up to 60 degrees C and to at least 4 freeze-thaw's cycles. Thus, Galf-ase demonstrated to be an efficient and stable biocatalyst with greatly improved specificity toward the galactofuranosyl entity, thus paving the way to the further development of transglycosylation and thioligation reactions.

Published
2019

22. An ethoxylated surfactant enhances the penetration of the sulfated laminarin through leaf cuticle and stomata, leading to increased induced resistance against grapevine downy mildew

Author

Frédéric Domergue, Vincent Ferrières, Marielle Adrian, Christian Gauvrit, Sophie Trouvelot, Jérôme Joubès, Franck Paris, Laurent Legentil, Frank Jamois, Xavier Daire, Yuko Krzyzaniak, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-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)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), Agroécologie [Dijon], Institut National de la Recherche Agronomique (INRA)-Université de Bourgogne (UB)-AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement, Laboratoire de biogenèse membranaire (LBM), Université Bordeaux Segalen - Bordeaux 2-Centre National de la Recherche Scientifique (CNRS), Région Bretagne, Conseil Régional de Bourgogne, Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Institut National de la Recherche Agronomique ( INRA ) -Université de Bourgogne ( UB ) -AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement, Laboratoire de biogenèse membranaire ( LBM ), Université Bordeaux Segalen - Bordeaux 2-Centre National de la Recherche Scientifique ( CNRS ), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-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), 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)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), 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), and Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Ethylene Oxide, 0106 biological sciences, 0301 basic medicine, Sucrose, Physiology, Plant Science, Biology, Disaccharides, [ CHIM ] Chemical Sciences, 01 natural sciences, Fluorescence, Diffusion, Cell wall, Surface-Active Agents, 03 medical and health sciences, Laminarin, chemistry.chemical_compound, Pulmonary surfactant, Polysaccharides, Botany, Genetics, [CHIM]Chemical Sciences, Vitis, Carbon Radioisotopes, Disease Resistance, Plant Diseases, Plant Stomata, food and beverages, Cell Biology, General Medicine, Penetration (firestop), Trichome, Kinetics, Horticulture, Cholesterol, 030104 developmental biology, Oomycetes, Plant cuticle, chemistry, Waxes, Downy mildew, 010606 plant biology & botany
Abstract

International audience; Some β-1,3-glucans and particularly sulfated laminarin (PS3) are known as resistance inducers (RIs) in grapevine against the downy mildew. However, their efficacy in vineyard is still often too low, which might be caused by a limited penetration through the leaf cuticle following spray application. We used (14) C-sucrose uptake experiments with grapevine leaves in order to select a surfactant as saccharide penetration enhancer. Our results showed that though sucrose foliar uptake was low, it was strongly enhanced by Dehscofix CO125 (DE), a highly ethoxylated surfactant. Fluorescent saccharides were then produced and laser scanning microscopy was used to analyze their foliar diffusion pattern in Arabidopsis thaliana and grapevine. Interestingly, sucrose and PS3 were seemingly able to penetrate the leaf cuticle only when formulated with DE. Diffusion could preferentially occur via stomata, anticlinal cell walls and trichomes. In grapevine, PS3 penetration rate was much higher on the stomateous abaxial surface of the leaf than on the adaxial surface. Finally, using DE allowed a higher level of downy mildew control by PS3, which corroborated diffusion observations. Our results have practical consequences for the improvement of treatments with saccharidic inducers on grape. That is, formulation of such RIs plays a critical role for their cuticular diffusion and consequently their efficacy. Also, spray application should preferentially target the abaxial surface of the leaves in order to maximize their penetration

Published
2015

23. Diversion of a thioglycoligase for the synthesis of 1-O-acyl arabinofuranoses

Author

Quentin Pavic, Laurent Legentil, Loïc Lemiègre, Sylvain Tranchimand, Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -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), ANR-15-CE07-0009-01, Agence Nationale de la Recherche, Ministère de l'Enseignement Supérieur et de la Recherche, Centre National de la Recherche Scientifique, ANR-15-CE07-0009,C-linkAse,Nouveau biocatalyseurs pour la C-glycosylation: mutation d'hydrolases pour l'obtention de C-glycosides modulables à fort potentiel industriel(2015), Université de Rennes ( UNIV-RENNES ), Ecole Nationale Supérieure de Chimie de Rennes, Centre National de la Recherche Scientifique ( CNRS ), 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), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
0301 basic medicine, Arabinose, Anomer, Glycoside Hydrolases, Stereochemistry, Carboxylic acid, Phenylalanine, 01 natural sciences, [ CHIM ] Chemical Sciences, Catalysis, 03 medical and health sciences, chemistry.chemical_compound, [ CHIM.ORGA ] Chemical Sciences/Organic chemistry, Materials Chemistry, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Molecular Structure, 010405 organic chemistry, Metals and Alloys, General Chemistry, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Amino acid, 030104 developmental biology, Enzyme, chemistry, Biocatalysis, Ceramics and Composites, Stereoselectivity
Abstract

International audience; An arabinofuranosylhydrolase from the GH51 family was transformed into an acyl transferase by mutation of the catalytic acid/base amino acid. The resulting enzyme was able to transfer carboxylic acid onto the anomeric position of arabinose with complete chemo- and stereoselectivity. A wide range of acyl α-l-arabinofuranoses was obtained with yields ranging from 25 to 83%. Using this method, ibuprofen and N-Boc phenylalanine were successfully transformed into their corresponding acyl conjugates, expanding the scope of the reaction to drugs and amino acids.

Published
2018

24. Molecular Interactions of β-(1→3)-Glucans with Their Receptors

Author

Sophie Trouvelot, Franck Paris, Xavier Daire, Laurent Legentil, Vincent Ferrières, Vaclav Vetvicka, Caroline Ballet, Vetvicka, Vaclav, Ferrières, Vincent, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-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)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Agroécologie [Dijon], Institut National de la Recherche Agronomique (INRA)-Université de Bourgogne (UB)-AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement, University of Louisville, Canceropole Grand Ouest, 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), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), and Institut National de la Recherche Agronomique ( INRA ) -Université de Bourgogne ( UB ) -AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement

Subjects
glycolipids, beta-Glucans, Pharmaceutical Science, Review, [ CHIM ] Chemical Sciences, Analytical Chemistry, 0302 clinical medicine, Drug Discovery, Receptor, CR3, chemistry.chemical_classification, Regulation of gene expression, Receptors, Scavenger, 0303 health sciences, biology, β-(1→3)-glucans, food and beverages, Biochemistry, Chemistry (miscellaneous), 030220 oncology & carcinogenesis, CBM, Dectin-1, langerin, Molecular Medicine, Signal transduction, Stramenopiles, Signal Transduction, Langerin, Macrophage-1 Antigen, Polysaccharide, Microbiology, lcsh:QD241-441, 03 medical and health sciences, Immune system, Glycolipid, Adjuvants, Immunologic, lcsh:Organic chemistry, Antigens, CD, Humans, [CHIM]Chemical Sciences, Chimie, Lectins, C-Type, Physical and Theoretical Chemistry, 030304 developmental biology, Organic Chemistry, fungi, Glucan 1,3-beta-Glucosidase, Enzyme, Mannose-Binding Lectins, chemistry, Gene Expression Regulation, Chemical Sciences, biology.protein, Agaricales, Edible Grain
Abstract

International audience; β-(1→3)-Glucans can be found as structural polysaccharides in cereals, in algae or as exo-polysaccharides secreted on the surfaces of mushrooms or fungi. Research has now established that β-(1→3)-glucans can trigger different immune responses and act as efficient immunostimulating agents. They constitute prevalent sources of carbons for microorganisms after subsequent recognition by digesting enzymes. Nevertheless, mechanisms associated with both roles are not yet clearly understood. This review focuses on the variety of elucidated molecular interactions that involve these natural or synthetic polysaccharides and their receptors, i.e., Dectin-1, CR3, glycolipids, langerin and carbohydrate-binding modules

Published
2015

25. Recherche de dérivés conjugués de médicaments dans l’eau de surface et en cours de potabilisation

Author

Dominique Wolbert, Guy Randon, Nicolas Cimetiere, Léa Bazus, and Laurent Legentil

Subjects
Médicaments, eau de surface, conjugated metabolite, Social Sciences and Humanities, dérivés conjugués, eau en cours de potabilisation, Pharmaceuticals, surface water, Sciences Humaines et Sociales, SPE-LC-MS/MS, drinking water treatment, 6. Clean water, Water Science and Technology
Abstract

Les médicaments à usage humain ou vétérinaire se retrouvent, par différents moyens, dans les milieux aquatiques et notamment dans les filières de potabilisation des eaux. Les médicaments sont en partie métabolisés après ingestion (le pourcentage dépend du principe actif et est compris entre 1 et 99 %). Des médicaments se retrouvent alors dans les eaux destinées à la consommation humaine avec des concentrations allant du ng/L à la centaine de ng/L. Différents types de métabolites existent, et parmi eux les dérivés conjugués. Ils peuvent représenter 90 % des métabolites d’un principe actif. Le travail présenté ici décrit le développement d’une méthode analytique par « Solid Phase Extraction » (SPE) en ligne – chromatographie liquide haute performance – spectrométrie de masse en tandem (LC-MS/MS) pour la détermination et la quantification de principes actifs et leurs dérivés conjugués dans les eaux de surface et en cours de potabilisation. Ces dérivés conjugués sont susceptibles de subir une déconjugaison lors des traitements de potabilisation conduisant au relargage du principe actif. C’est pourquoi il est nécessaire de s’intéresser à ces molécules et en particulier les conjugués glucuronides. Comme tous les standards ne se sont pas disponibles dans le commerce, une nouvelle voie de synthèse en milieu aqueux a été explorée. Des analyses sont effectuées en entrée et sortie de filière de potabilisation d’eau afin de déterminer les concentrations présentes en principes actifs et leurs dérivés conjugués. Les limites de détection et de quantification obtenues sont de l’ordre du ng/L ou la dizaine de ng/L., Pharmaceuticals for human or veterinary use are found, by various means, in aquatic environments and particularly in drinking water treatment plants. Pharmaceuticals are partially metabolized after ingestion (the percentage depends on the parent drug and falls between 1 and 99%), and consequently pharmaceuticals can be found in drinking water at concentrations ranging from the ng∙L‑1 to hundreds of ng∙L‑1. Different types of metabolites exist, among them conjugates that can represent up to 90% of the released metabolites of a pharmaceutical. The present work describes the development of an analytical method using "on-line Solid Phase Extraction" (SPE) - high performance liquid chromatography - tandem mass spectrometry (LC-MS/MS) for the determination and quantification of the active substances and their conjugates in surface waters and during drinking water treatment. These conjugates may be subjected to a deconjugation during treatment, resulting in the release of the parent pharmaceutical. Hence, it is necessary to focus on these molecules and in particular on the glucuronide conjugates. As all standards are not commercially available, a new synthetic route in an aqueous medium has been explored. Analyses are performed on the input and output of drinking water treatment plants to determine the concentrations of parent drugs and their conjugates. The obtained limits of detection and quantification are in the order of 1 to 10 ng∙L‑1.

Published
2015

26. Microwave-Assisted Reduction of Nitroarenes by Aminothiophenol/dithiotreitol

Author

Loïc Lemiègre, Richard Daniellou, Thomas Vives, Cédric Peyrot, Laurent Legentil, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-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)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Organique et Analytique (ICOA), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Region Bretagne, Region Centre, 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), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Reaction conditions, aminophenyl glycosides, 010405 organic chemistry, Chemistry, aminothiophenol, General Chemistry, 010402 general chemistry, 01 natural sciences, Microwave assisted, 0104 chemical sciences, Catalysis, Reduction (complexity), Organic chemistry, [CHIM]Chemical Sciences, nitroarene reduction
Abstract

International audience; Anilines are important intermediates in medicinal chemistry. They are usually obtained from the corresponding nitroarenes by reduction. The present work describes novel conditions for such transformation. Aminothiophenol reduced nitroarenes to corresponding anilines under mild and neutral conditions. The microwave assisted reduction proceeded well in MeOH for several functionalized nitroarenes. The reaction conditions were optimized such as the aminothiophenol could be used in a catalytic amount thanks to its regeneration by dithiotreitol. This methodology was applied to various nitroarenes including pnitrophenyl glycosides. A general mechanism is proposed.

Published
2017

27. Regioselective Galactofuranosylation for the Synthesis of Disaccharide Patterns Found in Pathogenic Microorganisms

Author

Charles Tellier, Franck Daligault, Laurent Legentil, Olivier Tasseau, Vincent Ferrières, Yari Cabezas, 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), Unité de fonctionnalité et ingénierie de protéines (UFIP), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS), CNRS, Ministere de l'enseignement superieur et de la recherche, French Agence Nationale de la Recherche [ANR-10-BLAN-0718], ANR-10-BLAN-0718,SynBioLeish,Synthèse biocatalysée d'oligosaccharides leishmaniens en vue d'applications diagnostiques et thérapeutiques (Biocatalysis - Medical applications - Carbohydrates - Leishmania)(2010), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-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)-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), and 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)

Subjects
Glycosylation, Glycoconjugate, Stereochemistry, Diol, Disaccharide, Disaccharides, 010402 general chemistry, 01 natural sciences, Adduct, chemistry.chemical_compound, Bromide, Orthoester, Furans, chemistry.chemical_classification, Bacteria, Molecular Structure, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Fungi, Regioselectivity, Galactosides, Stereoisomerism, 0104 chemical sciences, chemistry, Quantum Theory, Trypanosomatina
Abstract

International audience; Koenigs-Knorr glycosylation of acceptors with more than one free hydroxyl group by 2,3,5,6-tetrabenzoyl galactofuranosyl bromide was performed using diphenylborinic acid 2-aminoethyl ester (DPBA) as inducer of regioselectivity. High regioselectivity for the glycosylation on the equatorial hydroxyl group of the acceptor was obtained thanks to the transient formation of a borinate adduct of the corresponding 1,2-cis diol. Nevertheless formation of orthoester byproducts hampered the efficiency of the method. Interestingly electron-withdrawing groups on O-6 or on C-1 of the acceptor displaced the reaction in favor of the desired galactofuranosyl containing disaccharide. The best yield was obtained for the furanosylation of p-nitrophenyl 6-O-acetyl mannopyranoside. Precursors of other disaccharides, found in the glycocalix of some pathogens, were synthesized according to the same protocol with yields ranging from 45 to 86%. This is a good alternative for the synthesis of biologically relevant glycoconjugates.

Published
2017

28. Synthesis and biological properties of galactofuranosyl-containing fluorescent dyes

Author

Jean-Pierre Gangneux, Vincent Ferrières, Sorya Belaz, Laurent Legentil, Florence Robert-Gangneux, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-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)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de recherche en santé, environnement et travail (Irset), Structure Fédérative de Recherche en Biologie et Santé de Rennes ( Biosit : Biologie - Santé - Innovation Technologique )-Institut National de la Santé et de la Recherche Médicale (INSERM)-École des Hautes Études en Santé Publique [EHESP] (EHESP)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Université d'Angers (UA), Service de Parasitologie-Mycologie [Rennes], Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Hôpital Pontchaillou-CHU Pontchaillou [Rennes], The authors are grateful to the GlycoOuest network, supported by the Région Bretagne and the Région Pays de la Loire., 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), Université d'Angers (UA)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-École des Hautes Études en Santé Publique [EHESP] (EHESP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Structure Fédérative de Recherche en Biologie et Santé de Rennes ( Biosit : Biologie - Santé - Innovation Technologique ), 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 d'Angers (UA)-Université de Rennes (UR)-École des Hautes Études en Santé Publique [EHESP] (EHESP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Structure Fédérative de Recherche en Biologie et Santé de Rennes ( Biosit : Biologie - Santé - Innovation Technologique ), and Université de Rennes (UR)-Hôpital Pontchaillou-CHU Pontchaillou [Rennes]

Subjects
Antiparasitic, medicine.drug_class, Clinical Biochemistry, Leishmania donovani, Antiprotozoal Agents, Carbohydrates, Pharmaceutical Science, Galactofuranosides, 010402 general chemistry, 01 natural sciences, Biochemistry, Fluorescence, Rhodamines, Rhodamine 6G, chemistry.chemical_compound, Biological property, Drug Discovery, medicine, Humans, [CHIM]Chemical Sciences, Fluorescein, Molecular Biology, Fluorescent Dyes, Leishmania, biology, 010405 organic chemistry, Chemistry, Macrophages, Organic Chemistry, Galactosides, biology.organism_classification, Fluoresceins, 0104 chemical sciences, 3. Good health, Molecular Medicine
Abstract

International audience; Two fluorescent galactofuranosides were synthesized and their biological activities evaluated on non-infected and Leishmania infected macrophages. Both tagged scaffolds were able to penetrate macrophages. Compared to the activity of the parent octyl galactofuranoside used as a reference, the fluorescein-conjugate showed altered biological properties while the rhodamine 6G one synergistically acted with the lipid chain to significantly increase antiparasitic activity.

Published
2017

29. Regioselective glycosylation: What's new?

Author

Laurent Legentil, Vincent Ferrieres, Ecole Nationale Supérieure de Chimie de Rennes (ENSCR), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
Residue (chemistry), chemistry.chemical_compound, Low energy, Glycosylation, Chemistry, [CHIM]Chemical Sciences, Regioselectivity, Chemical synthesis, Combinatorial chemistry
Abstract

International audience; The aim of this chapter is to show how increased understanding of the mechanisms related to both carbohydrate-processing enzymes and intrinsic properties of monoglycosyl residue have significantly impacted our way of thinking about the glycosylation reaction. A focus is made on the importance of low energy interactions. Some recent examples related to biocatalytic approaches and chemical synthesis are given.

Published
2017

30. Environmentally benign glycosylation of aryl pyranosides and aryl/alkyl furanosides demonstrating the versatility of thermostable CGTase from Thermoanaerobacterium sp

Author

Luis Herrera-Estrella, Anne-Laure Chauvin, Caroline Nugier-Chauvin, Laurent Legentil, Vincent Ferrières, Alizé Pennec, 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 européenne de Bretagne - European University of Brittany (UEB), Langebio (CINVESTAV), 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), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
chemistry.chemical_classification, Glycosylation, Anomer, Cyclodextrin, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Stereochemistry, Aryl, Disproportionation, Glycosidic bond, [CHIM.CATA]Chemical Sciences/Catalysis, Pollution, chemistry.chemical_compound, Glucosyltransferases, chemistry, Environmental Chemistry, Organic chemistry, Alkyl
Abstract

International audience; An extensive study on the specificity of transglycosylation and disproportionation of Thermoanaerobacterium sp. cyclodextrin glucosyltranferases against aryl glucopyranosides or furanosides was achieved. While a mixture of maltoside and isomaltoside was obtained respectively using p-nitrophenyl glucopyranoside as acceptor, only one regioisomer, namely the p-nitrophenyl α-D-Glcp-(1,3)-α-L-Araf was isolated using p-nitrophenyl arabinofuranoside as acceptor. Interestingly, similar outcomes were found when using p-nitrophenyl galactofuranoside. Furthermore, activation by microwave irradiation resulted in faster reaction times and higher yields and led to glucosidic oligosaccharides with up to 70% conversion. The influence of the anomeric and C-4 configurations of the glycosidic acceptors on the transglycosylation, previously stated for the CGTase family, was not observed and unconventional substrate specificity towards alkyl furanosides was highlighted.

Published
2014

31. Application foliaire et biodisponibilité des stimulateurs de défenses des plantes. Spécificités et limites en viticulture

Author

Sophie TROUVELOT, Franck Paris, Yuko Krzyzaniak, Samuel Marchat, Grégory Lecollinet, Christian Gauvrit, Laurent Legentil, Vincent Ferrières, Xavier Daire, Marielle Adrian, Agroécologie [Dijon], Institut National de la Recherche Agronomique (INRA)-Université de Bourgogne (UB)-AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement-Université Bourgogne Franche-Comté [COMUE] (UBFC), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-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)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS), Laboratoires Goëmar S.A.S., Ecole Nationale Supérieure de Chimie de Rennes, Institut National de la Recherche Agronomique (INRA)-Université de Bourgogne (UB)-AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement, Ecole Nationale Supérieure de Chimie de Rennes (ENSCR), Goëmar – Parc Technopolitain Atalante, 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), ProdInra, Archive Ouverte, Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-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), EL Mjiyad, Noureddine, 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), 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)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Université de Bourgogne (UB)-Institut National de la Recherche Agronomique (INRA)-Université Bourgogne Franche-Comté [COMUE] (UBFC)-AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement, Institut National de la Recherche Agronomique ( INRA ) -Université de Bourgogne ( UB ) -AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement-Université Bourgogne Franche-Comté ( UBFC ), Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Centre National de la Recherche Scientifique ( CNRS ), and Parc Technopolitain Atalante

Subjects
[SDE] Environmental Sciences, [ SDV ] Life Sciences [q-bio], [SDV]Life Sciences [q-bio], éliciteur, hydrophile, stimulateur de défenses des plantes, [SDV] Life Sciences [q-bio], biodisponibilité, sdp, [SDE]Environmental Sciences, [SDV.BV]Life Sciences [q-bio]/Vegetal Biology, cuticule, vigne, ComputingMilieux_MISCELLANEOUS
Abstract

IPMSPEINRAUBDOCT; Application foliaire et biodisponibilité des stimulateurs de défenses des plantes. Spécificités et limites en viticulture

Published
2016

32. Evidence for foliar uptake of sulfated laminarin into grapevine depending on surfactant use and leaf surface

Author

Yuko Krzyżaniak, Franck Paris, Christian Gauvrit, Lecollinet, G., Vincent Ferrières, Marielle Adrian, Laurent Legentil, Xavier Daire, Sophie Trouvelot, Agroécologie [Dijon], Institut National de la Recherche Agronomique (INRA)-Université de Bourgogne (UB)-AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement, Ecole Nationale Supérieure de Chimie de Rennes (ENSCR), Laboratoires Goëmar S.A.S., and Association Française de Protection des Plantes (AFPP). FRA.

Subjects
microscopie, induction de résistance, Vitis vinifera, perméabilité cuticulaire, [SDV]Life Sciences [q-bio], [SDE]Environmental Sciences, polysaccharides, [SDV.BV]Life Sciences [q-bio]/Vegetal Biology
Abstract

SPE IPM UB CT?; International audience; Certains ß-1,3-glucanes, en particulier la laminarine sulfatée (PS3), sont connus pour être des inducteurs de résistance de la vigne contre l’agent pathogène Plasmopara viticola. Bien que leur efficacité soit incontestable, la protection induite reste variable au vignoble. Pour être perçue par la plante, ils nécessitent de franchir les barrières constitutives, et notamment la cuticule. Ainsi, leur faible efficacité au champ pourrait être liée par une pénétration limitée à travers la cuticule des feuilles, suite à leur pulvérisation. Dans cette étude, nous avons mis au point une méthode pour analyser les comportements de diffusion du PS3 dans les feuilles de Vitis vinifera, à l’aide d’un microscope biphotonique. Nos résultats ont révélé que ce polysaccharide est vraisemblablement capable de pénétrer à travers la cuticule des feuilles de vigne, lorsqu’il est formulé dans un adjuvant adéquat. Par ailleurs, les stomates, les parois anticlines et les trichomes se sont révélés être des zones de diffusion préférentielle pour cette molécule. Il a été intéressant de constater que son taux de pénétration était plus important sur la face abaxiale des feuilles (stomatique), que la face adaxiale (sans stomate). De plus, nous sommes parvenus à lier le taux de pénétration, avec l’efficacité de PS3 en tant qu’inducteur de résistance contre le mildiou.

Published
2015

33. Synthetic UDP-furanoses inhibit the growth of the parasite Leishmania

Author

Richard Daniellou, Rémy Dureau, Caroline Nugier-Chauvin, Jean-Pierre Gangneux, Vincent Ferrières, Laurent Legentil, Florence Robert-Gangneux, 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), Signalisation et Réponses aux Agents Infectieux et Chimiques (SeRAIC), Université de Rennes (UR), the Bresmat network, Université européenne de Bretagne, 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), Université de Rennes 1 (UR1), and Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)

Subjects
Pentoses, Antiprotozoal Agents, Leishmania donovani, 010402 general chemistry, 01 natural sciences, Biochemistry, Chemical synthesis, Uridine Diphosphate, Analytical Chemistry, Microbiology, Hexofuranosides, medicine, Animals, Potency, Parasite hosting, MESH: Animals, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, MESH: Uridine Diphosphate, MESH: Antiprotozoal Agents, Leishmania, Visceral leishmaniasis, UDP-furanoses, MESH: Leishmania donovani, biology, 010405 organic chemistry, Chemistry, Organic Chemistry, Leishmaniasis, General Medicine, medicine.disease, biology.organism_classification, 3. Good health, 0104 chemical sciences, carbohydrates (lipids), [SDV.MP]Life Sciences [q-bio]/Microbiology and Parasitology, MESH: Pentoses
Abstract

International audience; The chemical synthesis of UDP-6-NHAc-6-deoxy-Galf was performed and it led to the isolation of both pure anomers. They were then evaluated together with the previously prepared UDP-furanoses for their anti-parasitic properties against Leishmania donovani promastigotes, one of the agents responsible for visceral leishmaniasis. Amongst them, the unnatural 1,2-trans UDP-6-NHAc-Galf demonstrated a high potency in inhibiting the growth of the parasite.

Published
2010

34. Expedient Synthesis of Substituted (Diphenylphosphinoylmethyl)benzenes

Author

Rebecca A. Brimage, Sean P. Bew, Sunil V. Sharma, Martin A. Wilson, Laurent Legentil, and David L. Hughes

Subjects
chemistry.chemical_classification, Molecular Structure, Carboxylic acid, Organic Chemistry, General Medicine, Ethylenes, Chemical synthesis, Catalysis, chemistry.chemical_compound, chemistry, Transition metal, Reagent, Microwave irradiation, Benzene Derivatives, Chlorodiphenylphosphine, Organic chemistry, Microwaves, Benzene
Abstract

An efficient protocol for the synthesis of structurally diverse (diphenylphosphinoylmethyl)benzenes is described. The reaction employs readily available carboxylic acids, chlorodiphenylphosphine, and water as the reagents. A 97% reduction in the reaction times and substantially higher yields of products result, up to a 60% increase, if the reactions are performed under microwave irradiation. The first examples of transition-metal-catalyzed reactions applied to 4-bromo-1,3-bis(diphenylphosphinoylmethyl)benzene are also reported.

Published
2007

35. ChemInform Abstract: Leishmania Cell Wall as a Potent Target for Antiparasitic Drugs. A Focus on the Glycoconjugates

Author

Jean-Pierre Gangneux, Charles Tellier, Yari Cabezas, Vincent Ferrières, Florence Robert-Gangneux, Franck Daligault, Sorya Belaz, Caroline Nugier-Chauvin, Laurent Legentil, and Sylvain Tranchimand

Subjects
chemistry.chemical_classification, biology, Antiparasitic Drugs, Chemistry, Glycoconjugate, Mucocutaneous zone, Leishmaniasis, General Medicine, medicine.disease, Leishmania, biology.organism_classification, Cell wall, Glycolipid, Immunology, medicine, Glycoprotein
Abstract

Although leishmaniasis has been studied for over a century, the fight against cutaneous, mucocutaneous and visceral forms of the disease remains a hot topic. This review refers to the parasitic cell wall and more particularly to the constitutive glycoconjugates. The structures of the main glycolipids and glycoproteins, which are species-dependent, are described. The focus is on the disturbance of the lipid membrane by existing drugs and possible new ones, in order to develop future therapeutic agents.

Published
2015

36. Synthesis and evaluation of 1,2-trans alkyl galactofuranoside mimetics as mycobacteriostatic agents

Author

Rémy Dureau, Laurent Legentil, Fabienne Berrée, Isabelle Artur, Maxime Gicquel, Vincent Ferrières, Jean-Paul Guégan, Bertrand Carboni, 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), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
Stereochemistry, Mycobacterium smegmatis, Substituent, Microbial Sensitivity Tests, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Biochemistry, Structure-Activity Relationship, chemistry.chemical_compound, medicine, [CHIM]Chemical Sciences, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Physical and Theoretical Chemistry, Alkyl, chemistry.chemical_classification, Bacteriostatic agent, Dose-Response Relationship, Drug, Molecular Structure, biology, 010405 organic chemistry, Aryl, Organic Chemistry, Galactosides, Stereoisomerism, biology.organism_classification, Anti-Bacterial Agents, 3. Good health, 0104 chemical sciences, chemistry, Mechanism of action, lipids (amino acids, peptides, and proteins), Growth inhibition, medicine.symptom, medicine.drug
Abstract

International audience; The simple octyl β-d-galactofuranoside was previously described as a good bacteriostatic agent against Mycobacterium smegmatis, a non-pathogenic model of M. tuberculosis. In order to decipher its mechanism of action, STD NMR on whole M. smegmatis cells was implemented. It outlined the crucial role of the alkyl chain and the possibility of modulation on the furanosyl entity. Then, 16 new alkyl furanosides were synthesized in order to optimize the mycobacteriostatic activity. They all present the pending alkyl chain in a 1,2-trans configuration relative to the sugar ring. Three families were studied that differ by a substituent on the primary position of the galactofuranose ring, the series or the pending alkyl chain. Four of these neofuranosides showed growth inhibition inferior to the parent octyl β-d-galactofuranoside. Double alkyl chains at C-1 and a polar substituent on the primary position of the furanoside significantly favored the activity. Finally, a mixed biantennary alkyl/aryl β-d-galactofuranoside exhibited the best growth inhibition concentration at 90 μM.

Published
2015

37. Structural and biochemical characterization of the laminarinase ZgLamCGH16 from Zobellia galactanivorans suggests preferred recognition of branched laminarin

Author

Laurent Legentil, Gurvan Michel, Mirjam Czjzek, Aurore Labourel, Vincent Ferrières, Jan-Hendrik Hehemann, Murielle Jam, Balla Sylla, Laboratoire de Biologie Intégrative des Modèles Marins (LBI2M), Station biologique de Roscoff [Roscoff] (SBR), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-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 européenne de Bretagne - European University of Brittany (UEB), Agence française de financement de la recherche sur projets, l’ANRCancéropole Grand Ouest, Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Station biologique de Roscoff [Roscoff] (SBR), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-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)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Models, Molecular, beta-Glucans, Protein Conformation, Molecular Sequence Data, Biology, Crystallography, X-Ray, Polysaccharide, medicine.disease_cause, laminarinase, Substrate Specificity, Laminarin, chemistry.chemical_compound, Marine bacteriophage, Structural Biology, Catalytic Domain, Hydrolase, medicine, Cellulases, oligosaccharide, [CHIM]Chemical Sciences, Glycoside hydrolase, Glycosyl, carbohydrate metabolism, glycoside hydrolase, Amino Acid Sequence, β-1, Glucans, Escherichia coli, Glucan, chemistry.chemical_classification, algae, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Medicine, 3-glucan, chemistry, Biochemistry, marine bacteria, Proteoglycans, GH16, Flavobacteriaceae, Sequence Alignment
Abstract

Laminarin is a β-1,3-D-glucan displaying occasional β-1,6 branches. This storage polysaccharide of brown algae constitutes an abundant source of carbon for marine bacteria such asZobellia galactanivorans. This marine member of the Bacteroidetes possesses five putative β-1,3-glucanases [four belonging to glycosyl hydrolase family 16 (GH16) and one to GH64] with various modular architectures. Here, the characterization of the β-glucanaseZgLamC is reported. The catalytic GH16 module (ZgLamCGH16) was produced inEscherichia coliand purified. This recombinant enzyme has a preferential specificity for laminarin but also a significant activity on mixed-linked glucan (MLG). The structure of an inactive mutant ofZgLamCGH16in complex with a thio-β-1,3-hexaglucan substrate unravelled a straight active-site cleft with three additional pockets flanking subsites −1, −2 and −3. These lateral pockets are occupied by a glycerol, an acetate ion and a chloride ion, respectively. The presence of these molecules in the vicinity of the O6 hydroxyl group of each glucose moiety suggests thatZgLamCGH16accommodates branched laminarins as substrates. Altogether,ZgLamC is a secreted laminarinase that is likely to be involved in the initial step of degradation of branched laminarin, while the previously characterizedZgLamA efficiently degrades unbranched laminarin and oligo-laminarins.

Published
2015

38. Leishmania cell wall as a potent target for antiparasitic drugs. A focus on the glycoconjugates

Author

Sylvain Tranchimand, Franck Daligault, Laurent Legentil, Jean-Pierre Gangneux, Florence Robert-Gangneux, Caroline Nugier-Chauvin, Charles Tellier, Sorya Belaz, Vincent Ferrières, Yari Cabezas, 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), Service de Parasitologie-Mycologie [Rennes], Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Hôpital Pontchaillou-CHU Pontchaillou [Rennes], Institut de recherche en santé, environnement et travail (Irset), Structure Fédérative de Recherche en Biologie et Santé de Rennes ( Biosit : Biologie - Santé - Innovation Technologique )-Institut National de la Santé et de la Recherche Médicale (INSERM)-École des Hautes Études en Santé Publique [EHESP] (EHESP)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Université d'Angers (UA), Unité de fonctionnalité et ingénierie de protéines (UFIP), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS), Université européenne de Bretagne - European University of Brittany (UEB), 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)-Hôpital Pontchaillou-CHU Pontchaillou [Rennes], and Université d'Angers (UA)-Université de Rennes (UR)-École des Hautes Études en Santé Publique [EHESP] (EHESP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Structure Fédérative de Recherche en Biologie et Santé de Rennes ( Biosit : Biologie - Santé - Innovation Technologique )

Subjects
Glycoconjugate, Mucocutaneous zone, Pharmacology, Biology, 01 natural sciences, Biochemistry, Cell wall, 03 medical and health sciences, Glycolipid, Cell Wall, medicine, [CHIM]Chemical Sciences, Molecular Targeted Therapy, Physical and Theoretical Chemistry, 030304 developmental biology, Leishmania, chemistry.chemical_classification, 0303 health sciences, Antiparasitic Agents, 010405 organic chemistry, Antiparasitic Drugs, Cell Membrane, Organic Chemistry, Leishmaniasis, biology.organism_classification, medicine.disease, 0104 chemical sciences, 3. Good health, chemistry, Immunology, Glycoprotein, Glycoconjugates
Abstract

International audience; Although leishmaniasis has been studied for over a century, the fight against cutaneous, mucocutaneous and visceral forms of the disease remains a hot topic. This review refers to the parasitic cell wall and more particularly to the constitutive glycoconjugates. The structures of the main glycolipids and glycoproteins, which are species-dependent, are described. The focus is on the disturbance of the lipid membrane by existing drugs and possible new ones, in order to develop future therapeutic agents

Published
2015

39. Towards new camptothecins. Part 3: Synthesis of 5-methoxycarbonyl camptothecin

Author

Thierry Brunin, Benoît Rigo, Laurent Legentil, and Jean‐Pierre Henichart

Subjects
chemistry.chemical_compound, Chemistry, Reagent, Organic Chemistry, Drug Discovery, medicine, Organic chemistry, Pyroglutamic acid, Ring (chemistry), Biochemistry, Mannich reaction, Camptothecin, medicine.drug
Abstract

The synthesis of two camptothecin analogs substituted by a carbonyl function on position 5 of cycle C was realized. New conditions were studied to obtain the E-lactone ring of these heterocycles. These compounds were obtained from the reaction of Bredereck's reagent with indolizines derived from pyroglutamic acid. This yielded dimethylaminovinyl groups whose oxidation by NaIO4 yielded ketones. The indolizinones obtained were reacted in Friedlander condition, to give the scaffold of the desired camptothecins.

Published
2006

40. Oligo-β-(1 → 3)-glucans: impact of thio-bridges on immunostimulating activities and the development of cancer stem cells

Author

Vaclav Vetvicka, Vincent Ferrières, Sujata Saraswat-Ohri, Aruna Vashishta, Hsei-Wei Wang, Laurent Legentil, Balla Sylla, Richard Daniellou, 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), Université européenne de Bretagne - European University of Brittany (UEB), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
β 1 3 glucan, Molecular Sequence Data, Drug Evaluation, Preclinical, Thio, chemistry.chemical_element, Chemistry Techniques, Synthetic, Polysaccharide, Cell Line, Laminarin, chemistry.chemical_compound, Structure-Activity Relationship, Adjuvants, Immunologic, Phagocytosis, In vivo, Cancer stem cell, Drug Discovery, Carbohydrate Conformation, Animals, Humans, [CHIM]Chemical Sciences, Glucans, chemistry.chemical_classification, Mice, Inbred BALB C, Sulfur, 3. Good health, chemistry, Biochemistry, Carbohydrate Sequence, Neoplastic Stem Cells, Molecular Medicine, Cytokines, Female, Stem cell, Trisaccharides
Abstract

International audience; Recent developments of innovative anticancer therapies are based on compounds likely to stimulate the immune defense of the patients. β-(1 → 3)-Glucans are natural polysaccharides well-known for their immunostimulating properties. We report here on the synthesis of small oligo-β-(1 → 3)-glucans characterized by thioglycosidic linkages. The presence of sulfur atom(s) was not only crucial to prolong in vivo immunoactive activities in time, compared to native polysaccharides, but sulfur atoms also had a direct impact on the development of colorectal cancer stem cells. As a result, a short, pure, and structurally well-defined trisaccharidic thioglucan demonstrated similar activities compared to those of natural laminarin.

Published
2014

42. ChemInform Abstract: Chemical Synthesis of Oligo-(1→3)-β-D-glucans

Author

Vincent Ferrières, Karine Descroix, Laurent Legentil, Caroline Nugier-Chauvin, Balla Sylla, and Richard Daniellou

Subjects
chemistry.chemical_classification, stomatognathic diseases, Chemistry, Biomolecule, Biological property, Organic chemistry, General Medicine, Chemical synthesis
Abstract

The synthesis of β-(13)-glucans is at present has more than a chemical challenge. The discovery of their biological properties found development for new anti- cancer therapies, the efficient preparation of pure and structurally well-defined β-(13)-glucans has generated interest in the glycochemist community. This chapter highlights recent strategies that not only yielded the target biomolecules but have also drawn attention on basic limitations. It also shows how it is possible to strengthen the activity of β-glucans by conjugation to non saccharidic derivatives.

Published
2014

43. Alkyl galactofuranosides strongly interact with Leishmania donovani membrane and provide anti-leishmanial activity

Author

Jean-Pierre Gangneux, Florence Robert-Gangneux, Agnès Burel, Vincent Ferrières, Laurent Legentil, Rémy Dureau, Muhammad Suleman, Yari Cabezas, Christelle Manuel, Sorya Belaz, Franck Daligault, Odile Sergent, Institut de recherche en santé, environnement et travail (Irset), Université d'Angers (UA)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-École des Hautes Études en Santé Publique [EHESP] (EHESP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Structure Fédérative de Recherche en Biologie et Santé de Rennes ( Biosit : Biologie - Santé - Innovation Technologique ), 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), Service de Parasitologie-Mycologie [Rennes], Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Hôpital Pontchaillou-CHU Pontchaillou [Rennes], Biotechnologie et Gestion des Agents Pathogènes en agriculture (BioGAP), Institut Supérieur d'Agriculture de Lille (ISA)-Institut Charles Viollette (ICV) - EA 7394 (ICV), Université d'Artois (UA)-Institut National de la Recherche Agronomique (INRA)-Université du Littoral Côte d'Opale (ULCO)-Institut Supérieur d'Agriculture-Université de Lille-Université d'Artois (UA)-Institut National de la Recherche Agronomique (INRA)-Université du Littoral Côte d'Opale (ULCO)-Institut Supérieur d'Agriculture-Université de Lille, Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-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)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), Institut Charles Viollette (ICV) - EA 7394 (ICV), Université d'Artois (UA)-Institut National de la Recherche Agronomique (INRA)-Université du Littoral Côte d'Opale (ULCO)-Institut Supérieur d'Agriculture-Université de Lille-Université d'Artois (UA)-Institut National de la Recherche Agronomique (INRA)-Université du Littoral Côte d'Opale (ULCO)-Institut Supérieur d'Agriculture-Université de Lille-Institut Supérieur d'Agriculture de Lille (Groupe ISA), Université d'Angers (UA)-Université de Rennes (UR)-École des Hautes Études en Santé Publique [EHESP] (EHESP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Structure Fédérative de Recherche en Biologie et Santé de Rennes ( Biosit : Biologie - Santé - Innovation Technologique ), 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)-Hôpital Pontchaillou-CHU Pontchaillou [Rennes], Institut Supérieur d'Agriculture de Lille (ISA), and Université catholique de Lille (UCL)-Université catholique de Lille (UCL)-Institut Charles Viollette (ICV) - EA 7394 (ICV)

Subjects
Magnetic Resonance Spectroscopy, Stereochemistry, Phosphorylcholine, Leishmania donovani, Antiprotozoal Agents, Biology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Cell Line, 03 medical and health sciences, Microscopy, Electron, Transmission, medicine, Membrane fluidity, Humans, Pharmacology (medical), Amastigote, Mechanisms of Action: Physiological Effects, 030304 developmental biology, Pharmacology, chemistry.chemical_classification, 0303 health sciences, Reactive oxygen species, 030306 microbiology, Electron Spin Resonance Spectroscopy, Nuclear magnetic resonance spectroscopy, biology.organism_classification, Furanose, 3. Good health, Infectious Diseases, Membrane, chemistry, Mechanism of action, medicine.symptom, Reactive Oxygen Species
Abstract

We investigated the in vitro effects of four alkyl-galactofuranoside derivatives, i.e., octyl-β- d -galactofuranoside (compound 1), 6-amino-β- d -galactofuranoside (compound 2), 6- N -acetamido-β- d -galactofuranoside (compound 3), and 6-azido-β- d -galactofuranoside (compound 4), on Leishmania donovani . Their mechanism of action was explored using electron paramagnetic resonance spectroscopy (EPR) and nuclear magnetic resonance (NMR), and ultrastructural alterations were analyzed by transmission electron microscopy (TEM). Compound 1 showed the most promising effects by inhibiting promastigote growth at a 50% inhibitory concentration (IC 50 ) of 8.96 ± 2.5 μM. All compounds exhibit low toxicity toward human macrophages. Compound 1 had a higher selectivity index than the molecule used for comparison, i.e., miltefosine (159.7 versus 37.9, respectively). EPR showed that compound 1 significantly reduced membrane fluidity compared to control promastigotes and to compound 3. The furanose ring was shown to support this effect, since the isomer galactopyranose had no effect on parasite membrane fluidity or growth. NMR showed a direct interaction of all compounds (greatest with compound 1, followed by compounds 2, 3, and 4, in descending order) with the promastigote membrane and with octyl-galactopyranose and octanol, providing evidence that the n -octyl chain was primarily involved in anchoring with the parasite membrane, followed by the putative crucial role of the furanose ring in the antileishmanial activity. A morphological analysis of compound 1-treated promastigotes by TEM revealed profound alterations in the parasite membrane and organelles, but this was not the case with compound 3. Quantification of annexin V binding by flow cytometry confirmed that compound 1 induced apoptosis in >90% of promastigotes. The effect of compound 1 was also assessed on intramacrophagic amastigotes and showed a reduction in amastigote growth associated with an increase of reactive oxygen species (ROS) production, thus validating its promising effect.

Published
2014

44. Total synthesis of the marine pyrroloiminoquinone alkaloid tsitsikammamine A

Author

Laurent Legentil, Arnaud Rives, Evelyne Delfourne, and Tamara Delaine

Subjects
Indole test, chemistry.chemical_compound, Ethanol, chemistry, Alkaloid, Organic Chemistry, Drug Discovery, Structural isomer, Michael reaction, Organic chemistry, Total synthesis, Biochemistry
Abstract

A concise route to the marine pyrroloiminoquinone alkaloid tsitsikammamine A and a regioisomer was developed. The synthesis was based on a Michael reaction between the indole dione 6 and 2′-amino-1-(4-methoxyphenyl)ethanol.

Published
2009

45. α-Amino acid Tröger base derivatives, possible conformationally restricted scaffolds?

Author

Sunil Sharma, Vincent Scholier, Laurent Legentil, and Sean P. Bew

Subjects
Models, Molecular, chemistry.chemical_classification, Molecular Structure, Chemistry, Stereochemistry, Molecular Conformation, Metals and Alloys, General Chemistry, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Amino acid, Ab initio quantum chemistry methods, Materials Chemistry, Ceramics and Composites, Amino Acids, Peptides, Base (exponentiation), Conjugate
Abstract

The first synthesis of innovative alpha-amino acid conjugates of Tröger base is reported; their potential application as conformationally restricted scaffolds is proposed and has been investigated using high level ab initio calculations.

Published
2007

46. Aza-analogues of the marine pyrroloquinoline alkaloids wakayin and tsitsikammamines: Synthesis and topoisomerase inhibition

Author

Laurent Legentil, Brigitte Lesur, and Evelyne Delfourne

Subjects
Stereochemistry, Clinical Biochemistry, Pharmaceutical Science, Topoisomerase-I Inhibitor, Biochemistry, Chemical synthesis, Indole Alkaloids, Structure-Activity Relationship, chemistry.chemical_compound, Dna cleavage, Drug Discovery, medicine, Animals, Humans, Structure–activity relationship, Pyrroles, heterocyclic compounds, Molecular Biology, chemistry.chemical_classification, Indole test, Aza Compounds, Molecular Structure, biology, Chemistry, Alkaloid, Topoisomerase, Organic Chemistry, Biological activity, General Medicine, Cycloaddition, Enzyme, Cyclization, Quinolines, biology.protein, Molecular Medicine, Topoisomerase I Inhibitors, Derivative (chemistry), Camptothecin, medicine.drug
Abstract

Two aza-analogues of the marine pyrroloquinoline alkaloids wakayin and tsitsikammamines A and B have been synthesized. The strategy used was based on a 1,3-dipolar cycloaddition reaction between indole 4,7-dione and a diazo-aminopropane derivative. One of the two analogues partially inhibits human topoisomerase I, whereas synthetic intermediates inhibit the enzyme DNA cleavage activity at a concentration comparable to that of the control drug camptothecin.

Published
2006

47. Contribution of Biocatalysis to the Synthesis of β-(1,3)-Glucans

Author

Karine Descroix, Richard Daniellou, Laurent Legentil, Balla Sylla, Caroline Nugier-Chauvin, Vincent Ferrieres, 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), Vaclav Vetvicka and Miroslav Novak, Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-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)

Subjects
Green chemistry, β 1 3 glucan, synthesis, biocatalysis, biocatalyst, transferase, enzymes, Thio, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, conjugate, residue, oligo, branching, thioglycosides, donor, Chemistry, thio, Environmentally friendly, Combinatorial chemistry, Glucan, NMR, Biocatalysis, carbohydrate, glycans, strategy, laminarin
Abstract

The lightning progress in the understanding of enzymatic mechanisms, democratization of molecular biology tools and their introduction in chemistry laboratories, the pressure of green chemistry notions leading to the need for alternative sustainable and more environmentally friendly approaches, and probably economic factors as well, all these parameters allowed the development of new synthetic strategies based on biocatalysis. This chapter is dedicated to the use of glucosyl hydrolases and some of their mutants, i.e., glucosynthases and thioligases, to the preparation of β-(1,3)-(thio)glucosides.

Published
2013

48. A Total Synthesis of Subarine, a Marine Alkaloid Related to the Pyridoacridine Family

Author

Francis Darro, Jean Bastide, Christelle Rochart, Laurent Bijeire, Evelyne Delfourne, and Laurent Legentil

Subjects
Antitumor activity, Stereochemistry, Chemistry, Yield (chemistry), Natural compound, Alkaloid, Organic Chemistry, Total synthesis, Organic chemistry, Physical and Theoretical Chemistry, Human cancer
Abstract

The synthesis of the marine alkaloid subarine has been accomplished in four steps in 70% overall yield starting from 4-bromo-1,10-phenanthroline. The natural compound and three intermediates in the synthesis were tested at six concentrations on six different human cancer cell lines, including various histopathological types. None of these compounds exhibits significant antitumor activity. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Published
2004

49. Specific and non-specific enzymes for furanosyl-containing conjugates: biosynthesis, metabolism, and chemo-enzymatic synthesis

Author

Ilona Chlubnova, Rémy Dureau, Vincent Ferrières, Alizé Pennec, Laurent Legentil, Caroline Nugier-Chauvin, Mélanie Almendros, Richard Daniellou, 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), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
Glycoside Hydrolases, Molecular Sequence Data, Chemo enzymatic, Polysaccharide, 01 natural sciences, Biochemistry, Uridine Diphosphate, Analytical Chemistry, Fungal Proteins, 03 medical and health sciences, chemistry.chemical_compound, Non specific, Biosynthesis, Bacterial Proteins, Polysaccharides, Intramolecular Transferases, 030304 developmental biology, chemistry.chemical_classification, 0303 health sciences, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Monosaccharides, Galactose, Glycosyltransferases, General Medicine, Metabolism, Lipase, Furanosides, 0104 chemical sciences, Enzymes, Hexofuranosyl-containing conjugates, Enzyme, chemistry, Carbohydrate Sequence, Biocatalysis, Glycoconjugates, Conjugate
Abstract

International audience; There is no doubt now that the synthesis of compounds of varying complexity such as saccharides and derivatives thereof continuously grows with enzymatic methods. This review focuses on recent basic knowledge on enzymes specifically involved in the biosynthesis and degradation of furanosyl-containing polysaccharides and conjugates. Moreover, and when possible, biocatalyzed approaches, alternative to standard synthesis, will be detailed in order to strengthen the high potential of these biocatalysts to go further with the preparation of rare furanosides. Interesting results will be also proposed with chemo-enzymatic processes based on nonfuranosyl-specific enzymes.

Published
2012

50. Two-step synthesis of per-O-acetylfuranoses: optimization and rationalization

Author

Vincent Ferrières, Richard Daniellou, Rémy Dureau, Laurent Legentil, 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), CNRS, Ministère de l'enseignement supérieur et de la recherche, 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), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Steric effects, Arabinose, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Stereochemistry, Organic Chemistry, Monosaccharides, Acetylation, Chemistry Techniques, Synthetic, Silanes, 010402 general chemistry, 01 natural sciences, Tautomer, Fucose, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Nucleophile, Reactivity (chemistry), Protecting group, Isomerization, Ethers
Abstract

International audience; A simple two-step procedure yielding peracetylated furanoses directly from free aldoses was implemented. Key steps of the method are (i) highly selective formation of per-O-(tert-butyldimethylsilyl)furanoses and (ii) their clean conversion into acetyl ones without isomerization. This approach was easily applied to galactose and structurally related carbohydrates such as arabinose, fucose, methyl galacturonate and N-acetylgalactosamine to give the corresponding peracetylated targets. The success of this procedure relied on the control of at least three parameters: (i) the tautomeric equilibrium of the starting unprotected oses, (ii) the steric hindrance of both targeted furanoses and silylating agent, and finally, (iii) the reactivity of each soft nucleophile during the protecting group interconversion.

Published
2012

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