Synthesis of regioselectively and uniformly modified maltoheptaose derivatives from cyclomaltoheptaose precursors

Lesur, David; Gassama, Abdoulaye; Moreau, Vincent; Pilard, Serge; Djedaïni‐Pilard, Florence

doi:10.1016/j.carres.2005.01.021

Cited by 10 publications

(12 citation statements)

References 17 publications

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“…[33] Subsequent per-acetylation with acetic anhydride and per-benzoylation with benzoyl bromide followed by nucleophilic substitution with sodium azide allowed isolation of the compounds 8 and 9, respectively. [34] Several methodologies are reported to form the linear malto-oligosaccharide from the corresponding CDs with Lewis or Brønsted acids such as H 2 SO 4 /Ac 2 O, [35] FeCl 3 / Ac 2 O, [36] ZnBr 2 /PhSSiMe 3 , [37] HClO 4 /Ac 2 O, [38,39] TiCl 4 , or BF 3 /MeOCH 2 CO 2 H. [40] These different protocols were evaluated on the acetylated derivative 8 without any success. The expected linear heptasaccharide was only formed with H 2 SO 4 /Ac 2 O [35] and in a low yield (less than 10 %) due to the formation of shorter linear oligomers by a depolymerization process.…”

Section: Resultsmentioning

confidence: 99%

Clustering of Escherichia coli Type‐1 Fimbrial Adhesins by Using Multimeric Heptyl α‐D‐Mannoside Probes with a Carbohydrate Core

Almant

Moreau

Kovensky

et al. 2011

Chemistry A European J

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Heptyl α-D-mannoside (HM) is a strong inhibitor of the FimH lectin that mediates the initial adhesion of the uropathogenic Escherichia coli (E. coli) to the bladder cells. We designed a set of multivalent HM ligands based on carbohydrate cores with structural valencies that range from 1 to 7. The chemical strategy used to construct the regular hydrophilic structures consisted of the repetition of a critical glucoside fragment. A primary amino group was grafted at the sugar reducing end to couple the multimers to a fluorescent label. A one-pot synthetic approach was developed to tether the ligands and the fluorescein isothiocyanate (FITC) probe to the scaffold simultaneously. Isothermal calorimetry with the monomeric FimH lectin revealed nanomolar affinities and saturation of all structurally available binding sites on the multivalent HM ligands. Direct titrations domain showed almost strict correlation of enthalpy-entropy compensation with increasing valency of the ligand, whereas reverse titration calorimetry demonstrated negative cooperativity between the first and the second binding site of the divalent heptyl mannoside. A multivalency effect was nevertheless observed by inhibiting the haemagglutination of type-1 piliated UTI89 E. coli, with a titer as low as 60 nM for the heptavalent HM ligand. An FITC-labeled HM trimer showed capture and cross-linking of living bacteria in solution, a phenomenon not previously described with low-valency ligands.

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Section: Resultsmentioning

confidence: 99%

Clustering of Escherichia coli Type‐1 Fimbrial Adhesins by Using Multimeric Heptyl α‐D‐Mannoside Probes with a Carbohydrate Core

Almant

Moreau

Kovensky

et al. 2011

Chemistry A European J

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“…Maltoheptaose was prepared using a previously described procedure. 35 Briefly, β-cyclodextrin was perbenzoylated with benzoyl chloride in pyridine, then regioselective opening in AcOH/H 2 SO 4 was performed, followed by deacetylation and debenzoylation in standard conditions (using sodium methanolate in methanol).…”

Section: Methodsmentioning

confidence: 99%

High resolution MALDI-TOF-MS and MS/MS: Application for the structural characterization of sulfated oligosaccharides

Lesur

Duhirwe

Kovensky

2019

Eur J Mass Spectrom (Chichester)

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Sulfated oligosaccharides are involved in important biological events that are often modulated by specific sequences and sulfation patterns, but their structural analysis remains challenging. Matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) analysis of three different sulfated oligosaccharides (Fondaparinux, the octasulfated pentasaccharide, a disulfated heparin-derived tetrasaccharide 1, and an octasulfated maltoheptaose) 2 was performed using the 2-(4-hydroxyphenylazo)benzoic acid-tetramethylguanidinium (HABA-TMG2) matrix. High resolution mass spectrometry of the main ions observed was successful, and this was complemented by tandem mass spectrometry (MS/MS) analysis for structural assessment. Despite sulfate losses, fully sulfated molecular ions were observed and these allowed the determination of oligosaccharide structures: UA-GlcNAc-UA(2S)-AnhMan(6S) for compound 1 and (Glc6S)6-Glc (1S,6S) for compound 2.

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“…Nevertheless, it is known that maltooligosaccharides (linear oligosaccharides constituted of glucose monomer molecules α (1 → 4) linked) with a degree of polymerization (DP) from 6 to 8 can be obtained readily by acetolysis of esterified α ‐, β ‐ and γ ‐cyclomaltooligosaccharides (cyclodextrins, CDs) under H 2 SO 4 catalysis (Kuzuhara's method5, 6) or under HClO 4 catalysis (Vasella's method7). We have recently adapted these procedures8 to synthesize regioselectively C‐6‐derivatized maltoheptaoses (DP7) 4 to 10 in high purity and yield, starting from natural β ‐CD (Scheme ). These compounds are highly suitable for further chemical modifications and are expected to give access to anionic, cationic, zwitterionic or amphiphilic oligosaccharides.…”

Section: Methodsmentioning

confidence: 99%

Electrospray ionization mass spectrometry: a key analytical tool for the characterization of regioselectively derivatized maltooligosaccharides obtained starting from natural β‐cyclodextrin

Lesur

Gassama

Moreau

et al. 2006

Rapid Comm Mass Spectrometry

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The development of natural cyclodextrins (CDs) for various industrial applications (agroalimentary, cosmetic or pharmaceutical) constitutes a continuous challenge. For the integration of these agricultural plant products in the creation of super-absorbent biodegradable and hypoallergenic materials (water-retaining agents, cosmetic hydrating and texturing, pharmaceutical and horticultural products) to replace synthetic polymers, we have developed chemical methods to access regioselectively C-6-derivatized maltooligosaccharides starting from CDs. These compounds are highly suitable for further chemical modifications and are expected to give access to a new class of polymeric materials with potential applications such as water-retaining agents in the disposable nappies industry. For the structural analysis of carbohydrates, electrospray ionization mass spectrometry (ESI-MS) offers precise results, analytical versatility and very high sensitivity. We report herein the rapid and convenient follow-up of chemical reactions, the purity evaluation of intermediates and final products, and the structural characterization of derivatized maltooligosaccharides, obtained by acidic cleavage (acetolysis) of halogenated and esterified CDs, using ESI-MS in combination with the high-resolution (HRMS) and tandem mass spectrometry (MS/MS) capabilities of a quadrupole orthogonal time-of-flight (Q-TOF) mass spectrometer.

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Synthesis of regioselectively and uniformly modified maltoheptaose derivatives from cyclomaltoheptaose precursors

Cited by 10 publications

References 17 publications

Clustering of Escherichia coli Type‐1 Fimbrial Adhesins by Using Multimeric Heptyl α‐D‐Mannoside Probes with a Carbohydrate Core

Clustering of Escherichia coli Type‐1 Fimbrial Adhesins by Using Multimeric Heptyl α‐D‐Mannoside Probes with a Carbohydrate Core

High resolution MALDI-TOF-MS and MS/MS: Application for the structural characterization of sulfated oligosaccharides

Electrospray ionization mass spectrometry: a key analytical tool for the characterization of regioselectively derivatized maltooligosaccharides obtained starting from natural β‐cyclodextrin

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