title: Proof of principle for the synthesis of hydroxy-aryl esters of glycosidic polyols and non-reducing oligosaccharides with subsequent enzymatic coupling to a tyrosine-containing tripeptide.
abstract: To enable enzymatic coupling of saccharides to proteins, several di- and trisaccharides were hydroxy-arylated using anhydrous transesterification with methyl 3-(4-hydroxyphenyl)propionate, catalyzed by potassium carbonate. This transesterification resulted in the attachment of up to 3 hydroxy-aryl units per oligosaccharide molecule, with the monosubstituted product being by far the most abundant. The alkaline reaction conditions, however, resulted in a partial breakdown of reducing sugars. This breakdown could easily be bypassed by a preceding sugar reduction step converting them to polyols. Hydroxy-arylated products were purified by using solid phase extraction, based on the number of hydroxy-aryl moieties attached. Monohydroxy-arylated saccharose was subsequently linked to a tyrosine-containing tripeptide using horseradish peroxidase, as monitored by LC-MS(n). This proof of principle for peptide and protein glycation with a range of possible saccharides and glycosidic polyols can lead to products with unique new properties.
authors.affiliation: Wageningen University, Laboratory of Food Chemistry, Bomenweg 2, 6703 HD Wageningen, The Netherlands.
authors.forename: Ruud
authors.initials: R
authors.lastname: ter Haar
authors.forename: Jelle
authors.initials: J
authors.lastname: Wildschut
authors.forename: Asaf K
authors.initials: AK
authors.lastname: Sugih
authors.forename: W
authors.initials: W
authors.lastname: Bart Möller
authors.forename: Pieter
authors.initials: P
authors.lastname: de Waard
authors.forename: Carmen G
authors.initials: CG
authors.lastname: Boeriu
authors.forename: Hero J
authors.initials: HJ
authors.lastname: Heeres
authors.forename: Henk A
authors.initials: HA
authors.lastname: Schols
authors.forename: Harry
authors.initials: H
authors.lastname: Gruppen
mesh_terms: D040761:Biomimetic Materials / Q000737:chemistry / Q000378:metabolism; D002240:Carbohydrate Sequence; D002374:Catalase / Q000378:metabolism; D004951:Esterification; D004952:Esters; D006027:Glycosides / Q000138:chemical synthesis* / Q000737:chemistry*; D006031:Glycosylation; D006735:Horseradish Peroxidase / Q000378:metabolism*; D006878:Hydroxides / Q000737:chemistry*; D009842:Oligopeptides / Q000737:chemistry / Q000378:metabolism*; D009844:Oligosaccharides / Q000138:chemical synthesis / Q000737:chemistry / Q000378:metabolism*; D010084:Oxidation-Reduction; D010636:Phenols / Q000737:chemistry; D011108:Polymers / Q000737:chemistry*; D014443:Tyrosine / Q000737:chemistry* / Q000378:metabolism
chemical_list: D004952:Esters; D006027:Glycosides; D006878:Hydroxides; D009842:Oligopeptides; D009844:Oligosaccharides; D010636:Phenols; D011108:Polymers; C024617:polyol; D014443:Tyrosine; C031356:hydroxide ion; D006735:Horseradish Peroxidase; D002374:Catalase