Artificial glycosyl phosphorylases

Cyril Rousseau, Fernando Ortega-Caballero, Lars Ulrik Nordstrøm, Brian Christensen, Torben Ellebaek Petersen, Mikael Bols

Research output: Contribution to journalArticle

40 Scopus citations

Abstract

α- and β-Cyclodextrin 6A,6Ddiacids (1 and 2), β-cyclodextrin-6monoacid (14), β-cyclodextrin 6,6 D-diO-sulfate (16) and β-cyclodextrin-6heptasulfate (19) were synthesised. Acids 1, 2 and 14 were made from perbenzylated α- or β-cyclodextrin, by diisobutylaluminum hydride (DIBAL)promoted debenzylation, oxidation and deprotection. Addition of molecular sieves was found to improve the debenzylation reaction. Sulfates 16 and 19 were made by sulfation of the appropriately partially protected derivatives and deprotection. Catalysis of 4-nitrophenyl glycoside cleavage by these cyclodextrin derivatives was studied. Compounds 1, 2 and 16 were found to catalyse the reaction, with the catalysis following Michaelis-Menten kinetics and depending first order on the phosphate concentration. In a phosphate buffer (0.5 M, 59 °C, pH 8.0), KM varied from 2-10 mM and the kcat/kuncat ratio from 80-1000 depending on the stereochemistry of the substrate and the catalyst, with 2 being the best catalyst and with the sulfated 16 also displaying catalytic ability. The monoacid 14 and the heptasulfate 19 were not catalytic.

Original languageEnglish (US)
Pages (from-to)5094-5101
Number of pages8
JournalChemistry - A European Journal
Volume11
Issue number17
DOIs
StatePublished - Aug 19 2005
Externally publishedYes

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Keywords

  • Artificial enzymes
  • Cyclodextrins
  • Glycosides
  • Hydrolysis
  • Kinetics

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

Cite this

Rousseau, C., Ortega-Caballero, F., Nordstrøm, L. U., Christensen, B., Petersen, T. E., & Bols, M. (2005). Artificial glycosyl phosphorylases. Chemistry - A European Journal, 11(17), 5094-5101. https://doi.org/10.1002/chem.200500364