title: Enzymatic acylation of flavonoids: effect of the nature of the substrate, origin of lipase, and operating conditions on conversion yield and regioselectivity.
abstract: The conversion yield at equilibrium, the initial rate, and the regioselectivity of the enzymatic acetylation of aglycone flavonoids (quercetin, naringenin, hesperetin, and chrysin) were investigated and compared to those obtained with a glycosylated one (isoquercitrin). The effects of a wide range of operating conditions were quantified. Fourier transform infrared spectrometry (FT-IR), NMR, and high performance liquid chromatography electrospray ionization mass spectrometry (HPLC-ESI-MS) analyses showed that for glycosylated flavonoids, in the presence of Candida antarctica (CAL-B), the acetylation occurred on the 2''-OH, 3''-OH, and 6''-OH of the glucose part, while with Pseudomonas cepacea lipase (PSL-C) acetylation takes place on 6''-OH of the sugar and 4'-OH of the B-ring. For aglycone flavonoids, the acetylation occurred only with PSL-C on 4'-OH, 3'-OH, and 7-OH hydroxyls. The conversion yield and the number and the relative proportions of the synthesized products were found dependent on the nature of the enzyme, the molar ratio, and the flavonoid structure. The initial rate was affected only by the origin of the enzyme.
authors.affiliation: Laboratoire Biocatalyse Bioprocédés, ENSAIA-INPL, Nancy-Université, 2, Av de la Forêt de Haye 54500, Vandoeuvre, France.
authors.forename: Latifa
authors.initials: L
authors.lastname: Chebil
authors.forename: Julie
authors.initials: J
authors.lastname: Anthoni
authors.forename: Catherine
authors.initials: C
authors.lastname: Humeau
authors.forename: Christine
authors.initials: C
authors.lastname: Gerardin
authors.forename: Jean-Marc
authors.initials: JM
authors.lastname: Engasser
authors.forename: Mohamed
authors.initials: M
authors.lastname: Ghoul
mesh_terms: D000215:Acylation; D016956:Burkholderia cepacia / Q000201:enzymology; D005419:Flavonoids / Q000737:chemistry / Q000378:metabolism*; D005656:Fungal Proteins; D006031:Glycosylation; D008049:Lipase / Q000378:metabolism*; D012997:Solvents; D013379:Substrate Specificity
chemical_list: D005419:Flavonoids; D005656:Fungal Proteins; D012997:Solvents; D008049:Lipase; C431349:lipase B, Candida antarctica