Enzymatic Acylation of Flavonoids: Effect of the Nature of the Substrate, Origin of Lipase, and Operating Conditions on Conversion Yield and Regioselectivity

• Published in: Journal of agricultural and food chemistry Vol. 55; no. 23; pp. 9496 - 9502
• Main Authors: Chebil, Latifa, Anthoni, Julie, Humeau, Catherine, Gerardin, Christine, Engasser, Jean-Marc, Ghoul, Mohamed
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 14.11.2007; Amer Chemical Soc
• Subjects: acetylation; Acylation; Agriculture; Agriculture, Multidisciplinary; Biological and medical sciences; Biotechnology; Burkholderia cepacia; Burkholderia cepacia - enzymology; Candida antarctica; Candida antarcticalipase B; Chemical and Process Engineering; chemical structure; Chemistry; Chemistry, Applied; chrysin; Engineering Sciences; enzyme activity; Flavonoid; flavonoids; Flavonoids - chemistry; Flavonoids - metabolism; Food industries; Food Science & Technology; Fundamental and applied biological sciences. Psychology; Fungal Proteins; Glycosylation; hesperetin; isoquercitrin; Life Sciences & Biomedicine; Lipase - metabolism; naringenin; Physical Sciences; Pseudomonas; Pseudomonas cepacialipase C; regioselectivity; Science & Technology; Solvents; Substrate Specificity; triacylglycerol lipase; acetylation; regioselectivity; Candida antarctica lipase B; Flavonoid; Pseudomonas cepacia lipase C; HYDROXYL-GROUPS; DIETARY FLAVONOIDS; ESTERIFICATION; FATTY-ACIDS; DEPROTECTION; PLANT PIGMENTS; ORGANIC-SOLVENTS; ANTIOXIDANT; ESTERS; flavonoid; CANDIDA-ANTARCTICA LIPASE; Origin; candida antarctica; Regioselectivity; Enzyme; Triacylglycerol lipase; Esterases; Carboxylic ester hydrolases; Operating conditions; Fungi; Polyphenol; Burkholderia cepacia; Bacteria; Hydrolases; Yield; Fungi Imperfecti; Acetylation; Thallophyta; Acylation; Enzymatic reaction
• ISSN: 0021-8561; 1520-5118
• DOI: 10.1021/jf071943j

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.