Apigenin-7-O-glucoside oxidation catalyzed by P450-bioinspired systems

• Published in: Journal of inorganic biochemistry 2017-05, Vol.170, p.117-124
• Main Authors: Bolzon, Lucas B., dos Santos, Joicy S., Silva, Denise B., Crevelin, Eduardo J., Moraes, Luiz A.B., Lopes, Norberto P., Assis, Marilda D.
• Format: Article
• Language: English
• Subjects: A7G; Apigenin - chemistry; Biomimetic catalysis; Catalysis; Cytochrome P-450 Enzyme System; Hydrogen Peroxide - chemistry; Jacobsen catalyst; Metalloporphyrin; Metalloporphyrins - chemistry; Oxidation-Reduction; P450
• ISSN: 0162-0134; 1873-3344
• DOI: 10.1016/j.jinorgbio.2017.02.016

Apigenin-7-O-glucoside (A7G) is the main flavonoid of Bidens gardneri Bak., a Brazilian plant with wide application in folk medicine. Despite the popular use of this plant, its biological effects are not completely known. This work tested the 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin iron(III) and manganese(III) chloride (Fe(TFPP)Cl and Mn(TFPP)Cl), and Jacobsen's catalyst as P450-bioinspired catalysts for A7G oxidation by different oxidants (PhIO, H2O2, m-CPBA, and t-BuOOH). Up to nine different products were detected by HPLC analysis; Reactions with metalloporphyrin/PhIO systems afforded high catalytic conversions (58–89%). In spite of providing smaller product yields, the metalloporphyrin/H2O2 systems led to superior product distribution. Fe(TFPP)Cl yielded the highest A7G conversion rates (79–93%) with the four different oxidants tested herein. In the presence of PhIO, the oxidative profile of the manganese catalysts was very close to the oxidative profile of Fe(TFPP)Cl. However, in medium containing peroxide, the reactivity of the manganese catalysts was lower as compared to the reactivity of Fe(TFPP)Cl. Reactions with Fe(TFPP)Cl/oxidant systems were analyzed by UPLC-MS; up to thirteen compounds were detected. A7G oxidation catalyzed by Fe(TFPP)Cl yielded seven compounds. Three other compounds had m/z profile compatible with the profile of the A7G metabolites. The A7G oxidation assays performed in the presence of P450-bioinspired catalysts demonstrated their great catalytic potential toward A7G. The present results may be useful to many areas of knowledge and to the research and development of numerous chemical and phamarcological processes, especially in terms of drug design, biological assays, and applications in medicinal chemistry. Apigenin-7-O-glucoside (A7G) is the main flavonoid of Bidens gardneri Bak., with wide application in folk medicine. Despite the popular use of this plant, its biological effects are not completely known. This work tested metalloporphyrins and Jacobsen's catalyst as P450-bioinspired catalysts for A7G oxidation by different oxygen donors. [Display omitted] •P450-Bioinspired catalytic assays in oxidation of Apigenin-7-O-glucoside (A7G)•Iron porphyrin (Fe(TFPP)Cl, or FeP) is the most faithful P450 model system.•Fe(TFPP)Cl promotes the highest A7G conversions among the tested catalysts.•From 13 products attained in FeP-catalysis, 3 are metabolites in living-systems.