Caracterization and identification of compounds with antioxidant activity in Brazilian organic propolis

Author(s)

Ana Paula Tiveron

• Document type: Doctoral Thesis
• Press: Piracicaba.
• Institution: Universidade de São Paulo (USP). Centro de Energia Nuclear na Agricultura (CENA/STB)
• Defense date: 2015-03-20

Examining board members

Severino Matias de Alencar; Luciana Ferracini dos Santos; Bruno Bueno Silva; Carmen Silvia Favaro Trindade

• Advisor: Severino Matias de Alencar

Abstract

Propolis is a complex resinous substance and has many biological properties, such as antiviral, antifungal, antioxididant, anti-inflamatory, antitumor, among others. These activities have been attributed mainly due to the presence of phenolic compounds and/ or derivatives. However, propolis chemical composition depends on the vegetation around the hive. In this study, 78 samples of organic propolis were collected in permanent preservation and reflorestation areas, properly certified, in southern Paraná and north of Santa Catarina. The aim of this work was to evaluate the chemical composition of organic propolis as well as isolate the compounds responsible for the antioxidant activity. The volatile composition and application of ethanol extracts of propolis (EEP) and microcapsules of organic propolis, produced by complex coacervation, in soybean oil with no antioxidant addition were also evaluated. Among the 78 samples analysed, seven different chromatographic profiles were found. Using criteria such as recurrence and and antioxidant activity profile 1 was selected for isolation of bioactive compounds. The profile 1 was then fractionated by the technique of liquid-liquid extraction, resulting in hexane, ethyl acetate, butanol and water fractions. Fractions ethyl acetate and butanol were the ones that showed the highest antioxidant activity by radicals DPPH, ABTS and peroxyl scavenging methods, as well as similarity in chemical composition. Therefore, these fractions were pooled and rechromatographed in sequence in an open glass column with silica C18, yelding 19 subfractions. The subfractions 2-5 showed the highest antioxidant activity, ranging from 16,25 to 26,26 ?mol Trolox/mg e and 2,28 to 5,71 ?mol Trolox/mg for ORAC and ABTSo+ methods, respectively. Thus, from this subfractions were isolated seven compounds with antioxidant activity, two lignans precursors, such as coniferyl alcohol and coniferyl aldehyde and five lingans, wich were identified as pinoresinol, lariciresinol, secolariciresinol, matairesinol and balajaponin D. These four last lignans are novel in propolis. The application of microcapsules containing profile 1 of organic propolis in soybean oil was no effective to prevent oxidation. In the volatile fraction of the seven profiles, terpenoids, ketones, aldehydes and alcohols were found, and ? and ?-pinenes were the predominant compounds. The results obtained showed a very peculiar chemical composition of organic propolis when compared to other Brazilian ones. According to the results its possible to conclude that OP1 is a good source of bioactive compounds to be explored (AU)