Elsevier

Phytochemistry

Volume 93, September 2013, Pages 222-229
Phytochemistry

Component analysis of propolis collected on Jeju Island, Korea

https://doi.org/10.1016/j.phytochem.2012.02.018Get rights and content

Abstract

A study of propolis from Jeju Island, located off the southern tip of Korea, led to the isolation and identification of eight chalcones: (±)-(E)-4′-methoxy-4,2′-dihydroxy-3′-(2″,3″-dihydroxy-3″-methylbutyl)-chalcone, (E,E,E)-4,2′,4′-trihydroxy-3′-(7″-hydroxy-3″,7″-dimethyloct-2″,5″-dienyl)-chalcone, (±)-(E,E)-4,2′,4′-trihydroxy-3′-(5″-hydroxy-3″,7″-dimethyloct-2″,6″-dienyl)-chalcone, (±)-(E)-4′-methoxy-4,3″,4″-trihydroxy-2″,2″-dimethyldihydropyrano-(2′,3′)-chalcone, (±)-(E)-4′-methoxy-4,3″-dihydroxy-2″-(1″′-hydroxyisopropyl)-dihydrofurano-(2′,3′)-chalcone, (–)-(E)-4,4′-dihydroxy-2″-(1″′-hydroxy-1″′,5″′-dimethylhex-4″′-enyl)-dihydrofurano-(2′,3′)-chalcone, (+)-(E)-4,2′-dihydroxy-2″-methyl-2″-(3″′,4″′-dihydroxy-4″′-methylpentanyl)-2H-pyrano-(3′,4′)-chalcone and (–)-(E)-4,2′-dihydroxy-2″-methyl-2″-(3″′,4″′-dihydroxy-4″′-methylpentanyl)-2H-pyrano-(3′,4′)-chalcone. Nineteen other known compounds were also isolated. Their structures were determined by spectroscopic analyses and comparison with literature data. The propolis from Jeju Island contained compounds not present in propolis from other regions.

Graphical abstract

Eight chalcones, named jejuchalcones A–H, and nineteen known compounds, were isolated from propolis collected on Jeju Island, Korea. This propolis from Jeju Island contained compounds not present in propolis from other regions.

  1. Download : Download full-size image

Highlights

► Eight chalcones were isolated from the propolis collected on Jeju Island, Korea. ► Nineteen known compounds were also isolated. ► The known compounds from this propolis were components from Angelica keiskei. ► A. keiskei is believed to be one of the plant origins of the Jeju Island propolis.

Introduction

Propolis is a natural substance that honeybees, Apis mellifera, collect from buds and exudates of certain trees and plants. Propolis has various biological activities such as antibacterial, anti-inflammatory, antioxidant and anticancer properties, and has long been used as a folk medicine in many regions of the world (Bankova et al., 2000, Banskota et al., 2001, Marcucci, 1995). In recent decades, propolis has attracted much attention, and is extensively used in foods, beverages, supplements and cosmetics intended to prevent diseases such as inflammation, heart disease and cancer, and as a cosmetic (Lotfy, 2006, Salantino et al., 2011, Sforcin and Bankova, 2011).

The chemical components of propolis depend on the vegetation at the region of collection, since honeybees preferentially target plants grown near beehives as sources of propolis. For example, propolis collected in temperate regions contains many kinds of flavonoids and phenolic acid esters, particularly pinocembrin, pinobanksin, galangin, chrysin and caffeic acid phenetyl ester, as the major source of the propolis is bud exudates of the Populus species (Bankova et al., 2000, Kumazawa et al., 2004b). On the other hand, green propolis from Minas Gerais State, Brazil, contains many kinds of terpenoids and prenylated derivatives of p-coumaric acids, such as artepillin C and (E)-3-prenyl 4-(dihydrocinnamoyloxy)-cinnamic acid, as the source of the propolis in young leaves of Baccharis dracunculifolia (Kumazawa et al., 2003). Furthermore, differences in plant origin also cause the variations in propolis properties such as biological activity, texture, flavor and color.

Salantino et al. (2011) have stated that although the focus of propolis research has centered mainly on Brazilian green propolis and temperate poplar propolis, propolis collected on many other regions are also promising. Previously, it was found that propolis from Okinawa, which is the southern-most prefecture in Japan, has many prenylflavonoids with strong antioxidant activity not present in propolis from other regions (Kumazawa et al., 2004a, Kumazawa et al., 2007). Moreover, the components of Korean propolis were also studied from various geographical locations and it was found that the components of propolis from Jeju Island, located off the southern coast of Korea, differed from propolis from other regions (Ahn et al., 2004, Kumazawa et al., 2006). In these previous studies, three compounds were isolated and identified from the propolis collected on Jeju Island; however, the other components in it have remained unknown.

Thus, to investigate the potential utility of propolis, the components of propolis collected on Jeju Island, Korea were studied further. Eight new chalcones (1, 4, 5, 10 and 1316) and nineteen known compounds were isolated, and their structures were determined by spectroscopic analyses. In this report, the isolation and structural determination of these compounds are described.

Section snippets

Results and discussion

The MeOH soluble fraction of propolis from Jeju Island was subjected to silica gel column chromatography and preparative reversed phase HPLC (RP-HPLC). Eight new chalcones (1, 4, 5, 10 and 1316), ten known chalcones (2, 3, 69, 11, 12, 17 and 18) and nine known coumarins (1927) (Fig. 1) were isolated.

Compound 1 was isolated as a yellow oil. Its molecular formula was determined to be C21H24O6 by high resolution FABMS (HRFABMS). The 1H NMR spectrum of 1 (Table 1) showed signals assignable to

Concluding remarks

From this study, propolis collected on Jeju Island was confirmed to be a new type of propolis containing many chalcones and coumarins as its main components. The known compounds (2, 3, 69, 11, 12, 1721, 23, 25 and 26) from this propolis were previously reported as components of Angelica keiskei (Akihisa et al., 2003, Baba et al., 1990a, Baba et al., 1990b, Takara Bio Inc. et al., 2005). In particular, 2 and 7 have been reported to be the main components of A. keiskei (Akihisa et al., 2003,

General experimental procedures

Melting points (mp) were measured using a Yanaco MP-500 micro melting point apparatus and were uncorrected. Optical rotations for 24, 69, 1925 and 27 were measured using a Horiba SEPA-200 polarimeter, and for 1, 5, 1018 and 26 using a Jasco DIP-1000 digital polarimeter. UV–Vis spectra were measured using a Jasco V-560 UV/VIS spectrophotometer. FABMS spectra were obtained on a JEOL JMS-700 MStation spectrometer. ESIMS spectra were acquired on a Thermo Fisher Scientific LCQ. 1D and 2D NMR

References (38)

  • K. Baba et al.

    Chemical components of Angelica keiskei Koidzumi (V). Components of the fruits, and comparison of coumarins and chalcones in the fruits, roots and the leaves

    Shoyakugaku Zasshi.

    (1990)
  • V.S. Bankova et al.

    Propolis: recent advances in chemistry and plant origin

    Apidologie

    (2000)
  • A.H. Banskota et al.

    Recent progress in pharmacological research of propolis

    Phytother. Res.

    (2001)
  • D.R. Boyd et al.

    Absolute configuration assignment and enantiopurity determination of chiral alkaloids and coumarins derived from O- and C-prenyl epoxides

    Chem. Commun.

    (2002)
  • P.C. Bulman Page et al.

    Highly enantioselective total synthesis of (−)-(3′S)-lomatin and (+)-(3′S,4′R)-trans-khellactone

    Org. Lett.

    (2009)
  • S.-C. Fang et al.

    Cytotoxic effects of new geranyl chalcone derivatives isolated from the leaves of Artocarpus communis in SW 872 human liposarcoma cells

    J. Agric. Food Chem.

    (2008)
  • D.H. Jung et al.

    New synthetic routes to biologically interesting geranylated flavanones and geranylated chalcones: first total synthesis of (±)-prostratol F, xanthoangelol, and (±)-lespeol

    Helv. Chim. Acta

    (2010)
  • J.S. Kim et al.

    Chemical constituents of the root of Dystaenia takeshimana and their anti-inflammatory activity

    Arch. Pharm. Res.

    (2006)
  • L.-Y. Kong et al.

    Coumarins from Peucedanum wulongense

    J. Asian Nat. Prod. Res.

    (2003)
  • Cited by (16)

    • PTP1B inhibitors from stems of Angelica keiskei (Ashitaba)

      2015, Bioorganic and Medicinal Chemistry Letters
    View all citing articles on Scopus
    View full text