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5,5',6,6'-Tetrahydroxy-3,3'-biindoIyl from Beetroot {Beta vulgaris) Peel Extract
Tytti Kujala*, Karel Klika, Vladimir Ovcharenko, Jyrki Loponen, Maarit Vienola
and Kalevi Pihlaja
Department of Chemistry, Vatselankatu 2, FIN-20014 University of Turku, Finland
Fax: +3582-333 6700. E-mail: tytti.kujala@utu.fi
* Author for correspondence and reprint requests
Z. Naturforsch. 56c, 714-718 (2001); received May 2/May 31, 2001
Beta vulgaris, Beetroot, Nitrogen Heterocycles, Biindolyls
A compound of unusual structure was isolated
extract and identified as 5,5',6,6'-tetrahydroxy-3,3'
NMR and MS studies.
Introduction
Recently, plant material extracts containing phe
nolic compounds have been screened as potential
new sources of natural antioxidants. Beet extracts,
especially the extracts from the peel, have shown
strong antioxidant activity in these evaluations re
sulting in increased attention to the natural pro
ducts present in beetroot (Vinson et al., 1998;
Kähkönen et al., 1999). As part of our ongoing
investigation into the distribution and properties
of known phenolics in red beetroot peel
(Kähkönen et al., 1999; Kujala et al., 2000), a novel
compound, 5,5',6,6'-tetrahydroxy-3,3'-biindolyl (1,
Fig. 1), was isolated. It was shown to be a phenolic
compound by a modified Folin-Ciocalteu phenol
test (Nurmi et al., 1996) and was thus of prime
interest to our work despite its highly unstable na
ture when isolated.
Materials and Methods
Extraction and isolation
Red beetroots (Beta vulgaris, cultivar “Rubia“)
were washed, hand-peeled, and the collected peels
cut into small pieces and stored at -25° C until
lyophilisation. After the lyophilised plant material
was reduced to powder by mortar and pestle, 96 g
of the peel was extracted in 8.0 g portions by ho
mogenising (Ultra-Turrax T25, Janke & Kunkel,
IKA-Labortechnik, Germany) each portion twice
for four min with 160 ml of 80% aq. MeOH. Sam
ples were centrifuged (10 min, 1500xg) and the
combined extracts evaporated to syrup under re
from red beetroot (Beta vulgaris) peel
-biindolyl based on the combination of
duced pressure. The syrups were stirred with
MeCN (3 x 50 ml for 30 min) in a planar mixer
(Promax 2020, Heidolp, Germany). The combined
MeCN extracts of all syrups were taken to dryness
under reduced pressure and the residue was ex
tracted with EtOAc. The EtOAc was evaporated
to dryness under reduced pressure and the water-
soluble fraction of the extract was removed to
water. A small portion of the sample was ace-
tylated with the remainder subjected to semiprep
arative purification using a LiChrocart column
{Lichrospher 100 RP-18, 250 x 10 mm I. D., 10 /um,
Merck, Darmstadt, Germany; elution with MeCN
(A) and HCOOH - water (B) (1:99, v/v), 0 -
10 min, 95% B followed by 10-25 min, 5-16% A
in B (linear gradient) with detection at 305 nm}.
From the combined fractions, a distinct and attrac
tive yellow/orange isolate (as an aqueous solution)
was obtained which quickly discoloured to a dark
brown solution (several hours) followed by the
formation of black precipitate (one to several
days).
A syrup was also prepared as mentioned earlier
from 4.0 g of dried peel and dissolved in water
(6.0 ml) for HPLC-MS analysis.
NMR
NMR spectra were acquired on a JEO L Alpha
500 NMR spectrometer operating at 500.16 MHz
for :H and 125.78 MHz for 13 C. Spectra were re
corded at 25° C in D 2 0 ; both XH and 13C spectra
were referenced internally to TMS (0 ppm for
both). ID proton and carbon spectra were ac-
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