Anthraquinoid pigments from the deep-water starfish Henricia SP

Full text of DOI:10.1007/s10600-010-9484-x

Chemistry of Natural Compounds, Vol. 45, No. 6, 2009
ANTHRAQUINOID PIGMENTS FROM
THE DEEP-WATER STARFISH Henricia SP.
N. K. Utkina
UDC 547.673+593.93
Previous studies have shown that starfish of the family Echinasteridae collected in shallow waters contain a series of
anthraquinoid pigments [1–4]. In continuation of the search for biologically active metabolites in marine organisms, we
studied the alcohol extract from a deep-water starfish of the genus Henricia that was collected in Okhotsk Sea at a depth of
200 m during the 31st cruise of Research Ship Akademik Oparin.
Starfish (10 g) was extracted with EtOH. The extract was separated over a column of Sephadex LH-20 using
CHCl :MeOH (3:1) to produce 1 (5 mg), 2 (1 mg), 3 (0.6 mg), and 4 (0.5 mg). Compounds 1–4 were identified by comparison
3
of their spectral characteristics with the literature for 1,3,8-trihydroxy-6-propyl-9,10-anthraquinone (crinoemodin, 1) [1,
3–5]; 1,3,8-trihydroxy-6-(2′-hydroxypentyl)-9,10-anthraquinone (2) [1, 4, 6]; 1,3,8-trihydroxy-6-(2′-hydroxypropyl)-
9,10-anthraquinone (isorhodoptilometrin, 3) [1, 3, 4]; and 1,3,8-trihydroxy-6-(3′-hydroxypropyl)-9,10-anthraquinone
(ω-rhodoptilometrin, 4) [2, 4], respectively.
OH
O
OH
1
9a
8a
7
9
10
3
4a
HO
10a
R
5
O
1 - 4
1: R = CH CH CH ; 2: R = CH CH(OH)CH CH CH
3
2
2
3
2
2
2
3: R = CH CH(OH)CH ; 4: R = CH CH CH OH
2
3
2
2
2
Compounds 1–4 (0.1 mM) were checked for ability to inhibit oxidation of linoleic acid (5 mM) induced by
2,2′-azobis(2-amidinopropane) dihydrochloride (AAPH) (1 mM). The oxidation process was monitored by the absorption
increase at 234 nm from linoleic acid diene hydroperoxides formed during it (Fig. 1). It was found that 1–4 exhibited under
these conditions weak anti-oxidant properties with a decrease of the linoleic acid oxidation rate by 2.6, 1.8, 1.7, and 1.9 times,
respectively. Standard antioxidants trolox (6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid) and ionol (2,6-di-t-
butyl-4-methylphenol, BHT) (0.1 mM) reduced the oxidation rate by 17.4 and 13.2 times, respectively.
Methylation of 1–4 by diazomethane in ether gave the corresponding C-3 methyl ethers, the spectral characteristics
of which agreed with the literature [1, 2]. Monomethyl ethers of 1–4 (0.1 mM) did not reduce the oxidation rate of linoleic
acid. Thus, the observed antioxidant activity of these compounds was related to the C-3 hydroxyl, which is capable of
donating a proton to the peroxyl radical.
Pacific Institute of Bioorganic Chemistry, Far-East Branch, Russian Academy of Sciences, 690022, Vladivostok,
prosp. 100-Letiya Vladivostoka, 159, Russia, fax: (4232) 31 40 50, e-mail: utkinan@mail.ru. Translated from Khimiya
Prirodnykh Soedinenii, No. 6, p. 729, November–December, 2009. Original article submitted June 10, 2009.
©
870
0009-3130/09/4506-0870 2009 Springer Science+Business Media, Inc.

2.0
1.8
1.6
7
1.4
1.2
3
2
4
1
1.0
0.8
0.6
0.4
0.2
6
5
0
0
10
20
30
40
50
60
Time, min
Fig. 1. Oxidation of linoleic acid induced by AAPH without
antioxidants (control, 7) and with 1–4, trolox (5), and ionol
(BHT, 6).
ACKNOWLEDGMENT
The work was supported by grants 09-III-A-05-145 (FEB RAS), NSh-2813.2008.4 (State Foundation for Support of
Leading Scientific Schools of the RF), and the RAS Presidium Program “Molecular and Cellular Biology.”
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