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Triterpene Saponins from the Sea Cucumber Stichopus chloronotus


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Sea cucumbers have been used as a dietary delicacy and importantingredient in Asian traditional medicine and functional foods over many centuries. Using combined chromatographic methods, six triterpene saponins (1-6), including a new compound, stichloroside F (1), were isolated from a methanol extract of the sea cucumber Stichopus chloronotusBrandt. Their structures were determined on the basis of spectroscopic (1H and 13C NMR, HSQC, HMBC, 1H-1H COSY, ROESY) and FTICR-MS data and by comparison with literature values.
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Department of Organic Chemistry,
University of Granada,
Campus de Fuente Nueva, s/n, 18071, Granada, Spain
Dipartimento di Chimica Bioorganicae Biofarmacia,
Universita di Pisa,
via Bonanno 33, 56126 Pisa, Italy
State Key Laboratory of Natural and Biomimetic Drugs,
School of Pharmaceutical Sciences,
Peking University,
Beijing 100083, China
School of Pharmacy,
Tokyo University of Pharmacy and Life Sciences,
Horinouchi 1432-1, Hachioji, Tokyo 192-0392, Japan
Department of Chemistry
University of Wollongong
Wollongong, New South Wales, 2522, Australia
Department of Chemistry,
Texas Christian University,
Forts Worth, TX 76129, USA
Department of Chemistry
The University of Alabama in Huntsville
Huntsville, AL 35809, USA
Faculty of Pharmaceutical Sciences
Hokuriku University
Ho-3 Kanagawa-machi, Kanazawa 920-1181, Japan
Department of Pharmaceutical and Biological Chemistry,
The School of Pharmacy,
University of London, 29-39 Brunswick Square,
London WC1N 1AX, UK
Prof. Viqar Uddin Ahmad
Karachi, Pakistan
Prof. Giovanni Appendino
Novara, Italy
Prof. Yoshinori Asakawa
Tokushima, Japan
Prof. Roberto G. S. Berlinck
São Carlos, Brazil
Prof. Anna R. Bilia
Florence, Italy
Prof. Maurizio Bruno
Palermo, Italy
Prof. César A. N. Catalán
Tucumán, Argentina
Prof. Josep Coll
Barcelona, Spain
Prof. Geoffrey Cordell
Chicago, IL, USA
Prof. Fatih Demirci
Eskişehir, Turkey
Prof. Dominique Guillaume
Reims, France
Prof. Ana Cristina Figueiredo
Lisbon, Portugal
Prof. Cristina Gracia-Viguera
Murcia, Spain
Prof. Duvvuru Gunasekar
Tirupati, India
Prof. Hisahiro Hagiwara
Niigata, Japan
Prof. Kurt Hostettmann
Lausanne, Switzerland
Prof. Martin A. Iglesias Arteaga
Mexico, D. F, Mexico
Prof. Leopold Jirovetz
Vienna, Austria
Prof. Vladimir I Kalinin
Vladivostok, Russia
Prof. Niel A. Koorbanally
Durban, South Africa
Prof. Chiaki Kuroda
Tokyo, Japan
Prof. Hartmut Laatsch
Gottingen, Germany
Prof. Marie Lacaille-Dubois
Dijon, France
Prof. Shoei-Sheng Lee
Taipei, Taiwan
Prof. Imre Mathe
Szeged, Hungary
Prof. Ermino Murano
Trieste, Italy
Prof. M. Soledade C. Pedras
Saskatoon, Canada
Prof. Luc Pieters
Antwerp, Belgium
Prof. Peter Proksch
Düsseldorf, Germany
Prof. Phila Raharivelomanana
Tahiti, French Polynesia
Prof. Luca Rastrelli
Fisciano, Italy
Prof. Stefano Serra
Milano, Italy
Prof. Monique Simmonds
Richmond, UK
Dr. Bikram Singh
Palampur, India
Prof. John L. Sorensen
Manitoba, Canada
Prof. Johannes van Staden
Scottsville, South Africa
Prof. Valentin Stonik
Vladivostok, Russia
Prof. Winston F. Tinto
Barbados, West Indies
Prof. Sylvia Urban
Melbourne, Australia
Prof. Karen Valant-Vetschera
Vienna, Austria
The School of Pharmacy & Biomedical Sciences,
University of Portsmouth,
Portsmouth, PO1 2DT U.K.
Triterpene Saponins from the Sea Cucumber Stichopus chloronotus
Nguyen Phuong Thao
, Bui Thi Thuy Luyen
, Le Thi Vien
, Bui Huu Tai
, Le Duc Dat
Nguyen Xuan Cuong
, Nguyen Hoai Nam
, Phan Van Kiem
, Chau Van Minh
and Young Ho Kim
Institute of Marine Biochemistry (IMBC), Vietnam Academy of Science and Technology (VAST),
18 Hoang Quoc Viet, Caugiay, Hanoi, Vietnam
College of Pharmacy, Chungnam National University, Daejeon 305–764, Republic of Korea (Minh, C.V.); (Kim, Y. H.)
Received: January 6
, 2014; Accepted: February 17
, 2014
Sea cucumbers have been used as a dietary delicacy and important ingredient in Asian traditional medicine and functional foods over many centuries. Using
combined chromatographic methods, six triterpene saponins (16), including a new compound, stichloroside F (1), were isolated from a methanol extract of
the sea cucumber Stichopus chloronotus Brandt. Their structures were determined on the basis of spectroscopic (
H and
COSY, ROESY) and FTICR-MS data and by comparison with literature values.
Keywords: Stichopus chloronotus, Stichopodidae, Sea cucumber, Stichloroside F.
Sea cucumbers belonging to the family Stichopodidae (phylum
Echinodermata, class Holothurioidea, order Aspidochirotida) are
usually served as a culinary delicacy and traditional tonic. Among
the members of this family, Stichopus chloronotus Brandt is a
marine invertebrates found in benthic areas and deep seas in the
Pacific, Indo-Pacific, and Atlantic oceans [1]. Sea cucumbers
represent one of several marine organisms used as food, particularly
among the Asian population [2-3]. They have also been popular as a
traditional tonic in Japan, Vietnam, China, Taiwan, and Korea [4-7].
Chemical investigation of S. chloronotus dates back to the 1980s
when its fatty acid [8], glycosphingolipid [9], and triterpene
oligoglycoside (saponin) [10-12] components were reported to have
antifungal [11], antitumor, cytotoxic [13], anticoagulant,
antioxidation, antithrombotic, and anticancer activities [3-14]. Most
of the known sea cucumber glycosides have a lanostane aglycone
(so called holostane aglycone) with an 18(20)-lactone [15] and a
sugar chain composed of up to six monosaccharide units linked to
C-3 of the aglycone [12].
During our ongoing investigations to catalog the chemical
constituents of Vietnamese echinoderms [16-19], we studied the
Figure sea cucumber S. chloronotus. The present study addresses
the isolation and structure elucidation of six holostane glycosides
(16, Figure 1), including a new compound, stichloroside F (1),
from this sea cucumber.
A methanol extract (10.45 g) of S. chloronotus was suspended in
water and partitioned successively with n-butanol. Six holostane
glycosides (16) were isolated from the n-butanol residue (2.42 g)
by using combined chromatographic methods. Detailed analysis of
the spectroscopic data (1D, 2D NMR, and MS) and comparison
with previously reported values led to the elucidation of the known
compounds as stichoposide D (2) [20-21], stichloroside A
(3) [20],
stichoposide E (4) [20], neothyonidioside (5) [22], and holothurin B
(6) [23]. Notably, compound 5 was isolated for the first time from a
Stichopus species, and from all other representatives of the family
Stichopodidae studied so far.
Figure 1: Structures of compounds 16 from the sea cucumber S. chloronotus.
NPC Natural Product Communications
Vol. 9
No. 5
615 - 618
616 Natural Product Communications Vol. 9 (5) 2014 Thao et al.
Table 1:
H and
C NMR spectroscopic data of compound 1 in pyridine-d
Position δ
mult. (J in Hz)
Position δ
mult. (J in Hz)
Aglycon Xyl I
1 36.3 1.48 m
107.3 4.78 d (8.0)
2 27.2 1.95 m/2.20 m
75.2 4.00
3 89.1 3.39 dd (4.0, 11.5)
76.0 4.16
4 39.5 -
76.8 4.27
5 48.1 1.08 m
64.5 3.71
6 23.3 2.02 m Xyl II
7 119.9 5.68 m
103.3 4.91 d (8.0)
8 146.9 -
72.4 4.03
9 47.5 3.52 br d (14.0)
86.8 4.14
10 36.6 -
69.3 4.04
11 23.0 1.52 m/1.78 m
66.6 3.60 dd (3.0, 11.0)
12 30.5 1.95 m/2.10 m 4.29
13 58.6 - MeGlc
14 51.4 -
105.3 5.28 d (7.5)
15 34.3 1.70 m/1.80 m
75.1 3.99
16 25.2 1.93 m/2.06 m
88.0 3.85
17 53.7 2.44 dd (4.5, 10.5)
70.5 4.15
18 180.2 -
78.3 3.95 m
19 24.6 1.20 s
62.1 4.26
20 84.9 -
60.8 3.85 s
21 28.1 1.82 s
22 47.6 2.00 m/2.13 m
23 65.4 4.00 m
24 49.2 1.30 m/1.65 m
25 24.0 2.04 m
26 23.8 0.95 d (6.5)
27 22.1 0.98 d (6.5)
28 17.6 1.07 s
29 28.9 1.33 s
30 31.0 1.11 s
125 MHz;
500 MHz;
Overlapped signals; All assignments were made by HSQC,
COSY, HMBC, and ROESY experiments.
Figure 2: Important
H COSY and HMBC correlations of compound 1.
Stichloroside F (1) was obtained as a white amorphous powder. Its
molecular formula, C
(contained ten degrees of
unsaturation), was identified from a pseudo-molecular ion peak at
m/z 935.49804 [M+Na]
in the Fourier transform ion cyclotron
resonance mass spectrum (FTICR-MS). The IR spectrum showed an
absorption band due to a γ-lactone moiety (1762 cm
) and strong
broad absorptions (3384 and 1074 cm
) reminiscent of a glycosidic
structure. Acid hydrolysis of 1 with 10% HCl produced
stichlorogenol [10] and two
D-xylose and one 3-O-methyl-D-
glucose moieties, characterized by GC-MS analysis of their
persilylated derivatives (see Experimental). The NMR features
indicated a triterpene saponin, one of the main constituents of sea
cucumbers [14]. The
C NMR spectrum exhibited 47 carbon
signals, including 30 aglycone carbon signals similar to those of
stichlorogenol [10]. The presence was detected of a trisubstituted
double bond [δ
119.9 (CH, C-7)/δ
5.68 (1H, m, H-7) and 146.9
(C, C-8)], one γ-lactone carbonyl group [δ
180.2 (C, C-18)], seven
methyls [δ
24.6 (CH
, C-19)/δ
1.20 (3H, s, H-19); δ
28.1 (CH
1.82 (3H, s, H-21); δ
23.8 (CH
, C-26)/δ
0.95 (3H, d,
J = 6.5 Hz, H-26); δ
22.1 (CH
, C-27)/δ
0.98 (3H, d, J = 6.5
Hz,H-27); δ
17.6 (CH
, C-28)/δ
1.07 (3H, s, H-28); δ
28.9 (CH
Figure 3: Key ROESY correlations of the aglycone portion of compound 1.
1.33 (3H, s, H-29); δ
31.0 (CH
, C-30)/δ
1.11 (3H, s,
H-30)], two oxymethines [δ
89.1 (CH, C-3)/δ
3.39 (1H, dd, J =
4.0, 11.5 Hz, H-3); δ
65.4 (CH, C-23)/δ
4.00 (1H, m, H-23)], and
an oligosaccharide chain composed of three sugar units (Table 1).
Most sea cucumber triterpene glycosides have a 18(20)-lactone
structure and either a Δ
- or Δ
-double bond in holostane
aglycones [24-25]. Assignment of the NMR data of 1 was further
confirmed by the HMBC analysis. The HMBC cross-peaks between
H-6 (δ
2.02) and C-7 (δ
119.9)/C-8 (δ
146.9) and H-30 (δ
and C-8 (δ
146.9), clearly indicated the position of the double bond
at C-7/C-8. The γ-lactone moiety was assigned at C-18 due to the
obvious HMBC correlations of H-12 (δ
1.95/2.10) and H-17 (δ
2.44) with C-18 (δ
180.2). Detailed analysis of the other HMBC
H COSY peaks (Figure 2) unambiguously determined the
planar structure of the aglycone.
In the ROESY spectrum, the correlation of H-3 (δ
3.39) with H-5
1.08) and that of H-17 (δ
2.44) with H-21 (δ
1.82) and H-30
1.11) suggested an α-orientation for both H-3 and H-17 (Fig. 3).
The S-configuration at C-23 was suggested by the coexistence of
compounds 14 in S. chloronotus, which was further supported by
an agreement of the
C NMR chemical shift at C-23 (δ
65.4) of 1
with that of variegatuside B (from S. variegatus having 23S
configuration) at δ
65.6 (C-23) [26].
In addition, analysis of the NMR spectra of 1 revealed three
anomeric carbon signals at δ
107.3 (C-1), 103.3 (C-1), and 105.3
(C-1), which correlated with corresponding anomeric protons at
4.78 (1H, d, J = 8.0 Hz, H-1), 4.91 (1H, d, J = 8.0 Hz, H-1),
and 5.28 (1H, d, J = 7.5 Hz, H-1) in the HSQC spectrum,
confirming the presence of three sugar moieties. The large coupling
constants of the anomeric protons (J = 7.5 or 8.0 Hz) suggested the
presence of β-glycosidic linkages. The positions of attachment of
the sugar units were determined by HSQC, COSY, HMBC, and
ROESY experiments. Detailed analysis of the correlations in the
COSY spectrum allowed the assignment of proton positions for
all of the sugar moieties (Figure 2) with their configurations
identified by acid hydrolysis of 1 followed by GC-MS analysis.
These NMR data and the HMBC correlations of H-1 (δ
4.78) with
C-3 (δ
89.1), H-1 (δ
4.91) with C-4 (δ
76.8), and H-1
5.28) with C-3 (δ
86.8) clearly indicated the attachments of
the first
D-xylose at C-3, the second D-xylose at C-4, and 3-O-
D-glucose at C-3. Thus, the structure of stichloroside F (1)
was elucidated as 3β,23(S)-dihydroxyholost-7-ene 3-O-[3-O-
Triterpene saponins from the sea cucumber Stichopus chloronotus Natural Product Communications Vol. 9 (5) 2014 617
General: Optical rotations were determined on a JASCO P-2000
polarimeter (Hachioji, Tokyo, Japan). IR spectra were obtained on a
Bruker TENSOR 37 FT-IR spectrometer (Bruker Optics, Ettlingen,
Germany). The high resolution mass spectra were gained using a
Varian 910 FT-ICR mass spectrometer (Varian, CA, USA). The
NMR spectra were recorded on Bruker AM500 (Billerica, MA,
USA) and JEOL ECA 600 (Tokyo, Japan) FT-NMR spectrometers.
TMS was used as an internal standard. GC-MS was carried out on a
Shimadzu-2010 spectrometer: detector, FID; detection temperature,
C; capillary column SPB
-1 (0.25 mm i.d.×30 m); column
temperature, 230
C; carrier gas, He (2 mL/min), injection
temperature, 250
C; injection volume, 0.5 μL. Column
chromatography (CC) was performed on silica gel (Kieselgel 60,
70–230 mesh and 230–400 mesh, Merck, Darmstadt, Germany) and
YMC RP-18 resins (30–50 μm, Fuji Silysia Chemical Ltd., Kasugai,
Aichi, Japan). TLC used pre-coated silica gel 60 F
(1.05554.0001, Merck, Darmstadt, Germany) and RP-18 F
(1.15685.0001, Merck, Darmstadt, Germany), and compounds were
visualized by spraying with aqueous 10% H
and heating for
35 min.
Biological material: The sample of the sea cucumber S. chloronotus
Brandt was collected at Cat Ba, Haiphong, Vietnam, in November
2011, and identified by Professor Do Cong Thung (Institute of
Marine Environment and Resources, VAST). A voucher specimen
(SC-11-2011_01) was deposited at the Institute of Marine
Biochemistry and Institute of Marine Environment and Resources,
VAST, Vietnam.
Extraction and isolation: The fresh body walls of S. chloronotus
(0.6 kg) were cut into small pieces and immersed in hot methanol (3
times for 6 h each) to afford a MeOH extract (10.45 g, A) after
removal of the solvent under reduced pressure. This extract was
partitioned between H
O and n-butanol, 3 times (0.7 L each). The n-
butanol soluble portion (2.42 g, B) was subjected to CC over silica
gel (230400 mesh) eluting with a gradient (dichloromethane
methanol 10:1, 3:1, 1:1, v/v.). Combination of similar fractions on
the basis of TLC analysis afforded 3 fractions (Fr. B1B3). Fraction
B3 (0.45 g) was further separated by reverse-phase silica (75 μm)
MPLC eluting with a H
OH (35–65%) gradient into two
fractions (Fr. B3.1–B3.2). Subfraction B3.2 (0.27 g) was gel-filtered
on Sephadex LH-20 (CH
O, 4.5:1) followed by silica gel CC
O, 1.8:1:0.2) to yield glycosides 2 (34.11 mg,
% of fresh weight) and 4 (27.56 mg, 4.59×10
% of fresh
weight). Subfraction B3.1 (0.18 g) was subjected to silica gel CC
with CH
O (2.5:1:0.15) and further separated by
YMC RP-18 CC using CH
O (3.5:1, v/v) as the eluent to
afford 3 (18.81 mg, 3.13×10
% of fresh weight) and 5 (12.25 mg,
% of fresh weight) as a white solid. Next, fraction B2
(0.62 g) was further subjected to silica gel CC with a CH
O (65:15:2–10:10:2) gradient to obtain 3 subfractions
(Fr. B2.1–B2.3). Subfraction B2.1 (0.33 g) was further separated by
YMC RP-18 CC using acetonewater (2:1, v/v) as eluent to give 6
(15.82 mg, 2.64×10
% of fresh weight). Finally, compound 1
(15.78 mg, 2.63×10
% of fresh weight) was purified as a white
amorphous powder from subfraction B2.2 (0.29 g) following a two-
stage separation beginning with silica gel CC eluting with
O (4:1:0.1, v/v), followed by YMC CC eluting
with MeOHwater (3:1, v/v).
Acid hydrolysis and determination of absolute conguration of
monosaccharides: Compound 1 (3 mg) was heated in 3 mL of 10%
HCldioxane (1:1) at 80
C for 3 h. After the solvent was removed
in vacuo, the residue was partitioned between EtOAc and H
O to
give the aglycone and the sugar, respectively. The sugar
components in the aqueous layer were analyzed by silica gel TLC
by comparison with standard sugars. The solvent system was
O (1.5:1:0.2), and compounds were visualized
by spraying with 95% EtOHH
anisaldehyde (7:0.5:0.5, v/v),
and heating at 180
C for 5 min. The R
values of D-xylose and 3-O-
D-glucose by TLC were 0.30 and 0.65, respectively. The
results were confirmed by GC-MS analysis. The aqueous layer was
evaporated to dryness to give a residue, which was dissolved in
anhydrous pyridine (100 μL), and then mixed with a pyridine
solution of 0.1 M
L-cysteine methyl ester hydrochloride (100 μL).
After warming at 60
C for 2 h, trimethylsilylimidazole solution was
added, and the reaction solution was warmed at 60
C for 2 h. The
mixture was evaporated in vacuo to give a dried product, which was
partitioned between n-hexane and H
O. The n-hexane layer was
filtered and analyzed by GC. The retention times of the persilylated
monosaccharide derivatives were as follows: D-xylose (t
, 5.78),
and 3-O-methyl-
D-glucose (t
, 8.19 min). Their identities were
confirmed by comparison with authentic standards.
Stichloroside F (1)
White amorphous powder
: –18.9 (c 0.26, MeOH);
IR (KBr): ν
3384, 2954, 1762, 1074, 972 cm
FTICR-MS: m/z 935.49804 [M+Na]
(Calcd. for C
H (Pyridine-d
, 500 MHz) and
C NMR (Pyridine-d
, 125 MHz):
Table 1.
Acknowledgment - This study was supported by Vietnam Ministry
of Science and Technology (MOST), The World Academy of
Science (RGA No: 12-066 RG/CHE/AS_G-UNESCO FR:
3240271332), and the Priority Research Center Program through the
National Research Foundation of Korea (NRF) funded by the
Ministry of Education, Science and Technology (2009-0093815),
Republic of Korea. The authors are grateful to the Institute of
Chemistry, VAST for the provision of the spectroscopic instrument.
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Natural Product Communications Vol. 9 (5) 2014
Published online (
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Antioxidant Activity and Phenolic Composition of Corylus colurna
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Glycosylation of Artepillin C with Cultured Plant Cells of Phytolacca americana
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Synthesis of Substituted 1,3-Diesters of Glycerol Using Wittig Chemistry
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Rosa Tundis, Khaled Rashed, Ataa Said, Francesco Menichini and Monica R. Loizzo 691
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Continued inside backcover
... Whereas saponins have been detected in animals, such as sea cucumbers and starfish (Thao et al., 2014), higher plants that belong to the class of dicotyledonous (Dicotyledones) are the richest source of triterpene saponins (saponosides). Triterpene saponins are abundant in Primulaceae, Araliaceae, Caryophyllaceae and Hippocastanaceae. ...
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Triterpene saponins (saponosides) are found in a variety of higher plants and display a wide range of pharmacological activities, including expectorant, anti-inflamatory, vasoprotective, gastroprotective and antimicrobial properties. Recently, a potential anticancer activity of saponins has been suggested by their cytotoxic, cytostatic, pro-apoptotic and anti-invasive effects. At high concentrations (more than 100 µM) saponins exert cytotoxic and haemolytic effects via permeabilization of the cell membranes. Noteworthy, the inhibition of cancer cell proliferation, the induction of apoptosis and attenuation of cell invasiveness is observed in the presence of low saponin concentrations. Saponins might affect the expression of genes associated with malignancy. These alterations are directly related to the invasive phenotype of cancer cells and depend on "cellular context". It illustrates the relationships between the action of saponins, and the momentary genomic/proteomic status of cancer cells. Here, we discuss the hallmarks of anti-cancer activity of saponins with the particular emphasis on anti-invasive effect of diverse groups of saponins that have been investigated in relation to tumor therapy.
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Background: Triterpenoid saponins from sea cucumbers exhibit significant antitumour, antifungal, and antibacterial activities. However, the associated molecular mechanisms have yet to be elucidated. In this study, we screened and explored the antitumour activity and underlying mechanisms of triterpenoid saponins isolated from Thelenota ananas. Methods: We isolated and purified sea cucumber saponins, determined their chemical structures, and confirmed their function in vitro. We also screened and explored the antitumour activity and underlying mechanisms of triterpenoid saponins isolated from Thelenota ananas. Results: Four saponins were discovered from sea cucumber Thelenota ananas collected from the South China Sea. We found that stichloroside C2 (STC2) inhibited the proliferation and clonogenesis of the human triple-negative breast cancer (TNBC) cell line MDA-MB-231 and mouse TNBC cell line 4 T1 in a dose-dependent manner and induced apoptosis and cycle arrest in these two TNBC cell lines. STC2 induced DNA damage in two TNBC cell lines and significantly increased the protein expression level of the DNA double-strand break marker γ-H2AX. STC2 downregulated the protein expression levels of phosphorylated cyclin-dependent kinase 1 (CDK1), cyclin B1, CDK2, and cyclin A2 in MDA-MB-231 and 4 T1 cells. STC2 upregulated Bax and cleaved PARP protein expression in two types of breast cancer cells. In addition, STC2 promoted E-cadherin expression; inhibited vimentin expression; upregulated the phosphorylation levels of the mitogen-activated protein kinase (MAPK) signalling pathway-related proteins p38, JNK, and ERK1/2; and downregulated Akt phosphorylation. Conclusions: STC2 exerts anti-TNBC activity, inhibits epithelial-mesenchymal transition (EMT), and induces apoptosis by regulating the cell cycle, EMT-related proteins, and MAPK signalling pathway.
As reported, cancer stem cells (CSCs) are in charge of dangerous characteristics including drug resistance, metastasis, recurrence and therapeutic effectiveness. Therefore, CSCs are an important target for discovering of novel effective and specific anticancer drugs. In Vietnam, the Stichopus chloronotus sea cucumber is found as a potential biological source with various active ingredients. Particularly, the active triterpene saponin stichoposide D, which was isolated from S. chloronotus, showed strong cytotoxic activity in leukemias. Herein, stichoposide D was further studied its potential anti-CSCs activities on pluripotent human embryonic carcinomas NTERA-2 cells. The compound exhibited its promising and specific cytotoxic activities in NTERA-2 cells with the IC50 = 0.26 ± 0.02 µM, in comparison with that ranging from 0.35 ± 0.02 µM to 0.53 ± 0.03 µM (P<0.05), tested on non-CSCs cancer cell lines, which were breast carcinoma (MCF-7) and lung adenocarcinoma (SK-LU-1), respectively. The working fashion of the compound on NTERA-2 cells could be apoptotic induction. Significantly, treatment of stichoposide D at 1 µM induced 76.4% of apoptotic cells as well as 1.72 relatively fold change of caspase-3 activation in comparision with the control (P<0.05). Meanwhile, stichoposide D was the first time recorgnized its positive efficacy on reducing the number of highly expressed CD44+/CD24+ cells, which were reported as typically CSCs characterized population. The compound also exhibited some effects on NTERA-2 cell cycle of which it arrested cells at sub-G1 phase (15.03%) and prevented those CSCs to enter the S-phase for DNA synthesis. In conclusion, stichoposide D presents potential anti-CSCs activities and should be further studied for future applications.
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Using various chromatographic methods, four new steroids, astropectenols A–D (1–4), along with three known compounds (5–7) were isolated from a methanol extract of the starfish Astropecten polyacanthus. The structure elucidation was confirmed by spectroscopic methods, including one dimensional (1D)-, 2D-NMR and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The CH 2 Cl 2 fraction and compound 7 exhibit potent cytotoxic effects against HL-60 human leukemia cells with the IC 50 of 8.29 µg/mL and 2.70 µM, respectively, comparing to the positive control, mitoxantrone (IC 50 6.80 µM). When HL-60 cells were treated with the CH 2 Cl 2 fraction or compound 7, several apoptosis events like chromatin condensation and the increase of the population of sub-G1 hypodiploid cells were observed. Investigations for the possible mechanism underlying the induction of apoptosis showed that CH 2 Cl 2 fraction or compound 7 induced apo-ptosis through down-regulation of Bcl-2, up-regulation of Bax, cleavage of caspase-9, cleavage of caspase-3 and cleavage of poly(ADP-ribose) polymerase (PARP) in HL-60 cells. Furthermore, the apoptosis induction of HL-60 cell by CH 2 Cl 2 fraction or compound 7 was attended by the decreasing of phospho-extracellular signal-regulated kinase (ERK) 1/2 and C-myc. These results indicated that the CH 2 Cl 2 fraction and compound 7 could induce the apoptosis of HL-60 cells via the inactivation of ERK 1/2 and the decrease of C-myc. Our finding suggested the potential using of the CH 2 Cl 2 fraction and compound 7 for leukemia treatment. Echinoderms represent an outstanding source of polar ster-oids of a great structural diversity, showing various biological activities. Among five living classes of the phylum Echinoder-mata, two classes Asteroidea (starfish) and Ophiuroidea (brittle stars) are especially rich in polar steroids. 1) The research on starfish has expanded rapidly over the past few years, which has been prompted by the discovery of a variety of unique structures and the interest in their pharmacological properties. Starfish have attracted organic chemists, biochemists, and pharmacologists as a fascinating source of bioactive marine natural products, especially steroids and steroidal glycosides. 2)
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Inflammation is important in biomedical research, because it plays a key role in inflammatory diseases including rheumatoid arthritis and other forms of arthritis, diabetes, heart disease, irritable bowel syndrome, Alzheimer's disease, Parkinson's disease, allergies, asthma, and even cancer. In the present study, we describe the inhibitory effect of crude extracts and steroids isolated from the starfish Astropecten polyacanthus on pro-inflammatory cytokine (Interleukin-12 (IL-12) p40, interleukin-6 (IL-6), and tumor necrosis factor α (TNF-α)) production in lipopolysaccharide (LPS)-stimulated bone marrow-derived dendritic cells (BMDCs). Among those tested, compounds 5 and 7 showed potent inhibitory effects on the production of all three pro-inflammatory cytokines with IC 50 values ranging from 1.82 ± 0.11 to 7.00 ± 0.16 μM. Potent inhibitory activities were also observed for compound 1 on the production of IL-12 p40 and IL-6 with values of 3.96 ± 0.12 and 4.07 ± 0.13 μM, respectively, and for compounds 3 and 4 on the OPEN ACCESS Mar. Drugs 2013, 11 2918 production of IL-12 p40 with values of 6.55 ± 0.18 and 5.06 ± 0.16 μM, respectively. Moreover, compounds 2 (IC 50 = 34.86 ± 0.31 μM) and 6 (IC 50 = 79.05 ± 2.05 μM) exhibited moderate inhibitory effects on the production of IL-12 p40, whereas compounds 3 (IC 50 = 22.80 ± 0.21 μM) and 4 (IC 50 = 16.73 ± 0.25 μM) moderately inhibited the production of TNF-α and IL-6, respectively.
Aim: To study the constituents from the sea cucumber Stichopus variegatus Semper. Method: Triterpene glycosides from Stichopus variegatus Semper were separated and purified by silica gel chromatography, reversed-phase silica gel chromatography and reversed-phase HPLC. Their structures were elucidated on the basis of chemical evidence and spectral data. Results: Two new triterpenes were isolated and their chemical structures were established as 3-O-[3-O-methyl-β-D-glucopyranosyl-(1 → 3)-β-D-xylopyranosyl-(1 → 3)-β-D-glucopyranosyl-(1 → 2)-β-D-xylopyranosyl]-holosta-7-ene-3β, 23S-diol; 3-O-[3-O-methyl-β-D-glucopyranosyl-(1 → 3)-β-D-xylopyranosyl-(1 → 3)-β-D-glucopyranosyl-(1 → 2)-β-D-xylopyranosyl]-holosta-8-ene-3β, 23S-diol. Conclusion: The glycosides are both new compounds, which are named variegatuside A and B.
The ethanol extracts of the sea cucumbers Holothuria nobilis, Bohadschia aff. tenuissima and Actinopyga mauritana furnishes three distinct fractions; a mixture of sterol glycosides, a mixture of cerebrosides and a mixture of triterpenoid glycosides identified as holothurin B, bivittosides C and D and echinoside B, respectively, from a comparison of the 1H NMR and 13C NMR spectral data reported earlier. Hydrolysis of triterpenoid glycosides yield three new artificial genins (1, 1a and 2) along with seven known genins (3-9). The structures of these new genins have been determined by their physical and spectral data (UV, [α]D, 1H NMR and mass).
The structures of some secondary metabolites and their distribution in the Phylum Echinoder-mata are described. Gangliosides, quinoid pigments and steryl sulfates in echinoderms are widespread, although these compounds are absent or rare in the majority of other marine invertebrates. There are numerous phylogenetic parallelisms dealing with directions of the biosynthesis of low molecular weight natural products between starfishes and sea cucumbers, sea urchins and ophiuroids, sea lilies and starfishes and so on. They indicate a monophyletic origin of all echinoderms. At the same time such metabolites as triterpene glycosides, some gangliosides, Δ 9(11)-sterols, steroid oligoglycosides are linked to separate groups of these animals. Of particular interest among them as chemotaxonomic characters are triterpene glycosides from sea cucumbers, which have been utilized in a meaningful classification of Holothurioidea. The application of these and other secondary metabolites for taxonomic purposes is possible only by considering the cases of biochemical convergence and by invoking Vavilov’s law of homologous series.
Four new asterosaponins, astrosteriosides A−D (1−3 and 5), and two known compounds, psilasteroside (4) and marthasteroside B (6), were isolated from the MeOH extract of the edible Vietnamese starfish Astropecten monacanthus. Their structures were elucidated by chemical and spectroscopic methods including FTICRMS and 1D and 2D NMR experiments. The effects of the extracts and isolated compounds on pro-inflammatory cytokines were evaluated by measuring the production of IL-12 p40, IL-6, and TNF-α in LPS-stimulated bone marrow-derived dendritic cells. Compounds 1, 5, and 6 exhibited potent anti-inflammatory activity comparable to that of the positive control. Further studies are required to confirm efficacy in vivo and the mechanism of effects. Such potent anti-inflammatory activities render compounds 1, 5, and 6 important materials for further applications including complementary inflammation remedies and/or functional foods and nutraceuticals. S tarfish (called also sea stars) are invertebrates belonging to the class Asteroidea, phylum Echinodermata. Research on starfish is a mature, largely explored area (with more than 30 years of activity) and has continuously expanded as prompted by the discovery of chemical constituents with unique structures and interesting pharmacological properties. 1−3 The secondary metabolites from starfish are characterized by a diversity of polar steroids, including polyhydroxylated steroids and steroid glycosides. Starfish contain two main structural groups of steroid glycosides, namely, asterosaponins and glycosylated polyhydroxysteroids. 1−5 Asterosaponins boast 3,6-dihydroxylation and Δ 9(11) unsaturation of the aglycone with sulfonation at C-3 and a saccharide (usually five or six sugars) attachment at C-6. These compounds have exhibited a variety of biological activities, such as cytotoxic, hemolytic, antimicrobial, and antifouling effects. 1−5
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Chemical structures are reported for six antifungal lanostane-type triterpene-oligoglycosides from the Okinawan sea cucumber Stichopus chloronotus (BRANDT). The compounds are : stichlorosides A1 (9), B1 (15), C1 (20) [having stichlorogenol (3) as the aglycone] and A2 (10), B2 (16), C 2 (21) [dehydrostichlorogenol (4) as the aglycone].
Fucosylated chondroitin sulfate (FuCS) is a glycosaminoglycan from sea cucumber, made up of alternating beta-D-glucuronic acid and N-acetyl-beta-D-galactosamine units. The beta-D-glucuronic acid residues have branches of sulfated fucose, while the fucose branches may have distinguishable patterns and proportions of sulfate substitution. The structure of the sulfated fucose branches of the fucosylated chondroitin sulfate from the sea cucumber Thelenata ananas has been characterized by mild acid hydrolysis and NMR technology. The results showed that the fucose residues are made up of 3-,4-mono-O-sulfated fucose and 2,4-di-O-sulfated fucose with about 25:22:53, respectively. The sulfated fucose branches are essential for the anticoagulant action of FuCS, and this potent effect is possibly related to the occurrence of 2,4-di-O-sulfated fucose units. Furthermore, these branches could constitute the structural requirement for the binding of the glycosaminoglycan to coagulant enzymes, such as thrombin by HCII, factor X by the intrinsic tenase complex. Crown Copyright