Anti-breast cancer triterpenoid saponins from the thorns of Gleditsia sinensis

Article abstract of DOI:10.1080/14786419.2018.1443092

One new triterpenoid saponin (1), as well as six known ones (2–7), were isolated from the ethanol extract of the thorns of Gleditsia sinensis. Their structures were elucidated by extensive spectroscopic analysis in conjunction with chemical evidence. Cytotoxic activity of compounds 1–6 was evaluated against human breast cancer MCF 7 cells in vitro by the MTT method. Our results revealed moderate activities for compounds 1–6 with IC₅₀ values of 18.43, 30.47, 18.46, 10.02, 30.76, and 17.32?μM, respectively. Furthermore, compounds 1, 3, 4, and 6 induced apoptosis in MCF 7 cell, with 1 and 6 causing late apoptosis of MCF 7 cells, while 3 and 4 acting oppositely.

Full text of DOI:10.1080/14786419.2018.1443092

Natural Product Research
Formerly Natural Product Letters
ISSN: 1478-6419 (Print) 1478-6427 (Online) Journal homepage: http://www.tandfonline.com/loi/gnpl20
Anti-breast cancer triterpenoid saponins from the
thorns of Gleditsia sinensis
Jinqian Yu, Gang Li, Yan Mu, Honglei Zhou, Xiao Wang & Peng Yang
To cite this article: Jinqian Yu, Gang Li, Yan Mu, Honglei Zhou, Xiao Wang & Peng Yang (2018):
Anti-breast cancer triterpenoid saponins from the thorns of Gleditsia sinensis, Natural Product
Research, DOI: 10.1080/14786419.2018.1443092
To link to this article: https://doi.org/10.1080/14786419.2018.1443092
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Natural Product research, 2018
ꢁꢁpꢂ://ꢃꢄi.ꢄꢅg/10.1080/14786419.2018.1443092
ꢀ
Anti-breast cancer triterpenoid saponins from the thorns of
Gleditsia sinensis
Jinqian Yu , Gang Li , Yan Mu , Honglei Zhou , Xiao Wang and Peng Yangc
a
b
a
b
a,b
ꢆ
sꢀꢆnꢃꢄng Kꢇy lꢆbꢄꢅꢆꢁꢄꢅy ꢄf tcM Qꢈꢆꢉiꢁy cꢄnꢁꢅꢄꢉ tꢇꢊꢀnꢄꢉꢄgy, sꢀꢆnꢃꢄng anꢆꢉyꢂiꢂ ꢆnꢃ tꢇꢂꢁ cꢇnꢁꢇꢅ, Qiꢉꢈ
b
univꢇꢅꢂiꢁy ꢄf tꢇꢊꢀnꢄꢉꢄgy (sꢀꢆnꢃꢄng aꢊꢆꢃꢇmy ꢄf sꢊiꢇnꢊꢇꢂ), Jinꢆn, P.r. cꢀinꢆ; cꢄꢉꢉꢇgꢇ ꢄf Pꢀꢆꢅmꢆꢊy, sꢀꢆnꢃꢄng
univꢇꢅꢂiꢁy ꢄf tꢅꢆꢃiꢁiꢄnꢆꢉ cꢀinꢇꢂꢇ Mꢇꢃiꢊinꢇ, Jinꢆn, P.r. cꢀinꢆ; sꢇnkꢆng sꢆnfꢇng Biꢄꢉꢄgiꢊꢆꢉ enginꢇꢇꢅing
ꢊ
tꢇꢊꢀnꢄꢉꢄgy cꢄ. lꢁꢃ., Jinꢆn, P.r. cꢀinꢆ
ABSTRACT
ARTICLE HISTORY
One new triterpenoid saponin (1), as well as six known ones (2–7),
were isolated from the ethanol extract of the thorns of Gleditsia
sinensis. Their structures were elucidated by extensive spectroscopic
analysis in conjunction with chemical evidence. Cytotoxic activity of
compounds 1–6 was evaluated against human breast cancer MCF
rꢇꢊꢇivꢇꢃ 9 Nꢄvꢇmbꢇꢅ 2017
aꢊꢊꢇpꢁꢇꢃ 13 Fꢇbꢅꢈꢆꢅy 2018
KEYWORDS
Gleditsia sinensis; ꢁꢅiꢁꢇꢅpꢇnꢄiꢃ
ꢂꢆpꢄnin; ꢊyꢁꢄꢁꢄxiꢊ ꢆꢊꢁiviꢁy;
ꢆpꢄpꢁꢄꢂiꢂ
7
cells in vitro by the MTT method. Our results revealed moderate
activities for compounds 1–6 with IC values of 18.43, 30.47, 18.46,
5
0
1
3
0.02, 30.76, and 17.32 μM, respectively. Furthermore, compounds 1,
, 4, and 6 induced apoptosis in MCF 7 cell, with 1 and 6 causing late
apoptosis of MCF 7 cells, while 3 and 4 acting oppositely.
1
. Introduction
Gleditsia sinensis Lam. is a deciduous arbor from the Fabaceae family, which is widely culti-
vated in China, such as the Shandong, Hebei and Jiangsu provinces. Its thorns, known as
‘Zao Jiao Ci ’, are traditional Oriental medicine as an efficacious therapeutic agent for the
CONTACT Jinqiꢆn Yꢈ
yꢈjinqiꢆn87528@126.ꢊꢄm, yꢈjq@ꢂꢃꢆꢂ.ꢄꢅg; Xiꢆꢄ Wꢆng
wꢆngx@ꢂꢃꢆꢂ.ꢄꢅg
sꢈppꢉꢇmꢇnꢁꢆꢉ ꢃꢆꢁꢆ fꢄꢅ ꢁꢀiꢂ ꢆꢅꢁiꢊꢉꢇ ꢊꢆn bꢇ ꢆꢊꢊꢇꢂꢂꢇꢃ ꢆꢁ ꢀꢁꢁpꢂ://ꢃꢄi.ꢄꢅg/10.1080/14786419.2018.1443092
©
2018 Infꢄꢅmꢆ uK limiꢁꢇꢃ, ꢁꢅꢆꢃing ꢆꢂ tꢆyꢉꢄꢅ & Fꢅꢆnꢊiꢂ Gꢅꢄꢈp

2
J. YU ET AL.
treatment of carbuncle, cancers, skin diseases and suppuration (Lee et al. 2013). In previous
studies of G. sinensis, several classes of compounds were obtained, including triterpenoid
saponins from the fruit (Zhong et al. 2004; Melek et al. 2014; Liu et al. 2016), flavonoids (Zhou
et al. 2007a; Yu et al. 2017), ellagic acid glycosides and ferulic acid esters from the thorns
(
Zhou et al. 2007b; Yu et al. 2015). On the basis of the significant cytotoxicity of the ethanol
extract of the thorns of G. sinensis against human breast cancer MCF 7 cells by our earlier
phytochemical investigation, a search for novel anti-cancer metabolites were investigated
and led to the isolation of one new triterpenoid saponin (1) and six known ones (2–7) for
the first time from the thorns of G. sinensis (Figure 1), as well as the in vitro evaluation of their
cytotoxic activities against MCF 7 tumor cells by the MTT method. Compounds 1–6 showed
potential anticancer activity with IC values of 18.43, 30.47, 18.46, 10.02, 30.76, and 17.32 μM,
50
respectively. Furthermore, the apoptotic activities of compounds 1, 3, 4, and 6 were evalu-
ated on MCF 7 cells, with 1 and 6 causing late apoptosis of MCF 7 cells, while 3 and 4 acting
oppositely.
Figure 1. sꢁꢅꢈꢊꢁꢈꢅꢇꢂ ꢄf ꢊꢄmpꢄꢈnꢃꢂ 1–7.

NATURAL PRODUCT RESEARCH
3
2
. Results and discussion
Compound 1 was isolated as a white amorphous powder and gave positive Libermann–
Burchard reaction, indicating its triterpenoid nature. Its molecular formula was determined
+
to be C H126O37 by the molecular ion peak [M + Na] at m/z 1689.7851 detected in the
7
9
positive HRESIMS analysis (calcd. for C H O Na, 1689.7876), and indicative of 17 unsatu-
7
9
126 37
ration degrees. The IR spectrum of 1 exhibited characteristic absorptions of hydroxy group
−
1
−1
(
(
1
3411 cm ), ester carbonyl group (1709 cm ), and conjugated ester carbonyl group
−1
13
1651 cm ). The C NMR spectrum of 1 exhibited 79 carbon signals assignable to 10 methyls,
8 methylenes including one terminal double bond at δ 111.12 (MT-C-8), 40 methines
C
including 34 oxygen-connected methines, three non oxygen-connected methines and three
olefinic methines at δ 122.24 (C-12), 143.02 (MT-C-3) and 144.54 (MT-C-7), and 11 quaternary
C
carbons including two ester carbonyl groups at δ 175.57 (C-28) and 168.08 (MT-C-1), and
C
two olefinic carbons at 143.10 (C-13) and 127.02 (MT-C-2), with 30 signals being assigned as
aglycone, 39 as the oligosaccharide moiety of three hexoses, one methylpentose and three
pentoses, and the remaining 10 signals as a monoterpenic acid. The oligosaccharide moiety
of 1 contained seven anomeric proton signals at δ 4.31 (1H, d, J = 6.0 Hz, Glc-H-1), 4.39 (1H,
H
d, J = 7.8 Hz, Gal-H-1), 4.42 (1H, d, J = 7.2 Hz, Xyl-H-1), 4.52 (2H, overlapped, Ara-H-1, Xyl′-H-1),
5.36 (1H, d, J = 7.8 Hz, Glc′-H-1), and 5.69 (1H, d, J = 1.2 Hz, Rha-H-1), as well as their corre-
sponding carbon signals at δ 105.13 (Glc-1), 101.89 (Ara-1), 105.22 (Xyl-1), 93.02 (Glc′-1),
C
99.05 (Rha-1), 105.08 (Xyl′-1), and 105.87 (Gal-1), respectively, as shown in the HSQC spec-
trum. The chemical shift of δ 88.54 (C-3) and 175.57 (C-28) indicated that 1 was a bisdes-
C
mosidic glycoside (Zhang et al. 1999a). Comparison of the NMR spectroscopic data of
compound 1 with those of 3 (Zhang et al. 1999b) verified them to be almost consistent with
each other, except for the sugar chain linked at C-28. Acid hydrolysis of 1 afforded -xyloses,
d
l-arabinose, d-glucoses, d-galactose, and l-rhamnose as sugar components by GC analysis.
The trisaccharide chain linked at C-3 was unequivocally established by HMBC correlations
from δ 4.42 (Xyl-H-1) to δ 79.91 (Ara-C-2), δ 4.52 (Ara-H-1) to δ 68.13 (Glc-C-6), δ 4.31
H
C
H
C
H
(
Glc-H-1) to δ 88.54 (C-3); similarly, the tetrasaccharide chain attached to C-28 was also
C
based on the HMBC correlations from δ 4.52 (Xyl′-H-1) to δ 82.03 (Rha-C-4), δ 4.39 (Gal-
H
C
H
H-1) to δ 80.55 (Rha-C-2), δ 5.69 (Rha-H-1) to δ 75.52 (Glc′-C-2), δ 5.36 (Glc′-H-1) to δ
C
H
C
H
C
175.57 (C-28). Additionally, the monoterpenic acid in 1 was indicated the same as that in 3,
as well as the attachment position, which was substantiated by HMBC correlations of δ 3.47
H
(
Glc′-H-6α) with 168.08 (MT-C-1). Therefore, the structure of 1 was elucidated as 3-O-β-d-
xylopyranosyl-(1→2)-α-l-arabinopyranosyl-(1→6)-β-d-glucopyranosyl echinocystic acid
8-O-β-d-xylopyranosyl-(1→4)-[β-d-galactopyranosyl-(1→2)]-α-l-rhamnopyranosyl-(1→2)-
(6S,2E)-6-hydroxy-2,6-dimethyl-2,7-octadienoyl-(1→6)]-β-d-glucopyranosyl ester, named
2
[
glespinoside A.
The known compounds, gleditsioside A (2) (Zhang et al. 1999b), gleditsioside D (3) (Zhang
et al. 1999b), gleditsioside F (4) (Zhang et al. 1999a), gleditsioside G (5) (Zhang et al. 1999a),
caspicaoside G (6) (Melek et al. 2014), and caspicaoside I (7) (Melek et al. 2014), were identified
by comparison with NMR data in the literature. This study presents the isolation of these
triterpenoid saponins from the thorns of G. sinensis for the first time, while some known
saponins have previously been repoted from the fruit of G. sinensis. This could lead to a
conclusion that the thorns of G. sinensis contain triterpenoid saponins, thus tending to inter-
link with the fruit.

4
J. YU ET AL.
To evaluate the cytotoxic activity of the isolated compounds (1–6), a MTT method was
applied to test their in vitro growth inhibition against human breast cancer MCF 7 cells with
cisplatin as positive control (IC value of 5.24 μM). Compounds 1–6 showed moderate activ-
50
ity with IC50 values of 18.43, 30.47, 18.46, 10.02, 30.76, and 17.32 μM, respectively, which
provided some support for the application of the thorns of G. sinensis in some Chinese
medicine prescriptions to treat breast cancer. Flow cytometry analysis was used to determine
cell apoptosis induction of compounds 1, 3, 4, and 6, with IC50 values less than 20 μM.
Measured results indicated that 1 and 6 mainly caused late apoptosis of MCF 7 cells, while
3
and 4 acting oppositely (Figure 2).
3
. Experimental
3
.1. General experimental procedures
The instruments used for IR, NMR, ESI-MS, HRESI-MS, and preparative HPLC experiments
were the same as those in our previous study (Yu et al. 2017). Silica gel (200–300 mesh,
Qingdao Haiyang Chemical Co. Ltd., China), D-101 resin (16–60 mesh, Bochum Tianjin Resin
Figure 2. cꢄmpꢄꢈnꢃꢂ 1, 3, 4 ꢆnꢃ 6 ꢊꢆꢈꢂꢇꢃ ꢆpꢄpꢁꢄꢂiꢂ ꢄf McF-7 ꢊꢇꢉꢉꢂ). 1, 3 ꢆnꢃ 6 ꢆꢁ 6.25 μM ꢊꢆꢈꢂꢇꢃ ꢇꢆꢅꢉy
ꢆpꢄpꢁꢄꢂiꢂ ꢄf 10.4, 38.2, ꢆnꢃ 1.9%, ꢅꢇꢂpꢇꢊꢁivꢇꢉy, ꢆnꢃ ꢉꢆꢁꢇ ꢆpꢄpꢁꢄꢂiꢂ ꢄf 24.2, 5.4, ꢆnꢃ 2.0%, ꢅꢇꢂpꢇꢊꢁivꢇꢉy;
ꢆꢁ 12.5 μM ꢊꢆꢈꢂꢇꢃ ꢇꢆꢅꢉy ꢆpꢄpꢁꢄꢂiꢂ ꢄf 8.0, 38.4 ꢆnꢃ 23.7%, ꢅꢇꢂpꢇꢊꢁivꢇꢉy, ꢆnꢃ ꢉꢆꢁꢇ ꢆpꢄpꢁꢄꢂiꢂ ꢄf 24.8, 4.6,
ꢆnꢃ 32.3%, ꢅꢇꢂpꢇꢊꢁivꢇꢉy; ꢆꢁ 25 μM ꢊꢆꢈꢂꢇꢃ ꢇꢆꢅꢉy ꢆpꢄpꢁꢄꢂiꢂ ꢄf 3.7, 37.8 ꢆnꢃ 21.3%, ꢅꢇꢂpꢇꢊꢁivꢇꢉy, ꢆnꢃ ꢉꢆꢁꢇ
ꢆpꢄpꢁꢄꢂiꢂ ꢄf 38.5, 7.5, ꢆnꢃ 44.7%, ꢅꢇꢂpꢇꢊꢁivꢇꢉy; ꢆꢁ 50 μM ꢊꢆꢈꢂꢇꢃ ꢇꢆꢅꢉy ꢆpꢄpꢁꢄꢂiꢂ ꢄf 4.5, 51.5 ꢆnꢃ 16.8%,
ꢅꢇꢂpꢇꢊꢁivꢇꢉy, ꢆnꢃ ꢉꢆꢁꢇ ꢆpꢄpꢁꢄꢂiꢂ ꢄf 57.4, 79.7, ꢆnꢃ 57.0%, ꢅꢇꢂpꢇꢊꢁivꢇꢉy; wꢀiꢉꢇ, ꢆꢁ ꢊꢄnꢊꢇnꢁꢅꢆꢁiꢄnꢂ ꢄf 1.0,
5.0, 10 ꢆnꢃ 15 μM, 4 ꢊꢆꢈꢂꢇꢃ ꢇꢆꢅꢉy ꢆpꢄpꢁꢄꢂiꢂ ꢄf 35.9, 43.0, 44.8, ꢆnꢃ 53.4%, ꢅꢇꢂpꢇꢊꢁivꢇꢉy, ꢆꢂ wꢇꢉꢉ ꢆꢂ ꢉꢆꢁꢇ
ꢆpꢄpꢁꢄꢂiꢂ ꢄf 7.5, 7.9, 9.7, ꢆnꢃ 25.5%, ꢅꢇꢂpꢇꢊꢁivꢇꢉy.

NATURAL PRODUCT RESEARCH
5
Technology Co. Ltd., China), and ODS (45 μm, YMC Co. Ltd., Japan) were used for Flash column
chromatography (CC). Acetonitrile used in preparative HPLC was in HPLC grade, and other
solvents were of analytical grade.
3
.2. Plant material
The origin of the thorns of G. sinensis was the same as that reported in our previous study
(
Yu et al. 2017).
−1
White amorphous powder. IR (KBr) νmax: 3411, 2932, 1709, 1651, 1281, 1043 cm ; ESI-MS
+
(
[
positive-ion mode): m/z 1689.5 [M + Na] ; HRESI-MS (positive-ion mode): m/z 1689.7851
+
1
M + Na] (calcd for C H O Na, 1689.7870). H NMR (CD OD, 600 MHz) δ (ppm) aglycon:
7
9
126 37
3
H
H-1α (1.58), H-1β (1.04), H-2α (1.82), H-2β (1.61), H-3 (3.26), H-5 (0.75), H-6α (1.53), H-6β (1.33),
H-7α (1.69), H-7β (1.39), H-9 (1.59), H2–11 (1.82), H-12 (5.27, br s), H-15α (1.60), H-15β (1.40),
H-16 (4.44, t, J = 4.2 Hz), H-18 (2.85), H-19α (2.27), H-19β (1.01), H-21α (1.88), H-21β (1.12),
H-22α (1.81), H-22β (1.74), Me-23 (1.03, s), Me-24 (0.82, s), Me-25 (0.90, s), Me-26 (0.70, s),
Me-27 (1.35, s), Me-29 (0.84, s), Me-30 (0.92, s); sugar moiety: Glc-H-1 (4.31, d, J = 6.0 Hz),
Glc-H-2 (3.30), Glc-H-3 (3.31), Glc-H-4 (3.54), Glc-H-5 (3.42), Glc-H-6α (3.70), Glc-H-6β (3.99),
Ara-H-1 (4.52, overlapped), Ara-H-2 (3.67), Ara-H-3 (3.68), Ara-H-4 (3.19), Ara-H-5α (4.16),
Ara-H-5β (4.29), Xyl-H-1 (4.42, d, J = 7.2 Hz), Xyl-H-2 (3.27), Xyl-H-3 (3.48), Xyl-H-4 (3.45), Xyl-
H-5α (3.90), Xyl-H-5β (3.16), Glc′-H-1 (5.36, d, J = 7.8 Hz), Glc′-H-2 (3.50), Glc′-H-3 (3.51),
Glc′-H-4, 5 (3.27, overlapped), Glc′-H-6α (3.47), Glc′-H-6β (3.84), Rha-H-1 (5.69, d, J = 1.2 Hz),
Rha-H-2 (3.99), Rha-H-3 (3.89), Rha-H-4 (3.51), Rha-H-5 (3.67), Rha-H3–6 (1.27, d, J = 7.8 Hz),
Gal-H-1 (4.39, d, J = 7.8 Hz), Gal-H-2 (4.43), Gal-H-3 (3.47), Gal-H-4 (3.80), Gal-H-5 (3.45), Gal-
H-6α (3.69), Gal-H-6β (3.83), Xyl′-H-1 (4.52, overlapped), Xyl′-H-2 (3.73), Xyl′-H-3 (3.29), Xyl′-H-4
(
(
3.77), Xyl′-H-5α (3.91), Xyl′-H-5β (3.17), MT-H-3 (6.77, t, J = 7.8 Hz), MT-H2–4 (2.23), MT-H2–5
1.60), MT-H-7 (5.88, dd, J = 10.8, 17.4 Hz), MT-H-8a (5.05, dd, J = 1.8, 10.8 Hz), MT-H-8b (5.21,
1
3
dd, J = 1.8, 17.4 Hz), MT-H3–9 (1.79, s), MT-H3–10 (1.26, s). C NMR (CD OD, 150 MHz) δ (ppm)
3
C
aglycon: C-1 (38.50), C-2 (25.85), C-3 (88.54), C-4 (38.84), C-5 (55.66), C-6 (17.99), C-7 (32.84),
C-8 (39.39), C-9 (46.47), C-10 (36.47), C-11 (23.16), C-12 (122.24), C-13 (143.10), C-14 (41.20),
C-15 (34.97), C-16 (73.31), C-17 (48.58), C-18 (40.32), C-19 (46.68), C-20 (29.92), C-21 (34.97),
C-22 (30.68), C-23 (27.07), C-24 (15.67), C-25 (14.86), C-26 (16.49), C-27 (25.85), C-28 (175.57),
C-29 (31.97), C-30 (23.82); sugar moiety: Glc-C-1 (105.13), Glc-C-2 (74.29), Glc-C-3 (76.73),
Glc-C-4 (71.44), Glc-C-5 (74.56), Glc-C-6 (68.13), Ara-C-1 (101.89), Ara-C-2 (79.91), Ara-C-3
(
71.72), Ara-C-4 (67.08), Ara-C-5 (63.10), Xyl-C-1 (105.22), Xyl-C-2 (74.21), Xyl-C-3 (76.10), Xyl-
C-4 (69.64), Xyl-C-5 (65.81), Glc′-C-1 (93.02), Glc′-C-2 (75.52), Glc′-C-3 (77.75), Glc′-C-4 (70.16),
Glc′-C-5 (73.37), Glc′-C-6 (64.01), Rha-C-1 (99.05), Rha-C-2 (80.55), Rha-C-3 (70.38), Rha-C-4
(
82.03), Rha-C-5 (67.43), Rha-C-6 (17.09), Gal-C-1 (105.87), Gal-C-2 (72.19), Gal-C-3 (73.42),
Gal-C-4 (68.93), Gal-C-5 (75.22), Gal-C-6 (61.32), Xyl′-C-1 (105.08), Xyl′-C-2 (72.19), Xyl′-C-3
76.62), Xyl′-C-4 (69.61), Xyl′-C-5 (65.81), MT-C-1 (168.08), MT-C-2 (127.02), MT-C-3 (143.02),
MT-C-4 (23.12), MT-C-5 (40.78), MT-C-6 (70.69), MT-C-7 (144.54), MT-C-8 (111.12), MT-C-9
11.09), MT-C-10 (26.46).
(
(
4
. Conclusion
The phytochemical investigation of the active ethanol extract from the thorns of G. sinensis
resulted in the isolation of seven triterpenoid saponins (1–7), one of which is new (1). Six

6
J. YU ET AL.
compounds (1–6) showed potential cytotoxic activity against MCF 7 cells, while only 1, 3,
, and 6 showed moderate cytotoxicities with IC50 values less than 20 μM. Obviously, an
4
additional hydroxyl group with α-configuration at C-16 is favorable for the cytotoxic activity.
Additionally, compounds 1, 3, 4, and 6 induced apoptotic cell death in MCF 7 cells, with 1
and 6 causing late apoptosis, while 3 and 4 acting oppositely. Collectively, the results warrant
further preclinical investigations of these saponins with α-OH at C-16 as potential novel
anticancer agents.
Supplementary material
The extraction and isolation experiments, acid hydrolysis experiments, cytotoxicity assay and the orig-
inal spectra of HR-ESI-MS, NMR data of compound 1 are available as Supporting Information, as well
1
13
as the H and C NMR data of 2–7.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This work was supported by grants from Shandong Provincial Natural Science Foundation, China
[grant number BS2015YY035], [grant number ZR2016YL006] and The Priority Research Program of
the Shandong Academy of Sciences [grant number Lanping Guo].
References
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Liu C, Sun H, Wang WT, Zhang JB, Cheng AW, Guo X, Sun JY. 2016. A new triterpenoid saponin from
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