Four new sesquiterpenes from Atractylodes lancea

Article abstract of DOI:10.1016/j.phytol.2018.05.023

Four new sesquiterpene compounds, (5R,7R,10S)-3-O-β-D-glucopyranosylisopterocarpolone-11-O-β-D-apiofuranosyl-(1 → 6)-β-D-glucopyranoside (1), (5R,7R,10S)-14-carboxylisopterocarpolone-11-O-β-D-glucopyranoside (2), (1R,7R,10R)-1-hydroxylcarissone-11-O-β-D-g

Full text of DOI:10.1016/j.phytol.2018.05.023

PhytochemistryLetters26(2018)88–92
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Phytochemistry Letters
journal homepage: www.elsevier.com/locate/phytol
Four new sesquiterpenes from Atractylodes lancea
Jian-Shuang Jiang1, Kuo Xu1, Zi-Ming Feng, Ya-Nan Yang, Pei-Cheng Zhang⁎
State Key Laboratory of Bioactive Substance and Function of Natural Medicines, Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union
Medical College, Beijing 100050, People’s Republic of China
A R T I C L E I N F O
A B S T R A C T
Keywords:
Sesquiterpenes
Chemical constituents
Atractylodes lancea
Calculated electronic circular dichroism
Four new sesquiterpene compounds, (5R,7R,10S)-3-O-β-D-glucopyranosylisopterocarpolone-11-O-β-D-apiofur-
anosyl-(1 → 6)-β-D-glucopyranoside (1), (5R,7R,10S)-14-carboxylisopterocarpolone-11-O-β-D-glucopyranoside
(2), (1R,7R,10R)-1-hydroxylcarissone-11-O-β-D-glucopyranoside (3), and (1R,7R,10S)-10,11-dihydroxy-4-
guaien-3-one 11-O-β-D- glucopyranoside (4), were isolated from the Atractylodes lancea by high-performance
liquid chromatography. The compounds’ structures were elucidated through detailed spectroscopic methods.
1. Introduction
m/z 709.3283 [M+H]+. The 1H NMR spectrum (Table 1) showed four
methyl protons at δH 0.83, 1.14, 1.18, and 1.88, three anomeric proton
The rhizomes of Areactylodes lanceae (Compositae) are used as
Chinese folk medicines. It is reported that these rhizomes can remove
dampness, invigorate the spleen, and dispel pathogenic wind and cold
effects (Chinese Pharmacopoeia Commission, 2005). The root of A.
lanceae has shown therapeutic potential for treating such maladies as
rheumatic diseases, digestive disorders, night blindness, and influenza
(Koonrungsesomboon et al., 2014). The plant is mainly distributed in
the provinces of Jiangsu, Hubei and Henan, China. The Maoshan area in
the Jiangsu is the area of the genuine medicinal herb. To date, many
compounds, such as sesquiterpenes and polyacetylenes, have been
isolated from this plant (Meng et al., 2010; Xu et al., 2016a,b; Xu et al.,
2017). In our continuing research, four new sesquiterpenes were ob-
tained from A. lancea. These compounds’ structures were identified as
eudesmane sesquiterpenes (1–3) and guaiane sesquiterpene (4) by de-
tailed spectroscopic means (Fig. 1). In the bioactive assays, compounds
1–4 were evaluated against the inhibitory effect on PTP1 B and α-gly-
cosidase enzyme. All of the compounds exhibited weak α-glycosidase
enzyme inhibition activities and weak PTP1 B inhibition activities.
signals at δH 4.79 (d, J = 3.0 Hz), 4.51 (d, J = 7.5 Hz) and 4.31 (d,
J = 7.5 Hz), which suggested the presence of four methyl and three
sugars in compound 1. Additionally, a series of aliphatic hydrogen
signals at δH 1.00–2.50 were also observed. The 13C NMR spectrum
showed 32 carbon signals (Table 1). According to HSQC, the 13C NMR
spectra displayed 3 sets of sugar carbon signals at δC 109.2, 75.9, 78.6,
73.2, 63.3, δC 103.0, 74.2, 77.0, 69.9, 76.4, 61.0, and δC 96.9, 73.6,
76.9, 70.3, 75.1, 67.9. The three saccharide moieties were assigned to
be β-form (apiose and glucose) by the 13C NMR data and the coupling
constants of the anomeric proton signals. Furthermore, acid hydrolysis
of 1 yielded D-glucose and D-apiose based on the GC analysis, which
suggested that there were two β-D-glucopyrancoses and one β-D-apiose
in compound 1. Except for 17 saccharide moiety carbons, the rest of the
15 carbon signals suggested the existence of sesquiterpene group with
α,β-unsaturated ketone coupling with olefinic carbon signals at δC
144.9 and 150.0 and a carbonyl carbon signal at δC 193.8. Apart from
two unsaturations of α,β-unsaturated ketone fragments and three un-
saturations of the sugar groups, the remaining two unsaturations de-
termined that aglycone was a bicyclic sesquiterpene. Furthermore, the
NMR data of bicyclic sesquiterpene were closely similar to those of
eudesmane aglycone of 3-hydroxylisopterocarpolone-3-O-β-D-gluco-
pyranoside (Xu et al., 2016b), which confirmed that bicyclic sesqui-
terpene of 1 was α,β-unsaturated ketone eudesmane. Thus, compound 1
included a eudesmane aglycone, two β-D-glucopyrancoses, and a β-D-
apiose. In the HMBC spectrum, it was found that the relations of H-1′′′/
C-6′′, H-1′′/C-11, and H-1′/C-3 indicated that the apiose group and two
glucose groups were located at the C-6′′ of glucose, C-11, and C-3 of
2. Results and discussion
Compound 1 was obtained as a white powder, [α]2D0 −5.5° (c 0.09,
MeOH). The IR spectrum of 1 showed the presence of hydroxyl groups
(3401 cm−1), carbonyl groups (1658 cm−1), and an olefinic bond
(1617 cm−1). The UV spectrum showed the maximum absorption at
256 nm, suggesting the existence of the conjugated system. 1 possessed
a molecular formula of C32H52O17 (Ω = 7) on the basis of HR-ESI–MS at
⁎
Corresponding author.
E-mail address: pczhang@imm.ac.cn (P.-C. Zhang).
Both authors contributed equally to this work.
1
https://doi.org/10.1016/j.phytol.2018.05.023
Received 13 March 2018; Received in revised form 4 May 2018; Accepted 11 May 2018
1874-3900/©2018PhytochemicalSocietyofEurope.PublishedbyElsevierLtd.Allrightsreserved.

J.-S. Jiang et al.
PhytochemistryLetters26(2018)88–92
Fig. 1. Structures of compounds 1–4.
Table 1
NMR Data (500 MHz) Spectroscopic Data for Compounds 1−4 in DMSO-d6.
NO.
1
2
3
4
δH
δC
δH
δC
δH
δC
δH
δC
1a
1b
2a
2b
2.35, d (16.0)
2.14, m
53.6
193.8
2.47, d (18.5)
2.38, overlap
53.1
201.2
3.55, dd (5.0, 13.0)
72.7
42.5
2.61, dd (2.0, 6.5)
53.1
36.5
2.45, dd (13.0, 16.0)
2.33, dd (5.0, 13.0)
2.33, dd (2.0, 18.0)
2.19, dd (6.5, 18.0)
3
4
5
6a
6b
7
8a
8b
144.9
150.0
46.2
6.46, d (3.0)
130.7
147.2
41.1
196.9
127.9
163.0
28.2
208.0
135.1
174.9
28.4
2.46, d (12.0)
2.16, m
1.02, m
1.52, m
1.55, m
2.35, dt (3.0,12.5)
1.99, d (12.5)
0.97, d (12.5)
1.44, overlap
1.68, brd (13.0)
1.20, m
23.7
21.3
2.91, overlap
1.89, overlap
1.45, m
1.70, m
1.39, m
3.01, overlap
2.01, t (11.5)
1.74, overlap
1.76, overlap
1.38, m
47.4
21.3
46.4
20.9
47.5
21.6
44.4
22.4
1.25, m
9a
9b
1.45, m
1.33, m
39.0
1.59, brd (12.5)
1.44, overlap
39.4
2.02, d (13.5)
1.15, m
37.6
1.93, dt (4.5, 14.0)
1.64, dt (4.5, 14.0)
37.0
10
11
12
13
14
15
Glc-1′
2′
3′
4′
5′
6′a
6′b
Glc-1′′
2′′
3′′
4′′
5′′
6′′a
6′′b
Api-1′′′
2′′′
3′′′
4′′′a
4′′′b
5′′′
36.5
78.6
22.5
24.8
14.5
16.4
103.0
74.2
77.0
69.9
76.4
61.0
36.5
78.2
23.4
24.1
167.9
16.6
96.9
73.6
77.1
70.4
76.4
61.3
41.1
78.0
22.2
24.7
10.6
16.2
97.1
73.7
77.1
70.4
76.4
61.3
70.5
79.1
21.3
24.3
7.5
31.4
97.0
73.8
77.2
70.4
76.4
61.3
1.14, s
1.18, s
1.88, s
0.83, s
1.13, s
1.13, s
1.18, s
1.20, s
1.67, s
1.05, s
4.31, d (7.5)
2.91, m
3.15, t (8.5)
3.02, t (8.5)
3.05, m
1.14, s
1.16, s
1.59, s
1.15, s
4.32, d (7.5)
2.93, t (8.5)
3.15, t (8.5)
3.02, overlap
3.05, m
0.74, s
4.51, d (7.5)
3.12, overlap
3.16, overlap
3.10, overlap
3.02, overlap
3.61,brd (11.5)
3.43, m
4.31, d (7.5)
2.91, overlap
3.16, overlap
2.95, overlap
3.24, m
4.28, d (7.5)
2.89, t (8.5)
3.14, t (8.5)
3.00, m
3.05, m
3.62, brd (11.0)
3.35, overlap
3.61, brd (11.0)
3.39, m
3.62, brd (11.5)
3.35, dd (5.5, 11.5)
96.9
73.6
76.9
70.3
75.1
67.9
3.80, brd (10.5)
3.36, overlap
4.79, d (3.0)
3.70, d (3.0)
109.2
75.9
78.6
73.2
3.83, d (9.5)
3.57, d (9.5)
3.32, overlap
63.3
89

J.-S. Jiang et al.
PhytochemistryLetters26(2018)88–92
Fig. 2. ROESY correlations of compounds 1–4.
aglycone positions, respectively. Thus, compound 1 was preliminarily
identified as 3-O-β-D-glucopyranosylisopterocarpolone-11-O-β-D-apio-
furanosyl-(1 → 6)-β-D-glucopyranoside.
The stereochemistry of 1 was determined on the basis of its ROESY
and ECD spectra (Figs. 2 and 3). In the ROESY spectrum, the relations of
H-5/H-1a, H-6a, H-7, and H-9b (δH 1.33, m), H3-15/H-1b, H-6b, and H-
9a suggested that the relative configuration of C-5, C-7 and C-10 was
consistent with that of (5R,7R,10S)-3-hydroxylisopterocarpolone-3-O-β-
D-glucopyranoside (Xu et al., 2016b). In the ECD spectrum, 1 exhibited
an identical negative Cotton effect at 322 nm (Δe = −1.74) with
(5R,7R,10S)-3-hydroxylisopterocarpolone-3-O-β-D-glucopyranoside,
explaining the same absolute configurations (Snatzke, 1965;
Gawronski, 1982). Thus, the absolute stereochemistry at the C-5,7,10
positions in 1 were shown to be 5R,7R,10S. Finally, compound 1 was
identified and named (5R,7R,10S)-3-O-β-D-glucopyranosylisopter-
ocarpolone-11-O-β-D-apiofuranosyl-(1 → 6)-β-D-glucopyranoside.
Compound 2 was isolated as a white powder, [α]2D0 −4.6° (c 0.1,
MeOH). The IR spectrum of 2 showed the absorptions attributable to
hydroxyl (3386 cm−1), carbonyl (1716, 1650 cm−1), and an olefinic
bond (1610 cm−1). The molecular formula C21H32O9 (Ω = 6) of
Fig. 3. Experimental and calculated ECD spectra of compounds 1–4.
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J.-S. Jiang et al.
PhytochemistryLetters26(2018)88–92
compound 2 was determined by HR-ESI–MS at m/z 429.2058 [M+H]+
(calcd 429.2125).
which was determined by HR-ESI–MS at m/z 415.2312 [M+H]+ (calcd
415.2332).
The 1H NMR spectrum (Table 1) showed a single olefinic hydrogen
signal at δH 6.46, an anomeric proton signal at δH 4.28, three methyl
protons at δH 1.13 (6H), and 0.74 (3H), and a series of aliphatic hy-
drogen signals at δH 1.00–2.50. The 13C NMR spectrum showed 21
carbon signals (Table 1). Except for β-D-pyranoglucose carbon signals at
δC 96.9, 73.6, 77.1, 70.4, 76.4, and 61.3, the remaining 15 carbon
signals were confirmed as a sesquiterpene skeleton. Additionally, two
olefinic carbon signals at δH 130.7 and 147.2, two conjugated carbonyl
carbon signals at δC 167.9 and 201.2 in the 13C NMR and a series of
aliphatic hydrogen signals at δH 1.00–2.50 in the 1H NMR, were ob-
served. Combining with unsaturation, sesquiterpene groups were con-
cluded to be an α,β-unsaturated ketone fragment sesquiterpene with a
bicyclic structure. Furthermore, the NMR data of bicyclic sesquiterpene
were similar to aglycone of 3-hydroxylisopterocarpolone-3-O-β-D- glu-
copyranoside (Xu et al., 2016b), except for the olefinic hydrogen signals
(H-3). The relations of H-3/COOH (δC 167.9) in HMBC confirmed that
the C-4 position linked with a carboxy group instead of methyl group.
Therefore, bicyclic sesquiterpene was concluded to be eudesmane with
a carboxy group. Additionally, β-D-pyranoglucose was confirmed to be
located at C-11 by the relation of H-1′/C-11 in HMBC. Thus, the planar
structure of 2 was identified as 14-carboxylisopterocarpolone-11-O-β-D-
glucopyranoside.
The 1H and 13C NMR data showed that compound 4 (Table 1)
possessed four methyl protons at δH 1.14, 1.15, 1.16, and 1.59, an
anomeric proton signal at δH 4.32, β-D-pyranoglucose carbon signals at
δC 97.0, 73.8, 77.2, 70.4, 76.4, and 61.3, and a carbonyl group at δC
208.0. Compound 4 also has an α,β-unsaturated ketone sesquiterpene
aglycone according to the above data. Compared with eudesmane ses-
quiterpene of compound 3, the chemical shifts of α,β-unsaturated ke-
tone in 4 moved to the low field. Thus, the α,β-unsaturated ketone was
preliminarily deduced to be located in the structure of cyclopentane,
rather than cyclohexane. According to the reported results, the data of
the sesquiterpene moiety of compound 4 were in agree with those of
11-O-β-D-glucopyranosyl-4-guaien-3-one (Yu et al., 2011), so the ses-
quiterpene structure of compound 4 was confirmed to be a guaiane
sesquiterpene. In addition, OH and glucose were located at C-7 and C-
11 by the correlation signals OH/C-1 and C-9, H-1′/C-11 in the HMBC
spectrum, respectively. Thus, the planar structure of 4 was identified as
10,11-dihydroxy-4-guaien-3-one 11-O-β-D-glucopyranoside.
Similarly, the stereochemistry of 4 was elucidated on its ROESY and
ECD spectra data (Figs. 2 and 3). In the ROESY spectrum, the relations
of H-1/H-7 and H-15, H-7/H-15 suggested that the relative configura-
tions of C-1, C-7 and C-10 were consistent with that of (1S,7R,10R)-
11,15-dihydroxy-4-guaien-3-one 11-O-β-D-glucopyranoside (Xu et al.,
2017). At the same time, compound 4 exhibited similar Cotton effects
in the range of 200 ∼ 400 nm in the ECD spectra, indicating that their
absolute configurations were consistent. Thus, the absolute stereo-
chemistry at the C-1, 7, 10 positions in 4 were shown to be 1R,7R,10S.
Finally, compound 4 was identified and named (1R,7R,10S)-10,11-di-
hydroxy-4-guaien-3-one 11-O-β-D-glucopyranoside.
The stereochemistry of 2 was determined by the same method as
compound 1. Furthermore, 2 displayed a similar negative Cotton effect
at
348 nm
(Δε = −1.03)
with
(5R,7R,10S)-3-hydro-
xylisopterocarpolone-3-O-β-D-glucopyranoside (Xu et al., 2016b), ex-
plaining the same absolute configurations of C-5, C-7 and C-10 in the
ECD spectrum. Consequently, the absolute stereochemistry of 2 was
shown to be 5R,7R,10S. Thus, compound 2 was defined as (5R,7R,10S)-
14-carboxylisopterocarpolone-11-O-β-D-glucopyranoside.
Sesquiterpenes were the main ingredients isolated from A. lanceae,
which primarily existed as types of eudesmane, guaiane and spir-
ovetivane. Compounds 1–3 were eudesmane-type, and 4 was guaiane-
type, as determined by detailed spectroscopic means (NMR, and MS
et al.). The compounds’ absolute configurations were determined by
using experimental ROESY and ECD spectra, as well as chemical
methods. The findings of these compounds add to the diversity of these
ingredients. The bioactive assays showed that compounds 1–4 ex-
hibited weak α-glycosidase enzyme inhibition activities and weak
PTP1 B inhibition activities.
Compound 3 was obtained as a white powder, [α]2D0 +42.1° (c 0.15,
MeOH). The IR spectrum of 3 showed the presence of hydroxyl groups
(3380 cm−1), carbonyl groups (1651 cm−1), and an olefinic bond
(1604 cm−1). The molecular formula was determined to be C21H34O8
(Ω = 6) based on the m/z 415.2311 [M+H]+ in HR-ESI–MS.
Analysis of the 1H and 13C NMR data (Table 1) indicated the pre-
sence of four methyl groups, a carbonyl group, an olefinic bond, and β-
D-pyranoglucose. These groups were similar to those of compounds 1
and 2. The aglycone of 3 was concluded preliminarily to be eudesmane
sesquiterpene and showed an oxymethine (H-1) at δC 72.7 in 13C NMR.
The oxymethine confirmed that the hydroxyl was linked with C-1 by the
correlations of H-15/C-1, and H-2/C-1 in the HMBC spectrum. In ad-
dition, the correlations of H-15/C]C (C-5, δC 163.0) and H-2/C]C (C-
4, δC 127.9) confirmed that the double bond was located at the C-4 and
C-5 positions, and the carbonyl group was assigned to C-3 position by
the correlations of H-2 and H-14/C-3 in the HMBC spectrum. According
to the above conclusions, eudesmane sesquiterpene of 3 was 1-hydroxy-
3-carbonyl-Δ-4,5-eudesmane. Additionally, β-D-pyranoglucose was
confirmed to be located at C-11 by the relation of H-1′/C-11 in HMBC.
Thus, the planar structure of 3 was identified as 1-hydroxylcarissone-
11-O-β-D-glucopyranoside.
3. Materials and methods
3.1. Generals
The specific rotations, UV, and ECD data were individually mea-
sured on JASCO P-2000, JASCO V-650, and JASCO J-815 spectrometers
(JASCO, Easton, MD, U.S.A.). IR spectra were collected by a Nicolet
5700 instrument (Thermo Scientific, Waltham, MA, U.S.A.). NMR
spectra were run on a Bruker 500 Hz spectrometer (Bruker-Biospin,
Billerica, MA, U.S.A.), and chemical shifts were given in δ (ppm) with
DMSO-d6 peaks as the reference. HRESIMS data were collected using an
Agilent 1100 series LC/MSD ESI/TOF instrument (Agilent
Technologies, Waldbronn, Germany). GC analyses were performed on
an Agilent 7890A system. Reversed-phase preparative HPLC (P-HPLC)
was run on a Shimadzu LC-10AT system quipped with an SPD-10A
detector (Shimadzu, Japan). An Agilent 1260 series system equipped
with an Apollo C18 column (250 × 4.6 mm, 5 μm, Grace Davison) was
used for HPLC analyses.
Furthermore, the stereochemistry of 3 was also confirmed by its
ROESY and ECD spectra data (Figs. 2 and 3). In the ROESY spectrum,
the relations of H-7/H-6a, H-15/OH-1 and H-15/H-6b suggested that H-
1 and H-7 were on the same side of the eudesmane ring plane. In the
ECD spectrum, compound 3 exhibited an identical negative Cotton ef-
fect at 317 nm (Δε = −1.43) (Snatzke, 1965; Gawronski, 1982). Thus,
the absolute stereochemistry of 3 was determined to be 1R,7R,10R.
Finally, compound
3 was identified as depicted and named
3.2. Plant material
(1R,7R,10R)-1-hydroxylcarissone-11- O-β-D-glucopyranoside.
Compound 4 was also obtained as a white powder, [α]2D0 −61.2° (c
0.08, MeOH). The IR of 4 showed the presence of hydroxyl groups
(3394 cm−1), carbonyl groups (1680 cm−1), and an olefinic bond
(1630 cm−1). Compound 4 possessed a molecular formula of C21H34O8,
The rhizomes of A. lancea were collected at Huanggang City (Hubei
Province, China) in June 2014 and were identified by Prof. Lin Ma. A
voucher specimen (ID-s-2596) was deposited in the herbarium at the
Department of Medicinal Plants, Institute of Materia Medica, Chinese
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J.-S. Jiang et al.
PhytochemistryLetters26(2018)88–92
Academy of Medical Sciences (Beijing 100050, China).
3.4.2. α-glycosidase enzyme activity assay
A total of 3 mM PNPG (p-Nitrophenyl-alpha-D-glucopyranoside)
(20 μL) and α-glucosidase (20 μL, 1 U/mL in PBS, pH 6.8), PBS (50 μL)
and the sample solution (10 μL) were placed in a 96-well microplate
and pre-cultured for 15 min at 37 °C. 0.4 M Na2CO3 (50 μL) was added
and the mixture was incubated for an additional 35 min. The absor-
bance of each well was measured at 400 nm with a microplate spec-
trophotometer.
3.3. Extraction and isolation
The root of Areactylodis Lanceae (100.0 kg) was exhaustively ex-
tracted with 80% ethanol under reflux conditions. The extracts were
later concentrated under reduced pressure to give a residue (25.6 kg).
The residue was suspended in H2O (50 L) again, and the suspension was
then extracted with petroleum ether, EtOAc and nBuOH. The nBuOH
extracts were evaporated and freeze-dried in vacuum to give a residue
(1.2 kg). The residue was dissolved in H2O (1.5 L) again, then chro-
matographed over a macroporous adsorbent resin (HP-20) column
(120 cm × 15 cm). After eluting with H2O (40 L), the adsorbed con-
stituents were eluted with 15% ethanol, 30% ethanol, 50% ethanol, and
95% ethanol, respectively. The eluting parts were then concentrated
under reduced pressure to give H2O part 824.0 g (A), 15% ethanol part
88.6 g (B), 30% ethanol part 106.4 g (C), 50% ethanol part 53.3 g (D),
95% ethanol part 19.5 g (E) (25.6 kg). The 30% ethanol part (96.4 g)
was chromatographed over reversed-phase preparative medium pres-
sure, eluting with H2O–MeOH (from 100:0 to 0:100) to give 10 frac-
tions. Fr5 part (50 g) was chromatographed over Sephadex LH-20
eluting with H2O to give 20 fractions. Fr5 was further purified by re-
versed-phase preparative HPLC using H2O–CH3OH (65:35, 5 mL/min)
as the mobile phase to yield compound 1 (18.1), 2 (39.0 mg), and 4
(15.7 mg). Fr9 was further purified by reversed-phase preparative HPLC
using H2O–CH3OH (65:5,5 mL/min) as the mobile phase to yield
compound 3 (20.7 mg).
3.5. Acid hydrolysis of compounds
Compound 1 (5 mg) was dissolved in 1 mol/L HCl–dioxane (1:1,
5 mL) and maintained at 60 °C for 6 h. After drying in a vacuum, the
residue was partitioned in H2O (5 mL) and extracted thrice with EtOAc
(5 mL). The aqueous solution was evaporated in vacuum to obtain the
monosaccharide residue. These monosaccharide residues were pro-
cessed using a reported method (Hara et al., 1987; Feng et al., 2013;
Shen et al., 2013). The configurational assignments of apiose and glu-
cose were established by comparing the retention times of their chiral
derivatives with those of standard substances, which were prepared
using the identical procedure (D-apiose 14.56 min, D-glucose
20.56 min). The same procedure was operated on compounds 2, 3 and
4, respectively.
Acknowledgments
The authors thank Professor Lin Ma for the plant identification. The
authors thank Yinghong Wang for processing NMR data. This project
was funded by CAMS Innovation Fund for Medicial Sciences (2016-I2M-
1-010).
(5R,7R,10S)-3-O-β-D-glucopyranosylisopterocarpolone-11-O-β-D-
apiofuranosyl-(1 → 6)-β-D-glucopyranoside (1): white powder powder;
[α]2D0 −5.5 (c 0.09, MeOH);UV (MeOH) λmax (log ε): 256 (3.90) nm; ECD
(MeOH) λmax (Δε): 257 (+2.91), 322 (−1.74) nm; IR(KBr) νmax: 3401,
2927, 2881, 1658, 1617, 1440, 1380, and 1077 cm−1; HR-ESI–MS m/z:
709.3245 [M+H]+ (Calcd. for C32H53O17, 709.3283); 1H NMR (DMSO-
d6, 500 MHz) and 13C NMR (DMSO-d6, 125 MHz) data see Table 1.
(5R,7R,10S)-14-carboxylisopterocarpolone-11-O-β-D-glucopyrano-
side (2): white powder powder; [α]2D0 −4.6 (c 0.10, MeOH);UV (MeOH)
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at https://doi.org/10.1016/j.phytol.2018.05.023.
λ
max (log ε): 239 (3.73) nm; ECD (MeOH) λmax (Δε): 212 (+4.84), 348
References
(−1.03) nm; IR (KBr) νmax: 3386, 2926, 2874, 1716, 1650, 1610,
1453, 1372, 1078, 1039 cm−1; HR-ESI–MS m/z: 429.2058 [M+H]+
Chinese Pharmacopoeia Commission, 2005. Pharmacopoeia of China. Chemical Industry
Press, Beijing, pp. 111.
Feng, Z.M., Song, S., He, J., Yang, Y.N., Jiang, J.S., Zhang, P.C., 2013. Acyl glycosides
with rare β-D-apiofuranosyl-β-D-glucopyranosyl-β-D-apiofuranosyl from Erycibe hai-
nanesis. Carbohydr. Res. 380, 59–63.
(Calcd. for C21H33O9, 429.2125); 1H NMR (DMSO-d6, 500 MHz) and 13
NMR (DMSO-d6, 125 MHz) data see Table 1.
C
(1R,7R,10R)-1-hydroxylcarissone-11-O-β-D-glucopyranoside
(3):
white powder powder; [α]2D0 +42.1 (c 0.15, MeOH);UV (MeOH) λmax
(log ε): 249 (4.03) nm; ECD (MeOH) λmax (Δε): 248 (+9.91), 317
(−1.43) nm; IR (KBr) νmax: 3380, 2973, 2936, 2879, 1651, 1604,
1430, 1370, 1079, 1031 cm−1; HR-ESI–MS m/z: 415.2311 [M+H]+
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clohexenones. Tetrahedron 38, 3–26.
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(Calcd. for C21H33O9, 415.2332); 1H NMR (DMSO-d6, 500 MHz) and 13
NMR (DMSO-d6, 125 MHz) data see Table 1.
C
(1R,7R,10S)-10,11-dihydroxy-4-guaien-3-one
11-O-β-D-glucopyr-
anoside (4): white powder powder; [α]2D0 −61.2 (c 0.08, MeOH); UV
(MeOH) λmax (log ε): 242 (3.99) nm; ECD (MeOH) λmax (Δε): 255
(−0.25), 302 (−0.86) nm; IR (KBr) νmax: 3394, 2972, 2924, 1680,
1630, 1453, 1387, 1080, 1034 cm−1; HR-ESI–MS m/z: 415.2312 [M
+H]+ (Calcd. for C21H33O9, 415.2332); 1H NMR (DMSO-d6, 500 MHz)
and 13C NMR (DMSO-d6, 125 MHz) data see Table 1.
3.4. Biological assay
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eremophilane-type sesquiterpenoids from Atractylodes lancea. Fitoterapia 114,
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3.4.1. PTP1B activity assay
Xu, K., Feng, Z.M., Jiang, J.S., Yang, Y.N., Zhang, P.C., 2017. Sesquiterpenoid and C14-
polyacetylene glycosides from the rhizomes of Atractylodes lancea. Chin. Chem. Lett.
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258–261.
The recombinant human PTP1B protein was amplified by
hGSTPTP1B-BL21 Escherichia coli pellets and purified by a GST beads
column. The dephosphorylation of para-nitrophenyl phosphate (pNPP)
was catalyzed to para-nitrophenol (pNP) by PTP1B. The amount of p-
nitrophenol produced was measured at 405 nm wavelength using
Microplate spectrophotometer (uQuant, Bio-tek, USA).
92