Triterpenoid saponins and anti-inflammatory activity of Codonopsis lanceolata

Article abstract of DOI:10.1691/ph.2007.6.6672

The ethanolic root extract of Codonopsis lanceolata were evaluated for anti-inflammatory activity using the carrageenan induced rat hind paw edema model and displayed a significant activity of 51.82% inhibition at 200 mg/kg at 3 h (p < 0.05). Further isolation of the extract yielded two new triterpenoid saponins, named codonolaside I (1) and codonolaside II (2). The spectroscopic and chemical data revealed their structures to be 3-O-[β-D-xylopyranosyl (1→3)-(6′-O-methyl)-β-D-glucuronopyranosyl]-3β, 16α-dihydroxyolean-12-ene-28-oic acid 28-O-[β-D-xylopyranosyl (1→4)-α-L-rhamnpyranosyl (1→2)-α-L-arabinopyranosyl] ester (1), and 3β, 16α-dihydroxyolean-12-ene-28-oic acid 28-O [β-D-xylopyranosyl (1→3)-β-D-xylopyranosyl (1→4)-α-L- rhamnpyranosyl (1→2)-α-L-arabinopyranosyl] ester (2).

Full text of DOI:10.1691/ph.2007.6.6672

ORIGINAL ARTICLES
School of Pharmacy, Changchun College of Traditional Chinese Medicine, Changchun; School of Traditional Chinese Materia
Medica, Shenyang Pharmaceutical University, Shenyang, People’s Republic of China
Triterpenoid saponins and anti-inflammatory activity of
Codonopsis lanceolata
Jian-Ping Li, Zhi-Min Liang, Zhong Yuan
Received August 9, 2006, accepted September 11, 2006
Dr. Zhong Yuan, Department of Analysis of Traditional Chinese Medicine, School of Traditional Chinese
Materia Medica, Shenyang Pharmaceutical University, Shenyang 110016, People’s Republic of China
yuanzhong@syphu.edu.cn
Pharmazie 62: 463–466 (2007)
doi: 10.1691/ph.2007.6.6672
The ethanolic root extract of Codonopsis lanceolata were evaluated for anti-inflammatory activity using
the carrageenan induced rat hind paw edema model and displayed a significant activity of 51.82%
inhibition at 200 mg/kg at 3 h (p < 0.05). Further isolation of the extract yielded two new triterpenoid
saponins, named codonolaside I (1) and codonolaside II (2). The spectroscopic and chemical data
revealed their structures to be 3-O-[b-d-xylopyranosyl (1!3)-(60-O-methyl)-b-d-glucuronopyranosyl]-3b,
16a-dihydroxyolean-12-ene-28-oic acid 28-O-[b-d-xylopyranosyl (1!4)-a-l-rhamnpyranosyl (1!2)-a-l-
arabinopyranosyl] ester (1), and 3b, 16a-dihydroxyolean-12-ene-28-oic acid 28-O- [b-d-xylopyranosyl
(1!3)-b-d-xylopyranosyl (1!4)-a-l-rhamnpyranosyl (1!2)-a-l-arabinopyranosyl] ester (2).
1. Introduction
column, and eluted gradiently with ethanol-H2O. The 75%
ethanol eluate fraction was subjected to repeated column
chromatography over silica gel, as well as Sephadex LH-20
to afford compounds 1 and 2.
Codonopsis lanceolata (Sieb et Zucc) Bentham et Hooker
(Campanulaceae) is a perennial, twining vine that occurs
in the northeast districts of China. Its roots have been
used as an herbal drug for the treatment of bronchitis,
cough, spasm, and inflammation in China, and as a tonic
crude drug and an edible plant in Korea (Jiangsu New
Medical College 1977). Apart from medicinal folklore
background of C. lanceolata as mentioned above, the dis-
covery of anti-mutagenic effect (Han et al. 2004a) asso-
ciated with inhibition of the micronucleus rate in the bone
marrow cells in mice (Han et al. 2003), inducing caspase-
dependent apoptosis in human acute promyelocytic leuke-
mia HL-60 cells (Lee et al. 2005), hepatoprotective activ-
ity (Han et al. 2004b), and anti-oxidative effect has been
reported (Han et al. 1999). Codonoposide (Lee et al. 2002),
a triterpenoid saponin, was reported as characteristic con-
stituent of C. lanceolata roots and considered to be par-
tially responsible for the therapeutic effects of this crude
drug. However, saponin constituents of C. lanceolata
seemed not to be completely known and thus deserved
further studies. Our current study led to purification of
two new triterpenoid saponins from a saponins-rich frac-
tion of the root ethanol extract. This paper deals with the
structural elucidation of the new triterpenoid saponins on
the basis of chemical and spectral means, especially 1D
and 2D NMR spectroscopy. The anti-inflammatory activ-
ity of the root ethanol extract is also reported.
Compound 1 was isolated as a colorless powder, and had
a molecular formula of C58H92O26 determined from its
negative ion HR-ESI-MS (at m/z 1239.55940 [M þ Cl]ꢀ).
Its IR spectrum indicated the presence of hydroxyl
(3426 cmꢀ1) and ester carbonyl group (1736 cmꢀ1). The
1H NMR spectrum of 1 showed signals for seven tertiary
methyl groups at d 1.80, 1.27, 1.14, 1.05, 1.00, 0.95 and
0.82 (each s), and a trisubstituted olefinic proton at d 5.59
(brs), which were characteristics of the olean-12-ene skele-
ton. Furthermore, five anomeric proton signals were iden-
tified at d 6.49 (brs), 5.69 (brs), 5.22 (d, J ¼ 7.6 Hz), 5.18
(d, J ¼ 7.3 Hz), and 4.98 (d, J ¼ 7.8 Hz). The 13C NMR
spectrum of 1 showed the presence of 58 carbon atoms in
the molecule, 30 carbon signals were due to the triterpe-
noid aglycone, a carbon signal at d 52.08 was observed
for a methoxyl group, the remaining 27 carbon signals,
including five anomeric carbon resonating at d 107.32,
106.23, 106.08, 101.03, and 93.47, were seen for the su-
gar moieties, indicating the presence of two hexose and
three pentose units. Evaluation of spin-spin couplings and
1
chemical shifts with the aid of H––1H COSY and NOESY
experiments allowed the identification of one b-glucurono-
pyranosyl, one a-arabinopyranosyl, one a-rhamnopyrano-
syl and two b-xylopyranosyl units (Corea et al. 2004).
Comparison of the 13C NMR data of the aglycone moiety
of 1 with those of echinocystic acid (Zhang et al. 1999)
showed that the signals for C-3 (d 89.20) and C-28 (d
175.98) were significantly shifted owing to glycosidation.
These were confirmed by the fact that the acid hydrolysis
of 1 with 1 M HCl gave a triterpene (1a) which was iden-
tified as echinocystic acid by 13C NMR data (Zhang et al.
2. Investigations, results and discussion
A concentrated root ethanol extract of Codonopsis lanceo-
lata was suspended in water and defatted with petroleum
ether, then extracted with EtOAc. The remaining aqueous
solution was passed through a HPD-100 absorbent resin
Pharmazie 62 (2007) 6
463

ORIGINAL ARTICLES
1999) and co-TLC with authentic sample, and the sugar
moieties were shown to be glucuronic acid, xylose, rham-
nose, and arabinose on TLC analysis. Alkaline hydrolysis
of 1 furnished a prosapogenin (1b), identified as 3-O-b-d-
glucuronopyranosyl echinocystic acid from its spectral
data (Lee et al. 2002, 2005).
O
C
O
OH
O
COOCH3
OH
OH
O
GluA
O
The sugar chain attached at C-3 of the aglycone was es-
tablished from the HMBC correlations: the anomeric pro-
ton signal at d 5.22 (Xyl-I) and C-3 of glucuronosyl at d
87.11, the anomeric proton signal at d 4.98 (GluA) and
C-3 of the aglycone at d 89.20. In addition, the HMBC
correlation between the methoxyl protons at d 3.72 and
C-6 of the glucuronosyl at d 170.90 indicated that the
glucuronosyl moiety is a 6-methoxyl-derivative. The char-
acteristic signals for the anomeric proton (d 6.49) and car-
bon (d 93.47) of the arabinosyl unit suggested that the
arabinosyl should be directly attached to C-28 of the agly-
cone through an ester bond, which was confirmed by
HMBC correlation of the anomeric proton at d 6.49 (Ara)
with C-28 of the aglycone at d 175.98. Furthermore, the
HMBC correlations between the anomeric proton signal at
d 5.17 (Xyl-II) and C-4 of rhamnosyl at d 83.40, the
anomeric proton signal at d 5.69 (Rha) and C-2 of arabi-
nosyl at d 75.35 suggested the sugar sequence and linkage
position of sugar chain attached at C-28 shown in Fig.1.
Based on extensive analysis of its 2DNMR spectra
O
Ara
Xyl-I
OH
OH
O
O
O
O
OH
OH
O
CH3
OH
OH
OH
Rha
OH
OH
OH
Xyl-II
codonoposide I
O
C
OH
O
OH
O
HO
OH
Ara
O
O
Xyl-I
O
O
CH3
O
Rha
Xyl-II
O
OH
1
(1H––1H COSY, NOESY, HSQC, and HMBC), the H and
OH
OH
OH
OH
OH
13C NMR data for 1 were summarized in Table 1, which
were found to be similar to those reported for codonopo-
side (Lee et al. 2002), However, 1 was characterized by
the presence of a 6-methoxyl glucuronosyl unit instead of a
glucuronosyl moiety. Besides, the terminal xylosyl (Xyl-II)
OH
codonoposide II
Fig.: Structures of codonoposide I (1) and II (2) and selected HMBC cor-
relations
1
Table 1: 1H and 13C NMR data of codonoposide I (1) in pyridine-d5
Position
dH
dC
Position
dH
dC
Aglycone
1
2
3
4
5
6
7
8
Sugar at C-3
GluA 1
2
3
4
5
6
––OMe
Xyl-I 1
2
3
4
5
Sugar at C-28
Ara 1
2
3
4
5
Rha 1
2
3
4
5
6
1.45, 0.89 t (8.0)
2.14, 1.85
3.36 dd-like
38.79
4.98 d (7.8)
4.08
4.03
4.04
4.60 d (9.7)
107.32
75.46
87.11
69.06
77.24
170.90
52.08
106.08
74.96
78.23
70.97
67.36
26.67
89.20
39.56
55.91
18.55
33.49
40.06
47.19
37.02
23.84
122.85
144.46
42.10
36.02
74.11
49.59
41.29
47.19
30.98
36.20
32.19
28.21
17.00
15.68
17.61
27.23
175.98
33.33
24.82
0.79 t (12.1)
1.45
1.59 t (11.1), 1.43
3.72 s
5.22 d (7.6)
4.02
4.13
4.16
9
1.74 t (8.4)
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
1.89
5.59 brs
4.27, 3.67 t (10.5)
6.49 brs
4.52
4.52
93.47
75.35
75.27
69.53
62.78
101.03
71.87
72.73
83.40
68.55
18.41
106.23
73.24
77.94
70.97
66.87
2.42, 1.80
5.26 brs
4.54
3.58
4.53, 3.95
5.69 brs
4.51
4.55
4.36
2.77 t (13.3), 1.35
2.30, 1.30
2.30, 2.19
1.27 s
0.95 s
0.82 s
4.37
1.70 d (4.3)
5.18 d (7.3)
4.47
4.26
4.16
Xyl-II 1
1.05 s
1.80 s
2
3
4
5
1.00 s
1.14 s
4.17, 3.42
1
J values (in Hz) in parentheses
464
Pharmazie 62 (2007) 6

ORIGINAL ARTICLES
was assigned to attach to C-4 of the middle rhamnosyl
carbons resonated at d 93.49, 101.19, 106.08, and 106.26
respectively, indicated the presence of one a-arabinopyra-
nosyl, one a-rhamnopyranosyl and two b-xylopyranosyl
units. Furthermore, in the 13C NMR spectrum of 2, the C-3
and C-28 carbon signals were observed at d 78.14, and d
175.96 suggesting that no sugar linkage was formed at the
C-3 hydroxyl group and that a tetrasaccharide was attached
to the C-28 carboxyl group of the aglycone through an
ester bond. The acid hydrolysis of 2 with 1 M HCl af-
forded sugars, which were identified as xylose, rhamnose,
and arabinose by co-TLC with authentic samples.
The sugar chain attached at C-28 of the aglycone was
established as shown in Fig. 1 from the HMBC correla-
tions: the anomeric proton signal at d 5.25 (Xyl-II) and C-3
of xylosyl (Xyl-I) at d 87.11, the anomeric proton signal
at d 5.20 (Xyl-I) and C-4 of rhamnosyl at d 83.44, the
anomeric proton signal at d 5.73 (Rha) and C-2 of arabi-
nosyl at d 75.35, the anomeric proton at d 6.53 (Ara) and
C-28 of the aglycone at d 175.96. Thus, the structure of 3
rather than C-3 of the rhamnosyl, since both the anomeric
proton signal at d 5.17 (Xyl-II) and the secondary methyl
signal at d 1.70 (Rha) showed the long-range correlations
with C-4 of rhamnosyl at d 83.40 in the HMBC spectra.
Accordingly, 1 was concluded to be 3-O-[b-d-xylopyranosyl
(1!3)-(60-O-methyl)-b-d-glucuronopyranosyl]-3b, 16a-di-
hydroxyolean-12-ene-28-oic acid 28-O-[b-d-xylopyranosyl
(1!4)-a-l-rhamnpyranosyl (1!2)-a-l-arabinopyranosyl]
ester, and named codonolaside I.
Compound 2 was obtained as a colorless powder. Its nega-
tive ion HR-ESI-MS showed a quasi-molecular ion peak
at m/z 1013.53130 [M––H]ꢀ), corresponding to a formula
1
of C51H82O20. A comparison of the H and 13C NMR data
of 2 (Table 2) with those of codonolaside I (1) showed
1
that they share the same aglycone. In addition, the H and
13C NMR data of the sugar moiety, including four anome-
ric proton signals at d 6.53 (brs), 5.73 (brs), 5.25 (d, J ¼
7.6 Hz), and 5.20 (d, J ¼ 7.0 Hz) correlated with anomeric
1
Table 2: 1H and 13C NMR data of codonoposide II (2) in pyridine-d5
Position
dH
dC
Position
dH
dC
Aglycone
1
2
3
4
5
6
7
8
Sugar at C-28
Ara 1
2
3
4
5
1.61, 1.05
1.83
3.47
39.13
6.53 brs
4.56
4.56
4.57
4.56,
3.98 dd (3.9, 10.5)
5.73 brs
4.55
4.59
4.40
93.49
28.18
78.14
39.42
55.96
18.88
33.58
40.09
47.31
37.43
23.90
122.89
144.49
42.13
36.00
74.11
49.61
41.32
47.16
30.96
36.21
32.17
28.80
16.60
15.79
17.65
27.21
175.96
33.29
24.80
75.35
75.30
69.60
62.83
0.90 d (11.9)
1.58, 1.43
1.65, 1.47
Rha 1
2
3
4
5
6
Xyl-I 1
2
3
4
101.19
71.87
72.73
83.44
68.55
18.41
106.26
75.35
87.11
69.05
66.86
106.08
74.96
78.22
70.96
67.35
9
1.81
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
1.99
5.66 brs
4.41
1.75 d (4.7)
5.20 d (7.0)
4.04
4.05
4.06
4.21, 3.46
5.25 d (7.6)
4.04
4.16
4.18
2.44, 1.83
5.29 brs
5
3.61
Xyl-II 1
2.80 t (13.6), 1.41
2
3
4
5
2.35, 1.33
2.35, 2.22
1.23 s
1.05 s
0.95 s
4.30 dd (4.5, 11.1),
3.68 t (10.4)
1.13 s
1.81 s
1.02 s
1.17 s
1
J values (in Hz) in parentheses
Table 3: Effects of the roots ethanol extract of Codonopsis lanceolata (REE) and acetylsalicylic acid (ASA) on carrageenan-
induced rat paw edema1
Treatment
Dose mg/kg
Diameter (in mm) at each measure time (h)
1.0
2.0
3.0
4.0
Control (normal saline)
REE
1.78 ꢁ 0.08
2.16 ꢁ 0.07
2.47 ꢁ 0.04
2.85 ꢁ 0.06
50
100
200
100
1.76 ꢁ 0.11 (1.12)
1.43 ꢁ 0.07 (19.66)
1.41 ꢁ 0.02 (20.79)
1.08 ꢁ 0.02 (39.33)
1.79 ꢁ 0.08 (17.13)
1.40 ꢁ 0.06 (35.19)
1.32 ꢁ 0.03 (38.89)
0.79 ꢁ 0.33 (63.43)
1.53 ꢁ 0.09 (38.06)
1.39 ꢁ 0.06 (43.72)
1.19 ꢁ 0.11 (51.82)
0.52 ꢁ 0.07 (78.95)
1.98 ꢁ 0.08 (30.53)
1.70 ꢁ 0.04 (40.35)
1.53 ꢁ 0.10 (46.32)
0.82 ꢁ 0.08 (71.23)
*
**
*
**
**
ASA
1
Each value represents the mean ꢁ S.E.M. of six observations; percentage inhibitions in parentheses are indicated as %
*
**
indicates significant activity compared to control (P < 0.05)
indicates significant activity compared to control (P < 0.01)
Pharmazie 62 (2007) 6
465

ORIGINAL ARTICLES
3.5.2. Codonolaside II (2)
was established as 3b,16a-dihydroxyolean-28-oic acid 28-
O-[b-d-xylopyranosyl (1!3)-b-d-xylopyranosyl (1!4)-
a-l-rhamnpyranosyl (1!2)-a-l-arabinopyranosyl] ester,
named codonolaside II.
Colorless amorphous solid, [a]2D0 ꢀ 33.3ꢂ (C, 0.300, MeOH). IR (nmax
,
cmꢀ1): 3428 (OH), 2926, 1733 (C¼O), 1633, 1384, 1043, 618. Positive
ion ESI-MS m/z: 1037 [M þ Na]þ, 471; negative ion ESI-MS m/z: 1013
[M––H]ꢀ. Negative ion HR-ESI-MS m/z: 1013.53130 [M––H]ꢀ (calcd for
C51H81O20 1013.53207). 1H NMR (600 MHz, pyridine-d5) and 13C NMR
(150 MHz, pyridine-d5) d: see Table 2.
The anti-inflammatory effect of the ethanolic root extract
of Codonopsis lanceolata was evaluated using the carra-
geenan induced hind paw edema of healthy adult albino
rats. The oral pre-treatment with 100 mg/kg of the extract
gave a mild activity (Table 3). It exhibited a significant
(p < 0.05, n ¼ 6) anti-inflammatory activity with the high-
est percentage of inhibition of 51.82% at 200 mg/kg dose
level at 3 h, while the reference acetylsalicylic acid (ASA)
exhibited an activity of 78.95% inhibition at 100 mg/kg
dose level at 3 h. The low yields of codonolaside I and II
did not permit their biological evaluation in the animal
model employed in the present study. According to the
literature (Navarro et al. 2001), some oleanane-type triter-
penoid saponins have shown anti-inflammatory activity in
vivo, so further chemical and pharmacological studies are
necessary for the correlation between the isolated saponins
and the traditional use of Codonopsis lanceolata in the
treatment of inflammatory-based diseases.
3.6. Acid hydrolysis of 1 and 2
Compound 1 (15 mg) in 3 mL of 1 M HCl (MeOH : H2O, v : v ¼ 2 : 8) was
refluxed at 100ꢂ for 6 h, and then neutralized with NH4OH. The solution
was extracted with EtOAc (1 mL ꢃ 2). The EtOAc and water layer were
evaporated in vacuo. The EtOAc layer contained the aglycone (1a) and the
water layer contained sugars. The aglycone (1a) was identified as echino-
cystic acid through comparison with its reported spectral data (Zhang et al.
1999) and by co-TLC (CHCl3––MeOH, v : v ¼ 12 : 1). Glucuronic acid, xy-
lose, rhamnose, and arabinose in the water layer were revealed by co-TLC
(EtOAc : MeOH : H2O : AcOH, v : v ¼ 15 : 5 : 3 : 3). By the same method,
compound 2 was acid-hydrolyzed and yielded xylose, rhamnose, and arabi-
nose from the water layer.
3.7. Alkaline hydrolysis of 1
Compound 1 (15 mg) in 3 mL of 1 M NaOH (MeOH : H2O, v : v ¼ 2 : 8)
was refluxed at 90ꢂ for 1.5 h, and then neutralized with 1 M HCl. The
solution was extracted with EtOAc (1 mL ꢃ 2). The EtOAc layer was eva-
porated in vacuo and afforded a prosapogenin (1b), which was identified
as 3-O-b-d-glucuronopyranosyl echinocystic acid through comparison with
its reported spectral data (Lee et al. 2002, 2005).
3. Experimental
3.8. Anti-inflammatory activity evaluation
3.1. Equipment
The carrageenan-induced rat hind paw edema was used as a model of
acute inflammation (Mascolo et al. 1997). Animals were divided into
groups of six each and pretreated as follows: control group (physiological
saline solution, 0.9%, 10 ml/kg, p.o.), acetylsalicylic acid (ASA) group
(100 mg/kg, p.o.), the roots ethanol extract of Codonopsis lanceolata
(REE) group I (200 mg/kg, p.o.), REE group II (100 mg/kg, p.o.), and
REE group III (50 mg/kg, p.o.). Sixty minutes after treatment, 1 ml of
0.1% (w/v) carrageenan (Sigma products) suspension in normal saline was
injected into the right hind paw of each rat. The linear diameter of the
injected paw was measured using a micrometer screw gauge for 4 h at
60 min interval after the administration of the phlogistic agent. The percen-
tage inhibition of the inflammation was calculated from Eq. (1)
Optical rotations were obtained on a Perkin-Elmer 241MC polarimeter. IR
spectra were recorded in KBr discs using a Bruker IFS-55 spectrometer.
NMR spectra were recorded on a Bruker ARX-600 (600 MHz) instrument
with TMS as internal standard. ESI-MS were obtained on an Angilent
LCQ mass spectrometer. For column chromatography, HPD-100 absorbent
resin (Cangzhou Bon Chemical Co. Ltd, China), silica gel (200–300 mesh,
Marine Chemical Industry Factory, Qingdao, China), ODS C18 (75 mm,
YMC Co. Ltd, Japan), Sephadex LH-20 (Merck, German) were employed
in the separations. TLC was performed with silica gel G (Marine Chemical
Industry Factory, Qingdao, China), and developed by spraying with 10%
ethanolic H2SO4 reagent followed by heating.
% Inhibition ¼ D0 ꢀ Dt=D0 ꢃ 100
ð1Þ
3.2. Plant material
where D0 is the average linear diameter of the injected paw of the control
group rats at a given time; and Dt is the average linear diameter of the
injected paw of the drug (i.e. REE or reference ASA) treated rats at the
same time (Moody et al. 2006).
The roots of Codonopsis lanceolata were collected in Liaoyang, Liaon-
ing province, China, on May 2004. The plant material was identified by
Professor Wei-Chun Wu of Shenyang Phamaceutical University, She-
nyang, China. A voucher specimen (NO. 20041007) is preserved in
School of Traditional Chinese Materia Medica, Shenyang Pharmaceutical
University.
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3.3. Animals
Animals used in this study were male Wistar rats with a weight of 150–
180 g. Animals were allowed free access to food and water, except for the
day of experiment.
3.4. Extraction and isolation
The dried underground parts (5.0 kg) of C. lanceolata were extracted twice
with hot 70% ethanol. After concentration in vacuo, the ethanol extract
(REE, 834 g) was suspended in water, and defatted with petroleum ether,
then extracted with EtOAc. The remaining aqueous solution was passed
through a HPD-100 absorbent resin column, and eluted gradiently with
ethanol-H2O. The 75% ethanol eluate fraction, in which triterpenoid sapo-
nins were enriched, was subjected to column chromatography over silica
gel, eluting gradiently with CHCl3––MeOH. The fraction eluted by
CHCl3––MeOH (85 : 15) contained 1 and 2, and was repeatedly chromato-
graphed over Sephadex LH-20, as well as octadecylsilanized (ODS) silica
gel, to yield compounds 1 (70 mg), compounds 2 (30 mg).
Lee KT, Choi J, Jun WT, Nam JH, Jung HJ, Park HJ (2002) Structure of a
new echinocystic acid bisdesmoside isolated from Codonopsis lanceolata
roots and the cytotoxic activity of prosapogenins. J Agric Food Chem
50: 4190–4193.
Navarro P, Giner RM, Recio MC, Manez S, Cerda-Nicolas M, Rios JL
(2001) In vivo anti-inflammatory activity of saponins from Bupleurum
rotundifolium. Life Sci 68: 1199–1206.
Zhang Z, Koike K, Jia Z, Nikaido T, Guo D, Zheng J (1999) Triterpenoidal
saponins acylated with two monoterpenic acids from Gleditsia sinensis.
Chem Pharm Bull 47: 388–393.
3.5. Compounds isolated
3.5.1. Codonolaside I (1)
Colorless amorphous solid, [a]2D0 ꢀ 62.0ꢂ (C, 0.685, MeOH). IR (nmax, cmꢀ1
)
3426 (OH), 2925, 1736 (ester carbonyl), 1630, 1385, 1211, 1043, 616.
Positive ion ESI-MS m/z: 1227 [M þ Na]þ, 1095 [M þ Na-xylose]þ; nega-
tive ion ESI-MS m/z: 1240 [M þ Cl]ꢀ, 471. Negative ion HR-ESI-MS m/z:
1239.55940 [M þ Cl]ꢀ (calcd for C58H92O26Cl 1239.55648). 1H NMR
(600 MHz, TMS, pyridine-d5) and 13C NMR (150 MHz, pyridine-d5) d:
see Table 1.
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