New benzophenone and quercetin galloyl glycosides from Psidium guajava L.

Article abstract of DOI:10.1007/s11418-010-0400-2

New benzophenone and flavonol galloyl glycosides were isolated from an 80% MeOH extract of Psidium guajava L. (Myrtaceae) together with five known quercetin glycosides. The structures of the novel glycosides were elucidated to be 2,4,6-trihydroxybenzophenone 4-O-(6′-O-galloyl)-β-D- glucopyranoside (1, guavinoside A), 2,4,6-trihydroxy-3,5-dimethylbenzophenone 4-O-(6′-Ogalloyl)-β-D-glucopyranoside (2, guavinoside B), and quercetin 3-O-(5′-O-galloyl)-a-L-arabinofuranoside (3, guavinoside C) by NMR, MS, UV, and IR spectroscopies. Isolated phenolic glycosides showed significant inhibitory activities against histamine release from rat peritoneal mast cells, and nitric oxide production from a murine macrophage- like cell line, RAW 264.7. The Author(s) 2010.

Full text of DOI:10.1007/s11418-010-0400-2

J Nat Med (2010) 64:252–256
DOI 10.1007/s11418-010-0400-2
ORIGINAL PAPER
New benzophenone and quercetin galloyl glycosides
from Psidium guajava L.
Keiichi Matsuzaki
Susumu Kitanaka
•
Rie Ishii
•
Kaori Kobiyama
•
Received: 28 October 2009 / Accepted: 15 January 2010 / Published online: 31 March 2010
Ó The Author(s) 2010. This article is published with open access at Springerlink.com
Abstract New benzophenone and flavonol galloyl gly-
cosides were isolated from an 80% MeOH extract of
Psidium guajava L. (Myrtaceae) together with five known
quercetin glycosides. The structures of the novel glycosides
were elucidated to be 2,4,6-trihydroxybenzophenone 4-O-
studies of this plant have led to the isolation of tannins
[1, 2], tannins and other phenolic compounds [3], flavonol
glycosides [4, 5], triterpenoids [6], terpenoids [7], and
carotenoids [8]. It is well known that an extract of the
leaves of P. guajava improves symptoms of allergic dis-
ease, and we are interested in small molecules from the
leaves of P. guajava, other than tannins, and their potential
anti-inflammatory activities.
00
(
6 -O-galloyl)-b-D-glucopyranoside (1, guavinoside A),
00
,4,6-trihydroxy-3,5-dimethylbenzophenone 4-O-(6 -O-
2
galloyl)-b-D-glucopyranoside (2, guavinoside B), and
00
quercetin 3-O-(5 -O-galloyl)-a-L-arabinofuranoside (3,
guavinoside C) by NMR, MS, UV, and IR spectroscopies.
Isolated phenolic glycosides showed significant inhibitory
activities against histamine release from rat peritoneal mast
cells, and nitric oxide production from a murine macro-
phage-like cell line, RAW 264.7.
In this investigation, two new benzophenone galloyl
glycosides, guavinosides A (1) and B (2), and a quercetin
galloyl glycoside, guavinoside C (3), were isolated from
the leaves of P. guajava together with known quercetin
glycosides (4–8). These structures of the novel glycosides
were established through detailed analysis of their spec-
troscopic data and chemical evidence, and their inhibitory
activities against histamine release from rat mast cells and
nitric oxide (NO) from RAW 264.7 were also determined.
Keywords Psidium guajava L. ꢀ Benzophenone
galloyl glycoside ꢀ Flavonol galloyl glycoside
Introduction
Results and discussion
Psidium guajava (Myrtaceae) is a small medicinal tree that
is native to South America. All parts of this tree, including
fruits, leaves, bark, and roots, have been used for treating
stomachache and diarrhea in many countries. Previous
Guavinoside A (1) was obtained as a yellow powder. The
positive ion mode FAB-MS of 1 showed a quasimolecular
?
ion peak at m/z 545 [M ? H] , and the molecular formula
was determined to be C H O based on its high-reso-
26 24 13
lution (HR)-FAB-MS (found 545.8418, calcd. 545.8413 for
C H O ). In the IR spectrum, the strong absorbance at
2
6 25 13
-
,700 cm indicated the presence of conjugated carbonyl
1
1
K. Matsuzaki ꢀ K. Kobiyama ꢀ S. Kitanaka (&)
Research Unit of Pharmacognosy, College of Pharmacy,
Nihon University, 7-7-1 Narashinodai, Funabashi,
Chiba 274-8555, Japan
groups in 1. Acid hydrolysis of 1 furnished D-glucose
which was identical with HPLC analysis, using an optical
1
rotation (OR) detector. In the H-NMR spectrum of 1, two
e-mail: kitanaka.susumu@nihon-u.ac.jp
aromatic signals at dH 6.11 (2H, s) and 6.98, (2H, s)
indicated the presence of two 1,3,4,5-tetrasubstituted
phenyl groups, and the spin system of dH 7.68 (2H, dd,
J = 7.0, 1.0 Hz), 7.46 (2H, t, J = 7.0 Hz), and 7.57 (1H, t,
R. Ishii
Saitama Institute of Public Health, Kami-Ohkubo,
Saitama 338-0824, Japan
1
23

J Nat Med (2010) 64:252–256
253
J = 7.0 Hz) showed the presence of a phenyl group.
Additionally, an anomeric proton signal at d 4.86 (1H, d,
at d 6.11 (2H, s, 3, 5-H) correlated with C-4 (d 159.8)
H
C
4
and the carbonyl carbon by weak J correlation. Further-
more, the anomeric proton signal correlated with C-4. NOE
enhancement was observed between the anomeric proton
signal and the signal of 3, 5-H. These data suggested that
the aglycone of 1 was 2,4,6-trihydroxybenzophenone, and
H
J = 7.6 Hz) indicated that the glucose residue was in the
1
1
b-form. Correlations in the H– H-COSY spectrum were
observed from the anomeric proton to dH 3.15 (1H, m),
3
.20 (1H, m), 3.50 (1H, m), 3.30 (1H, m), and 4.39 (2H, br
0
0
s) indicating the presence of b-glucose. The signal pattern
in the aromatic region of the C-NMR spectrum indicated
a sugar was attached at C-4. The signal of 6 -H, however,
1
3
was downfield shifted at d 4.39 (2H, br s), and correlated
H
1
the presence of three aromatic rings. In addition, the C-
3
with the galloyl carbonyl carbon signal at d 165.7 in the
C
NMR and DEPT spectra showed an anomeric carbon (dC
HMBC experiment. From these data, the structure of 1 was
0
0
1
00.5), four oxymethines (d 73.0, 76.1, 68.9, and 73.6), an
established to be 2,4,6-dihydroxybenzophenone 4-O-(6 -
O-galloyl)-b-D-glucopyranoside (Figs. 1, 2).
C
oxymethylene (dC 62.5), and two carbonyl carbons (dC
65.7 and 195.3). All proton–carbon connectivities
assigned by using HMQC experiments are summarized in
1
Guavinoside B (2) was obtained as a brownish solid.
The negative ion mode FAB-MS of 2 showed quasimo-
-
lecular ion peak at m/z 571 [M - H] , and the molecular
0
00
000
Table 1. The HMBC correlations from 2 , 6 -H (d 6.98,
H
000
0
00
000
000
2
H, s) to C-1 (d 119.2), C-3 , 5 (d 145.4), C-4 (dC
formula was determined to be C H O based on its HR-
28 28 13
C
C
1
38.4), and a carbonyl carbon (dC 165.7) revealed the
FAB-MS (found 571.1474, calcd. 571.1451 for
presence of a galloyl moiety. A phenyl proton signal at d
C H O ). The molecular weight was 28 mass units
28 27 13
H
0
0
1
13
7
.68 (2H, dd, J = 7.0, 1.0 Hz, 2 , 6 -H) correlated with a
carbonyl carbon signal at d 195.3, and an aromatic proton
(C H ) greater than that of 1. The H- and C-NMR
2 4
spectra of 2 were very similar to those of 1 except for
C
13
1
Table 1 C- and H-NMR spectral data of guavinosides A (1) and B (2)
1
2
d
C
d
H
d
C
d
H
Aglycone
1
108.9 s
157.3 s
94.9 d
113.0 s
151.8 s
110.8 s
155.6 s
138.7 s
128.6 d
128.1 d
132.3 d
196.7s
9.9 q
2
3
4
1
2
3
4
, 6
, 5
6.11 (2H, s)
159.8 s
138.4 s
128.7 d
128.2 d
132.5 d
195.3 s
0
0
0
0
, 6
7.68 (2H, dd, J = 7.0, 1.0 Hz)
7.46 (2H, t, J = 7.0 Hz)
7.57 (1H, t, J = 7.0 Hz)
7.65 (2H, dd, J = 7.0, 1.0 Hz)
7.45 (2H, t, J = 7.0 Hz)
7.54 (1H, t, J = 7.0 Hz)
0
, 5
0
C=O
3
, 5-CH
3
2.00 (6H, s)
Glucosyl
0
0
0
0
0
0
0
0
0
0
0
0
1
2
3
4
5
6
100.5 d
73.0 d
76.1 d
68.9 d
73.6 d
62.5 t
4.86 (1H, d, J = 7.6 Hz)
3.15 (1H, m)
104.2 d
74.2 d
76.1 d
69.3 d
73.5 d
62.7 t
4.63 (1H, d, J = 8.5 Hz)
3.36 (1H, m)
3.20 (1H, m)
3.30 (1H, m)
3.50 (1H, m)
3.44 (1H, m)
3.30 (1H, m)
3.42 (1H, m)
4.39 (2H, br s)
4.23 (1H, d, J = 11.0, 3.0 Hz)
4
.32 (1H, d, J = 11.0 Hz)
Galloyl
0
0
0
0
00
00
00
00
1
2
3
4
119.2 s
108.6 d
145.4 s
138.4 s
165.7 s
13
119.6 s
108.5 d
145.3 s
138.3 s
165.6 s
000
000
, 6
, 5
6.98 (2H, s)
6.96 (2H, s)
C=O
1
6
H-NMR (600 MHz) and C-NMR (150 MHz) spectra were measured in DMSO-d with TMS as internal standard
123

2
54
J Nat Med (2010) 64:252–256
OH
(
1H, d, J = 2.2 Hz), d 6.85 (1H, d, J = 8.8 Hz), and dH
H
3
´
OH
2
´
4´
5´
7
.49 (1H, dd, J = 8.8, 2.2 Hz) indicated the presence of a
8
1´
HO
O
O
0
0
13
O
7
6
9
2
3
6´
3 ,4 -dihydroxy B ring system in flavonol. In the C-NMR
spectrum, significant flavonol signals at dC 157.3 (C-2),
133.0 (C-3), and 177.4 (C-4) were observed. In the HMBC
R
10
2
´˝
6˝
4˝
HO
5
˝
O
O
R
3
OH
O
5´
2´
5
4
O
3
´˝
´˝
1´˝
6´˝ HO
HO
O
2˝
1
˝
4
5
2
1
6´
1´
4´
3´
1˝
4
OH
HO
2˝
OH
3
˝
OH
O
HO
5˝´
6
3˝
OH
0
OH
HO
HO
3˝´
4˝
experiment, the correlations from 2 -H to C-2, d 144.9 (C-
C
OH
5˝
4
˝´
˝´
2˝´
1˝´
0 0 0 0
0
5
3 ), 148.3 (C-4 ), and 121.3 (C-6 ), from 6 -H to C-2, C-4
0
O
6
˝´
7˝´
0
0
0
and d 115.6 (C-2 ), and from 5 -H to C-3 , C-4 , and d
O
C
C
0
1
2
R = H
R = CH3
120.8 (C-1 ) were observed. From these data, the aglycone
3
of 3 was determined to be quercetin. In addition, an aro-
matic methine (d 6.89, 2H, s) correlated with d 118.9 (C-
Fig. 1 Structures of guavinosides A (1), B (2), and C (3)
H
000
C
0
00
000
000
000
000
1
), 108.5 (C-2 , 6 ), 145.3 (C-3 , 5 ), 138.4 (C-4 ),
and 165.4 (carbonyl), indicating the presence of a galloyl
moiety the same as 1 and 2. Acid hydrolysis of 3 with 2 M
HCl afforded (?)-L-arabinose that was identical by HPLC
analysis using OR detector comparison to an authentic
sample of L-arabinose. The small coupling constant of the
anomeric proton (dH 5.56, d, J = 1.4 Hz) indicated the
presence of the a-form of arabinose. Correlations in the
O
HO
HO
4
J
O
O
O
OH
O
HO
HO
HO
NOE
OH
OH
O
NOE
O
HO
HO
O
O
HO
HO
OH
O
1
1
HO
H– H COSY spectrum were observed for a spin system
from the anomeric signal to three oxymethine signals at d
OH
OH
H
0
0
00
00
4
.18 (br s, 2 -H), 3.81 (m, 3 -H), and 3.74 (m, 4 -H), and
00
Fig. 2 Key HMBC and NOE correlations of guavinosides A (1) and
B (2)
methylene signals (d 4.11 and 4.02, 5 -H ) was observed.
H
2
Furthermore, two hydroxy signals at d 5.72 (br s) and 5.48
H
00 00
(
br s) both coupled with 2 -H and 3 -H, respectively.
0
0
absence of the aromatic methine signal [dH 6.11 (s); dC
Additionally, the signals of 5 -H of 3 were shifted
2
9
4.9] in 1, and a new aryl methyl signal [d 2.00 (6H, s);
downfield compared with those of 4 (dH 3.36 and 3.32),
and correlated with a galloyl carbonyl carbon signal in the
HMBC experiment. From these observations, the sugar
moiety was determined to be L-a-arabinofuranose. Thus,
the structure of 3 was determined to be quercetin 3-O-(5 -
O-galloyl)-a-L-arabinofuranoside.
H
d 9.9] and a quaternary carbon (d 110.8) were observed.
C
C
1
3
In the C-NMR spectrum, the appearance of a high-field
region shifted methyl signal suggested that the methyl is
linked to a benzene ring in the ortho-position and attached
via an oxygen atom [9]. HMBC correlations were observed
0
0
from the methyl proton signal to d 110.8 (C-3, 5), 151.8
The structures of 4–8 were elucidated to be quercetin 3-
O-a-L-arabinofuranoside (4), quercetin 3-O-a-L-arabino-
pyranoside (5), quercetin 3-O-b-D-xylopyranoside (6),
quercetin 3-O-b-D-galactopyranoside (7), and quercetin 3-
O-b-D-glucopyranoside (8) by comparison with spectro-
scopic data [10, 11] and chemical degradation methods.
Benzophenone glycosides have been isolated from many
kind of plants, but this is first reported isolation of a dim-
ethylbenzophene glycoside from a natural source. The
substitution pattern is the well-known A ring of flavonoid;
a possible biosynthesis pathway to the aglycone moiety of
2 would be methylation of the benzophenone skeleton.
Isolated compounds were evaluated for inhibitory
activities against histamine release from rat peripheral mast
cells [12] and nitric oxide (NO) production from a murine
macrophage-like cell line, RAW264.7 cells [13]. Com-
pounds 3–8 (at 100 lg/ml) inhibited histamine release
from mast cells with inhibition ratios of 94.4, 21.9, 30.5,
23.9, 100, and 93.5%, respectively. But 1 and 2 did not
show inhibitory activity against histamine release at this
concentration. Compounds 3–8 (at 100 lg/ml) inhibited
C
(
C-2, 6), and 155.6 (C-4). NOE enhancement was also
observed between the methyls and an anomeric proton at
dH 4.63. These data suggested that the aglycone of 2
was 2,4,6-trihydroxy-3,5-dimethylbenzophenone. Absolute
configuration of the glucose moiety was determined to be D
by using HPLC analysis with an OR detector. From the
above data, the structure of 2 was identified to be 2,4,6-
00
trihydroxy-3,5-dimethylbenzophenone 4-O-(6 -O-galloyl)-
b-D-glucopyranoside.
Guavinoside C (3) was obtained as a yellow powder. Its
HR-FAB-MS showed a quasimolecular ion peak at m/z
5
85.0868, corresponding to the molecular formula
C H O . The UV absorbances at 211, 265, and 355 nm
27 22 15
were characteristic of flavonol. The IR spectrum indicated
-
1
the presence of hydroxyl (3,400 cm ), ester (1,710 cm ),
-1
-
and conjugated carbonyl group (1,690 cm ). In the H-
1
1
NMR spectrum, meta-coupled signals at dH 6.20 and dH
6.41 and a hydrogen-bonded hydroxyl signal at dH 12.62
indicated the presence of a 5,7-dihydroxy A ring system in
flavonol. A spin system of three aromatic signals at d 7.46
H
1
23

J Nat Med (2010) 64:252–256
255
NO production by RAW 264.7 cells stimulated with lipo-
polysaccharide and interferon gamma with inhibition ratios
of 50.0, 33.2, 32.4, 65.1, 55.3, and 52.1%, respectively.
The isolated compounds therefore inhibited chemical
mediators, such as histamine and NO, and increased IL-12
release from RAW 264.7 cells.
Ltd., Tokyo, Japan) eluted stepwise with 0–25% MeOH,
and recrystallized from MeOH to give 1 (47 mg). Fraction
4 (124 mg) was purified by medium pressure liquid chro-
matography (Yamazen Baker-bond ODS Yamazen, Kyoto,
Japan) column eluted with MeCN–MeOH–H O (5:35:60)
2
to give 2 (44 mg). Fraction 3 (130 mg) was purified by
reversed-phase HPLC [column: Shiseido Capcell pak C18
UG120 (10-mm i.d. 9 250 mm, Shiseido, Tokyo, Japan);
In conclusion, phenolic compounds isolated from P.
guajava might be valuable candidates for treating various
inflammatory diseases.
mobile phase: MeCN–MeOH–H O (5:30:65); flow rate:
2
3.0 ml/min; detection: UV at 254 nm] to give 3 (14 mg).
The 100% MeOH eluate of Diaion HP-20 was dissolved in
MeOH, and chromatographed on a Sephadex LH-20 col-
umn (2.5 9 100 cm) to give ten fractions. Fraction 3
(1.9 g) was chromatographed on a silica gel column
Experimental
General
developed with CHCl –MeOH to give eight fractions.
3
The UV spectra were recorded on a Shimadzu model UV-
Fraction 6 (515 mg) was purified by reversed-phase HPLC
[column: Shiseido Capcell pak C18 UG120 (10-mm
1
60 spectrophotometer. IR spectra were recorded on a
Horiba FT-210 diffraction infrared spectrometer. FAB-MS
were obtained with a JEOL model JMS-AX505 HA spec-
i.d. 9 250 mm); mobile phase: MeCN–H O (18:82); flow
2
rate: 3.0 ml/min.; detection: UV at 250 nm] to give 4
(20 mg), 5 (50 mg), 6 (62 mg), 7 (62 mg), and 8 (30 mg),
respectively.
1
13
trometer. H-NMR (600 MHz) and C-NMR (150 MHz)
TM
spectra were obtained on a Varian Inova
600 spec-
trometer and a JEOL Delta 600 spectrometer. NMR spectra
Guavinoside A (1) was obtained as a yellow powder.
6
2
ꢃ
were measured in DMSO-d with TMS as internal stan-
6
½aꢁ ꢂ 114 (c = 0.1, MeOH); FAB-MS m/z 545
D
?
(M ? H) ; HR-FAB-MS (found 545.8418, calcd for
MeOH
dard. Optical rotation was measured with a Jasco DIP-370
polarimeter. The inhibitory activities against histamine
release from rat mast cells and NO production were carried
out as described in the literature method [14].
C H O : 545.8413); UV k
max
nm (e): 218 (26,800),
cm : 3,390 (OH), 1,700 (ester). H-
2
6
25 13
KBr
max
-1
1
288 (16,200); IR t
1
3
and C-NMR data, see Table 1.
Guavinoside B (2) was obtained as a yellow powder;
6
2
ꢃ
Plant material
½aꢁ ꢂ 83 (c = 0.5, MeOH); FAB-MS m/z 571 (M -
D
-
H) ; HR-FAB-MS (found 571.1474, calcd for C H O :
2
8 27 13
MeOH
max
Leaves of P. guajava were donated by OS Industrial Co.
Ltd. (Tokyo, Japan).
571.1451); UV k
nm (e): 218 (26,400), 283 (15,100);
cm : 3,410 (OH), 1,710 (ester), 1,690 (C=O). H-
KBr
max
-1
1
IR t
1
3
and C-NMR data, see Table 1.
Extraction and isolation
Guavinoside C (3) was obtained as a yellow powder;
6
2
ꢃ
½
aꢁ ꢂ 73 (c = 1.0, MeOH); FAB-MS m/z 585 (M -
D
-
H) ; HR-FAB-MS (found 585.0868, calcd for C H O :
The dried leaves of P. guajava (5 kg) were extracted with
1
2
7 21 15
MeOH
585.0880); kmax nm (e): 211 (32,000), 265 (16,200), 355
5 l of 80% MeOH at room temperature for 7 days. The
KBr
max
-1
cm : 3,400 (OH), 1,710 (ester), 1,690
solution was filtered and concentrated under reduced
pressure to give a crude extract. The extract was dissolved
in water and passed through a Diaion HP-20 column
(10,000); IR t
1
13
1
(C=O). H- and C-NMR data, see Table 2. H-NMR
3
(600 MHz) and C-NMR (150 MHz) spectra were mea-
1
(
Mitsubishi Kasei, Tokyo, Japan), and eluted stepwise with
0, 70, and 100% MeOH. The 70% MeOH eluate was
sured in DMSO-d with TMS as internal standard
6
5
dissolved in EtOH and passed through a Sephadex LH-20
column (Pharmacia, Uppsala, Sweden). The effluent was
chromatographed on a Diaion CHP-20P column (Mitsubi-
shi Kasei, Tokyo, Japan), and eluted with 50 and 70%
MeOH. All fractions were monitored by TLC, and the
fractions containing the same compound(s) (as evidenced
by TLC) were combined to give four fractions. Fraction 3
Acid hydrolysis of 1–3
Compound 1, 2, or 3 (3.0 mg, each) was treated with
0.5 ml of 2 M HCl for 2 h at 110°C in a sealed tube. The
reaction mixture was diluted with 1 ml of H O, and
2
extracted with an equal volume of EtOAc, and the water
layer was evaporated to dryness. The residue was dissolved
(
900 mg) was chromatographed on a Sephadex LH 20
in H O (200 ll) and subjected to HPLC analysis [column:
2
column developed with CHCl –MeOH (1:1) to give four
3
Asahi pak NH2P-50, (4.6-mm i.d. 9 250 mm, Showa
fractions. Fraction 2 (770 mg) was further applied to a
reversed-phase column (SSC ODS, Senshu Scientific Co.
Denko, Tokyo, Japan); mobile phase: MeCN–H O (75:25);
2
flow rate: 1.0 ml/min.; detection: OR detector (Shodex
123

2
56
J Nat Med (2010) 64:252–256
1
3
1
Table 2 C- and H-NMR spectral data of guavinoside C (3)
‘
‘Academic Frontier’’ Project for Private Universities matching fund
subsidy from MEXT (Ministry of Education, Culture, Sports, Science
and Technology) 2002–2007 and 2007–2010 of Japan.
No.
d
C
d
H
2
3
4
5
6
7
8
9
157.3 s
133.0 s
177.4 s
161.9 s
98.5 d
Open Access This article is distributed under the terms of the
Creative Commons Attribution Noncommercial License which per-
mits any noncommercial use, distribution, and reproduction in any
medium, provided the original author(s) and source are credited.
6.20 (1H, d, J = 1.5 Hz)
6.41 (1H, d, J = 1.5 Hz)
164.1 s
93.5 d
References
156.3 s
103.9 s
120.8 s
115.6 d
144.9 s
148.3 s
115.4 d
121.3 d
1
1
2
3
4
5
6
5
0
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0
0
0
0
0
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6
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-OH
Arabinosyl
0
0
0
0
0
0
0
0
0
0
1
2
3
4
5
107.7 d
81.7 d
76.9 d
81.9 d
62.5 t
5.56 (1H, J = 1.4 Hz)
4.18 (1H, br s)
3.81 (1H, m)
3.74 (1H, m)
. Osman AM, Younes M, Garby EL, Sheta AE (1974) Chemical
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4.11 (1H, dd, J = 12.0, 3.3 Hz)
4
.02 (1H, dd, J = 12.0, 5.8 Hz)
0
0
0
0
7. Smith RM, Siwatibau S (1975) Aeaquiterpene hydrocarbons of
Fijian guavas. Phytochemistry 14:2013–2015
2
3
-OH
-OH
5.72 (1H, br s)
5.48 (1H, br s)
8
. Mercadantre AZ, Steck A, Pfander H (1999) Carotenoids from
Guava (Psidium guajava L.): isolation and structure elucidation.
J Agric Food Chem 47:145–151
Galloyl
0
0
0
0
00
00
00
00
1
2
3
4
118.9 s
108.5 d
145.3 s
138.4 s
165.4 s
000
000
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, 5
6.89 (2H, s)
1
1
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(
positive), and 6.0 min (positive), respectively. Retention
(
time of standard samples of (?)-D-glucose, (?)-L-arabi-
nose, (-)-D-arabinose, and (?)-D-xylose were found to be
inhibitory effect of histamine release of naphthopyrone glyco-
sides from seeds of Cassia obtusifolia L. Chem Pharm Bull
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6:1650–1652
8
.5 min (positive), 6.0 min (positive), 6.0 min (negative),
1
1
3. Wang J, Matsuzaki K, Kitanaka S (2007) Antiallergic agents
from natural sources. Part 19. Stilbene derivatives from Pholidota
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and 6.3 min (positive), respectively.
Acknowledgments This work was supported in part by a Grant-in-
Aids from the Ministry of Health and Welfare of Japan (No.
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activity of Chinese herbal medicines toward histamine release
from mast cells and nitric oxide production by macrophage-like
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1
9980070), by a Special Research Grant-in Aid for the development
of characteristic education and High-Tech Research Centers from the
Ministry of Education, Science, Sports and Culture of Japan to Nihon
University, and by the Japan–China Medical Association, and
1
23