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Chemical constituents from the fruits of Cornus officinalis
Biochemical Systematics and Ecology 45 (2012) 120–123
Contents lists available at SciVerse ScienceDirect
Biochemical Systematics and Ecology journal homepage: www.elsevier.com/locate/biochemsyseco
Chemical constituents from the fruits of Cornus officinalis Xiao-Yu Xie a, b, Rui Wang a, Yan-Ping Shi a, * a
Key Laboratory of Chemistry of Northwestern Plant Resources and Key Laboratory for Natural Medicine of Gansu Province, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, PR China Graduate University of Chinese Academy of Sciences, Beijing 100039, PR China
b
a r t i c l e i n f o
a b s t r a c t
Article history: Received 5 May 2012 Accepted 15 July 2012 Available online 14 August 2012
A new sterol (1), five known flavonols (2–6), and four known iridoids (7–10) were isolated from the fruits of Cornus officinalis. The structure of compound 1 was elucidated using various spectroscopic methods. Compounds 3, 5, and 6 were reported for the first time from the species. The chemotaxonomic significance of these compounds was summarized. Ó 2012 Elsevier Ltd. All rights reserved.
Keywords: Cornaceae Cornus officinalis Flavonoids Iridoids
1. Subject and source Cornus officinalis Sieb. & Zucc., a species of the Cornaceae family, grows in most areas of China, Japan, and Korea (Flora compilation committee of Chinese Academy of Science, 2005). The fruits of C. officinalis were collected in Shaanxi Province, China. A voucher specimen (No. ZY2011C001) was deposited in the key laboratory for natural medicine of Gansu Province, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, China. 2. Previous work In the Chinese Pharmacopeia, the air-dried fruits of C. officinalis are named as “Shan-zhu-yu”, a traditional Chinese medicine which was prescribed as an astringent tonic for impotence, spermatorrhea, lumbago, vertigo, and night sweats. Previous phytochemical investigations on the species have revealed the presence of iridoids (Endo and Tagnchi, 1973; Wang et al., 2006), tannins (Hatano et al., 1989a, 1989b), flavonoids (Kim and Kwak, 1998; Zhang et al., 2009) and organic acid esters (Migyazawa and Kameoka, 1989; Wang et al., 2006). In addition, oleanolic acid, ursolic acid, and b-sitosterol have been isolated from the species (Yang et al., 2005). 3. Present study The present investigation on the chemical constituents of the fruits of C. officinalis led to the isolation of a new compound, daucosterol-60 -malate (1), together with nine known compounds (Fig. 1): kaempferol (2) (Wang et al., 2008), kaempferide (3)
* Corresponding author. Tel.: þ86 931 4968208; fax: þ86 931 4968094. E-mail address: [email protected] (Y.-P. Shi). 0305-1978/$ – see front matter Ó 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.bse.2012.07.025
X.-Y. Xie et al. / Biochemical Systematics and Ecology 45 (2012) 120–123
1''
O
O 6'
HO HO
3'
3''
OH O O 1' O OH
OH
19
1 3
5
11
10
O OH O
20
26
24
17
27
8
HO
O OH O
OH
COOMe
4 R= H 5 R = Glc 6 R = Gal
COOMe R
HO OR
OH
2 R= H 3 R = Me
1 OH
HO
14
OR
29
21 18
121
O Me
OGlc 7
O
O Me OGlc
8 R = OH 9 R = OH 10 R = OMe
Fig. 1. Structures of compounds 1–10.
(Banskota et al., 1998), quercetin (4) (Wang et al., 2008), isoquercitrin (5) (Datta et al., 2002), hyperoside (6) (Datta et al., 2002), loganin (7) (Chai et al., 2010), 7-a-morroniside (8) (Kakuda et al., 2000), 7-b-morroniside (9) (Kakuda et al., 2000), 7-b-O-methylmorroniside (10) (Dinda et al., 2009). Compounds 3, 5, and 6 have been isolated from the species for the first time. The dried fruits (4.5 kg) of C. officinalis were ground and extracted with 95% EtOH (3 5 L) at 60 C for 2 h each time. The crude extract (2.0 kg) was mixed with H2O (1.8 L) to form a suspension, then partitioned successively with petroleum ether (PE; 60–90 C), EtOAc, and n-BuOH. The EtOAc extract (132.5 g) was subjected to silica gel column chromatography (CC) with a CHCl3–MeOH gradient system (v/v, 50:1, 30:1, 10:1, 5:1, 3:1, 2:1, 1:1) to give fractions A–G according to TLC analyses. From fraction D, compounds 2 (16.5 mg), 3 (13.6 mg), and 4 (24.0 mg) were obtained by eluting on C18 reversed-phase silica gel CC with MeOH–H2O (v/v, 3:1), then repeated silica gel CC eluting with CHCl3–MeOH (v/v, 15:1). Fraction E was separated on silica gel CC eluting with CHCl3–MeOH (v/v, 10:1), then through Sephadex LH-20 CC eluting with CHCl3–MeOH (v/v, 1:1), which yielded compounds 5 (7.5 mg), 6 (14.4 mg). Fraction F was repeatedly separated on C18 reversed-phase silica gel CC eluting with MeOH–H2O (v/v, 3:1) to provide compound 1 (5.5 mg). The n-BuOH extract (456.2 g) was chromatographed over D101 macroporous resin column, eluting with H2O and 30%, 60% and 95% EtOH. The 30% eluate (64.3 g) was subjected to silica gel CC with a CHCl3–MeOH gradient system (v/v, 30:1, 15:1, 8:1, 4:1, 1:1) to give fractions A–E according to TLC analyses. Fraction C was separated on silica gel CC eluting with CHCl3–MeOH (v/v, 10:1), then using preparative TLC developing with CHCl3–MeOH (v/v, 5:1), which yielded the compounds the mixture of 8 and 9 (9.5 mg), and 10 (21.7 mg). Fraction D was separated on silica gel CC eluting with CHCl3–MeOH (v/v, 9:1) to provide compound 7 (213.0 mg). 26.3 (c 0.8, MeOH)). Its HR-ESI-MS Compound 1 was obtained as an optically active colorless gum (½a20 D spectrum showed ion peaks at m/z 691.4422 [M H] (calcd 691.4427), which, combined with NMR data, strongly indicated a molecular formula of C39H64O10. The IR spectrum demonstrated absorptions at 3432 (OH), 1739 (C]O), and 1631 cm1(C]C). Its 13C NMR and DEPT spectra (Table 1) displayed thirty-nine carbon signals, including six methyls, thirteen methenes, fifteen methines (six oxygen-bearing, and one C]C methines), and five quaternary carbons (two C ¼ 0, and one C]C quaternary carbons). Compared 13C NMR data with those of daucosterol (Wang et al., 2011) and methylmalic acid (Zhang et al., 2009), compound 1 has groups daucosterol and malate. The major difference between daucosterol and compound 1 is that the chemical shift value of C-50 shifts from 78.1 to 74.6 ppm and C-60 from 62.9 to 65.3 ppm, Which suggested the malate was attached to C-60 . In the HMBC experiment (Fig. 2), the correlation between H-60 (dH 4.27) and C-100 (dC 173.6) also suggested that the malate was attached to C-60 . Accordingly, compound 1 was determined to be daucosterol-60 -malate. 4. Chemotaxonomic significance The subgenus Cornus consists of four species: C. officinalis, Cornus chinensis, Cornus mas, and Cornus sessilis. Chemotaxonomically, Cornus subgenus is characterized by the presence of flavonoids, including flavonols, flavanones, and
122
X.-Y. Xie et al. / Biochemical Systematics and Ecology 45 (2012) 120–123
Table 1 1 H NMR (100 MHz, J in Hz) and
13
C NMR (400 MHz) data of compound 1 (acetone-d6).
No.
dH (J in Hz)
dC (DEPT)
No.
dH (J in Hz)
dC (DEPT)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
1.07 1.51 4.40 2.35
(1H, (1H, (1H, (2H,
m), 1.85 (1H, m) m), 1.84 (1H, m) m) m)
5.34 1.68 1.67 1.20
(1H, (1H, (1H, (1H,
br s) m), 2.08 (1H, m) m) m)
37.8 (CH2) 30.5 (CH2) 79.4 (CH) 39.5 (CH2) 141.5 (C) 122.1 (CH) 32.5 (CH2) 32.6 (CH) 50.9 (CH) 37.3 (C) 21.6 (CH2) 40.5 (CH2) 42.9 (C) 57.4 (CH) 24.8 (CH2) 28.8 (CH2) 56.7 (CH) 12.1 (Me) 19.6 (Me) 36.8 (CH)
21 22 23 24 25 26 27 28 29 10 20 30 40 50 60 100 200 300 400
0.95 1.06 1.26 1.51 1.67 0.86 0.82 1.19 0.86 4.41 3.53 3.51 3.64 3.71 4.27
19.1 (Me) 34.5 (CH2) 26.6 (CH2) 46.6 (CH) 29.7 (CH) 19.1 (Me) 19.9 (Me) 23.6 (CH2) 12.0 (Me) 102.4 (CH) 74.3 (CH) 77.7 (CH) 71.3 (CH) 74.6 (CH) 65.3 (CH2) 173.6 (C) 68.3 (CH) 37.9 (CH2) 171.7 (C)
1.58 (2H, m) 1.18 (1H, m), 2.21 (1H, m) 1.31 1.06 1.37 1.13 0.68 1.00 2.00
(1H, (1H, (1H, (1H, (3H, (3H, (1H,
m) m), 1.58 (1H, m) m), 1.93 (1H, m) m) s) s) m)
O O HO HO
(3H, (1H, (2H, (1H, (1H, (3H, (3H, (1H, (3H, (1H, (1H, (1H, (1H, (1H, (1H,
d, 6.4) m), 1.33 (1H, m) m) m) m) d, 8.0) d, 7.2) m), 1.23 (1H, m) t, 7.2) d, 8.0) m) m) m) m) m), 4.38 (1H, m)
4.54 (1H, t, 4.4) 2.64 (2H, dd, 15.6, 8.0)
OH OH O O O OH
Fig. 2. Key HMBC correlations of compound 1.
anthocyanidins (Kim and Kwak, 1998; Jayaprakasam et al., 2006; Pawlowska et al., 2010), and iridoids (Endo and Tagnchi, 1973; Jensen et al., 1973). In our present study, the isolation of five flavonols (2–6) and four iridoids (7–10), including a high content compound 7 (1.32%, Fig. 3 see Supporting Information), further confirmed the chemotaxonomic significance of flavonoids and iridoids in C. officinalis. Moreover, in earlier studies, some malates have been isolated from C. officinalis (Shang et al., 1989; Yang et al., 2005; Zhang et al., 2009) and they could be as the chemotaxonomic marker of this species. Our present study also found a new constituent, daucosterol-60 -malate (1), from the species, which was consistent with the earlier finding of the malate in C. officinalis. Acknowledgments This work was supported by the Important Directional Project of the Chinese Academy of Sciences (No. KSCX2-EW-R-15), and the Open Project from Key Laboratory of Chemistry of Northwestern Plant Resources, Chinese Academy of Sciences (No. CNPR-2011kfkt-05). Appendix A. Supplementary data Supplementary data related to this article can be found online at http://dx.doi.org/10.1016/j.bse.2012.07.025. References Banskota, A.H., Tezuka, Y., Parasain, J.K., Matsushige, K., Saiki, I., Kadota, S., 1998. J. Nat. Prod. 61, 896. Chai, X., Su, Y.F., Zheng, Y.H., Yan, S.L., Zhang, X., Gao, X.M., 2010. Biochem. Syst. Ecol. 38, 210. Datta, B.K., Datta, S.K., Rashid, M.A., Sarker, S.D., 2002. Biochem. Syst. Ecol. 30, 693. Dinda, B., Chowdhury, D.R., Mohanta, B.C., 2009. Chem. Pharm. Bull. 57, 765. Endo, T., Tagnchi, H., 1973. Yakugaku Zasshi 93, 30. Flora compilation committee of Chinese Academy of Science, 2005. Flora of China, vol. 14. Science Press, Beijing, p. 215. Hatano, T., Ogawa, N., Kira, R., Yasuhara, T., Okuda, T., 1989a. Chem. Pharm. Bull. 37, 2083. Hatano, T., Yasuhara, T., Okuda, T., 1989b. Chem. Pharm. Bull. 37, 2165. Jayaprakasam, B., Olson, L.K., Schutzki, R.E., Tai, M.H., Nair, M.G., 2006. J. Agric. Food Chem. 54, 243. Jensen, S.R., Kjær, A., Nielsen, B.J., 1973. Phytochemistry 12, 2064.
X.-Y. Xie et al. / Biochemical Systematics and Ecology 45 (2012) 120–123 Kakuda, R., Imai, M., Yaoita, Y., Machida, K., Kikuchi, M., 2000. Phytochemistry 55, 879. Kim, D.K., Kwak, J.H., 1998. Arch. Pharm. Res. 21, 787. Migyazawa, M., Kameoka, H., 1989. Agric. Biol. Chem. 53, 3337. Pawlowska, A.M., Camangi, F., Braca, A., 2010. Food Chem. 119, 1257. Shang, S.C., Zheng, P.G., Wu, X.F., 1989. Chin. Tradit. Herb. Drugs 12, 29. Wang, J.F., Yang, Y., Zhong, H.M., Cheng, Y.X., 2011. Chin. Tradit. Herb. Drugs 42, 2394. Wang, J.L., Zhang, S.X., Li, T.J., Zhang, W.Q., Wang, J.J., Zhang, S.J., 2008. Chin. Tradit. Herb. Drugs 39, 490. Wang, Y., Li, Z.Q., Chen, L.R., Xu, X.J., 2006. Prog. Nat. Sci. 16, 142. Yang, J., Chen, S.Q., Ji, C.R., Liu, Y.Z., 2005. Chin. Tradit. Herb. Drugs 36, 1780. Zhang, Y.E., Liu, E.H., Li, H.J., Li, P., 2009. Chin. J. Nat. Med. 7, 365.
123
Contents lists available at SciVerse ScienceDirect
Biochemical Systematics and Ecology journal homepage: www.elsevier.com/locate/biochemsyseco
Chemical constituents from the fruits of Cornus officinalis Xiao-Yu Xie a, b, Rui Wang a, Yan-Ping Shi a, * a
Key Laboratory of Chemistry of Northwestern Plant Resources and Key Laboratory for Natural Medicine of Gansu Province, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, PR China Graduate University of Chinese Academy of Sciences, Beijing 100039, PR China
b
a r t i c l e i n f o
a b s t r a c t
Article history: Received 5 May 2012 Accepted 15 July 2012 Available online 14 August 2012
A new sterol (1), five known flavonols (2–6), and four known iridoids (7–10) were isolated from the fruits of Cornus officinalis. The structure of compound 1 was elucidated using various spectroscopic methods. Compounds 3, 5, and 6 were reported for the first time from the species. The chemotaxonomic significance of these compounds was summarized. Ó 2012 Elsevier Ltd. All rights reserved.
Keywords: Cornaceae Cornus officinalis Flavonoids Iridoids
1. Subject and source Cornus officinalis Sieb. & Zucc., a species of the Cornaceae family, grows in most areas of China, Japan, and Korea (Flora compilation committee of Chinese Academy of Science, 2005). The fruits of C. officinalis were collected in Shaanxi Province, China. A voucher specimen (No. ZY2011C001) was deposited in the key laboratory for natural medicine of Gansu Province, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, China. 2. Previous work In the Chinese Pharmacopeia, the air-dried fruits of C. officinalis are named as “Shan-zhu-yu”, a traditional Chinese medicine which was prescribed as an astringent tonic for impotence, spermatorrhea, lumbago, vertigo, and night sweats. Previous phytochemical investigations on the species have revealed the presence of iridoids (Endo and Tagnchi, 1973; Wang et al., 2006), tannins (Hatano et al., 1989a, 1989b), flavonoids (Kim and Kwak, 1998; Zhang et al., 2009) and organic acid esters (Migyazawa and Kameoka, 1989; Wang et al., 2006). In addition, oleanolic acid, ursolic acid, and b-sitosterol have been isolated from the species (Yang et al., 2005). 3. Present study The present investigation on the chemical constituents of the fruits of C. officinalis led to the isolation of a new compound, daucosterol-60 -malate (1), together with nine known compounds (Fig. 1): kaempferol (2) (Wang et al., 2008), kaempferide (3)
* Corresponding author. Tel.: þ86 931 4968208; fax: þ86 931 4968094. E-mail address: [email protected] (Y.-P. Shi). 0305-1978/$ – see front matter Ó 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.bse.2012.07.025
X.-Y. Xie et al. / Biochemical Systematics and Ecology 45 (2012) 120–123
1''
O
O 6'
HO HO
3'
3''
OH O O 1' O OH
OH
19
1 3
5
11
10
O OH O
20
26
24
17
27
8
HO
O OH O
OH
COOMe
4 R= H 5 R = Glc 6 R = Gal
COOMe R
HO OR
OH
2 R= H 3 R = Me
1 OH
HO
14
OR
29
21 18
121
O Me
OGlc 7
O
O Me OGlc
8 R = OH 9 R = OH 10 R = OMe
Fig. 1. Structures of compounds 1–10.
(Banskota et al., 1998), quercetin (4) (Wang et al., 2008), isoquercitrin (5) (Datta et al., 2002), hyperoside (6) (Datta et al., 2002), loganin (7) (Chai et al., 2010), 7-a-morroniside (8) (Kakuda et al., 2000), 7-b-morroniside (9) (Kakuda et al., 2000), 7-b-O-methylmorroniside (10) (Dinda et al., 2009). Compounds 3, 5, and 6 have been isolated from the species for the first time. The dried fruits (4.5 kg) of C. officinalis were ground and extracted with 95% EtOH (3 5 L) at 60 C for 2 h each time. The crude extract (2.0 kg) was mixed with H2O (1.8 L) to form a suspension, then partitioned successively with petroleum ether (PE; 60–90 C), EtOAc, and n-BuOH. The EtOAc extract (132.5 g) was subjected to silica gel column chromatography (CC) with a CHCl3–MeOH gradient system (v/v, 50:1, 30:1, 10:1, 5:1, 3:1, 2:1, 1:1) to give fractions A–G according to TLC analyses. From fraction D, compounds 2 (16.5 mg), 3 (13.6 mg), and 4 (24.0 mg) were obtained by eluting on C18 reversed-phase silica gel CC with MeOH–H2O (v/v, 3:1), then repeated silica gel CC eluting with CHCl3–MeOH (v/v, 15:1). Fraction E was separated on silica gel CC eluting with CHCl3–MeOH (v/v, 10:1), then through Sephadex LH-20 CC eluting with CHCl3–MeOH (v/v, 1:1), which yielded compounds 5 (7.5 mg), 6 (14.4 mg). Fraction F was repeatedly separated on C18 reversed-phase silica gel CC eluting with MeOH–H2O (v/v, 3:1) to provide compound 1 (5.5 mg). The n-BuOH extract (456.2 g) was chromatographed over D101 macroporous resin column, eluting with H2O and 30%, 60% and 95% EtOH. The 30% eluate (64.3 g) was subjected to silica gel CC with a CHCl3–MeOH gradient system (v/v, 30:1, 15:1, 8:1, 4:1, 1:1) to give fractions A–E according to TLC analyses. Fraction C was separated on silica gel CC eluting with CHCl3–MeOH (v/v, 10:1), then using preparative TLC developing with CHCl3–MeOH (v/v, 5:1), which yielded the compounds the mixture of 8 and 9 (9.5 mg), and 10 (21.7 mg). Fraction D was separated on silica gel CC eluting with CHCl3–MeOH (v/v, 9:1) to provide compound 7 (213.0 mg). 26.3 (c 0.8, MeOH)). Its HR-ESI-MS Compound 1 was obtained as an optically active colorless gum (½a20 D spectrum showed ion peaks at m/z 691.4422 [M H] (calcd 691.4427), which, combined with NMR data, strongly indicated a molecular formula of C39H64O10. The IR spectrum demonstrated absorptions at 3432 (OH), 1739 (C]O), and 1631 cm1(C]C). Its 13C NMR and DEPT spectra (Table 1) displayed thirty-nine carbon signals, including six methyls, thirteen methenes, fifteen methines (six oxygen-bearing, and one C]C methines), and five quaternary carbons (two C ¼ 0, and one C]C quaternary carbons). Compared 13C NMR data with those of daucosterol (Wang et al., 2011) and methylmalic acid (Zhang et al., 2009), compound 1 has groups daucosterol and malate. The major difference between daucosterol and compound 1 is that the chemical shift value of C-50 shifts from 78.1 to 74.6 ppm and C-60 from 62.9 to 65.3 ppm, Which suggested the malate was attached to C-60 . In the HMBC experiment (Fig. 2), the correlation between H-60 (dH 4.27) and C-100 (dC 173.6) also suggested that the malate was attached to C-60 . Accordingly, compound 1 was determined to be daucosterol-60 -malate. 4. Chemotaxonomic significance The subgenus Cornus consists of four species: C. officinalis, Cornus chinensis, Cornus mas, and Cornus sessilis. Chemotaxonomically, Cornus subgenus is characterized by the presence of flavonoids, including flavonols, flavanones, and
122
X.-Y. Xie et al. / Biochemical Systematics and Ecology 45 (2012) 120–123
Table 1 1 H NMR (100 MHz, J in Hz) and
13
C NMR (400 MHz) data of compound 1 (acetone-d6).
No.
dH (J in Hz)
dC (DEPT)
No.
dH (J in Hz)
dC (DEPT)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
1.07 1.51 4.40 2.35
(1H, (1H, (1H, (2H,
m), 1.85 (1H, m) m), 1.84 (1H, m) m) m)
5.34 1.68 1.67 1.20
(1H, (1H, (1H, (1H,
br s) m), 2.08 (1H, m) m) m)
37.8 (CH2) 30.5 (CH2) 79.4 (CH) 39.5 (CH2) 141.5 (C) 122.1 (CH) 32.5 (CH2) 32.6 (CH) 50.9 (CH) 37.3 (C) 21.6 (CH2) 40.5 (CH2) 42.9 (C) 57.4 (CH) 24.8 (CH2) 28.8 (CH2) 56.7 (CH) 12.1 (Me) 19.6 (Me) 36.8 (CH)
21 22 23 24 25 26 27 28 29 10 20 30 40 50 60 100 200 300 400
0.95 1.06 1.26 1.51 1.67 0.86 0.82 1.19 0.86 4.41 3.53 3.51 3.64 3.71 4.27
19.1 (Me) 34.5 (CH2) 26.6 (CH2) 46.6 (CH) 29.7 (CH) 19.1 (Me) 19.9 (Me) 23.6 (CH2) 12.0 (Me) 102.4 (CH) 74.3 (CH) 77.7 (CH) 71.3 (CH) 74.6 (CH) 65.3 (CH2) 173.6 (C) 68.3 (CH) 37.9 (CH2) 171.7 (C)
1.58 (2H, m) 1.18 (1H, m), 2.21 (1H, m) 1.31 1.06 1.37 1.13 0.68 1.00 2.00
(1H, (1H, (1H, (1H, (3H, (3H, (1H,
m) m), 1.58 (1H, m) m), 1.93 (1H, m) m) s) s) m)
O O HO HO
(3H, (1H, (2H, (1H, (1H, (3H, (3H, (1H, (3H, (1H, (1H, (1H, (1H, (1H, (1H,
d, 6.4) m), 1.33 (1H, m) m) m) m) d, 8.0) d, 7.2) m), 1.23 (1H, m) t, 7.2) d, 8.0) m) m) m) m) m), 4.38 (1H, m)
4.54 (1H, t, 4.4) 2.64 (2H, dd, 15.6, 8.0)
OH OH O O O OH
Fig. 2. Key HMBC correlations of compound 1.
anthocyanidins (Kim and Kwak, 1998; Jayaprakasam et al., 2006; Pawlowska et al., 2010), and iridoids (Endo and Tagnchi, 1973; Jensen et al., 1973). In our present study, the isolation of five flavonols (2–6) and four iridoids (7–10), including a high content compound 7 (1.32%, Fig. 3 see Supporting Information), further confirmed the chemotaxonomic significance of flavonoids and iridoids in C. officinalis. Moreover, in earlier studies, some malates have been isolated from C. officinalis (Shang et al., 1989; Yang et al., 2005; Zhang et al., 2009) and they could be as the chemotaxonomic marker of this species. Our present study also found a new constituent, daucosterol-60 -malate (1), from the species, which was consistent with the earlier finding of the malate in C. officinalis. Acknowledgments This work was supported by the Important Directional Project of the Chinese Academy of Sciences (No. KSCX2-EW-R-15), and the Open Project from Key Laboratory of Chemistry of Northwestern Plant Resources, Chinese Academy of Sciences (No. CNPR-2011kfkt-05). Appendix A. Supplementary data Supplementary data related to this article can be found online at http://dx.doi.org/10.1016/j.bse.2012.07.025. References Banskota, A.H., Tezuka, Y., Parasain, J.K., Matsushige, K., Saiki, I., Kadota, S., 1998. J. Nat. Prod. 61, 896. Chai, X., Su, Y.F., Zheng, Y.H., Yan, S.L., Zhang, X., Gao, X.M., 2010. Biochem. Syst. Ecol. 38, 210. Datta, B.K., Datta, S.K., Rashid, M.A., Sarker, S.D., 2002. Biochem. Syst. Ecol. 30, 693. Dinda, B., Chowdhury, D.R., Mohanta, B.C., 2009. Chem. Pharm. Bull. 57, 765. Endo, T., Tagnchi, H., 1973. Yakugaku Zasshi 93, 30. Flora compilation committee of Chinese Academy of Science, 2005. Flora of China, vol. 14. Science Press, Beijing, p. 215. Hatano, T., Ogawa, N., Kira, R., Yasuhara, T., Okuda, T., 1989a. Chem. Pharm. Bull. 37, 2083. Hatano, T., Yasuhara, T., Okuda, T., 1989b. Chem. Pharm. Bull. 37, 2165. Jayaprakasam, B., Olson, L.K., Schutzki, R.E., Tai, M.H., Nair, M.G., 2006. J. Agric. Food Chem. 54, 243. Jensen, S.R., Kjær, A., Nielsen, B.J., 1973. Phytochemistry 12, 2064.
X.-Y. Xie et al. / Biochemical Systematics and Ecology 45 (2012) 120–123 Kakuda, R., Imai, M., Yaoita, Y., Machida, K., Kikuchi, M., 2000. Phytochemistry 55, 879. Kim, D.K., Kwak, J.H., 1998. Arch. Pharm. Res. 21, 787. Migyazawa, M., Kameoka, H., 1989. Agric. Biol. Chem. 53, 3337. Pawlowska, A.M., Camangi, F., Braca, A., 2010. Food Chem. 119, 1257. Shang, S.C., Zheng, P.G., Wu, X.F., 1989. Chin. Tradit. Herb. Drugs 12, 29. Wang, J.F., Yang, Y., Zhong, H.M., Cheng, Y.X., 2011. Chin. Tradit. Herb. Drugs 42, 2394. Wang, J.L., Zhang, S.X., Li, T.J., Zhang, W.Q., Wang, J.J., Zhang, S.J., 2008. Chin. Tradit. Herb. Drugs 39, 490. Wang, Y., Li, Z.Q., Chen, L.R., Xu, X.J., 2006. Prog. Nat. Sci. 16, 142. Yang, J., Chen, S.Q., Ji, C.R., Liu, Y.Z., 2005. Chin. Tradit. Herb. Drugs 36, 1780. Zhang, Y.E., Liu, E.H., Li, H.J., Li, P., 2009. Chin. J. Nat. Med. 7, 365.
123