- Email: [email protected]
Flavonols from Parnassia palustris Linn. (Saxifragaceae)
Biochemical Systematics and Ecology 48 (2013) 70–72
Contents lists available at SciVerse ScienceDirect
Biochemical Systematics and Ecology journal homepage: www.elsevier.com/locate/biochemsyseco
Flavonols from Parnassia palustris Linn. (Saxifragaceae) Yu-Li Hu, Qian-Quan Li, Jia Zhang, Chun-Hong Zhang, Na Zhang, Zhan-Hu Cui, Min-Hui Li* Baotou Medical College, No. 31 Construction Road, Baotou, Inner Mongolia 014060, China
a r t i c l e i n f o Article history: Received 19 October 2012 Accepted 1 December 2012 Available online 16 January 2013 Keywords: Parnassia palustris Linn. Saxifragaceae Flavonols Chemotaxonomy
1. Subject and source Parnassia palustris Linn. is mainly distributed in North America, Europe, Asia, and South Morocco (Simmons, 2004). It is a perennial herb used for the treatment of icteric hepatitis and angiitis. In this investigation, the aerial parts of this plant were collected from Inner Mongolia Virgin Forest near the boundary of China and Russia in August 2011. A voucher specimen (Bt 2011081606) has been deposited in Baotou Medical College, China. 2. Previous work The genus Parnassia (Saxifragaceae) has over 70 species, which is distributed in the arctic-alpine regions of the Northern Hemisphere, primarily in Southeast and Central Asia (Ku, 1995). Early phytochemical investigation of the genus Parnassia has led to the identification of kaempferol, quercetin and their 3-O-glucosides, 3-O-arabinosides, 3-O-rhamnosides and quercetin 3-O-rhamnosylrhamnoside-7-O-rhamnoside, 3,7-di-O-glucosides, 3-O-xyloside-7-O-rhamnosides by thin-layer chromatography (Bohm et al., 1986). Kharitonova (1967) also detected quercetin-3-O-glucoside from P. palustris, while Tamara and Jela (2004) detected tannin (cyanidine). 3. Present study The air-dried aerial parts of P. palustris (1.2 kg) were extracted with methanol for 3 times at 70 C. The extracts were evaporated in a rotary evaporator to obtain 270 g of syrupy residue. A sample (260 g) of the residue was suspended in water (2 L) and fractionated with petroleum ether, EtOAc, and n-BuOH, respectively. The EtOAc portion (24 g) was subjected to dry column on silica gel (200–300 mesh, 700 g) and eluted with CH2Cl2: MeOH (7:1, v/v) to get 4 main fractions (Frs. A1-4). Fraction A3 (3 g) was then further chromatographied on silica gel (300–400 mesh, * Corresponding author. Tel.: þ86 472 7167795. E-mail address: [email protected] (M.-H. Li). 0305-1978/$ – see front matter Ó 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.bse.2012.12.014
Y.-L. Hu et al. / Biochemical Systematics and Ecology 48 (2013) 70–72
71
90 g) eluted with CH2Cl2 and increased percentage of MeOH (0–90%, v/v) to give 50 fractions (Frs. B1-50). The combined fraction B6-18 and fraction B25-43 were further purified by repeated Sephadex LH-20 to obtain compound 1 (10 mg), 2 (12 mg), 3 (19 mg), 4 (24 mg), 5 (26 mg), 6 (27 mg), and 7 (35 mg). The n-BuOH portion (100 g) was subjected to dry column on silica gel (200–300 mesh, 2000 g) eluting with CH2Cl2: MeOH: H2O (7:3:0.5, v/v), 4 main fractions (Frs. C1-4) were obtained. Fraction C3 (20 g) was then further chromatographied on silica gel (300–400 mesh, 400 g) eluting with EtOAc: MeOH: H2O (8:2:1, v/v) to give 48 fractions (Frs. D1-48). The combined fraction D9-29 was further separated on Sephadex LH-20 with H2O and increasing percentage of MeOH (40–100%) to give 4 fractions (Frs. E1-4), and then the E2 fraction was purified by ODS with percentage of MeOH and H2O (45%) to give compound 8 (12 mg), 9 (20 mg), 10 (24 mg), and 11 (30 mg). The structures of these compounds were elucidated by different spectrometric methods (1HNMR, 13CNMR and ESI-MS) and in comparison with published data as kaempferol (1) (Lin et al., 2000), quercetin (2) (Schiber et al., 2005), kaempferol-7-O-glucoside (3) (Lin et al., 2000), kaempferol-3-O-glucoside (4) (Marlena and Irena, 2011), quercetin-3-O-rhamnoside (5) (Schiber et al., 2005), quercetin-3-O-glucoside (6) (Marlena and Irena, 2011), quercetin-7-O-glucoside (7) (Qin et al., 2003), kaempferol-3-O-rutinoside (8) (Yu et al., 1991), rutin (9) (Schiber et al., 2005), quercetin 3-O-gentiobioside (10) (Han et al., 2004), and quercetin-3, 7-di-O-glucoside (11) (Huang et al., 2002) (Fig. 1). 4. Chemotaxonomic significance Parnassia L., a rather homogeneous genus with unique external morphological characters (i.e. solitary, terminal, bisexual etc.), was established in 1753 by Linn. As a subfamily, it had been a member of Saxifragaceae for a long time (Engler, 1930; Ku,
OH
HO
HO
O
GlcO
O
OH
O
O OH
OH
OH OH
OH
OH
OH
OH
O
O
3
2
1
OH
OH
HO
HO
O
HO
O
OH
O
OH
HO
O
HO
O
OH
O
O
9 OH
OH
OH
OH GlcO
O
O OGlc
OGlc-Glc
10
OGlc-Rha OH
O
8
7
O
O
OGlc-Rha
OH
OH
OH
OH
OH
HO
O
6
OH
OH
OGlc OH
O
5
4
GlcO
O
ORha
OGlc OH
OH
OH
OH
OH
O
11 Fig. 1. Structures of compounds isolated from Parnassia palustris.
72
Y.-L. Hu et al. / Biochemical Systematics and Ecology 48 (2013) 70–72
1995; Gu and Hultgård, 2001). However, the classification of Parnassia has been controversial. Parnassia was treated in a family of its own, Parnassiaceae (Gray, 1821; Takhtajan, 1997) which was thought to be closely related to Celastraceae (Savolainen et al., 1997). Chemotaxonomy can be a useful tool in taxonomy of Parnassia. In this study, kaempferol (1), quercetin (2), their 3-Oglycosides (4–6, 8 and 10), 7-O-glycosides (3 and 7) and 3, 7-di-O-glucoside (11) were obtained from P. palustris. Kaempferol and quercetin are common in many families such as Anacardiaceae, Rosaeae, Saxifragaceae, Violaceae and Zingiberaceae (Bohm et al., 1986; Parveen and Khan, 1988; Jirovertz et al., 2003; Cai et al., 2004; Vukicsa et al., 2008). Quercetin-3-Ogentiobioside (10), isolated from P. palustris, occurs sporadically within the Saxifragaceae and this compound was previously found from some species of Bensoniella, Mitella and Tiarella such as Mitella diphylla L. and Bensoniella oregona (Abrams & Bacig.) C. V. Morton (Picman and Bohm, 1982; Nicholls et al., 1986). Kaempferol-7-O-glucoside (3), quercetin-7-O-glucoside (7), and quercetin-3, 7-di-O-glucoside (11) have limited distribution in the family Saxifragaceae in comparison with kaempferol and quercetin 3-O-glycosides (4–6, 8 and 10), but are found commonly available in some genera, such as Parnassia, Tiarella, Mitella and Lithophragma (Picman and Bohm, 1982; Nicholls and Bohm, 1984; Bohm et al., 1986; Nicholls et al., 1986). So these genera might be further distinguished from other genera of Saxifragaceae by its capacity to effect glycosylation at the 7-position, and the data supported some taxonomist’s suggestions that Parnassia stood apart from the Saxifragaceae (Gray, 1821; Takhtajan, 1997). In addition, kaempferol-7-O-glucoside (3) was reported from Euonymus alatus (Celastraceae) (Ba et al., 2012) and quercetin-3, 7-di-O-glucoside (11) was also reported from Euonymus maackii and Euonymus lanceifolia (Olechnowicz-Stepien, 1970).Moreover, kaempferol, quercetin and their 3-O-glucoside were also common in the Euonymus (Celastraceae) (Fang et al., 2008; Zhao et al., 2011), which suggested that there might be an association between the two genera. It should also be mentioned that Savolainen et al. (1997), on the basis of molecular phylogeny using atpB-rbcL analysis, suggested that Parnassia was the sister group of Euonymus (Celastraceae). Acknowledgment This research was supported by a grant (81060372) from National Natural Science Foundation of China, the key project of Chinese ministry of education (211033) and the “Twelfth Five-year Plan” Program supported by the Ministry of Science and Technology (2012BA128B02). References Ba, Y.Y., Liu, Q.Y., Shi, R.B., Zhang, L.Z., 2012. Chin. Tradit. Herbal Drugs 43, 242. Bohm, B.A., Donevan, L.S., Bhat, U.G., 1986. Syst. Ecol. 1, 75. Cai, Y.Z., Luo, Q., Sun, M., Corke, H., 2004. Life Sci. 74, 2157. Engler, A., 1930. Saxifragaceae. In: Engler, A., Prantl, K. (Eds.), Die Natürlichen Pflanzenfamillien, vol. 8. W Englmann, Leipzig, pp. 178–182. Fang, X.K., Gao, J., Zhu, D.N., 2008. Life Sci. 82, 615. Gray, S.F., 1821. Nat. Arr. Brit. Pl. 2, 623. Gu, C., Hultgård, U.M., 2001. Parnassia. In: Flora of China, vol. 8. Science Press and Missouri Botanical Garden Press, Beijing and St. Louis, pp. 358–379. Han, J.T., Bang, M.H., Chun, O.K., Kim, D.O., Lee, C.Y., Baek, N.I., 2004. Arch. Pharm. Res. 27, 390. Huang, S.Y., Shi, J.G., Yang, Y.C., 2002. Acta. Bot. Sin. 3, 199. Jirovertz, L., Buchbauer, G., Shafin, M.P., Leela, N.K., 2003. Acta Pharm. 2, 73. Kharitonova, N.P., 1967. Tr. Permsk. Farm. Inst. 2, 203. Ku, T.C., 1995. Parnassioideae. In: Flora Reipublica Popularis Sinicae, Beijing. Science Press, China, pp. 1–66. Lin, Y.L., Wang, W.Y., Kuo, Y.H., Chen, C.F., 2000. J. Chin. Chem. Soc. 47, 247. Marlena, D.M., Irena, M.A., 2011. Acta. Pol. Pharm. 3, 403. Nicholls, K.W., Bohm, B.A., 1984. Can. J. Bot. 62, 1636. Nicholls, K.W., Bohm, B.A., Wells, E.F., 1986. Can. J. Bot. 64, 525. Olechnowicz-Stepien, W., 1970. Diss. Pharm. Pharmacol. 22, 223. Parveen, N., Khan, N.U., 1988. J. Indian Chem. Soc. 65, 737. Picman, A.K., Bohm, B.A., 1982. Biochem. Syst. Ecol. 2, 139. Qin, B., Wang, H.Q., Zhu, D.Y., 2003. J. Plant Resour. Environ. 1, 6. Savolainen, V., Spichiger, R., Manen, J.F., 1997. Mol. Phylogenet. Evol. 7, 145. Schiber, A., Mihalev, K., Berardini, N., Mollov, P., Carle, R., 2005. Z. Naturforsch. C. 6, 379. Simmons, M.P., 2004. Parnassiaceae. In: Ked, K. (Ed.), The Families and Genera of Vascular Plants. Springer., Berlin, pp. 291–296. Takhtajan, A., 1997. Diversity and Classification of Flowering Plants. Columbia University Press, New York. 1–643. Tamara, B., Jela, G.V., 2004. Pharmacia (Sarajevo, Bosnia and Herzegovina) 15, 7. Vukicsa, V., Ringera, T., Keryb, A., Bonna, G.K., Guttmana, A., 2008. J. Chromatogr. 1, 11. Yu, R., Li, X., Zhu, T., Harigaya, Y., Konda, Y., Onda, M., 1991. China J. Magn. Reson. Imaging 1, 99. Zhao, Z.Y., Dong, L.L., Wu, Y.L., Lin, F., 2011. Food Bioprod. Process 89, 266.
Contents lists available at SciVerse ScienceDirect
Biochemical Systematics and Ecology journal homepage: www.elsevier.com/locate/biochemsyseco
Flavonols from Parnassia palustris Linn. (Saxifragaceae) Yu-Li Hu, Qian-Quan Li, Jia Zhang, Chun-Hong Zhang, Na Zhang, Zhan-Hu Cui, Min-Hui Li* Baotou Medical College, No. 31 Construction Road, Baotou, Inner Mongolia 014060, China
a r t i c l e i n f o Article history: Received 19 October 2012 Accepted 1 December 2012 Available online 16 January 2013 Keywords: Parnassia palustris Linn. Saxifragaceae Flavonols Chemotaxonomy
1. Subject and source Parnassia palustris Linn. is mainly distributed in North America, Europe, Asia, and South Morocco (Simmons, 2004). It is a perennial herb used for the treatment of icteric hepatitis and angiitis. In this investigation, the aerial parts of this plant were collected from Inner Mongolia Virgin Forest near the boundary of China and Russia in August 2011. A voucher specimen (Bt 2011081606) has been deposited in Baotou Medical College, China. 2. Previous work The genus Parnassia (Saxifragaceae) has over 70 species, which is distributed in the arctic-alpine regions of the Northern Hemisphere, primarily in Southeast and Central Asia (Ku, 1995). Early phytochemical investigation of the genus Parnassia has led to the identification of kaempferol, quercetin and their 3-O-glucosides, 3-O-arabinosides, 3-O-rhamnosides and quercetin 3-O-rhamnosylrhamnoside-7-O-rhamnoside, 3,7-di-O-glucosides, 3-O-xyloside-7-O-rhamnosides by thin-layer chromatography (Bohm et al., 1986). Kharitonova (1967) also detected quercetin-3-O-glucoside from P. palustris, while Tamara and Jela (2004) detected tannin (cyanidine). 3. Present study The air-dried aerial parts of P. palustris (1.2 kg) were extracted with methanol for 3 times at 70 C. The extracts were evaporated in a rotary evaporator to obtain 270 g of syrupy residue. A sample (260 g) of the residue was suspended in water (2 L) and fractionated with petroleum ether, EtOAc, and n-BuOH, respectively. The EtOAc portion (24 g) was subjected to dry column on silica gel (200–300 mesh, 700 g) and eluted with CH2Cl2: MeOH (7:1, v/v) to get 4 main fractions (Frs. A1-4). Fraction A3 (3 g) was then further chromatographied on silica gel (300–400 mesh, * Corresponding author. Tel.: þ86 472 7167795. E-mail address: [email protected] (M.-H. Li). 0305-1978/$ – see front matter Ó 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.bse.2012.12.014
Y.-L. Hu et al. / Biochemical Systematics and Ecology 48 (2013) 70–72
71
90 g) eluted with CH2Cl2 and increased percentage of MeOH (0–90%, v/v) to give 50 fractions (Frs. B1-50). The combined fraction B6-18 and fraction B25-43 were further purified by repeated Sephadex LH-20 to obtain compound 1 (10 mg), 2 (12 mg), 3 (19 mg), 4 (24 mg), 5 (26 mg), 6 (27 mg), and 7 (35 mg). The n-BuOH portion (100 g) was subjected to dry column on silica gel (200–300 mesh, 2000 g) eluting with CH2Cl2: MeOH: H2O (7:3:0.5, v/v), 4 main fractions (Frs. C1-4) were obtained. Fraction C3 (20 g) was then further chromatographied on silica gel (300–400 mesh, 400 g) eluting with EtOAc: MeOH: H2O (8:2:1, v/v) to give 48 fractions (Frs. D1-48). The combined fraction D9-29 was further separated on Sephadex LH-20 with H2O and increasing percentage of MeOH (40–100%) to give 4 fractions (Frs. E1-4), and then the E2 fraction was purified by ODS with percentage of MeOH and H2O (45%) to give compound 8 (12 mg), 9 (20 mg), 10 (24 mg), and 11 (30 mg). The structures of these compounds were elucidated by different spectrometric methods (1HNMR, 13CNMR and ESI-MS) and in comparison with published data as kaempferol (1) (Lin et al., 2000), quercetin (2) (Schiber et al., 2005), kaempferol-7-O-glucoside (3) (Lin et al., 2000), kaempferol-3-O-glucoside (4) (Marlena and Irena, 2011), quercetin-3-O-rhamnoside (5) (Schiber et al., 2005), quercetin-3-O-glucoside (6) (Marlena and Irena, 2011), quercetin-7-O-glucoside (7) (Qin et al., 2003), kaempferol-3-O-rutinoside (8) (Yu et al., 1991), rutin (9) (Schiber et al., 2005), quercetin 3-O-gentiobioside (10) (Han et al., 2004), and quercetin-3, 7-di-O-glucoside (11) (Huang et al., 2002) (Fig. 1). 4. Chemotaxonomic significance Parnassia L., a rather homogeneous genus with unique external morphological characters (i.e. solitary, terminal, bisexual etc.), was established in 1753 by Linn. As a subfamily, it had been a member of Saxifragaceae for a long time (Engler, 1930; Ku,
OH
HO
HO
O
GlcO
O
OH
O
O OH
OH
OH OH
OH
OH
OH
OH
O
O
3
2
1
OH
OH
HO
HO
O
HO
O
OH
O
OH
HO
O
HO
O
OH
O
O
9 OH
OH
OH
OH GlcO
O
O OGlc
OGlc-Glc
10
OGlc-Rha OH
O
8
7
O
O
OGlc-Rha
OH
OH
OH
OH
OH
HO
O
6
OH
OH
OGlc OH
O
5
4
GlcO
O
ORha
OGlc OH
OH
OH
OH
OH
O
11 Fig. 1. Structures of compounds isolated from Parnassia palustris.
72
Y.-L. Hu et al. / Biochemical Systematics and Ecology 48 (2013) 70–72
1995; Gu and Hultgård, 2001). However, the classification of Parnassia has been controversial. Parnassia was treated in a family of its own, Parnassiaceae (Gray, 1821; Takhtajan, 1997) which was thought to be closely related to Celastraceae (Savolainen et al., 1997). Chemotaxonomy can be a useful tool in taxonomy of Parnassia. In this study, kaempferol (1), quercetin (2), their 3-Oglycosides (4–6, 8 and 10), 7-O-glycosides (3 and 7) and 3, 7-di-O-glucoside (11) were obtained from P. palustris. Kaempferol and quercetin are common in many families such as Anacardiaceae, Rosaeae, Saxifragaceae, Violaceae and Zingiberaceae (Bohm et al., 1986; Parveen and Khan, 1988; Jirovertz et al., 2003; Cai et al., 2004; Vukicsa et al., 2008). Quercetin-3-Ogentiobioside (10), isolated from P. palustris, occurs sporadically within the Saxifragaceae and this compound was previously found from some species of Bensoniella, Mitella and Tiarella such as Mitella diphylla L. and Bensoniella oregona (Abrams & Bacig.) C. V. Morton (Picman and Bohm, 1982; Nicholls et al., 1986). Kaempferol-7-O-glucoside (3), quercetin-7-O-glucoside (7), and quercetin-3, 7-di-O-glucoside (11) have limited distribution in the family Saxifragaceae in comparison with kaempferol and quercetin 3-O-glycosides (4–6, 8 and 10), but are found commonly available in some genera, such as Parnassia, Tiarella, Mitella and Lithophragma (Picman and Bohm, 1982; Nicholls and Bohm, 1984; Bohm et al., 1986; Nicholls et al., 1986). So these genera might be further distinguished from other genera of Saxifragaceae by its capacity to effect glycosylation at the 7-position, and the data supported some taxonomist’s suggestions that Parnassia stood apart from the Saxifragaceae (Gray, 1821; Takhtajan, 1997). In addition, kaempferol-7-O-glucoside (3) was reported from Euonymus alatus (Celastraceae) (Ba et al., 2012) and quercetin-3, 7-di-O-glucoside (11) was also reported from Euonymus maackii and Euonymus lanceifolia (Olechnowicz-Stepien, 1970).Moreover, kaempferol, quercetin and their 3-O-glucoside were also common in the Euonymus (Celastraceae) (Fang et al., 2008; Zhao et al., 2011), which suggested that there might be an association between the two genera. It should also be mentioned that Savolainen et al. (1997), on the basis of molecular phylogeny using atpB-rbcL analysis, suggested that Parnassia was the sister group of Euonymus (Celastraceae). Acknowledgment This research was supported by a grant (81060372) from National Natural Science Foundation of China, the key project of Chinese ministry of education (211033) and the “Twelfth Five-year Plan” Program supported by the Ministry of Science and Technology (2012BA128B02). References Ba, Y.Y., Liu, Q.Y., Shi, R.B., Zhang, L.Z., 2012. Chin. Tradit. Herbal Drugs 43, 242. Bohm, B.A., Donevan, L.S., Bhat, U.G., 1986. Syst. Ecol. 1, 75. Cai, Y.Z., Luo, Q., Sun, M., Corke, H., 2004. Life Sci. 74, 2157. Engler, A., 1930. Saxifragaceae. In: Engler, A., Prantl, K. (Eds.), Die Natürlichen Pflanzenfamillien, vol. 8. W Englmann, Leipzig, pp. 178–182. Fang, X.K., Gao, J., Zhu, D.N., 2008. Life Sci. 82, 615. Gray, S.F., 1821. Nat. Arr. Brit. Pl. 2, 623. Gu, C., Hultgård, U.M., 2001. Parnassia. In: Flora of China, vol. 8. Science Press and Missouri Botanical Garden Press, Beijing and St. Louis, pp. 358–379. Han, J.T., Bang, M.H., Chun, O.K., Kim, D.O., Lee, C.Y., Baek, N.I., 2004. Arch. Pharm. Res. 27, 390. Huang, S.Y., Shi, J.G., Yang, Y.C., 2002. Acta. Bot. Sin. 3, 199. Jirovertz, L., Buchbauer, G., Shafin, M.P., Leela, N.K., 2003. Acta Pharm. 2, 73. Kharitonova, N.P., 1967. Tr. Permsk. Farm. Inst. 2, 203. Ku, T.C., 1995. Parnassioideae. In: Flora Reipublica Popularis Sinicae, Beijing. Science Press, China, pp. 1–66. Lin, Y.L., Wang, W.Y., Kuo, Y.H., Chen, C.F., 2000. J. Chin. Chem. Soc. 47, 247. Marlena, D.M., Irena, M.A., 2011. Acta. Pol. Pharm. 3, 403. Nicholls, K.W., Bohm, B.A., 1984. Can. J. Bot. 62, 1636. Nicholls, K.W., Bohm, B.A., Wells, E.F., 1986. Can. J. Bot. 64, 525. Olechnowicz-Stepien, W., 1970. Diss. Pharm. Pharmacol. 22, 223. Parveen, N., Khan, N.U., 1988. J. Indian Chem. Soc. 65, 737. Picman, A.K., Bohm, B.A., 1982. Biochem. Syst. Ecol. 2, 139. Qin, B., Wang, H.Q., Zhu, D.Y., 2003. J. Plant Resour. Environ. 1, 6. Savolainen, V., Spichiger, R., Manen, J.F., 1997. Mol. Phylogenet. Evol. 7, 145. Schiber, A., Mihalev, K., Berardini, N., Mollov, P., Carle, R., 2005. Z. Naturforsch. C. 6, 379. Simmons, M.P., 2004. Parnassiaceae. In: Ked, K. (Ed.), The Families and Genera of Vascular Plants. Springer., Berlin, pp. 291–296. Takhtajan, A., 1997. Diversity and Classification of Flowering Plants. Columbia University Press, New York. 1–643. Tamara, B., Jela, G.V., 2004. Pharmacia (Sarajevo, Bosnia and Herzegovina) 15, 7. Vukicsa, V., Ringera, T., Keryb, A., Bonna, G.K., Guttmana, A., 2008. J. Chromatogr. 1, 11. Yu, R., Li, X., Zhu, T., Harigaya, Y., Konda, Y., Onda, M., 1991. China J. Magn. Reson. Imaging 1, 99. Zhao, Z.Y., Dong, L.L., Wu, Y.L., Lin, F., 2011. Food Bioprod. Process 89, 266.