- Email: [email protected]
A new pyrrole alkaloid from Selaginella moellendorfii Hieron
Chinese Chemical Letters 24 (2013) 114–116
Contents lists available at SciVerse ScienceDirect
Chinese Chemical Letters journal homepage: www.elsevier.com/locate/cclet
Original article
A new pyrrole alkaloid from Selaginella moellendorfii Hieron Zhen-Xing Zou a, Kang-Ping Xu a, Fu-Shuang Li a, Hui Zou a, Min-Zhen Liu a, Qiong Zhang a, Kai Yu a, Lan-Fang Zhao a, Lei-Hong Tan a, Gui-Shan Tan a,b,* a b
School of Pharmaceutical Sciences, Central South University, Changsha 410013, China Xiangya Hospital of Central South University, Changsha 410008, China
A R T I C L E I N F O
A B S T R A C T
Article history: Received 9 November 2012 Received in revised form 17 December 2012 Accepted 5 January 2013 Available online 4 February 2013
One new pyrrole alkaloid, N-(2E)-3-(3,4-dihydrophenyl)prop-N10 -(4-aminobutyl)-3-pyrrole formaldehyde (1), was isolated from the whole herbs of Selaginella moellendorfii Hieron. The structure was elucidated by spectroscopic analyses including UV, IR, 1D NMR, 2D NMR and MS methods. Additionally, compound 1 exhibited potent protective effect against the injury of human umbilical vein endothelial cell (HUVECs) induced by high concentrations of glucose in vitro. ß 2013 Gui-Shan Tan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
Keywords: Selaginella Selaginella moellendorfii Hieron Pyrrole alkaloid HUVECs
1. Introduction Selaginella moellendorfii Hieron (Selaginellaceae) is mainly distributed in the southern area of the Yangtze River in China and is commonly used as Chinese Herbs and Ethnic Medicines. Modern pharmacological studies have shown that it has extensive pharmacological actions, such as antitumor, antibacterial, antiviral, and immune regulating agents [1,2]. Chemical constituents previously reported in this plant were mainly flavonoids, biflavonoids, lignans, alkaloids and so on [2–6]. Recently, a series of alkynyl phenols with a new carbon skeleton, selaginellin and selaginellins A-N, have been isolated from genus Selaginella sinensis [7], Selaginella tamariscina [8,9], and Selaginella pulvinata [10–15], respectively. In our continuing study on the chemical constituents in the genus S. moellendorfii Hieron, we report the isolation and structural elucidation of a new pyrrole alkaloid, named as N-(2E)3-(3,4-dihydrophenyl)prop-N10 -(4-aminobutyl)-3-pyrrole formaldehyde (1) (Fig. 1).
authenticated by Prof. Zhen-Ji Li (Xiamen University, Xiamen, China). A voucher specimen (No. 20080917) was deposited in School of Pharmaceutical Sciences, Central South University. The whole herbs of S. moellendorfii Hieron (10.0 kg) were refluxed in 70% EtOH for two times (100 L, 80 L, 2 h each time). After removal of the solvent at a reduced pressure, the extract (1.0 kg) was subjected to macroporous resin HPD-100 with gradient elution of H2O, 40%, 70%, 95% EtOH–H2O to afford four fractions. The 70% EtOH portion was subjected to polyamide column chromatography with gradient elution of H2O, 40%, 70%, 95% EtOH–H2O to afford four fractions. The 70% EtOH portion was subjected to column chromatography on silica gel with gradient elution of CHCl3/MeOH/H2O (1:0:0–0:1:1) to obtain eight subfractions (S1–S8). After the separation of subfraction S6 on Sephadex LH-20 (MeOH/H2O in gradient) and preparative HPLC (YMC-Pack ODS-A; 250 mm 10 mm 10 mm; 3 mL/min; 23% ACN/ H2O) sequentially, compound 1 (Fig. 1) (12 mg) was obtained. 3. Results and discussion
2. Experimental Herbs of S. moellendorfii Hieron were collected from Anguo Herb Market, Heibei Province, China, in September 2008, and
* Corresponding author at: School of Pharmaceutical Sciences, Central South University, Changsha 410013, China. E-mail address: [email protected] (G.-S. Tan).
Compound 1 was obtained as an amorphous powder. Its molecular formula was determined to be C18H20O4N2 by HREIMS (m/z: 328.1415; cacld. 328.1418). The IR spectrum revealed the presence of hydroxyl (3304 cm1), aromatic (1600, 1560, 1457 cm1) and carbonyl (1654 cm1, 1637 cm1) groups. The 1 H NMR spectrum of compound 1 (Table 1) displayed a 2,5,6trisubstituted aromatic ring at d 6.93 (d, 1H, J = 2.0 Hz), d 6.82 (dd, 1H, J = 8.5, 2.0 Hz) and d 6.73 (d, 1H, J = 8.5 Hz), two trans olefinic
1001-8417/$ – see front matter ß 2013 Gui-Shan Tan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved. http://dx.doi.org/10.1016/j.cclet.2013.01.028
Z.-X. Zou et al. / Chinese Chemical Letters 24 (2013) 114–116
8
3
2
9
1
H N 1'
2'
3'
4'
1 '' 5' N
O
2 ''
5 ''
3 ''
6'' O
4 ''
H
H
H
HO
H
N H H
H
O
H
H
H
O
N H
H
H
H
1H-1H-COSY
HMBC
Fig. 1. The structure of compound 1.
Fig. 2. Key 1H–1H COSY and HMBC correlations of compound 1.
protons at d 7.21 (d, 1H, J = 15.5 Hz) and d 6.30 (d, 1H, J = 15.5 Hz), four methylene groups at d 3.12–3.16 (m, 2H), d 1.35–1.38 (m, 2H), d 1.66–1.69 (m, 2H) and d 4.29 (t, 2H, J = 7.0 Hz), respectively, and one amino proton at d 7.97 (t, 1H, J = 5.5 Hz). The 13C NMR spectrum of compound 1 (Table 1) showed eighteen signals, which were classified as one aldehyde carbon (d 179.7), one a,bunsaturated lactone moiety (d 165.8, 139.4 and 119.0), six aromatic carbons (d 147.8, 146.0, 126.9, 120.8, 116.2 and 114.3), and four methylene carbons (d 48.1, 38.6, 29.1 and 26.8). Analyses of DEPT, HSQC and COSY spectra suggested that compound 1 was a pyrrole derivative that contained a paucine moiety [16]. Additionally, in the 1H NMR spectrum, a pair of coupled protons at d 6.23, 7.02 and another proton at d 7.31 with coupling constants of 2.5 and 2.0 Hz, respectively, showed that these three protons belonged to a pyrrole ring. The corresponding carbon signals were at d 109.8, 124.9 and 132.6, respectively. In the HMBC spectrum, the correlation between d 4.29 (H-50 ) and d 132.6 (C-200 ), d 9.50 (H600 ) and d 131.4 (C-300 ) indicated the linkages between the C-50 and N-100 , C-600 and C-300 . From these data, the structure of compound 1 (Fig. 1) was determined as N-(2E)-3-(3,4-dihydrophenyl)prop-N10 (4-aminobutyl)-3-pyrrole-formaldehyde. The full assignment of 1 H and 13C NMR spectra was accomplished with the aid of DEPT, HSQC, 1H–1H COSY and HMBC experiments (Fig. 2). Additionally, we investigated the protective effect of compound 1 on the injury of HUVECs induced by high concentrations of glucose. In this experiment, compound 1 showed potent protective affects at 101 mmol/L and 102 mmol/L on the HUVECs induced by high concentrations of glucose in vitro (Fig. 3). Numerous studies showed that the injury of HUVECs induced by glucose circumstance was closely related to the vascular complications of diabetes [17,18]. We will continue to conduct more pharmacological activity evaluations on compound 1 and explore the underlying mechanism of action.
0.4 0.3
##
##
*
0.2 0.1 0.0
(5 Gl uc .5 m os e ( mol /L 30 ) m m ol /L +1 ) 0 ¦Ìm ol /L +1 ¦Ìm o +1 0 -1 l/L ¦Ìm +1 o 0 -2 l/L ¦Ìm o +1 0 -3 l/L ¦Ìm o +1 0 -4 l/L ¦Ìm o +1 0 -5 l/L ¦Ìm ol /L
4
7
HO
H
5
Cell number (MTT assay) (Abs at 490 nm)
HO
6
co n
HO
115
Fig. 3. Effect of compound 1 on high concentration glucose-induced viability of HUVECs (mean SEM, n = 3), *P < 0.05 vs con (5.5 mmol/L), #P < 0.05, ##P < 0.01 vs glucose (30 mmol/L).
4. Conclusion We studied on the chemical constituents of the genus S. moellendorfii Hieron and report here the isolation and structural elucidation of a new pyrrole named as N-(2E)-3-(3,4-dihydrophenyl)prop-N10 -(4-aminobutyl)-3-pyrrole formaldehyde, together with its potent protective affect against the injury of HUVECs for the first time. Acknowledgments
Table 1 1 H NMR (500 MHz) and 13C NMR (125 MHz) data of compound 1 in DMSO-d6 (d in ppm, J in Hz). Position 1 2 3 4 5 6 7 8 9 10 20 30 40 50 100 200 300 400 500 600
dH 6.30 (d, 1H, J = 15.5) 7.21 (d, 1H, J = 15.5) 6.93 (d, 1H, J = 2.0)
6.73 (d, 1H, J = 8.5) 6.82 (d, 1H, d J = 8.5, 2.0) 7.97 (t, 1H, J = 5.5) 3.12–3.16 (m, 2H)a 1.35–1.38 (m, 2H)a 1.66–1.69 (m, 2H)a 4.29 (t, 2H, J = 7.0) 7.31 (1H, br.s) 6.23 (dd, 1H, J = 4.0, 2.5) 7.02 (dd, 1H, J = 4.0, 2.0) 9.50 (s, 1H)
dC 165.8 119.0 139.4 126.9 114.3 146.0 147.8 116.2 120.8 38.6 26.8 29.1 48.1 132.6 131.4 109.8 124.9 179.7
a Signal patterns are unclear due to overlapping, assignments were based on HSQC and HMBC experiments.
This research was supported by the Doctoral Program Foundation of Institutions of Higher Education of China (No. 20100162110057), National Natural Science Foundation (No. 30873149), Chinese Medicine Research Program of Hunan Province (Nos. 2009059 and 2010004), National Innovation Experiment Program for University Students (No. LA10031), Fundamental Research Funds for the Central South Universities of Central South University (No. 2012zzts115), and Independent Exploration Program of Central South University (No. 201011200235). References [1] S.Y. Shi, H.H. Zhou, Y.P. Zhang, et al., Hyphenated HSCCC-DPPH for rapid preparative isolation and screening of antioxidants from Selaginella moellendorffii, Chromatographia 68 (2008) 173–178. [2] Y. Cao, N.H. Tan, J.J. Chen, et al., Bioactive flavones and biflavones from Selaginella moellendorffii Hieron, Fitoterapia 81 (2010) 253–258. [3] Y.H. Wang, Q.Y. Sun, F.M. Yang, et al., Neolignans and pyrrole derivatives from Selaginella moellendorffii, Helv. Chim. Acta 93 (2010) 2467–2477. [4] H.S. Wang, L. Sun, Y.H. Wang, et al., Carboxymethyl flavonoids and a monoterpene glucoside from Selaginella moellendorffii, Arch. Pharm. Res. 34 (2011) 1283–1288. [5] B. Wu, J. Wang, Phenolic compounds from Selaginella moellendorfii, Chem. Biodivers 8 (2011) 1735–1747.
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Z.-X. Zou et al. / Chinese Chemical Letters 24 (2013) 114–116
[6] Y.H. Wang, C.L. Long, F.M. Yang, et al., Pyrrolidinoindoline alkaloids from Selainella moellendorfii, J. Nat. Prod. 72 (2009) 1151–1154. [7] L.P. Zhang, Y.M. Liang, X.C. Wei, et al., A new unusual natural pigment from Selaginella sinensis and its noticeable physicochemical properties, J. Org. Chem. 72 (2007) 3921–3924. [8] X.L. Cheng, S.C. Ma, J.D. Yu, et al., Selaginellin A and B, two novel natural pigments isolated from Selaginella tamariscina, Chem. Pharm. Bull. 56 (2008) 982–984. [9] G.G. Zhang, Y. Jing, H.M. Zhang, et al., Isolation and cytotoxic activity of selaginellin derivatives and biflavonoids from Selaginella tamariscina, Planta Med. 78 (2012) 390–392. [10] G.S. Tan, K.P. Xu, F.S. Li, et al., Selaginellin C, a new natural pigment from Selaginella pulvinata Maxim (Hook et Grev.), J. Asian Nat. Prod. Res. 11 (2009) 1001–1004. [11] Y. Cao, J.J. Chen, N.H. Tan, et al., Antimicrobial selaginellin derivatives from Selaginella pulvinata, Bioorg. Med. Chem. Lett. 20 (2010) 2456–2460. [12] Y. Cao, J.J. Chen, N.H. Tan, et al., Structure determination of selaginellins G and H from Selaginella pulvinata by NMR spectroscopy, Magn. Reson. Chem. 48 (2010) 656–659.
[13] K.P. Xu, H. Zou, Q. Tan, et al., Selaginellins I and J, two new alkynyl phenols, from Selaginella tamariscina (Beauv.) Spring, J. Asian Nat. Prod. Res. 13 (2011) 93–96. [14] K.P. Xu, H. Zou, F.S. Li, et al., Two new selaginellin derivatives from Selaginella tamariscina (Beauv.) Spring, J. Asian Nat. Prod. Res. 13 (2011) 356–360. [15] K.P. Xu, H. Zou, G.R. Liu, et al., Selaginellin M, a new selaginellin derivative from Selaginella pulvinata, J. Asian Nat. Prod. Res. 13 (2011) 1051–1055. [16] H. Keller, H. Hohlfeld, V. Wray, et al., Changes in accumulation of soluble and cell wall-bound phenolics in elicitor-treated cell suspension cultures and fungus-infected leaves of solanum tuberosum, Phytochemistry 42 (1996) 389–396. [17] A.V. Noe, P. Araceli, Z. Estrella, et al., HUVECs from newborns with a strong family history of diabetes show diminished ROS synthesis in the presence of high glucose concentrations, Diabetes Metab. Res. 23 (2007) 71–80. [18] G. Sedegheh, H. Tore, K. Svein, High glucose and N-(carboxymethyl) lysine bovine serum albumin modulate release of matrix metalloproteinases in cultured human endothelial cells, Eur. J. Clin. Nutr. 45 (2006) 283–290.
Contents lists available at SciVerse ScienceDirect
Chinese Chemical Letters journal homepage: www.elsevier.com/locate/cclet
Original article
A new pyrrole alkaloid from Selaginella moellendorfii Hieron Zhen-Xing Zou a, Kang-Ping Xu a, Fu-Shuang Li a, Hui Zou a, Min-Zhen Liu a, Qiong Zhang a, Kai Yu a, Lan-Fang Zhao a, Lei-Hong Tan a, Gui-Shan Tan a,b,* a b
School of Pharmaceutical Sciences, Central South University, Changsha 410013, China Xiangya Hospital of Central South University, Changsha 410008, China
A R T I C L E I N F O
A B S T R A C T
Article history: Received 9 November 2012 Received in revised form 17 December 2012 Accepted 5 January 2013 Available online 4 February 2013
One new pyrrole alkaloid, N-(2E)-3-(3,4-dihydrophenyl)prop-N10 -(4-aminobutyl)-3-pyrrole formaldehyde (1), was isolated from the whole herbs of Selaginella moellendorfii Hieron. The structure was elucidated by spectroscopic analyses including UV, IR, 1D NMR, 2D NMR and MS methods. Additionally, compound 1 exhibited potent protective effect against the injury of human umbilical vein endothelial cell (HUVECs) induced by high concentrations of glucose in vitro. ß 2013 Gui-Shan Tan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
Keywords: Selaginella Selaginella moellendorfii Hieron Pyrrole alkaloid HUVECs
1. Introduction Selaginella moellendorfii Hieron (Selaginellaceae) is mainly distributed in the southern area of the Yangtze River in China and is commonly used as Chinese Herbs and Ethnic Medicines. Modern pharmacological studies have shown that it has extensive pharmacological actions, such as antitumor, antibacterial, antiviral, and immune regulating agents [1,2]. Chemical constituents previously reported in this plant were mainly flavonoids, biflavonoids, lignans, alkaloids and so on [2–6]. Recently, a series of alkynyl phenols with a new carbon skeleton, selaginellin and selaginellins A-N, have been isolated from genus Selaginella sinensis [7], Selaginella tamariscina [8,9], and Selaginella pulvinata [10–15], respectively. In our continuing study on the chemical constituents in the genus S. moellendorfii Hieron, we report the isolation and structural elucidation of a new pyrrole alkaloid, named as N-(2E)3-(3,4-dihydrophenyl)prop-N10 -(4-aminobutyl)-3-pyrrole formaldehyde (1) (Fig. 1).
authenticated by Prof. Zhen-Ji Li (Xiamen University, Xiamen, China). A voucher specimen (No. 20080917) was deposited in School of Pharmaceutical Sciences, Central South University. The whole herbs of S. moellendorfii Hieron (10.0 kg) were refluxed in 70% EtOH for two times (100 L, 80 L, 2 h each time). After removal of the solvent at a reduced pressure, the extract (1.0 kg) was subjected to macroporous resin HPD-100 with gradient elution of H2O, 40%, 70%, 95% EtOH–H2O to afford four fractions. The 70% EtOH portion was subjected to polyamide column chromatography with gradient elution of H2O, 40%, 70%, 95% EtOH–H2O to afford four fractions. The 70% EtOH portion was subjected to column chromatography on silica gel with gradient elution of CHCl3/MeOH/H2O (1:0:0–0:1:1) to obtain eight subfractions (S1–S8). After the separation of subfraction S6 on Sephadex LH-20 (MeOH/H2O in gradient) and preparative HPLC (YMC-Pack ODS-A; 250 mm 10 mm 10 mm; 3 mL/min; 23% ACN/ H2O) sequentially, compound 1 (Fig. 1) (12 mg) was obtained. 3. Results and discussion
2. Experimental Herbs of S. moellendorfii Hieron were collected from Anguo Herb Market, Heibei Province, China, in September 2008, and
* Corresponding author at: School of Pharmaceutical Sciences, Central South University, Changsha 410013, China. E-mail address: [email protected] (G.-S. Tan).
Compound 1 was obtained as an amorphous powder. Its molecular formula was determined to be C18H20O4N2 by HREIMS (m/z: 328.1415; cacld. 328.1418). The IR spectrum revealed the presence of hydroxyl (3304 cm1), aromatic (1600, 1560, 1457 cm1) and carbonyl (1654 cm1, 1637 cm1) groups. The 1 H NMR spectrum of compound 1 (Table 1) displayed a 2,5,6trisubstituted aromatic ring at d 6.93 (d, 1H, J = 2.0 Hz), d 6.82 (dd, 1H, J = 8.5, 2.0 Hz) and d 6.73 (d, 1H, J = 8.5 Hz), two trans olefinic
1001-8417/$ – see front matter ß 2013 Gui-Shan Tan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved. http://dx.doi.org/10.1016/j.cclet.2013.01.028
Z.-X. Zou et al. / Chinese Chemical Letters 24 (2013) 114–116
8
3
2
9
1
H N 1'
2'
3'
4'
1 '' 5' N
O
2 ''
5 ''
3 ''
6'' O
4 ''
H
H
H
HO
H
N H H
H
O
H
H
H
O
N H
H
H
H
1H-1H-COSY
HMBC
Fig. 1. The structure of compound 1.
Fig. 2. Key 1H–1H COSY and HMBC correlations of compound 1.
protons at d 7.21 (d, 1H, J = 15.5 Hz) and d 6.30 (d, 1H, J = 15.5 Hz), four methylene groups at d 3.12–3.16 (m, 2H), d 1.35–1.38 (m, 2H), d 1.66–1.69 (m, 2H) and d 4.29 (t, 2H, J = 7.0 Hz), respectively, and one amino proton at d 7.97 (t, 1H, J = 5.5 Hz). The 13C NMR spectrum of compound 1 (Table 1) showed eighteen signals, which were classified as one aldehyde carbon (d 179.7), one a,bunsaturated lactone moiety (d 165.8, 139.4 and 119.0), six aromatic carbons (d 147.8, 146.0, 126.9, 120.8, 116.2 and 114.3), and four methylene carbons (d 48.1, 38.6, 29.1 and 26.8). Analyses of DEPT, HSQC and COSY spectra suggested that compound 1 was a pyrrole derivative that contained a paucine moiety [16]. Additionally, in the 1H NMR spectrum, a pair of coupled protons at d 6.23, 7.02 and another proton at d 7.31 with coupling constants of 2.5 and 2.0 Hz, respectively, showed that these three protons belonged to a pyrrole ring. The corresponding carbon signals were at d 109.8, 124.9 and 132.6, respectively. In the HMBC spectrum, the correlation between d 4.29 (H-50 ) and d 132.6 (C-200 ), d 9.50 (H600 ) and d 131.4 (C-300 ) indicated the linkages between the C-50 and N-100 , C-600 and C-300 . From these data, the structure of compound 1 (Fig. 1) was determined as N-(2E)-3-(3,4-dihydrophenyl)prop-N10 (4-aminobutyl)-3-pyrrole-formaldehyde. The full assignment of 1 H and 13C NMR spectra was accomplished with the aid of DEPT, HSQC, 1H–1H COSY and HMBC experiments (Fig. 2). Additionally, we investigated the protective effect of compound 1 on the injury of HUVECs induced by high concentrations of glucose. In this experiment, compound 1 showed potent protective affects at 101 mmol/L and 102 mmol/L on the HUVECs induced by high concentrations of glucose in vitro (Fig. 3). Numerous studies showed that the injury of HUVECs induced by glucose circumstance was closely related to the vascular complications of diabetes [17,18]. We will continue to conduct more pharmacological activity evaluations on compound 1 and explore the underlying mechanism of action.
0.4 0.3
##
##
*
0.2 0.1 0.0
(5 Gl uc .5 m os e ( mol /L 30 ) m m ol /L +1 ) 0 ¦Ìm ol /L +1 ¦Ìm o +1 0 -1 l/L ¦Ìm +1 o 0 -2 l/L ¦Ìm o +1 0 -3 l/L ¦Ìm o +1 0 -4 l/L ¦Ìm o +1 0 -5 l/L ¦Ìm ol /L
4
7
HO
H
5
Cell number (MTT assay) (Abs at 490 nm)
HO
6
co n
HO
115
Fig. 3. Effect of compound 1 on high concentration glucose-induced viability of HUVECs (mean SEM, n = 3), *P < 0.05 vs con (5.5 mmol/L), #P < 0.05, ##P < 0.01 vs glucose (30 mmol/L).
4. Conclusion We studied on the chemical constituents of the genus S. moellendorfii Hieron and report here the isolation and structural elucidation of a new pyrrole named as N-(2E)-3-(3,4-dihydrophenyl)prop-N10 -(4-aminobutyl)-3-pyrrole formaldehyde, together with its potent protective affect against the injury of HUVECs for the first time. Acknowledgments
Table 1 1 H NMR (500 MHz) and 13C NMR (125 MHz) data of compound 1 in DMSO-d6 (d in ppm, J in Hz). Position 1 2 3 4 5 6 7 8 9 10 20 30 40 50 100 200 300 400 500 600
dH 6.30 (d, 1H, J = 15.5) 7.21 (d, 1H, J = 15.5) 6.93 (d, 1H, J = 2.0)
6.73 (d, 1H, J = 8.5) 6.82 (d, 1H, d J = 8.5, 2.0) 7.97 (t, 1H, J = 5.5) 3.12–3.16 (m, 2H)a 1.35–1.38 (m, 2H)a 1.66–1.69 (m, 2H)a 4.29 (t, 2H, J = 7.0) 7.31 (1H, br.s) 6.23 (dd, 1H, J = 4.0, 2.5) 7.02 (dd, 1H, J = 4.0, 2.0) 9.50 (s, 1H)
dC 165.8 119.0 139.4 126.9 114.3 146.0 147.8 116.2 120.8 38.6 26.8 29.1 48.1 132.6 131.4 109.8 124.9 179.7
a Signal patterns are unclear due to overlapping, assignments were based on HSQC and HMBC experiments.
This research was supported by the Doctoral Program Foundation of Institutions of Higher Education of China (No. 20100162110057), National Natural Science Foundation (No. 30873149), Chinese Medicine Research Program of Hunan Province (Nos. 2009059 and 2010004), National Innovation Experiment Program for University Students (No. LA10031), Fundamental Research Funds for the Central South Universities of Central South University (No. 2012zzts115), and Independent Exploration Program of Central South University (No. 201011200235). References [1] S.Y. Shi, H.H. Zhou, Y.P. Zhang, et al., Hyphenated HSCCC-DPPH for rapid preparative isolation and screening of antioxidants from Selaginella moellendorffii, Chromatographia 68 (2008) 173–178. [2] Y. Cao, N.H. Tan, J.J. Chen, et al., Bioactive flavones and biflavones from Selaginella moellendorffii Hieron, Fitoterapia 81 (2010) 253–258. [3] Y.H. Wang, Q.Y. Sun, F.M. Yang, et al., Neolignans and pyrrole derivatives from Selaginella moellendorffii, Helv. Chim. Acta 93 (2010) 2467–2477. [4] H.S. Wang, L. Sun, Y.H. Wang, et al., Carboxymethyl flavonoids and a monoterpene glucoside from Selaginella moellendorffii, Arch. Pharm. Res. 34 (2011) 1283–1288. [5] B. Wu, J. Wang, Phenolic compounds from Selaginella moellendorfii, Chem. Biodivers 8 (2011) 1735–1747.
116
Z.-X. Zou et al. / Chinese Chemical Letters 24 (2013) 114–116
[6] Y.H. Wang, C.L. Long, F.M. Yang, et al., Pyrrolidinoindoline alkaloids from Selainella moellendorfii, J. Nat. Prod. 72 (2009) 1151–1154. [7] L.P. Zhang, Y.M. Liang, X.C. Wei, et al., A new unusual natural pigment from Selaginella sinensis and its noticeable physicochemical properties, J. Org. Chem. 72 (2007) 3921–3924. [8] X.L. Cheng, S.C. Ma, J.D. Yu, et al., Selaginellin A and B, two novel natural pigments isolated from Selaginella tamariscina, Chem. Pharm. Bull. 56 (2008) 982–984. [9] G.G. Zhang, Y. Jing, H.M. Zhang, et al., Isolation and cytotoxic activity of selaginellin derivatives and biflavonoids from Selaginella tamariscina, Planta Med. 78 (2012) 390–392. [10] G.S. Tan, K.P. Xu, F.S. Li, et al., Selaginellin C, a new natural pigment from Selaginella pulvinata Maxim (Hook et Grev.), J. Asian Nat. Prod. Res. 11 (2009) 1001–1004. [11] Y. Cao, J.J. Chen, N.H. Tan, et al., Antimicrobial selaginellin derivatives from Selaginella pulvinata, Bioorg. Med. Chem. Lett. 20 (2010) 2456–2460. [12] Y. Cao, J.J. Chen, N.H. Tan, et al., Structure determination of selaginellins G and H from Selaginella pulvinata by NMR spectroscopy, Magn. Reson. Chem. 48 (2010) 656–659.
[13] K.P. Xu, H. Zou, Q. Tan, et al., Selaginellins I and J, two new alkynyl phenols, from Selaginella tamariscina (Beauv.) Spring, J. Asian Nat. Prod. Res. 13 (2011) 93–96. [14] K.P. Xu, H. Zou, F.S. Li, et al., Two new selaginellin derivatives from Selaginella tamariscina (Beauv.) Spring, J. Asian Nat. Prod. Res. 13 (2011) 356–360. [15] K.P. Xu, H. Zou, G.R. Liu, et al., Selaginellin M, a new selaginellin derivative from Selaginella pulvinata, J. Asian Nat. Prod. Res. 13 (2011) 1051–1055. [16] H. Keller, H. Hohlfeld, V. Wray, et al., Changes in accumulation of soluble and cell wall-bound phenolics in elicitor-treated cell suspension cultures and fungus-infected leaves of solanum tuberosum, Phytochemistry 42 (1996) 389–396. [17] A.V. Noe, P. Araceli, Z. Estrella, et al., HUVECs from newborns with a strong family history of diabetes show diminished ROS synthesis in the presence of high glucose concentrations, Diabetes Metab. Res. 23 (2007) 71–80. [18] G. Sedegheh, H. Tore, K. Svein, High glucose and N-(carboxymethyl) lysine bovine serum albumin modulate release of matrix metalloproteinases in cultured human endothelial cells, Eur. J. Clin. Nutr. 45 (2006) 283–290.