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A new aromatic glycoside from Glehnia littoralis a

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a

Zi-Jin Feng , Xiao-Hong Zhang , Jian-Peng Zhang , Xiao-Hui a

a

a

a

Shang , Yun Gao , Xiao-Ling Lu , Xiao-Yu Liu & Bing-Hua Jiao

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a

Department of Biochemistry and Molecular Biology, College of Basic Medical Sciences, Second Military Medical University, Xiangyin Road 800, Shanghai, P.R. China b

Department of Medicine, Fuyang City Traditional Chinese Medicine Hospital, Beimen Road 4, Fuyang, Zhejiang Province, P.R. China Published online: 18 Feb 2014.

To cite this article: Zi-Jin Feng, Xiao-Hong Zhang, Jian-Peng Zhang, Xiao-Hui Shang, Yun Gao, Xiao-Ling Lu, Xiao-Yu Liu & Bing-Hua Jiao (2014) A new aromatic glycoside from Glehnia littoralis, Natural Product Research: Formerly Natural Product Letters, 28:8, 551-554, DOI: 10.1080/14786419.2014.886206 To link to this article: http://dx.doi.org/10.1080/14786419.2014.886206

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Natural Product Research, 2014 Vol. 28, No. 8, 551–554, http://dx.doi.org/10.1080/14786419.2014.886206

A new aromatic glycoside from Glehnia littoralis Zi-Jin Fenga†, Xiao-Hong Zhangb†, Jian-Peng Zhanga, Xiao-Hui Shanga, Yun Gaoa, Xiao-Ling Lua*, Xiao-Yu Liua* and Bing-Hua Jiaoa

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a Department of Biochemistry and Molecular Biology, College of Basic Medical Sciences, Second Military Medical University, Xiangyin Road 800, Shanghai, P.R. China; bDepartment of Medicine, Fuyang City Traditional Chinese Medicine Hospital, Beimen Road 4, Fuyang, Zhejiang Province, P.R. China

(Received 14 October 2013; final version received 19 January 2014) A new aromatic glycoside (1) was isolated from the roots of Glehnia littoralis Fr. Schmidtex Miq. Its structure was elucidated as vanillic acid 1-O-[b-D apiofuranosyl-(1 ! 6)-b-D -glucopyranoside] ester mainly by analysing the NMR and MS spectral data. In the in vitro assays, compound 1 displayed some TNF-a secretion inhibitory activity. Keywords: Glehnia littoralis; glycoside; TNF-a secretion

1. Introduction Glehnia littoralis Fr. Schmidtex Miq. is a perennial herb growing on the sandy beaches of eastern Asia. The dried roots of this plant, commonly known as ‘Bei Sha Shen’, are used in traditional Chinese medicine as a tonic, antiphlogistic and mucolytic for the treatment of respiratory and gastrointestinal disorders. It has been reported that this crude drug exhibited several potent pharmacological activities, including stopping cough, dispelling phlegm, antitumour activity, antimutation, antibacterial and immunosuppressive activities (Masamoto et al. 1980). Recently, it was found that this drug contained a number of coumarins, coumarin glycosides and polyacetylenes from the underground parts of G. littoralis (Kitajima et al. 1998). In this article, we describe a new aromatic glycoside (1) whose structure was elucidated on the basis of UV, HR-ESI-MS and NMR spectroscopic data, together with 14 known compounds. Some biological assay results are also reported (Figure 1). 2. Results and discussion Compound 1 was obtained as light yellow crystals, which was analysed for the molecular formula C19H26O13 by HR-ESI mass spectrometry [(m/z (M þ Na)þ485.1283)]. A detailed analysis of the NMR data revealed that compound 1 contains 19 carbons including one carbonyl (dC 164.4), 4 quaternary carbons, 10 methines, 3 methylenes, and 1 methyl (Supplementary Figure S6). Furthermore, the 1H NMR spectra (Supplementary Figure S5) indicated three olefinic protons at H-2 (dH 7.46), H-5 (dH 6.85) and H-6 (dH 7.50), which may contain a polysubstituted phenyl ring. Besides, it revealed 10 proton signals at dH 3.2 –4.8, which may contain two sugar moieties. Based on the literature, the spectroscopic data of 1 were similar to those of 2(4-hydroxy-3-methoxyphenyl)ethanol 1-O-[b-D-apiofuranosyl-(1-6)-b-D-glucopyranoside] in reference (Lin et al. 2007), except for the –CH2 –CH2 – replacing carbonyl group. The HMBC

*Corresponding authors. Email: [email protected]; [email protected] † These authors contributed equally to this work. q 2014 Taylor & Francis

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Z.-J. Feng et al. OH

O 3

4'' O 1'' 5'' O 6' 3'' HO O HO HO 1' O OH HO 3' OH 1 C7H15 OH

OH

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5

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H2N

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OH

O N

N

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OH HO

HO OH

2 C7H15 HO

OH 5

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C7H15O

C7H15

OH

6

O

7

O OH OCH3

Glc

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CH2OH O H HOH2C O H H H HO OH H O CH2OH HO H OH OH H 10

HO OH OH

H

O

Api O

OCH3 O

8

OH

O

OH

O

HO

O

OH 9 HO O O

OO H2C OH

HO HO HO

O

O O

O

OCH3

O

O

O

O

O

HOOC O

OH

O

O 15

11

13

12

14

Figure 1. Isolated compounds.

spectrum (Supplementary Figures S1 and S8) indicated that H-10 (5.50 ppm, d), H-2 (7.46 ppm, d) and H-6 (7.50 ppm, dd) coupled to C-9 (164.4 ppm, s). This new compound is named vanillic acid 1-O-[b-D -apiofuranosyl-(1 ! 6)-b-D -glucopyranoside] ester. In addition, the 14 known compounds were identified by comparing the spectroscopic data (UV, IR, ESI-MS, 1H and 13C NMR) with those reported in the literature as adenosine (2) (Pei et al. 2012), sitosterol (3) (Nes et al. 1992), (8E)-1,8-heptadecadiene-4,6-diyne-3,10-diol (4) (Kazuhiro et al. 1992), panaxynol (5) (Kazuhiro et al. 1992), falcarindiol (6) (Matsuura et al. 1996), ginsenoyne K (7) (Yang et al. 2008), 1-O-vanilloyl-b-D -glucose (8) (Irene et al. 2004), 4-[b-D -apiofuranosyl-(1 ! 6)-b-D -glucopyranosyloxy]-3-methoxypropiophenone (9) (Yuan et al. 2002), sucrose (10) (Yun et al. 2004), icariside F2 (11) (Wang et al. 1998), xanthotoxin (12) (Basnet et al. 1993), imperatorin (13) (Wang et al. 2008), isoimperatorin (14) (Li et al. 2006) and 4-O-b-D -glucopyranosyl vanillic acid (15) (Cui et al. 1993). Compounds 1–15 were tested for their TNF-a secretion inhibitory activities of mouse peritoneal macrophages. At a concentration of 1023 M, compound 1 expressed inhibition rate of 44.8% to TNFa secretion of mouse peritoneal macrophages, which indicated a little anti-inflammatory activity (Table 1). Besides, the aromatic glycosides with the same structures (compounds 1, 8, 9, 11, 15) revealed some structure–activity relationship. Compared with compounds 8 and 15, compound 1 possessed another sugar moiety (penta-ring carbohydrate), which indicated that this sugar moiety is Table 1. TNF-a secretion inhibitory activities of mouse peritoneal macrophages of compounds 1– 15. Compounds Inhibition ratio (%)

1

2

48.25 22.37

3

4

5

6

7

8

9



28.6



31.03





18.26

10 11 –



12

13

27.59



14

15

18.88 10.17

Note: ‘– ’ means this compound did not show TNF-a secretion inhibitory activities of mouse peritoneal macrophages.

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essential. Compound 15 displayed weak biological activity, which indicated that the p-hydroxyl group possesses strong biological activity compared with the carboxyl group of the aromatic ring. Compounds 1, 9 and 11 possess different glycosides, and compound 11 expressed no biological activity, which indicated that para- and meta-substituted group of aromatic ring is essential, and the p-hydroxyl group possesses strong biological activity compared with the acyl group.

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3. Experimental 3.1. General methods IR spectra were recorded on a Bruker Vector-22 spectrometer (Bruker Corporation, Billerica, MA, USA) with KBr pellet. NMR spectra were measured on a Bruker DRX-600 spectrometer (Bruker Corporation, Billerica, MA, USA) at 600 MHz for 1H NMR and 150 MHz for 13C NMR with TMS as internal standard. ESI-MS was recorded on a Varian Q-TOF micro mass spectrometer (Varian Corporation, Palo Alto, CA, USA). HPLC was performed on a highpressure gradient equipped with Waters 510 HPLC pump and Waters 2996 Photodiode Array Detector (Waters Corporation, Milford, MA, USA). Column chromatography was performed on Sephadex LH-20 (Pharmacia Corporation, Piscataway, NJ, USA); TLC analysis was run on HSGF254 pre-coated silica gel plates (10 – 40 mm, Yantai Chemical Plant, Yantai, P.R. China). All other reagents were of analytical grade (Shanghai Chemical Plant, Shanghai, P.R. China). 3.2. Plant material The roots of G. littoralis were collected from Anguo, Hebei Province, China and identified by Prof. Tu Pengfei, Peking University Modern Research Center for Traditional Chinese Medicine. A voucher specimen (No. 121012) has been deposited at the Department of Biochemistry and Molecular Biology, Second Military Medical University, Shanghai, P.R. China. 3.3. Extraction and isolation The air-dried roots of the G. littoralis (10 kg) were extracted with EtOH (3 £ 100 L) under reflux. Then, EtOH was removed by evaporation under reduced pressure. The total extract was suspended in H2O and successively partitioned with petroleum ether, EtOAc and BuOH. The BuOH fraction (50 g) was chromatographed over C18 (10 £ 60 cm) eluting with methanol–water (0:100 to 50:50) mixtures, to give four fractions (1–4). Fraction 2 (8076 mg) corresponds to compound 10, fraction 3 (5664 mg) corresponds to compounds 1, 2, 8 and 9 and fraction 4 (3269 mg) corresponds to compound 15. The EtOAc fraction (69 g) was chromatographed over silica gel eluting with petroleum ether–EtOAc (100:0 to 0:100) mixtures, to give five fractions (1–5). Fraction 2 (6904 mg) yields compounds 3–7 and fraction 3 (10763 mg) yields compounds 11–14. 3.3.1. Vanillic acid 1-O-[b-D -apiofuranosyl-(1 ! 6)-b-D -glucopyranoside] ester (1) Light yellow crystal; [a ]25 D ¼ 242.2 (c 0.15, CH3OH) (see Supplementary Figure S3), IR n (KBr) cm21: 3390, 2956, 2876, 1602, 1512, 1288, 1035, 820; UV lmax (CH3OH) (log 1) 219 (6.26), 265 (6.02), 293(5.80) (see Supplementary Figure S4); HR-ESI-MS m/z M 462.1373 (calcd for C19H26O13, 462.1392) (see Supplementary Figure S2), 1H NMR (CDCl3, 600 MHz): dH 3.09 (1H, m, H-40 ), 3.25 (2H, m, H-20 and H-50 ), 3.26 (1H, m, H-30 ), 3.29 (1H, s, H-500 ), 3.80 (1H, s, –OCH3), 3.41 (1H, dd, J ¼ 12 and 6.6 Hz, H-60 ), 3.54 (1H, d, J ¼ 9 Hz), 3.72 (1H, dd, J ¼ 3.0, 6.6 Hz, H-200 ), 3.81 (1H, m, H-60 ), 3.83 (1H, d, J ¼ 9.6 Hz, H-400 ), 4.76 (1H, d, J ¼ 3.0 Hz, H-100 ), 5.50 (1H, d, J ¼ 8.4 Hz, H-10 ), 6.85 (1H, d, J ¼ 7.8 Hz, H-5), 7.46 (1H, d, J ¼ 1.8 Hz, H-2), 7.50 (1H, dd, J ¼ 1.8, 7.8 Hz, H-6), 13C NMR (CDCl3, 150 MHz): dC 55.7 (–OCH3), 63.0 (C-500 ), 67.4 (C-60 ), 69.8 (C-40 ), 72.5 (C-20 ), 73.3 (C-400 ), 75.8 (C-200 ), 76.3 (C-30 ), 76.4 (C-50 ), 78.8 (C-300 ), 94.6 (C-10 ), 109.2 (C-100 ), 113.03 (C-2), 115.2 (C-5), 119.9 (C-1), 124.2 (C-6), 147.4 (C-3), 152.0 (C-4), 164.4 (C-7).

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3.4. TNF-a secretion inhibition assay The inhibition of TNF-a secretion by the isolated compounds was determined using the technique of reference (Lin et al. 2007). 4. Conclusions

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A new aromatic glycoside (1), together with 14 known compounds, was isolated from the roots of G. littoralis Fr. Schmidtex Miq. Several of them exhibited some TNF-a secretion inhibitory activities, and p-hydroxyl group of aromatic glycoside is an essential group to the TNF-a secretion inhibitory activities, which means that these compounds may be the material basis for efficacy of G. littoralis. Supplementary material Supplementary material relating to this article is available online, alongside Figures S1 – S9. Acknowledgements The work was funded by National Hi-tech R&D Program of China (863 Program) (SS2013AA093002).

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A new aromatic glycoside from Glehnia littoralis.

A new aromatic glycoside (1) was isolated from the roots of Glehnia littoralis Fr. Schmidtex Miq. Its structure was elucidated as vanillic acid 1-O-[β...
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