БИООРГАНИЧЕСКАЯ ХИМИЯ, 2013, том 39, № 2, с. 244-246
PYRANOCOUMARINS FROM Zosima absinthifolia (VENT) LINK ROOTS
© 2013 Seyed Mehdi Razavia, #, Gholamhasan Imanzadehb, Fatemeh Soghra Jahedb, Gholamreza Zarrinic
a Department of Biology, Faculty of Sciences, University of Mohaghegh Ardabili, Ardabil, Iran b Department of Chemisrty, Faculty of Sciences, University of Mohaghegh Ardabili, Ardabil, Iran c Department of Animal Biology, Faculty of Natural Sciences, University of Tabriz, Tabriz, Iran Received April 2, 2012; in final form June 22, 2012
Abstract—Zosima absinthifolia (Vfent) Link (Apiaceae) is a perennial herb indigenous to Iran. It has been used as a medicinal plant from ancient time in Iran, Turkey and Pakistan. In the present work, air-dried and powdered plant roots were extracted with n-hexane, dichloromethane and methanol, respectively, using Soxhlet apparatus. The dichloromethane extract was subjected to vacuum liquid chromatography (VLC) and preparative thin layer chromatography (P-TLC) to yield two pyranocoumarins, aegelinol and agasyllin. The antimicrobial assay was performed using agar dilution method. The results showed that purified compounds have modest to weak antibacterial and antifungal activity.
Keywords: Zosima absinthifolia, Aegelinol, Agasyllin, Pyranocoumarin
DOI: 10.7868/S0132342313010107
INTRODUCTION
Zosima absinthifolia (Vent) Link (Apiaceae) is a perennial herb distributed from middle east to Turkey, Iran and Afghanistan. The plant has a erect stem with fibrous base that reach up to 100 cm in height. This widespread plant produces whitish or pale yellow flowers and inflated elliptic to obovate fruits with tumid margins [1].
Zosima absinthifolia has been used as a medicinal plant from ancient time in Iran, Turkey and Pakistan. The aerial parts of this plant are edible after cooked in East Turkey [2]. Crushed fruits of the plant have been used in Iran and Eastern Turkey as a food spice and food flavoring [3].
Aerial parts of the plant have also some medicinal usage in Pakistan to relieve indigestion and Bowes disorders [4].
A literature review showed that a number of biological activity have been previously described for this plant. It was found to have anti inflammatory effect [5]. We previously reported that the plant fruits oil and extracts have anti microbial, cytotoxic and allelopath-ic activity [6, 3].
There are many reports in the literature on phy-tochemicals from Zosima absinthifolia. These reports revealed the presence of flavonoids, alkaloids and different coumarin derivatives in Z. absinthifolia [6—8].
Abbreviations: MIC, minimum inhibitory concentration. # Corresponding author: e-mail: razavi694@gmail.com.
In the present work, we report two pyranocoumarins from the plant.
RESULTS AND DISCUSSION
Chromatographic analyses of n-hexane and dichloromethane extracts of Z. absinthifolia roots afford two pyranocoumarins, agasyllin (compound 1) [9] and aegelinol (compound 2) [10]. The structures of the isolated compounds (figure) were elucidated by direct comparison of their spectral data (UV, IR, 13C NMR and 1H NMR) with published data and by comprehensive 1D and 2D NMR analyses.
Although simple and furano coumarins have previously been reported from the fruits of Z. absinthifolia, to our knowledge this is the first report on the occurrence of pyranocoumarins in the roots of this plant. It was previously pointed out that aegelinol and its derivatives like agasyllin were found in a few genera of Ru-taceae such as Aegle and a number of Apiaceae genera like Seseli, Cachrys, Xanthogalum and Zosima [11].
Agasyllin, which was reported from Zosima absinthifolia roots at the current study, has also formerly been isolated from the roots ofZ. korovinii [12]. Thus, agasyllin can be assumed to be as characteristic compound in the genus of Zosima and is interesting from a chemotaxonomic point of view.
It was well documented that the genus Zosima is allied to Heracleum. Although, Zosima was differentiated from the genus Heracleum on the basis of the fruits having hyaline wings, around which the lateral ridges
PYRANOCOUMARINS FROM Zosima absinthifolia (VENT) LINK ROOTS
245
H3C
4' 5 4
HO^ 6
H3C
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Structures of Aegelinol (1) and Agasyllin (2).
from a thickened rim, the boundary of the two genera is ill defined [13]. The results of present work together with those of Sklyar et al., 1982, can lead us to the conclusion that chemical content of two genera is different. Whereas the genus Zosima is enriched with pyra-nocoumarins, these compounds have been not found in the Heracleum species.
The results of antimicrobial assay showed that purified compounds have weak to modest antimicrobial and antifungal activities. The MIC values for all tested microorganisms were calculated as 2500 and 5000 ^g/mL for aegelinol and agasyllin, respectively (table).
These results are very different from the results of Basile et al., 2009, where the MIC values for aegelinol and agasyllin were reported as 16—36 ^g/mL for different gram positive and negative bacteria [14].
EXPERIMENTAL
Plant materials. The roots of Zosima absinthifolia were collected in 2008 from Vaniar in East Azerbaijan province, Iran. The voucher specimen (No: 1387-1) was deposited at the herbarium of Faculty of Sciences, University of Mohaghegh Ardabili, where the plant was identified.
Extraction and purification. Air-dried and powdered plant roots (105 g) were extracted with n-hexan, dichloromethane and methanol, respectively, using Soxhlet apparatus. The n-hexan extract produced white crystals (580 mg) on the standing at room temperature.
The crystals isolated from the extract were purified using preparative thin layer chromatography (mobile
phase: 88% chloroform, 12% acetone) to yield compound 1 (580 mg, Rf 0.81, light blue florescent).
The dichloromethane extract was concentrated using a rotary evaporator operating at 30°C to obtain 3 g of oily substance. The concentrated extract was subjected to vacuum liquid chromatography on silica gel, eluting with solvent mixtures of increasing polarity: 100% n-hexan, n-hexan-EtOAc, 100% EtOAc, to yield a number of fractions which upon initial TLC analyses grouped into 11 main fractions. Fraction 5(50%Et0Ac in n-hexan) was further analyzed by preparative TLC (mobile phase acetone: CHCl3 = 30 : 70) to afford compound 2 (70 mg, Rf = 0.73, blue florescent). The structure of isolated compounds have been elucidated by UV, IR, 1D and 2D NMR spectral data coinciding with those reported in the literature [9, 10]. The spectral data of the compounds are as:
Agasyllin (1) [9]: UV/Vis ^max (EtOH) nm (lg s): 328 (4.19), 257 (3.45), 247 (3.54), 219 (4.35); IR vmax (CHCl3) cm-1: 3427, 3083, 2981, 2931, 1829, 1723, 1645,1625,1566,1488,1445,1383,1259,1271,1228, 1121, 1081, 973, 928, 889, 846, 820, 753, 718, 613, 559, 546, 515, 503, 491, 449, 415; 1H NMR (400 MHz, CDCl3): 1.47 (6 H, s, Me), 1.51 (3 H, s, Me), 5.81 (1H, dd, J 8.4, 1.6 Hz, H3''), 1.74 (3 H, dd, J 8.4, 1.2 Hz, H4''), 4.91 (1 H, t, H3'), 3.14 (2 H, dd, J 6.1 Hz, H4'), 6.02 (1 H, d, J 9.5 Hz, H3), 7.49 (1 H, d, J9.5 Hz, H4) 6.52 (1 H, s, H5), 7.11 (1 H, s, H8),; 13C NMR (100 MHz, CDCl3): 19.1, 20.0, 20.7 (CH3), 165.5 (C1''), 127.2 (C2''), 136.2 (C3''), 14.2 (C4''), 87.8 (C2'), 80.5 (C3'), 27.9 (C4'), 161.9 (C2), 111.2 (C3), 142.7 (C4), 96.1 (C5), 154.2 (C6), 123.2 (C7),
Antimicrobial activity of the aegelinol and agasyllin. The data present MIC values in ^g/mL
Aegelinol Agasyllin Gentamicin Amphotricin B
Bacillus subtilis 2500 5000 4 -
Staphylococcus aureus 2500 5000 8 -
Escherichia coli 2500 5000 8 -
Salmonella typhi 2500 5000 8 -
Candida kefyr 2500 5000 - 4
Fusarium sp. 2500 5000 - 16
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110.5 (C8), 159.9 (C9), 122.0 (C10); ^-^C HMBC long range correlations: H3-C2 (/2), H4-C2, H4-C9, H4'-C3' (J2), H4'-C2' (J3), H4'-C7 (J3), H4'"-C2"(/3), H4''-C3"(/2), H3'-C1''(/3), H2'-CH3 (J2), H3''-CH3 (J3); 1H-1H COSY correlations: H3-H4, H3'-H4', H3''-H4''.
Aegelinol (2) [10]: UV/Vis ^max (Et OH) nm (lg s): 336 (3.19), 259 (1.45), 208 (4.35); IR vmax (CHCl3) cm-1: 3451, 3047, 2938, 2988, 2496, 2357, 2007, 1975, 1940, 1830, 1702,1830,1702,1628,1567,1487,1448, 1403, 1377, 1358, 1239, 1229, 1156, 1045, 959, 924, 889, 860, 837, 792, 757, 667, 613, 583, 556, 509, 487, 451; 1H NMR (400 MHz, CDCl3): 1.27 (3 H, s, Me), 1.37 (3 H, s, Me), 4.73(1 H, t, H3'), 3.22 (2 H, dd, J6.1 Hz, H4'), 6.18 (1 H, d, J9.4 Hz, H3), 7.58(1H, d, J9.4 Hz, H4) 6.70(1H, s, H5), 7.21(1H, s, H8); 13C NMR (100 MHz, CDCl3): 23.2, 25.0 (CH3), 90.1 (C2'), 70.5 (C3'), 28.4 (C4'), 162.1 (C2), 111.6(C3), 142.6(C4), 96.8 (C5), 154.5(C-6), 124.0(C7), 111.6(C8), 160.4(C9), 124.0(C10); 1H-13C HMBC long range correlations: H3-C2(J2), H4-C2, H4-C9, H4- C3' (J2), H4 -C2' (J3), H4'-C7 (J3), H2'-CH3 (J3), H2'-CH3 (J2) ; 1H-1H COSY correlations: H3-H4, H3'-H4,
Antimicrobial Bioassay. The antibacterial and antifungal activities of the purified compounds were determined against Bacilus subtilis (PTCC1254), Staphylococcus aureus (PTCC1112), Escherichia coli (PTCC 1047), Salmonella typhi (PTCC1609), Candida kefyr (ATCC 38296) and Fusarium sp. Muller-Hinton agar (MHA) and Sabouraud dextrose agar (SDA) was used to bacterial and fungal strains respectively. The MICs of the compounds against the test microorganisms were determined by the Agar dilution method [15].
ACKNOWLEDGMENTS
This work was supported by University of Mo-hghegh Ardabili. The authors would like to thank
Dr. S. Nejad-Ebrahimi for his technical support. We are also thankful to Mrs. F. Zahri for her assistance.
REFERENCES
1. Rechinger, K.H., Flora Iranica, NO.162, Graz: Akade-misehe Druck. U. Verlagsanstalt, 1987.
2. Aksakal, O., Kaya, Y., Plant used as a food in Erzrum province. Proceedings of the Turkish 10th food conference, Erzrum, Turkey, 2008.
3. Razavi, S.M., Nejad-Ebrahimi, S., Nat. Prod. Res., 2010, vol. 24, no.12, pp. 1125-1130.
4. Goodman, S.
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