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DOI: 10.14258/jcprm.2019034859
UDC 615.322:547.913
THE COMPONENT COMPOSITION OF THE TRAGOPOGON ORIENTALIS VOLATILE CONSTITUENTS AND ITS BIOLOGICAL ACTIVITY
© Ye.M. Suleimen1*, G. G. Sissengalieva1, M. Yu. Ishmuratova2, R.I. Jalmakhanbetova1'3
11nstitute of Applied Chemistry, L.N. Gumilyov Eurasian National University, st. K. Satpayev, 2, Nur-Sultan, 010008 (Republic of Kazakstan), e-mail: suleimen_em@enu.kz
2 E.A. Buketov Karaganda State University, st. University, 28, Karaganda, 100028 (Republic of Kazakstan)
3 Kazak University of Technology and Business, st. K. Muhamedkhanova, 37A, Nur-Sultan, 010008 (Republic of Kazakhstan)
The purpose of this study is the chemical investigation of the composition of Tragopogon orientalis volatile constituents (VC) and studying of its biological activity.
This article presents the results of research on the study of the chemical composition of species Tragopogon, as well as data of antiradical and cytotoxic activity. To study the dried and crushed aboveground part of the plant (leaves, flowers and stems) was taken. The raw material was collected in the flowering phase, growing in Northern Kazakstan. The VC was isolated from the plant of Tragopogon orientalis by hydrodistillation method on the Clevenger type apparatus. The chemical composition of the VC was determined by GC/MS.
The cytotoxic activity of the VC was determined by the survival rate of sea shrimp Artemia salina. VC of T. orientalis in all studied concentrations (1-10 mg ml"1) exhibit acute lethal toxicity - all larvae die. Antiradical activity was determined by the method of colorimetry of free radicals (DPPH). The experimental results showed that the VC of T. orientalis at all tested concentrations (0.1-1.0 mg ml"1) exhibit low antiradical activity compared with the butylhydroxyanisole standard drug.
Keywords: Tragopogon orientalis L., volatile constituents, hydrodistillation method, GC/MS-analysis, component composition, biological activity.
Introduction
We continued our research in the field of studying the component composition of essential oils and their biological activity of plants of Kazakhstan [1-10] and selected Tragopogon orientalis L. as the object.
Tragopogon orientalis L. (Asteraceae Family) widespread in the territory Central, Eastern and Northern Kazakstan, Russia (Central Black Earth), grows in meadows and on dry slopes, in glades, sandy soils in pine forests [11, 12]. This type is widely used in folk medicine as a choleretic, antiseptic, expectorant, antiscorbutic. In folk medicine in Siberia, the T. orientalis herb is used for hysteria, rheumatism, and gonorrhea [13], relieves headache, soothes and normalizes the state of health under stress [14, 15].
Suleimen Yerlan Melsuly - Candidate of Chem. Sciences, PhD, Director of the Institute of Applied Chemistry, Professor of Chemistry Department of L.N. Gumilev, e-mail: suleimen_em@enu.kz
Sissengaliyeva Gulsana Galimzhankyzy - MSc of Chemistry, Leading Researcher at the Institute of Applied Chemistry, e-mail: sissengaliyevag@gmail.com Ishmuratova Margarita Yulaevna - Candidate of biological Sciences, Professor of botany Department of Karaganda state University, e-mail: margarita.ishmur@mail.ru Jalmakhanbetova Roza Ilemisovna - Doctor of Chem. Sciences, Professor of Technology Department of Kazakh University of technology and business,, e-mail: rozadichem@mail.ru
Previously, its anatomical structure was studied [15], a number of flavonoids were detected spectropho-tometrically [16]. As noted above, the plant is widely used in traditional medicine, and therefore we decided to investigate the component composition of the volatile compounds of the plant. In the literature we have not found any information on T. orientalis volatile compound, therefore, in this article we presented a study component composition its volatile constituents (VC).
* Corresponding author.
Experimental part
Plant material. The elevated portion of raw materials T. orientalis (leaves, flowers and stems) was collected in the flowering phase in 20 June 2018 at surrounding of Astana city (under the bridge on Akzhol Street).
The well-developed samples of plants, without external signs of damages cut off with secateurs at the level of 4-5 cm from the surface of the soil; taking the top parts of stems, leaves and inflorescences. Collecting was carried out in the 1st half of day from 9 to 11 o'clock. The cut-off raw materials were packed into paper package.
The collected raw material was dried and crushed. Samples of this plant are stored in the herbarium fund of the Faculty of Biology and Geography of Academician E. A. Buketov Karaganda State University. Voucher specimen is 1996.07.04.01.03.
Isolation of volatile constituents. VC was obtained from crushed dried masses (125 g) plants (without coarse stems) by the method of water distillation on the Clevenger apparatus within 2 hours [17]. Hexane is used as a trap for taking the VC. Isolated VC was dried over Na2SC>4, weighed and stored in sealed dark glass bottles in a cool and dark place at 5 °C temperature.
Analytical GC. GC/MS-analysis of T. orientalis VC made 3 times under the same conditions [8]. Determination of the composition of VC carried out on a gas chromatograph Clarus-SQ 8 with a mass spectrometric detector. Chromatographic conditions: capillary column RestekRxi®-l ms 0.25 mm x 30 m x 0.25 |im: sample volume: 1.0 |il: carrier gas He (purity 99.9999); carrier gas rate: 1 ml/min; stream division 1 : 25; t columns: 45 °C (2 min), rise 1.5 °C/min to 200 °C, then 15 °C / min to 280 °C, isothermal mode at 280 °C for 10 min; evaporator t - 280 °C, mass spectrometry detector: t - 240 °C, EI+ = 70 eV; scan time from 4 to 120 minutes; ion scan mode 39-500 m/z. The percentage of components was calculated automatically, based on the peak areas of the total ion chromatogram. Components were identified by mass spectra and retention times using the NIST library. The retention time of the components was recalculated with respect to saturated hydrocarbons.
Cytotoxic activity. Separating funnel filled with 55 mL of artificial sea water and 200 mg of Artemia salina eggs. Allowed standing for 3 days at the air supply until soft crustaceans gave the egg. One side of the tube covered with aluminum foil, and 5 minutes later, the larvae that are going on the bright side of the funnel, removed with Pasteur pipette.
20-40 larvae were placed in 990 |iL of seawater into each of the 24 micro titer plates. Dead larvae were counted using a microscope. Added 10 |iL of dimethylsulfoxide solution of 10 mg ml1 sample. As a comparison, the drug actinomycin D or staurosporine was used. For a negative control 10 |iL was added only DMSO. After 24 h of incubation and further maintaining micro titer plates for 24 hours (to ensure immobility) counts the dead larvae by the microscope [18].
Mortality P determined by the following formula:
p = A-N-B 10Q% Z
Where A - amount of dead larvae after 24 h; N - amount of larvae died before the test; B - the average amount of larvae died in a negative control; Z - the total amount of larvae.
Antiradical activity. Determination of antiradical activity of VC was carried out by the known technique of the colorimetry of free radicals based on reaction of the radical a 2,2-diphenyl-l-picrylhydrazil (DPPH) with standard of antioxidant [19, 20].
For determination of inhibition of DPPH to 0,1 mL of the test sample in the range of concentration of 0.1; 0.25; 0.5; 0.75; 1 mg mL1 added 3 ml of 6><10"5 M solution of radical. Centrifuge test tubes were in a support, wrapped in black polyethylene. After intensive mixing, solutions were left in the dark and after 30 minutes were measured absorbance of solutions at 520 nm.
The values of antiradical activity (ARA) were calculated using the formula shown below:
ARA (%) = (Ao-At)/Ao-100% (2)
Where A0 - absorbance of control; At - absorbance of the working sample.
The optical density of the investigated samples measured on a spectrophotometer Cary 60 UV-Vis. Antiradical activity of volatile constituents, we compared with butylhydroxyanisole (BHA).
The discussion of the results
As can be seen from the table 1 and figure 1, the main components of the VC of T. onen talis are predominantly hydrocarbonsheneicosane - 15.6%, (E)-15-heptadecenal -11.2%, hentriacontane - 7.9%, nonacosane - 3.2%, heptacosane - 2.9%, 3,7,1 l,15-tetramethyl-2-hexadecen-l-ol - 2.7% and nonanal - 2.4%.
These components, mostly hydrocarbons - typical of plants in the family Asteraceae, subfamily Lactucoideae, the genus Tragopogon belongs to them, are usually characterized by the presence of milky juice (latex) contained in the glandules, that was confirmed by earlier anatomical studies of a number of authors [15].
We carried out the determination of the cytotoxic activity of the T. orientalis volatile constituents. Determination of activity was carried out according to the well-known method of survival of marine shrimp Artemia salina [18]. Based on the experiment, it was found that the VC of T. orientalis in all tested concentrations (10, 5 and 1 mg inl1) exhibits acute lethal toxicity (96%) - all larvae die (tabl. 2).
The determination of the antiradical activity of volatile constituents was carried out according to the method [19, 20]. According to the results of the experiment, it was found that the VC of T. orientalis has low antiradical activity compared with butylhydroxyanisole (tabl. 3).
j_aj
J_A_*
103.57 I
la.-... llLi
l
~Lu ^—i—L
22.30 27.30 32.30 37.30 42.3C
52.30 57.30 62.30 67.30 72.3C
Fig. 1. Chromatogram of VC of T. orientalis
92.30 97.30 102.30 107.30 112.31
Table 1. Chemical composition of T. orientalis volatile constituents
No Retention Riit Rcalc Component Probabil- Content,%
time ity
1 3 4 5 6 7
1 4.866 800 798 Octane 838 1.5±0.2
2 6.605 854±3 843 (£J-2-Hexanal 942 1.4±0.2
3 6.711 857±3 845 (ZJ-Hex-3-en-l-ol 940 0.7±0.1
4 7.148 868±4 857 eis-2 -Hexene-1 -ol 930 0.4±0.1
5 7.313 846±8 861 Isohexyl alcohol 870 0.4±0.1
6 8.211 891±2 884 2-Heptanone 805 0.1±0.1
7 8.809 901 ±2 899 Heptanal 8 47 0.3±0.1
8 13.3 979±2 969 l-Octen-3-on 883 0.1±0.1
9 15.12 1003±2 997 w-Caprylic aldehyde 921 0.2±0.1
10 15.336 1005±2 1000 c;'s-3-Hexenyl acetate 948 1.1±0.2
11 17.853 1045±4 1033 Benzaldehyde 924 0.6±0.1
12 18.436 1038±2 1040 ß-c/Ä-Ocimen 894 0.1±0.1
13 20.494 1071±3 1067 1-Octanol 787 0.2±0.1
14 23.162 1104±2 1101 Nonanal 924 2.4±0.3
15 27.777 1162±3 1152 (EJ-2-Nonenal 893 0.1±0.1
End of table 1
1 2 3 4 5 6 7
16 31.926 1206±2 1197 Decanal 885 0.4±0.1
17 32.524 1220±3 1204 P-Cyclocytral 875 0.2±0.1
18 36.655 1252±2 1254 (Z)-2-Decenal 839 0.4±0.1
19 38.402 1293±N/A 1276 Dihydroedulan 838 0.3±0.1
20 38.834 1318±0 1281 Dihydroedulan II 810 0.2±0.1
21 39.264 1302±4 1286 2,6,10,10-Tetramethyl-l-oxaspiro [4.5] dec-6-ene 760 0.2±0.1
22 39.421 1294±N/A 1288 a-Limonen diepoxide 637 0.3±0.1
23 40.317 1300 1299 Tridecane 837 0.5±0.1
24 40.68 1303 Not identified 1 0.5±0.1
25 46.26 1386±5 1369 P-Damascenon 652 0.2±0.1
26 46.84 1354±N/A 1376 1,2-Dihydro-1,5,8-trimethylnaphthalene 670 0.2±0.1
27 47.133 1373±0 1380 1,2-Dihydro-l ,4,6-trimethylnaphthalene 721 0.2±0.1
28 48.942 1401 Not identified 2 0.4±0.1
29 53.66 1449±1 1455 2,6,10-Trimethyltridecan 886 0.2±0.1
30 54.339 1457 iu 1462 P-Ionone 835 1.3±0.2
31 56.14 1492±1 1483 1-Pentadecene 927 1.8±0.3
32 57.398 1512±5 1497 Tricanal 825 0.2±0.1
33 65.15 1613±2 1609 Tetradecanal 923 0.4±0.1
34 70.107 1684±3 1682 a-Bisabolol 739 0.1±0
35 71.78 1700 1706 Heptadecan 817 0.1±0.1
36 72.539 1715±3 1718 1-Pentadecanal 908 0.4±0.1
37 79.579 1817±6 1821 Palmitaldehyde 849 0.1±0.1
38 81.238 1844±4 1845 Hexahydrofarnesilacetone 879 0.4±0.1
39 83.864 1880±3 1883 1-Hexadecanol 894 1.6±0.3
40 84.195 1871±N/A 1888 Methyl-6,9,12-hexadecatrienoate 715 0.2±0.1
41 85.347 1900 1905 «-Nonadecane 871 0.2±0.1
42 86.267 1900±N/A 1919 1,2-Epoxyoctadecane 854 0.1±0.1
43 89.225 1968±7 1962 «-Hexadecanoic acid 849 0.2±0.1
44 91.69 2000 1998 Eicosane 875 0.2±0.1
45 92.706 2021±11 2015 Octadecanal 914 0.9±0.2
46 94.375 2052±N/A 2043 (9Z, 12Z)-9,12- Octadecadiene -l-ol 854 0.3±0.1
47 96.646 2085±1 2081 (£)-15-Heptadecanal 858 11.2±0.4
48 97.175 2098±3 2090 Methyllinolenat 809 0.1±0.1
49 97.864 2100 2102 Heneicosane 933 15.6±0.4
50 98.015 2116±2 2104 3,7,11,15-Tetramethyl-2-hexadecen-l-ol 913 2.7±0.3
51 98.829 2114±5 2118 trans-Phytol 766 0.1±0.1
52 99.589 2141±11 2131 Oleic acid 692 0.2±0.1
53 103.569 2200 2197 Docosane 882 0.5±0.1
54 104.707 2236 Not identified 3 0.4±0.1
55 105.587 2299±N/A 2268 Octadecenyl vinyl ester carboxylic acid 816 0.2±0.1
56 105.829 2277 Not identified 4 0.3±0.1
57 107.168 2281±8 2326 1-Eicosanol 909 0.4±0.1
58 107.528 2340 Not identified 5 911 1.9±0.3
59 108.617 2363±2 2379 2-Methyltricosane 858 0.3±0.1
60 109.127 2400 2398 Tetracosane 889 1.9±0.3
61 109.443 2430±2 2427 «-Docosanal 808 0.2±0.1
62 109.56 2442 iu 2439 9-Octylheptadecane 867 0.5±0.1
63 110.21 2500 2505 Pentacosane 892 1.1±0.2
64 111.032 2582 iu 2591 Heptyl octadecyl ether 816 0.1±0.1
65 111.068 2600 2595 Hexacosane 882 0.3±0.1
66 111.197 2608 Not identified 6 0.3±0.1
67 111.945 2700 2688 Heptacosane 916 2.9±0.3
68 112.921 280 0 2793 Octacosane 856 0.2±0.1
69 113.328 2832±2 2827 Hexacosanal 786 0.1±0.1
70 114.044 2900 2885 Nonacosane 863 3.2±0.3
71 115.214 2979 Not identified 7 0.3±0.1
72 117.004 3100 3125 Gentriacontane 901 7.9±0.4
73 119.892 3242 Not identified 8 0.3±0.1
Total 75.5
Table 2. Cytotoxic activity of T. orientalis volatile constituents
Parallel Number of larvae in control Number of larvae in the sample % of surviving larvae in control % of surviving larvae in the sample Mortality A,% Presence of neurotoxicity, %
surv. dead surv. dead par.
10 mg ml"1
Med. 24 1 0 25 0 96 0 96 0
5 mg ml"1
Med. 24 1 0 28 0 96 0 96 0
1 mg ml"1
Med. 24 1 0 27 0 96 0 96 0
Table 3. Antiradical activity (%) of T. orientalis volatile constituents in different concentrations
Test substances Concentration of solutions (mg ml"1)
0.1 0.25 0.5 0.75 1.0
Butylhydroxyanisole (BHA) 80.82 81.23 80.30 83.08 83.88
VC oí Tragopogon orientalis (Torient-1) 6.13 6.71 7.48 7.62 7.87
Conclusion
Thus, we first investigated the component composition of the volatile constituents of T. orientalis, as well as studied cytotoxic and antiradical activity. As a result of researches it is revealed that the volatile constituents of T. orientalis show high cytotoxic and low antiradical activity.
Acknowledgments
Authors thank Dr, Associated Professor Iskakova Zh.B. from Kazak University of Technology and Business (Nur-Sultan, Kazakstan) for help in investigation of cytotoxic and antiradical activities.
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Received December 21, 2018 Revised February 18, 2019 Accepted April 9, 2019
For citing: Suleimen Ye.M., Sissengalieva G.G., Ishmuratova M.Yu., Jalmakhanbetova R.I. Khimiya Rastitel'nogo Syr'ya, 2019, no. 3, pp. 103-108. DOI: 10.14258/jcprm.2019034859.
