ENDEMİK CENTAUREA APHRODISEA BOISS.’İN SEKONDER METABOLİTLERİ

Öz

Amaç: Bu çalışmada endemik Centaurea aphrodisea Boiss. bitkisinin toprak üstü kısımlarında bulunan sekonder metabolitlerin, kromatografik yöntemlerle saflaştırılması ve spektroskopik yöntemlerlede yapılarının aydınlatılması amaçlanmıştır. Gereç ve Yöntem: Bu çalışmada, endemik C. aphrodisea’nın toprak üstü kısımları Bozdağ’dan (Ödemiş, İzmir) toplanmış, ve n-hekzan, kloroform ve metanol ekstreleri hazırlanmıştır. Kloroform ekstresi çeşitli kromatografik yöntemler kullanılarak incelenmiş ve izole edilen bileşiklerin yapıları spektroskopik yöntemler (1D-2D NMR ve LC-MS) kullanılarak aydınlatılmıştır. Sonuç ve Tartışma: Bir eleman tip seskiterpen (metil 8α,6α,15-trihidroksielema-1,3,11(13)-trien-12-oat) ve dört flavon türevi (sirsimaritin, 3'-O-metil öpatorin, öpatorin ve salvigenin) izole edilerek yapıları aydınlatılmıştır. Ayrıca İTK tekniği ve şahit bileşikler kullanılarak bir fraksiyonda fenilpropanoit glikozitinin (siringin) varlığı saptanmıştır. Bu bileşikler C. aphrodisea’dan tarafımızca ilk kez rapor edilmektedir.

Anahtar Kelimeler

• Centaurea aphrodisea
• elemane
• flavon
• sekonder metabolit
• seskiterpen

Proje Numarası

Project No: 15-ECZ-003

SECONDARY METABOLITES OF ENDEMIC CENTAUREA APHRODISEA BOISS.

Öz

Objective: This study aimed to isolate secondary metabolites from the aerial parts of endemic Centaurea aphrodisea Boiss. using several chromatographic methods and elucidate the structure of the compounds by using spectroscopic methods. Material and Method: Aerial parts of the endemic C. aphrodisea were collected from Bozdağ (Ödemiş, İzmir) and n-hexane, chloroform and metanol extracts were prepared. The chloroform extract was investigated by using various chromatographic methods, and the structures of the isolated compounds were determined using spectroscopic methods (1D-2D NMR and LC-MS). Result and Discussion: One elemane type sesquiterpene (methyl 8α,6α,15-trihydroxyelema-1,3,11(13)-trien-12-oate) and four flavone derivatives (cirsimaritin, 3'-O-methyl eupatorin, eupatorin and salvigenin) were isolated and identified. In addition, the presence of a phenylpropanoid glycoside (syringin) was determined in a fraction by comparison with a referance compound using TLC technique. These compounds are reported for the first time from C. aphrodisea with this study.

Anahtar Kelimeler

• Centaurea aphrodisea
• elemane
• flavone
• secondary metabolite
• sesquiterpene

Destekleyen Kurum

This study was supported by the Scientific Research Projects Directorate of Ege University

Proje Numarası

Project No: 15-ECZ-003

Teşekkür

The authors would like to thank Prof. Serdar Gokhan Senol for identification of the plant, and Dr. Salih Gunnaz for all NMR measurements. This study was supported by the Scientific Research Projects Directorate of Ege University (Project No: 15-ECZ-003).

Kaynakça

1. 1. Garcia-Jacas, N., Susanna, A., Mozaffarian, V., Ilarslan, R. (2000). The natural delimitation of Centaurea (Asteraceae : Cardueae): ITS sequence analysis of the Centaurea jacea group. Plant Systematics and Evolution, 223, 185-199. [CrossRef]
2. 2. Uysal, T. (2012). Centaurea L. In: A. Guner, S. Aslan, T. Ekim, M. Vural and M.T. Babac (Eds.), Türkiye Bitkileri Listesi (Damarlı Bitkiler), (pp. 127-140). İstanbul: Nezahat Gökyiğit Botanik Bahçesi ve Flora Araştırmaları Derneği.
3. 3. Akkol, E.K., Arif, R., Ergun, F., Yesilada, E. (2009). Sesquiterpene lactones with antinociceptive and antipyretic activity from two Centaurea species. Journal of Ethnopharmacology, 122(2), 210-215. [CrossRef]
4. 4. Ozcelik, B., Gurbuz, I., Karaoglu, T., Yesilada, E. (2009). Antiviral and antimicrobial activities of three sesquiterpene lactones from Centaurea solstitialis L. ssp solstitialis. Microbiological Research, 164(5), 545-552. [CrossRef]
5. 5. Erel, S.B., Demir, S., Nalbantsoy, A., Ballar, P., Khan, S., Yavasoglu, N.U.K., Karaalp, C. (2014). Bioactivity screening of five Centaurea species and in vivo anti-inflammatory activity of C. athoa. Pharmaceutical Biology, 52(6), 775-781. [CrossRef]
6. 6. Bruno, M., Bancheva, S., Rosselli, S., Maggio, A. (2013). Sesquiterpenoids in subtribe Centaureinae (Cass.) Dumort (tribe Cardueae, Asteraceae): Distribution, C-13 NMR spectral data and biological properties. Phytochemistry, 95, 19-93. [CrossRef]
7. 7. Formisano, C., Rigano, D., Senatore, F., Bancheva, S., Maggio, A., Rosselli, S., Bruno, M. (2012). Flavonoids in Subtribe Centaureinae (Cass.) Dumort. (Tribe Cardueae, Asteraceae): Distribution and 13C-NMR spectral data. Chemistry & Biodiversity, 9(10), 2096-2158. [CrossRef]
8. 8. Karamenderes, C., Konyalioglu, S., Khan, S., Khan, I.A. (2007). Total phenolic contents, free radical scavenging activities and inhibitory effects on the activation of NF-kappa B of eight Centaurea L. species. Phytotherapy Research, 21, 488-491. [CrossRef]

9. 9. Baykan Erel, S., Ballar, P., Karaalp, C. (2014). Antioxidant activities of phenolic compounds of Centaurea ensiformis P.H. Davis. Turkish Journal of Pharmaceutical Sciences, 11(1), 19-24.
10. 10. Gurbuz, I., Yesilada, E. (2007). Evaluation of the anti-ulcerogenic effect of sesquiterpene lactones from Centaurea solstitialis L. ssp. solstitialis by using various in vivo and biochemical techniques. Journal of Ethnopharmacology, 112, 284-291. [CrossRef]
11. 11. Demiroz, T., Albayrak, G., Nalbantsoy, A., Gocmen, B., Baykan, S. (2018). Anti-inflammatory properties of Centaurea calolepis Boiss. and cnicin against Macrovipera lebetina obtusa (Dwigubsky, 1832) and Montivipera xanthina (Gray, 1849) venoms in rat. Toxicon, 152, 37-42. [CrossRef]
12. 12. Wagenitz, G. (1975). Centaurea L. In: P.H. Davis (Ed.), Flora of Turkey and East Aegean Islands, (pp. 501-502). Edinburgh: Edinburgh University Press.
13. 13. Erel, S.B., Demirci, B., Demir, S., Karaalp, C., Baser, K.H.C. (2013). Composition of the essential oils of Centaurea aphrodisea, C. polyclada, C. athoa, C. hyalolepis and C. iberica. Journal of Essential Oil Research, 25(2), 79-84. [CrossRef]
14. 14. Cardona, L., Fernandez, I., Pedro, J.R., Vidal, R. (1992). Polyoxygenated terpenes and cyanogenic glucosides from Centaurea aspera var subinermis. Phytochemistry, 31(10), 3507-3509. [CrossRef]
15. 15. Demir, S., Karaalp, C., Bedir, E. (2017). Specialized metabolites from the aerial parts of Centaurea polyclada DC. Phytochemistry, 143, 12-18. [CrossRef]
16. 16. Salan, U., Topcu, G., Oksuz, S. (2001). Flavonoids of Centaurea kilaea and C. salonitana. Journal of Faculty of Pharmacy of Istanbul University, 34, 55-61.
17. 17. Cardona, L., Bardon, A., Garcia, B., Pedro, J.R. (1993). Eudesmane and elemane derivatives from Onopordon acaulon. Phytochemistry, 33(6), 1457-1460. [CrossRef]
18. 18. Formisano, C., Rigano, D., Russo, A., Cardile, V., Caggia, S., Arnold, N.A., Mari, A., Piacente, S., Rosselli, S., Senatore, F., Bruno, M. (2012). Phytochemical profile and apoptotic activity of Onopordum cynarocephalum. Planta Medica, 78(15), 1651-1660. [CrossRef]
19. 19. Bai, N., He, K., Roller, M., Lai, C.S., Shao, X., Pan, M.H., Bily, A., Ho, C.T. (2011). Flavonoid glycosides from Microtea debilis and their cytotoxic and anti-inflammatory effects. Fitoterapia, 82(2), 168-172. [CrossRef]
20. 20. Khademian, A., Tabefam, M., Mazarei, Z., Kanani, M.R., Sepehri, H., Delphi, L., Danton, O., Hamburger, M., Farimani, M.M. (2021). Chemical constituents and cytotoxic activity of Stachys pilifera Benth. South African Journal of Botany, 139, 226-229. [CrossRef]
21. 21. Pathak, G., Singh, S., Kumari, P., Raza, W., Hussain, Y., Meena, A. (2021). Cirsimaritin, a lung squamous carcinoma cells (NCIH-520) proliferation inhibitor. Journal of Biomolecular Structure & Dynamics, 39(9), 3312-3323. [CrossRef]
22. 22. Noori, S., Hassan, Z.M., Yaghmaei, B., Dolatkhah, M. (2013). Antitumor and immunomodulatory effects of salvigenin on tumor bearing mice. Cellular Immunology, 286(1-2), 16-21. [CrossRef]
23. 23. Shao, H., Chen, J.Y., Li, A., Ma, L.L., Tang, Y.Z., Chen, H.Z., Chen, Y.P., Liu, J.Y. (2023). Salvigenin suppresses hepatocellular carcinoma glycolysis and chemoresistance through inactivating the PI3K/AKT/GSK-3 beta pathway. Applied Biochemistry and Biotechnology, 195(8), 5217-5237. [CrossRef]