INVESTIGATION OF PHYTOCHEMICALS IN METHANOLIC HERBA EXTRACT OF SILENE RUSCIFOLIA BY LC-QTOF/MS AND GC/MS

Öz

Objective: Silene L. (Caryophyllaceae) species are traditionally used for the treatment of inflammation, urinary inflammation, eye trouble, skin problem, stomach ache, dysentery, tooth decay, fever, headache, malaria, pimples and backache. Chemical ingredients of Silene species consist of flavonoids, anthocyanidins, terpenoids, triterpene saponins, phytoecdysteroids, benzenoids, vitamins, and show antioxidant, anti-inflammatory, antitumor and antiviral activities. Silene ruscifolia (Hub.-Mor. & Reese) Hub.-Mor. is called "gizli nakıl" in Türkiye.
Material and Method: The plant material was collected from Beynam Forest (Ankara/Türkiye). The aerial parts of the plant were extracted with methanol in an ultrasonic bath. HPLC system (Agilent 1260 Series) with an autosampler, binary pump, column oven, and a UV detector was coupled with an iFunnel Quadrupole Time-of-Flight LC-MS system (Agilent G6550A) with a Dual Spray Agilent Jet Stream electrospray ionization source. Agilent TC C-18 (4.6 mm x 150 mm x 5 µm) column was used for the separation of the compounds. The GC-MS analysis of extract was performed using an Agilent 6890 gas chromatograph equipped with an Agilent 5973N quadrupole mass spectrometer (Agilent, USA). Mass Hunter software (Qualitative Analysis B.07.00) and the NIST Mass Spectral Library (2014) were used to determine and identify the compounds.
Result and Discussion: LC-MS Q-TOF analysis showed that S. ruscifolia contained rutin, narcissin, luteolin, isorhamnetin, rhamnetin and quercetin dimethyl ether. GC-MS analysis showed that the extract had the highest content of sugar (50.5%) and sugar alcohols (46.39%). It also contains carboxylic acid (0.47%), fatty acid (0.64%), sugar acid (0.42%), glycoside (0.48%), carotenoids (0.61%) and benzoic acid ester (0.49%). D-pinitol has the highest content in the extract with 41.14%.

Anahtar Kelimeler

• GC/MS
• Herba
• LC-QTOF/MS
• Silene ruscifolia

SILENE RUSCIFOLIA METANOLİK HERBA EKSTRESİNDEKİ FİTOKİMYASALLARIN LC-QTOF/MS VE GC/MS İLE İNCELENMESİ

Öz

Amaç: Silene L. (Caryophyllaceae) türleri geleneksel olarak iltihap, idrar yolu iltihabı, göz rahatsızlığı, cilt sorunu, mide ağrısı, dizanteri, diş çürümesi, ateş, baş ağrısı, sıtma, sivilce ve sırt ağrısı tedavisinde kullanılmaktadır. Silene türlerinin kimyasal bileşenleri flavonoidler, antosiyanidinler, terpenoidler, triterpen saponinler, fitoekdisteroidler, benzenoidler, vitaminlerden oluşur ve antioksidan, antiinflamatuar, antitümör, antiviral aktivite gösterirler. Silene ruscifolia (Hub.-Mor. & Reese) Hub.-Mor. Türkiye'de "gizli nakıl" olarak adlandırılır.
Gereç ve Yöntem: Bitki materyali Beynam Ormanı'ndan (Ankara/Türkiye) toplandı. Bitkinin toprak üstü kısımları ultrasonik banyoda metanol ile ekstre edildi. Otomatik örnekleyici, ikili pompa, kolon fırını ve bir UV dedektörüne sahip HPLC sistemi (Agilent 1260 Serisi), Çift Sprey Agilent Jet Stream elektrosprey iyonizasyon kaynağına sahip bir iFunnel Quadrupole Time-of-Flight LC-MS system (Agilent G6550A) ile birleştirildi. Bileşiklerin ayrılması için Agilent TC C-18 (4.6 mm x 150 mm x 5 µm) kolonu kullanıldı. Ekstrenin GC-MS analizi, bir Agilent 5973N dört kutuplu kütle spektrometresi (Agilent, ABD) ile donatılmış bir Agilent 6890 gaz kromatografı kullanılarak yapıldı. Bileşiklerin belirlenmesi ve tanımlanması için Mass Hunter yazılımı (Qualitative Analysis B.07.00) ve NIST Mass Spectral Library (2014) kullanıldı.
Sonuç ve Tartışma: LC-MS Q-TOF analizi, S. ruscifolia'nın rutin, narsissin, luteolin, izoramnetin, ramnetin ve kersetin dimetil eter içerdiğini gösterdi. GC-MS analizi, ekstrenin şeker (%50.5) ve şeker alkolleri (%46.39) olarak en yüksek içeriğe sahip olduğunu göstermiştir. Ayrıca karboksilik asit (%0.47), yağ asidi (%0.64), şeker asidi (%0.42), glikozit (%0.48), karotenoidler (%0.61) ve benzoik asit esteri (%0.49) içerir. D-pinitol, %41.14 ile ekstredeki en yüksek içeriğe sahiptir.

Anahtar Kelimeler

• GC/MS
• Herba
• LC-QTOF/MS
• Silene ruscifolia

Kaynakça

1. 1. Bittrich, V. (1993). Caryophyllaceae. In: Flowering Plants, Dicotyledons, (pp. 206-236). Berlin, Heidelberg: Springer.
2. 2. Cullen, J., Coode, M. (1967). Silene L. In: P.H. Davis (Ed.), Flora of Turkey and the East Aegean Islands, Vol. 2, (pp.179). Edinburgh: Edinburgh University Press.
3. 3. Stevens, P.F. (2001). Angiosperm Phylogeny Website. Version 14, July 2017. http://www.mobot.org (Accessed 17.06.2022).
4. 4. POWO (2022). Plants of the World Online. Facilitated by the Royal Botanic Gardens, Kew. Published on the Internet; http://www.plantsoftheworldonline.org (Accessed 17.06.2022).
5. 5. Güner, A., Aslan, S., Ekim, T., Vural, M., Babaç, M.T. (2012). Türkiye bitkileri listesi (damarlı bitkiler). Nezahat Gökyigit Botanik Bahçesi Yayınları Flora Dizisi I.
6. 6. Rigat, M., Bonet, M.À., Garcia, S., Garnatje, T., Valles, J. (2007). Studies on pharmaceutical ethnobotany in the high river Ter valley (Pyrenees, Catalonia, Iberian Peninsula). Journal of Ethnopharmacology, 113(2), 267-277. [CrossRef]
7. 7. Kayani, S., Ahmad, M., Sultana, S., Shinwari, Z.K., Zafar, M., Yaseen, G., Bibi, T. (2015). Ethnobotany of medicinal plants among the communities of Alpine and Sub-alpine regions of Pakistan. Journal of Ethnopharmacology, 164, 186-202. [CrossRef]
8. 8. Cakilcioglu, U., Khatun, S., Turkoglu, I., Hayta, S. (2011). Ethnopharmacological survey of medicinal plants in Maden (Elazig-Turkey). Journal of Ethnopharmacology, 137(1), 469-486. [CrossRef]

9. 9. Cornara, L., La Rocca, A., Terrizzano, L., Dente, F., Mariotti, M.G. (2014). Ethnobotanical and phytomedical knowledge in the North-Western Ligurian Alps. Journal of Ethnopharmacology, 155(1), 463-484. [CrossRef]
10. 10. Özdemir, E., Alpınar, K. (2015). An ethnobotanical survey of medicinal plants in western part of central Taurus Mountains: Aladaglar (Nigde-Turkey). Journal of Ethnopharmacology, 166, 53-65. [CrossRef]
11. 11. Leto, C., Tuttolomondo, T., La Bella, S., Licata, M. (2013). Ethnobotanical study in the Madonie Regional Park (Central Sicily, Italy)-Medicinal use of wild shrub and herbaceous plant species. Journal of Ethnopharmacology, 146(1), 90-112. [CrossRef]
12. 12. Rehman, K., Khan, M.A., Ullah, Z., Chaudhary, H.J. (2015). An ethno botanical perspective of traditional medicinal plants from the Khattak tribe of Chonthra Karak, Pakistan. Journal of Ethnopharmacology, 165, 251-259. [CrossRef]
13. 13. Polat, R., Cakilcioglu, U., Satıl, F. (2013). Traditional uses of medicinal plants in Solhan (Bingöl-Turkey). Journal of Ethnopharmacology, 148(3), 951-963. [CrossRef]
14. 14. Said, O., Khalil, K., Fulder, S., Azaizeh, H. (2002). Ethnopharmacological survey of medicinal herbs in Israel, the Golan Heights and the West Bank region. Journal of Ethnopharmacology, 83(3), 251-265. [CrossRef]
15. 15. Mamadalieva, N.Z. (2012). Phytoecdysteroids from Silene plants: distribution, diversity and biological (antitumour, antibacterial and antioxidant) activities. Boletín Latinoamericano y del Caribe de Plantas Medicinales y Aromáticas, 11(6), 474-497.
16. 16. Mamadalieva, N.Z., Lafont, R., Wink, M. (2014). Diversity of secondary metabolites in the genus Silene L. (Caryophyllaceae)-Structures, distribution, and biological properties. Diversity, 6(3), 415-499. [CrossRef]
17. 17. Gaidi, G., Miyamoto, T., Laurens, V., Lacaille-Dubois, M.A. (2002). New acylated triterpene saponins from Silene fortunei that modulate lymphocyte proliferation. Journal of Natural Products, 65(11), 1568-1572. [CrossRef]
18. 18. Dötterl, S., Wolfe, L.M., Jürgens, A. (2005). Qualitative and quantitative analyses of flower scent in Silene latifolia. Phytochemistry, 66(2), 203-213. [CrossRef]
19. 19. Eshmirzaeva, N.E., Khidyrova, N.K., Khodzhaeva, M., Mezhlumyan, L.G., Shakhidoyatov, K.M. (2005). Chemical composition of Silene viridiflora. Chemistry of Natural Compounds, 41(4), 451-453.
20. 20. Chandra, S., Rawat, D.S. (2015). Medicinal plants of the family Caryophyllaceae: a review of ethno-medicinal uses and pharmacological properties. Integrative Medicine Research, 4(3), 123-131. [CrossRef]
21. 21. Lacaille-Dubois, M.A., Hanquet, B., Cui, Z.H., Lou, Z.C., Wagner, H. (1995). Acylated triterpene saponins from Silene jenisseensis. Phytochemistry, 40(2), 509-514. [CrossRef]
22. 22. Karamian, R., Ghasemlou, F. (2013). Screening of total phenol and flavonoid content, antioxidant and antibacterial activities of the methanolic extracts of three Silene species from Iran. International Journal of Agriculture and Crop Sciences, 5(3), 305.
23. 23. Mamadalieva, N.Z., Ul’chenko, N.T., Yuldasheva, N.K., Zhanibekov, A.A., Egamberdieva, D.R., Glushenkova, A.I. (2010). Neutral lipids and biological activity of the CHCl3 extract of the aerial part of Silene guntensis. Chemistry of Natural Compounds, 46(4), 621-622. [CrossRef]
24. 24. Mamadalieva, N.Z., Egamberdieva, D., Zhanibekov, A.A., Triggiani, D., Tiezzi, A. (2009). Chemical components of Silene viridiflora and their biological properties. Chemistry of Natural Compounds, 45(4), 589-591. [CrossRef]
25. 25. Kurtul, E., Eryilmaz, M., Sarialtin, S.Y., Teki̇n, M., Acikara, Ö.B., Çoban, T. (2022). Bioactivities of Alchemilla mollis, Alchemilla persica and their active constituents. Brazilian Journal of Pharmaceutical Sciences, 58, e18373. [CrossRef]
26. 26. Guijas, C., Montenegro-Burke, J.R., Domingo-Almenara, X., Palermo, A., Warth, B., Hermann, G., Koellensperger, G., Huan, T., Uritboonthai, W., Aisporna, A.E., Wolan, D.W., Spilker, M.E., Benton, P., Siuzdak, G. (2018). METLIN: a technology platform for identifying knowns and unknowns. Analytical Chemistry, 90(5), 3156-3164. [CrossRef]
27. 27. Pinheiro, P.F., Justino, G.C. (2012). Structural analysis of flavonoids and related compounds-a review of spectroscopic applications. In: V. Rao (Ed.), Phytochemicals: A Global Perspective of Their Role in Nutrition and Health, (pp. 33-56). Rijeka, Croatia: InTech.
28. 28. Kıymacı, M.E., Tok, K.C., Hürkul, M.M. (2022). A study on phytochemical analysis and antibacterial activity of Quercus macranthera subsp. syspirensis (K. Koch) Menitsky branch and leaf extracts. Journal of Faculty of Pharmacy of Ankara University, 46(1), 160-169. [CrossRef]
29. 29. Tok, K.C., Yayla, Ş. (2022). Gas Chromatography-Mass Spectrometry (GC-MS) analysis of Consolida thirkeana extract. Journal of Faculty of Pharmacy of Ankara University, 46(2), 444-449. [CrossRef]
30. 30. Shen, N., Wang, T., Gan, Q., Liu, S., Wang, L., Jin, B. (2022). Plant flavonoids: Classification, distribution, biosynthesis, and antioxidant activity. Food Chemistry, 132531. [CrossRef]
31. 31. Gökbulut, A., Özhan, O., Karacaoğlu, M., Şarer, E. (2012). Radical scavenging activity and vitexin content of Vitex agnus castus leaves and fruits. FABAD Farmasötik Bilimler Dergisi, 35(2), 85-91.
32. 32. Ağca, A.C., Ekici, A.N.Y., Sarıaltın, S.Y., Çoban, T., İşcan, G.S., Yılmaz, B.S. (2021). Antioxidant, anti-inflammatory and antidiabetic activity of two Sternbergia taxons from Turkey. South African Journal of Botany, 136, 105-109. [CrossRef]
33. 33. Fernández, S.P., Wasowski, C., Loscalzo, L.M., Granger, R.E., Johnston, G.A., Paladini, A.C., Marder, M. (2006). Central nervous system depressant action of flavonoid glycosides. European Journal of Pharmacology, 539(3), 168-176. [CrossRef]
34. 34. Schwingel, T.E., Klein, C.P., Nicoletti, N.F., Dora, C.L., Hadrich, G., Bica, C.G., Lopes, T.G., Da Silva, V.D., Morrone, F. B. (2014). Effects of the compounds resveratrol, rutin, quercetin, and quercetin nanoemulsion on oxaliplatin-induced hepatotoxicity and neurotoxicity in mice. Naunyn-Schmiedeberg's Archives of Pharmacology, 387(9), 837-848. [CrossRef]
35. 35. Arima, H., Ashida, H., Danno, G.I. (2002). Rutin-enhanced antibacterial activities of flavonoids against Bacillus cereus and Salmonella enteritidis. Bioscience, Biotechnology and Biochemistry, 66(5), 1009-1014. [CrossRef]
36. 36. Pimentel, R.B.D.Q., Da Costa, C.A., Albuquerque, P.M., Junior, S.D. (2013). Antimicrobial activity and rutin identification of honey produced by the stingless bee Melipona compressipes manaosensis and commercial honey. BMC Complementary and Alternative Medicine, 13(1), 1-14. [CrossRef]
37. 37. Araruna, M.K., Brito, S.A., Morais-Braga, M.F., Santos, K.K., Souza, T.M., Leite, T.R., Costa, J.G.M., Coutinho, H.D. (2012). Evaluation of antibiotic & antibiotic modifying activity of pilocarpine & rutin. The Indian Journal of Medical Research, 135(2), 252-254.
38. 38. Han, Y. (2009). Rutin has therapeutic effect on septic arthritis caused by Candida albicans. International immunopharmacology, 9(2), 207-211. [CrossRef]
39. 39. Johann, S., Mendes, B.G., Missau, F.C., Resende, M.A.D., Pizzolatti, M.G. (2011). Antifungal activity of five species of Polygala. Brazilian Journal of Microbiology, 42, 1065-1075. [CrossRef]
40. 40. Nieoczym, D., Socała, K., Raszewski, G., Wlaź, P. (2014). Effect of quercetin and rutin in some acute seizure models in mice. Progress in Neuro-Psychopharmacology and Biological Psychiatry, 54, 50-58. [CrossRef]
41. 41. Carvalho, O.V., Botelho, C.V., Ferreira, C.G.T., Ferreira, H.C.C., Santos, M.R., Diaz, M.A.N., Oliveira, T.T., Soares-Martins, J.A.P., Almeida, M.R., Junior, A.S. (2013). In vitro inhibition of canine distemper virus by flavonoids and phenolic acids: implications of structural differences for antiviral design. Research in Veterinary Science, 95(2), 717-724. [CrossRef]
42. 42. Ibrahim, A.K., Youssef, A.I., Arafa, A.S., Ahmed, S.A. (2013). Anti-H5N1 virus flavonoids from Capparis sinaica Veill. Natural Product Research, 27(22), 2149-2153. [CrossRef]
43. 43. Tran, N.Q., Joung, Y.K., Lih, E., Park, K.D. (2011). In situ forming and rutin-releasing chitosan hydrogels as injectable dressings for dermal wound healing. Biomacromolecules, 12(8), 2872-2880. [CrossRef]
44. 44. Almeida, J.S., Benvegnú, D.M., Boufleur, N., Reckziegel, P., Barcelos, R.C.S., Coradini, K., De Carvalho, L.M., Bürger, M.E. Beck, R.C.R. (2012). Hydrogels containing rutin intended for cutaneous administration: efficacy in wound healing in rats. Drug Development and Industrial Pharmacy, 38(7), 792-799. [CrossRef]
45. 45. Machado, D.G., Bettio, L.E., Cunha, M.P., Santos, A.R., Pizzolatti, M.G., Brighente, I.M., Rodrigues, A.L.S. (2008). Antidepressant-like effect of rutin isolated from the ethanolic extract from Schinus molle L. in mice: evidence for the involvement of the serotonergic and noradrenergic systems. European Journal of Pharmacology, 587(1-3), 163-168. [CrossRef]
46. 46. Alarcón-Alonso, J., Zamilpa, A., Aguilar, F.A., Herrera-Ruiz, M., Tortoriello, J., Jimenez-Ferrer, E. (2012). Pharmacological characterization of the diuretic effect of Hibiscus sabdariffa Linn (Malvaceae) extract. Journal of Ethnopharmacology, 139(3), 751-756. [CrossRef]
47. 47. Abdel‐Raheem, I.T. (2010). Gastroprotective effect of rutin against indomethacin‐induced ulcers in rats. Basic & Clinical Pharmacology & Toxicology, 107(3), 742-750. [CrossRef]
48. 48. La Casa, C., Villegas, I., De La Lastra, C.A., Motilva, V., Calero, M.M. (2000). Evidence for protective and antioxidant properties of rutin, a natural flavone, against ethanol induced gastric lesions. Journal of Ethnopharmacology, 71(1-2), 45-53. [CrossRef]
49. 49. Kappel, V.D., Zanatta, L., Postal, B.G., Silva, F.R.M.B. (2013). Rutin potentiates calcium uptake via voltage-dependent calcium channel associated with stimulation of glucose uptake in skeletal muscle. Archives of Biochemistry and Biophysics, 532(2), 55-60. [CrossRef]
50. 50. Hsu, C.Y., Shih, H.Y., Chia, Y.C., Lee, C.H., Ashida, H., Lai, Y.K., Weng, C.F. (2014). Rutin potentiates insulin receptor kinase to enhance insulin‐dependent glucose transporter 4 translocation. Molecular Nutrition & Food Research, 58(6), 1168-1176. [CrossRef]
51. 51. Kozachok, S., Pecio, Ł., Kolodziejczyk-Czepas, J., Marchyshyn, S., Nowak, P., Mołdoch, J., Oleszek, W. (2018). γ-Pyrone compounds: flavonoids and maltol glucoside derivatives from Herniaria glabra L. collected in the Ternopil region of the Ukraine. Phytochemistry, 152, 213-222. [CrossRef]
52. 52. Al-Rejaie, S.S., Aleisa, A.M., Sayed-Ahmed, M.M., Al-Shabanah, O.A., Abuohashish, H.M., Ahmed, M.M., Al-Hosaini, K.A., Hafez, M.M. (2013). Protective effect of rutin on the antioxidant genes expression in hypercholestrolemic male Westar rat. BMC Complementary and Alternative Medicine, 13(1), 1-9. [CrossRef]
53. 53. Kalgaonkar, S., Gross, H.B., Yokoyama, W., Keen, C.L. (2010). Effects of a flavonol-rich diet on select cardiovascular parameters in a Golden Syrian hamster model. Journal of Medicinal Food, 13(1), 108-115. [CrossRef]
54. 54. Mouria, M., Gukovskaya, A.S., Jung, Y., Buechler, P., Hines, O.J., Reber, H.A., Pandol, S.J. (2002). Food‐derived polyphenols inhibit pancreatic cancer growth through mitochondrial cytochrome C release and apoptosis. International Journal of Cancer, 98(5), 761-769. [CrossRef]
55. 55. Lima Gonçalves, C.F., De Souza dos Santos, M.C., Ginabreda, M.G., Soares Fortunato, R., Pires De Carvalho, D., Freitas Ferreira, A.C. (2013). Flavonoid rutin increases thyroid iodide uptake in rats. PLoS One, 8(9), e73908. [CrossRef]
56. 56. Alonso-Castro, A.J., Domínguez, F., García-Carrancá, A. (2013). Rutin exerts antitumor effects on nude mice bearing SW480 tumor. Archives of Medical Research, 44(5), 346-351. [CrossRef]
57. 57. Ali, M., Mudagal, M.P., Goli, D. (2009). Cardioprotective effect of tetrahydrocurcumin and rutin on lipid peroxides and antioxidants in experimentally induced myocardial infarction in rats. Die Pharmazie-An International Journal of Pharmaceutical Sciences, 64(2), 132-136. [CrossRef]
58. 58. Annapurna, A., Reddy, C.S., Akondi, R.B., Rao, S.R. (2009). Cardioprotective actions of two bioflavonoids, quercetin and rutin, in experimental myocardial infarction in both normal and streptozotocin-induced type I diabetic rats. Journal of Pharmacy and Pharmacology, 61(10), 1365-1374. [CrossRef]
59. 59. Panche, A., Diwan, A., Chandra, S. (2016). Flavonoids: An overview. Journal of Nutritional Science, 5, E47. [CrossRef]
60. 60. Havsteen, B.H. (2002). The biochemistry and medical significance of the flavonoids. Pharmacology & Therapeutics, 96(2-3), 67-202. [CrossRef]
61. 61. Sánchez-Hidalgo, M., León-González, A.J., Gálvez-Peralta, M., González-Mauraza, N.H., Martin-Cordero, C. (2021). D-Pinitol: A cyclitol with versatile biological and pharmacological activities. Phytochemistry Reviews, 20(1), 211-224. [CrossRef]