Abstract
In the current study the pyrrolizidine alkaloid profiles of the species Echium sabulicola ssp. decipiens (Pomel) Klotz and Solenanthus lanatus DC were studied in various extracts. In addition, a chemotaxonomic study within the genus and the family was carried out. The analysis was carried out by using gas chromatography coupled to mass spectrometry and by comparing the Kovats Indices and molecular and fragment ions with literature data. Twenty-three alkaloids were tentatively identified. The results showed the presence of already reported compounds as well as previously unreported ones leading both to a confirmation of the botanical classification of the two studied species and to a brand new path in the chemotaxonomy of Boraginaceae family. The presence of some pyrrolizidine alkaloids sets limits for the usage of these plants for medicinal purposes. The identified compounds confirm the botanical classification of the studied species as members of the Boraginaceae family and their presence advices against their use in the ethnopharmacological field.
Acknowledgments
The authors would like to thank the University of Oran1 (Project PRFU Number D01N01UN310120190003), LRZA, DGRSDT, Algeria, for the financial support and to thank Dr. Nadji Guenfoud and Dr. Amine Cherifi, Laboratory of Scientific Police of Oran, Oran, Algeria, for GC-MS analysis.
Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: None declared.
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.
References
1. Mädge, I, Gehling, M, Schöne, C, Winterhalter, P, These, A. Pyrrolizidine alkaloid profiling of four Boraginaceae species from Northern Germany and implications for the analytical scope proposed for monitoring of maximum levels. Food Addit Contam 2020. https://doi.org/10.1080/19440049.2020.1757166.Search in Google Scholar
2. El-Shazly, A, Wink, M. Diversity of pyrrolizidine alkaloids in the Boraginaceae. Structures, distribution, and biological properties. Diversity 2014;6:188–282. https://doi.org/10.3390/d6020188.Search in Google Scholar
3. Witte, L, Rubiolo, P, Bicchi, C, Hartmann, T. Comparative analysis of pyrrolizidine alkaloids from natural sources by gas chromatography-mass spectrometry. Phytochemistry 1993;32:187–96.10.1016/0031-9422(92)80130-7Search in Google Scholar
4. Hartmann, T, Ober, D. Biosynthesis, metabolism of pyrrolizidine alkaloids in plants, specialized insect herbivores. In: Leeper, FJ, Vederas, JC, editors. Topics in current chemistry, biosynthesis aromatic polyketides, isoprenoids, alkaloids. Berlin: Springer; 2000:207–44.10.1007/3-540-48146-X_5Search in Google Scholar
5. Hartmann, T, Toppel, G. Senecionine N-oxide, the primary product of pyrrolizidine alkaloid biosynthesis in root cultures of Senecio vulgaris. Phytochemistry 1987;26:1639–43. https://doi.org/10.1016/s0031-9422(00)82261-x.Search in Google Scholar
6. Van Dam, NM, Verpoorte, R, Van der Meijden, E. Extreme differences in pyrrolizidine alkaloid levels between leaves of Cynoglossum officinale L. Phytochemistry 1994;37:1013–6. https://doi.org/10.1016/s0031-9422(00)89519-9.Search in Google Scholar
7. Mattocks, AR. Chemistry and toxicology of pyrrolizidine alkaloids. London: Academic Press; 1986.Search in Google Scholar
8. Nazaire, M, Hufford, L. A broad phylogenetic analysis of Boraginaceae: implications for the relationships of Mertenisa. Syst Bot 2012;37:758–79. https://doi.org/10.1600/036364412x648715.Search in Google Scholar
9. Quezel, P, Santa, S. Nouvelle Flore de l’Algerie et des regions desertiques meridionales, Tome II. Paris: CNRS; 1963:759–79.Search in Google Scholar
10. Benamar, H, Tomassini, L, Frezza, C, Marouf, A, Bennaceur, M, Nicoletti, M. First study on the pyrrolizidine alkaloids of Pardoglossum cheirifolium (L.) E. Barbier & Mathez.: GC-MS analysis of their volatile components in the whole plant. Nat Prod Res 2020. https://doi.org/10.1080/14786419.2020.1721491.Search in Google Scholar
11. Benamar, H, Tomassini, L, Venditti, A, Marouf, A, Bennaceur, M, Serafini, M, et al.. Acetylcholinesterase inhibitory activity of pyrrolizidine alkaloids from Echium confusum Coincy. Nat Prod Res 2017;31:1277–85. https://doi.org/10.1080/14786419.2016.1242000.Search in Google Scholar
12. Benamar, H, Tomassini, L, Venditti, A, Marouf, A, Bennaceur, M, Nicoletti, M. Pyrrolizidine alkaloids from Solenanthus lanatus DC. with acetylcholinesterase inhibitory activity. Nat Prod Res 2016;30:2567–74. https://doi.org/10.1080/14786419.2015.1131984.Search in Google Scholar
13. Wagner, H, Bauer, R, Melchart, D, Xiao, P-G, Staudinger, A. Chromatographic fingerprint analysis of herbal medicines. Thin-layer and high performance liquid chromatography of Chinese drugs. New York: Springer; 2011:16.10.1007/978-3-7091-0763-8Search in Google Scholar
14. Kovats, E. Gas-chromatographische charakterisierung organischer verbindungen. Teil 1: retentions indices aliphatischer halogenide, alkohole, aldehyde und ketone. Helv Chim Acta 1958;41:1915–32. https://doi.org/10.1002/hlca.19580410703.Search in Google Scholar
15. Van Den Dool, H, Kratz, PD. A generalization of the retention index system including linear temperature programmed gas-liquid partition chromatography. J Chromatogr A 1963;11:463–71. https://doi.org/10.1016/s0021-9673(01)80947-x.Search in Google Scholar
16. El-Shazly, A, Sarg, T, Ateya, A, Abdel Aziz, A, El-Dahmy, S. Pyrrolizidine alkaloids from Echium setosum and Echium vulgare. J Nat Prod 1996a;59:310–3. https://doi.org/10.1021/np9600661.Search in Google Scholar
17. El-Shazly, A, El-Domiaty, M, Witte, L, Wink, M. Pyrrolizidine alkaloids in members of the Boraginaceae from Sinai (Egypt). Biochem Systemat Ecol 1998;26:619–36. https://doi.org/10.1016/s0305-1978(98)00028-3.Search in Google Scholar
18. El-Shazly, A, Abdel-All, M, Tei, A, Wink, M. Pyrrolizidine alkaloids from Echium rauwolfii and Echium horridum (Boraginaceae). Z Naturforsch C Biosci 1999;54:295–300. https://doi.org/10.1515/znc-1999-5-601.Search in Google Scholar
19. El-Shazly, A, Sarg, T, Ateya, A, Abdel-Aziz, E, El-Dahmy, S, Witte, L, et al.. Pyrrolizidine and tetrahydroisoquinoline alkaloids from Echium humile. Phytochemistry 1996b;42:225–30. https://doi.org/10.1016/0031-9422(95)00847-0.Search in Google Scholar
20. Damianakos, H, Jeziorek, M, Pietrosiuk, A, Chinou, I. The chemical profile of pyrrolizidine alkaloids from selected Greek endemic Boraginaceae plants determined by gas chromatography/mass spectrometry. J AOAC Int 2014;97:1244–9. https://doi.org/10.5740/jaoacint.sgedamianakos.Search in Google Scholar
21. El-Shazly, A, Sarg, T, Witte, L, Wink, M. Pyrrolizidine alkaloids from Cynoglossum creticum. Phytochemistry 1996c;42:1217–21. https://doi.org/10.1016/0031-9422(96)00112-4.Search in Google Scholar
22. El-Shazly, A, Sarg, T, Ateya, A, Abdel-Aziz, E, Witte, L, Wink, M. Pyrrolizidine alkaloids of Cynoglossum officinale and Cynoglossum amabile (family Boraginaceae). Biochem Syst Ecol 1996d;24:415–21. https://doi.org/10.1016/0305-1978(96)00035-x.Search in Google Scholar
23. Schoental, R. Toxicology and carcinogenic action of pyrrolizidine alkaloids. Cancer Res 1968;28:2237–46.Search in Google Scholar
24. Arseculeratne, SN, Gunatilaka, AAL, Panabokke, RG. Studies on medicinal plants of Sri Lanka: occurrence of pyrrolizidine alkaloids and hepatotoxic properties in some traditional medicinal herbs. J Ethnopharmacol 1981;4:159–77. https://doi.org/10.1016/0378-8741(81)90033-7.Search in Google Scholar
25. Brauchli, J, Ltithy, J, Zweifel, U, Schlatter, C. Pyrrolizidine alkaloids from Symphytum officinale L. and their percutaneous absorption in rats. Experientia 1982;38:1085–7. https://doi.org/10.1007/bf01955382.Search in Google Scholar
26. Fu, PP, Xia, Q, Chou, M, Lin, G. Detection, hepatotoxicity, and tumorigenicity of pyrrolizidine alkaloids in Chinese herbal plants and herbal dietary supplements. J Food Drug Anal 2007;15:400–15.10.38212/2224-6614.2392Search in Google Scholar
27. Sharma, RA, Singh, B, Singh, D, Chandrawat, P. Ethnomedicinal, pharmacological properties and chemistry of some medicinal plants of Boraginaceae in India. J Med Plants Res 2009;3: 1153–75.Search in Google Scholar
28. Moreira, R, Pereira, DM, Valentão, P, Andrade, PB. Pyrrolizidine alkaloids: chemistry, pharmacology, toxicology and food safety. Int J Mol Sci 2018;19:1668. https://doi.org/10.3390/ijms19061668.Search in Google Scholar
29. Debnath, B, Singh, WS, Das, M, Goswami, S, Singh, MK, Maiti, D. et al.. Role of plant alkaloids on human health: a review of biological activities. Mater Today Chem 2018;9:56–72. https://doi.org/10.1016/j.mtchem.2018.05.001.Search in Google Scholar
30. Zalkow, LH, Glinski, JA, Gelbaum, L, Fleischmann, TJ, McGowan, LS, Gordon, MM. Synthesis of pyrrolizidine alkaloids indicine, intermedine, lycopsamine, and analogues and their N-oxides. Potential antitumor agents. J Med Chem 1985;28:687–94. https://doi.org/10.1021/jm00383a001.Search in Google Scholar
31. Pomeroy, AR, Raper, C. Pyrrolizidine alkaloids: action on muscarinic receptors in the Guinea pig ileum. Br J Pharmacol 1971;41:683–90. https://doi.org/10.1111/j.1476-5381.1971.tb07076.x.Search in Google Scholar
32. Joosten, L, Van Veen, JA. Defensive properties of pyrrolizidine alkaloids against microorganisms. Phytochem Rev 2011;10:127–36. https://doi.org/10.1007/s11101-010-9204-y.Search in Google Scholar
33. Culvenor, CCJ. Tumor-inhibitory activity of pyrrolizidine alkaloids. J Pharm Sci 1968;57:1112–7. https://doi.org/10.1002/jps.2600570705.Search in Google Scholar
Supplementary material
The online version of this article offers supplementary material (https://doi.org/10.1515/znc-2020-0225).
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