GC-MS ANALYSIS OF MALUS DOMESTICA BARK AND LEAF EX-TRACTS IN PESTICIDE NON-EXPOSED AND EXPOSED MATRICES

Authors

  • Anda-Cristina COMAN-BABUSANU “Grigore T. Popa” University of Medicine and Pharmacy Iasi
  • Elena BUTNARU “Grigore T. Popa” University of Medicine and Pharmacy Iasi
  • Georgiana MARDARE-BALUSESCU “Alexandru Ioan Cuza” University of Iasi
  • R.I. OLARIU . “Alexandru Ioan Cuza” University of Iasi
  • Cecilia ARSENE “Alexandru Ioan Cuza” University of Iasi

Abstract

Aim: Research on phytochemical constituents’ existent in Malus domestica leaves and bark is a nowadays topic of interest especially due to the presence of various secondary metabolites with potential pharmacological characteristics. Quantifying the residual levels of singular pesticides, e.g. tebuconazole, and/or of chemicals in clearly stated combinational formulations is also of great interest especially due to all negative effects induced by pesticides on human health. Material and methods: The strategy within the present study corroborates field activities (i.e. clear treatment scheme, leaf and bark samples collection from the Golden Delicious and Jonathan apple varieties from an orchard in Miroslava, Iasi, Romania, before and after treatments spread) with sample analysis by gas chromatographic methods. Ultrasound-assisted techniques and clean-up procedures were used during the preparative steps. All methanol (MeOH) extracts were analyzed using a gas chromatograph, Agilent 7890A, in tandem with a mass spectrometer, Agilent 5975C, Agilent Technologies, United States of America. Results: Analysis of the chromatographic profiles obtained for the investigated pesticide non-exposed matrices revealed the existence of many potential therapeutic bioactive compounds with positive benefits on human health (e.g., lupeol, friedelin, α-tocopherol known also as vitamin E, mellein). Chromatographic run profiles of methanol extracts associated to sample matrices collected at different periods within the treatment scheme revealed the existence of the chromatographic peak corresponding to tebuconazole at a retention time of 13.75 minutes. Pesticides existent in the in-use clearly stated combinational formulations have been as well identified. Conclusions: A preliminary characterization of the secondary metabolites existent in Golden Delicious and Jonathan apple leaves and bark was achieved for the first time for samples collected from an orchard in Miroslava, Iasi, Northeastern Romania. In pesticide non-exposed matrix compounds of pharmacological interest have been identified. Clear evidence has been obtained about the existence of tebuconazole and of other pesticides from the in-use clearly stated combinational formulations, in all samples collected in a well-established time span from the treatment spread. Samples containing residual pesticides might induce possible negative consequences for human health.

Author Biographies

  • Anda-Cristina COMAN-BABUSANU, “Grigore T. Popa” University of Medicine and Pharmacy Iasi

    Faculty of Pharmacy
    Department of Toxicology

  • Elena BUTNARU, “Grigore T. Popa” University of Medicine and Pharmacy Iasi

    Faculty of Pharmacy
    Department of Toxicology

  • Georgiana MARDARE-BALUSESCU, “Alexandru Ioan Cuza” University of Iasi

    Faculty of Chemistry, Department of Chemistry

  • R.I. OLARIU, . “Alexandru Ioan Cuza” University of Iasi

    Faculty of Chemistry, Department of Chemistry
    Integrated Center of Environmental Science Studies in the North Eastern Region - CERNESIM

  • Cecilia ARSENE, “Alexandru Ioan Cuza” University of Iasi

    Faculty of Chemistry, Department of Chemistry
    Integrated Center of Environmental Science Studies in the North Eastern Region - CERNESIM

References

1. Pennell D. Crop Guide Apples. In: Food Standards Agency Pesticide Residue Minimization 2006, 1-54.
2. Boyer J, Liu RH. Apple phytochemicals and their health benefits. Nutrition Journal 2004; 3: 1-15.
3. Fallahi E, Colt WM, Fallahi B, Chun IJ. The importance of apple rootstocks on tree growth, yield, fruit quality, leaf nutrition, and photosynthesis with an emphasis on ‘Fuji’. Hort Technology 2002; 12: 38-44.
4. Ramarathnam N, Ochi H, Takeuchi M. Antioxidant defense system in vegetable extracts. In: Natural Antioxidants: Chemistry, Health Effects, and Applications; Shahidi, F., Ed.; AOCS Press: Champaign, IL, 1997, 76-87.
5. Wolszleger (Dragan) M, Stan CD, Apotrosoaei M, Vasincu I, Panzariu A, Profire L. New hydrazones of ferulic acid: synthesis, characterization and biological activity. Rev. Med. Chir. Soc. Med. Nat. Iasi 2014; 118(4): 1152-1156.
6. Stan CD, Dragan M, Iacob AT, Profire L. Assessment of in vitro antioxidant activity of some new ferulic acid derivatives. Rev. Med. Chir. Soc. Med. Nat.Iasi 2016; 120(3): 727-731.
7. Larson RA. The antioxidants of higher plants. Phytochemistry 1988; 27: 969-978.
8. Wang C, Wang F, Zhang Q, Liang W. Individual and combined effects of tebuconazole and car-bendazim on soil microbial activity. European Journal of Soil Biology 2016; 72: 6-13.
9. Fan K, Wang J, Fu L, et al., Sensitivity of Botryosphaeria dothidea from apple to tebuconazole in China. Crop Protection 2016; 87: 1-5.
10. Zhang X, Qiu H, Huang Z. Apple and tomato chains in China and the European Union. LEI report 2010-019, 2010.
11. Sivikova K, Dianovsky J, Holeckova B, Galdikova M, Kolesarova V. Assessment of cytogenetic damage in bovine peripheral lymphocytes exposed to in vitro tebuconazole-based fungicide. Chemo-sphere 2013; 92: 555-562.
12. Arsene C, Galon (Negru) AG, Mardare (Balusescu) G, Babusanu (Coman) A, Olariu RI. About ultra-sound assisted extraction and its suitability for studying physico-chemical processes in various complex matrices. Sample Treatment 2016, Proceedings Book, ISBN 978-989-99639-2-4, Lisbon, Portugal, 2016, 79-80.
13. Santos CCMP, Salvadori MS, Mota VG, et al. Antinociceptive and antioxidant activities of phytol in vivo and in vitro models. Journal of Neuroscience, ID 949452, 2013.
14. Saikia D, Parihar S, Chanda D, et al. Antitubercular potential of some semisynthetic analogues of phytol. Bioorganic & Medicinal Chemistry Letters 2010; 20: 508–512.
15. Inoue Y, Hada T, Shiraishi A, Hirose K, Hamashima H, Kobayashi S. Biphasic effects of geranylge-raniol, teprenone, and phytol on the growth of Staphylococcus aureus. Antimicrobial Agents and Chemotherapy 2005; 49: 1770–1774.
16. Blomhoff R. Role of dietary phytochemicals in oxidative stress. In: Bioactive compounds in plants. Benefits and risks for man and animals, Bernhoft, A. (ed),, 2010, 52-70.
17. Mardare (Balusescu) G, Olariu RI, Arsene C. Gas chromatography-mass spectrometry analysis of a lignin marker and an indirect contributor to secondary organic aerosols in the atmosphere: p-vinylguaiacol in Datura inoxia. Young Researchers' International Conference on Chemistry and Chemical Engineering (YRICCCE I), p. 33, Cluj-Napoca, Romania, 12-14 May, 2016.
18. Saleem M. Lupeol, a novel anti-inflammatory and anti-cancer dietary triterpene. Cancer Letters 2009; 285: 109–115.
19. Geetha T, Varalakshmi P. Anticomplement activity of triterpenes from Crataeva nurvala stem bark in adjuvant arthritis in rats. General Pharmacology 1999; 32: 495–497.
20. Antonisamy P, Duraipandiyan V, Ignacimuthu S. Anti-inflammatory, analgesic and antipyretic effects of friedelin isolated from Azima tetracantha Lam. in mouse and rat models. Journal of Pharmacy and Pharmacology 2011; 63: 1070–1077.
21. Antonisamy P, Duraipandiyan V, Ignacimuthu S, Kim JH. Anti-diarrhoeal activity of friedelin isolated from Azima tetracantha Lam. in Wistar rats. South Indian Journal of Biological Sciences 2015; 1: 34-37.
22. Pontius A, Mohamed I, Krick A, Kehraus S, Konig GM. Aromatic polyketides from marine algicolous fungi. Journal of Natural Products 2008; 71: 272–274.
23. Dai JR, Carte BK, Sidebottom PJ, et al. Circumdatin G, a new alkaloid from the fungus Aspergillus ochraceus. American Chemical Society and American Society of Pharmacognosy, 1-2, 2000.
24. Melo LR, Clemente HA, Bezerra DF, Dantas RCS, Ramalho HMM, Dimenstein R. Effect of maternal supplementation with vitamin E on the concentration of alfa-tocopherol in colostrum. Journal de Pe-diatria (Rio J) 2017; 93(1): 40-46.
25. Samano R, Martinez-Rojano H, Hernandez RM, et al. Retinol and α-tocopherol in the breast milk of women after a high-risk pregnancy. Nutrients 2017; 9,14: 1-18.

Additional Files

Published

2018-04-04