Download PDF
Planta Med 2017; 83(03/04): 312-317
DOI: 10.1055/s-0042-115773
Natural Product Chemistry and Analytical Studies
Original Papers
Georg Thieme Verlag KG Stuttgart · New York

Identification of Meliatoxins in Melia azedarach Extracts Using Mass Spectrometry for Quality Control

Vivian E. Cornelio
1   Department of Chemistry, Federal University of São Carlos, São Carlos, SP, Brazil
,
Moacir R. Forim
1   Department of Chemistry, Federal University of São Carlos, São Carlos, SP, Brazil
,
Bruno Perlatti
1   Department of Chemistry, Federal University of São Carlos, São Carlos, SP, Brazil
,
João B. Fernandes
1   Department of Chemistry, Federal University of São Carlos, São Carlos, SP, Brazil
,
Paulo C. Vieira
1   Department of Chemistry, Federal University of São Carlos, São Carlos, SP, Brazil
,
Michael P. Napolitano
2   Department of Chemistry, University of Florida, Gainesville, FL, USA
,
Richard A. Yost
2   Department of Chemistry, University of Florida, Gainesville, FL, USA
,
Maria Fátima G. F. da Silva
1   Department of Chemistry, Federal University of São Carlos, São Carlos, SP, Brazil
› Author Affiliations
Further Information

Publication History

received 19 April 2016
revised 19 July 2016

accepted 19 August 2016

Publication Date:
06 September 2016 (online)

    Permissions and Reprints

Abstract

Indiscriminate use of synthetic pesticides can be hazardous to both humans and the environment, but the use of natural products as a source of bio-based products, such as Melia azedarach extracts, is an interesting approach to overcome these hazards. Unfortunately, the limonoids found in M. azedarach with desired insecticidal properties (e.g. azadirachtin) may also be present with limonoids toxic to mammals. The goal of this report was to develop a fast and reliable MS-based experiment to characterize meliatoxins in crude extracts of M. azedarach, in order to provide unequivocal assessment of the safety for extracts for application in the field. MS and MS/MS experiments using MALDI ionization were evaluated as tools for the assignment of characteristic ions produced by each meliatoxin in crude extracts.

The use of different experiments in combination, such as the analysis of fragment m/z 557 and [M + Na]+ (adducts ions m/z 681 and m/z 667), MALDI-MS can be used for detection of meliatoxins A1/B1 or A2/B2 in a crude extract and may be used to discriminate meliatoxins A from B, respectively. Subsequent MS/MS experiments can distinguish between the presence of group 1 and/or 2 in each class of meliatoxins classifying the proposed approach as a quick and efficient quality control method of meliatoxins in real M. azedarach samples.

Key words

Melia azedarach - Meliaceae - MALDI-MS - Meliatoxin - limonoids - chinaberry

Supporting Information

 

  • References

  • 1 Dawson AH, Eddleston M, Senarathna L, Mohamed F, Gawarammana I, Boew SJ, Manuweera G, Buckley NA. Acute human lethal toxicity of agricultural pesticides: A prospective cohort study. PLoS Med 2010; 7: e1000357
    CrossrefPubMedGoogle Scholar
  • 2 Zhang W, Jiang F, Ou J. Global pesticide comsumption and pollution: with China as a focus. Proc Int Acad Ecol Environ Sci 2011; 1: 125-144
    PubMedGoogle Scholar
  • 3 Isman MB. Botanical insecticides, deterrents, and repellents in modern agriculture and an increasingly regulated world. Annu Rev Entomol 2006; 51: 45-66
    CrossrefPubMedGoogle Scholar
  • 4 Isman MB, Miresmailli S, Machial C. Commercial opportunities for pesticides based on plant essential oils in agriculture, industry and consumer products. Phytochem Rev 2011; 10: 197-204
    CrossrefPubMedGoogle Scholar
  • 5 Hassan E, Gökçe A. Production and Consumption of Biopesticides. In: Singh D. ed. Advances of Plant Biopesticides. New Delhi: Springer India; 2014: 361-379
    Google Scholar
  • 6 Akhtar Y, Yeoung YR, Isman MB. Comparative bioactivity of selected extracts from Meliaceae and some commercial botanical insecticides against two noctuid caterpillars, Trichoplusa ni and Pseudaletia unipuncta . Phytochem Rev 2008; 7: 77-88
    PubMedGoogle Scholar
  • 7 Zhao L, Huo CH, Shen LR, Yang Y, Zhang Q, Shi QW. Chemical constituents of plants from the genus Melia . Chem Biodivers 2010; 7: 839-859
    CrossrefPubMedGoogle Scholar
  • 8 Sultana S, Asif HM, Akhtar N, Waqas M, Rehman SU. Comprehensive review on ethnobotanical uses, phytochemistry and pharmacological properties of Melia azedarach Linn. Asian J Pharm Res Health Care 2014; 6: 26-32
    PubMedGoogle Scholar
  • 9 Takeya K, Qiao ZS, Hirobe C, Itokawa H. Cytotoxic trichilin-type limonoids from Melia azedarach . Bioorg Med Chem 1996; 4: 1355-1359
    CrossrefPubMedGoogle Scholar
  • 10 Zhou H, Hamazaki A, Fontana JD, Takahashi H, Esumi T, Wandscheer CB, Tsujimoto H, Fukuyama Y. New ring C-seco limonoids from Brazilian Melia azedarach and their cytotoxic activity. J Nat Prod 2004; 67: 1544
    CrossrefPubMedGoogle Scholar
  • 11 Wu SB, Ji YP, Zhao Y, Xia G, Hu YH, Hu JF. Steroids from the leaves of Chinese Melia azedarach and their cytotoxic effects on human cancer cell lines. Steroids 2009; 74: 761-765
    CrossrefPubMedGoogle Scholar
  • 12 Ntalli NG, Cottiglia F, Bueno CA, Alché LE, Leonti M, Vargiu S, Bifulco E, Menkissoglu-Spiroudi U, Caboni P. Cytotoxic tirucallane triterpenoids from Melia azedarach fruits. Molecules 2010; 15: 5866-5877
    CrossrefPubMedGoogle Scholar
  • 13 Pan X, Matsumoto M, Nakamura Y, Kikuchi T, Zhang J, Ukiya M, Suzuki T, Koike K, Akihisa R, Akihisa T. Three new and other limonoids from the hexane extract of Melia azedarach fruits and their cytotoxic activities. Chem Biodivers 2014; 11: 987-1000
    CrossrefPubMedGoogle Scholar
  • 14 Carpinella MC, Giorda LM, Ferrayoli CG, Palacios SM. Antifeedant and insecticide properties of a limonoid from Melia azedarach (Meliaceae) with potential use for pest management. J Agric Food Chem 2003; 51: 369-374
    CrossrefPubMedGoogle Scholar
  • 15 Su ZS, Yang SP, Zhang S, Dong L, Yue JM. Meliarachins A–K: Eleven limonoids from the twigs and leaves of Melia azedarach . Helv Chim Acta 2011; 94: 1515-1526
    CrossrefPubMedGoogle Scholar
  • 16 Kim M, Kim SK, Park BN, Lee KH, Min GH, Seoh JY, Park CG, Hwang ES, Cha CY, Kook YH. Antiviral effects of 28-deacetylsendanin on herpes simplex virus-1 replication. Antiviral Res 1999; 43: 103-112
    CrossrefPubMedGoogle Scholar
  • 17 Barquero AA, Michelini FM, Alché LE. 1-Cinnamoyl-3,11-dihydroxymeliacarpin is a natural bioactive compound with antiviral and nuclear factor-κB modulating. Biochem Biophys Res Commun 2006; 344: 955-962
    CrossrefPubMedGoogle Scholar
  • 18 Champagne DE, Koul O, Isman MB, Scudder GGE, Neil Towers GH. Biological activity of limonoids from the rutales. Phytochemistry 1992; 31: 377-394
    CrossrefPubMedGoogle Scholar
  • 19 Ascher KRS. Nonconventional insecticidal effects of pesticides available from the Neem tree, Azadirachta indica . Arch Insect Biochem Physiol 2005; 22: 433-449
    PubMedGoogle Scholar
  • 20 Da Silva MFGF, Gottlieb OR, Dreyer DL. Plant chemosystematics and phylogeny. 36. Evolution of limonoids in the Meliaceae. Biochem Syst Ecol 1984; 12: 299-310
    CrossrefPubMedGoogle Scholar
  • 21 Schmutterer H. Properties and potential of natural pesticides from the neem tree, Azadirachta indica . Annu Rev Entomol 1990; 35: 271-297
    CrossrefPubMedGoogle Scholar
  • 22 Mordue AJ, Blackwell A. Azadirachtin – An update. J Insect Physiol 1993; 39: 903-924
    CrossrefPubMedGoogle Scholar
  • 23 Nathan SS, Sehoon K. Effects of Melia azedarach L. extract on the teak defoliator Hyblaea puera Cramer (Lepidoptera: Hyblaeidae). Crop Prot 2006; 25: 287-291
    CrossrefPubMedGoogle Scholar
  • 24 Forim MR, Cornélio VE, da Silva MF, Rodrigues-Filho E, Fernandes JB, Vieira PC, Matinez SS, Napolitano MP, Yost RA. Chemical characterization of Azadirachta indica grafted on Melia azedarach and analyses of azadirachtin by HPLC-MS-MS (SRM) and meliatoxins by MALDI-MS. Phytochem Anal 2010; 21: 363-373
    CrossrefPubMedGoogle Scholar
  • 25 Macleod JK, Moeller PDR, Molinski TF, Koul O. Antifeedant activity against Spodoptera litura larvae and [13C] NMR spectral assignments of the meliatoxins. J Chem Ecol 1990; 16: 2511-2518
    CrossrefPubMedGoogle Scholar
  • 26 Nakatani M, Huang RC, Okamura H, Naoki H, Iwagawa T. Limonoid antifeedants from Chinese Melia azedarach . Phytochemistry 1994; 36: 39-41
    CrossrefPubMedGoogle Scholar
  • 27 Liner L, Vanloon JJA, Schoonhoven LM. Behavioral and sensory responses to some neem compounds by Pieris-Brassicae larvae. Physiol Entomol 1995; 20: 134-140
    CrossrefPubMedGoogle Scholar
  • 28 Huang RC, Tadera K, Yagi F, Minami Y, Okamura H, Iwagawa T, Nakatani M. Limonoids from Melia azedarach . Phytochemistry 1996; 43: 581-583
    CrossrefPubMedGoogle Scholar
  • 29 Wandscheer CB, Duque JE, da Silva MAN, Fukuyama Y, Wohlke JL, Adelmann J, Fontana JD. Larvicidal action of ethanolic extracts from fruit endocarps of Melia azedarach and Azadirachta indica against the dengue mosquito Aedes aegypti . Toxicon 2004; 44: 829-835
    CrossrefPubMedGoogle Scholar
  • 30 Scapinello J, de Oliveira JV, Chiaradia LA, Tomazelli jr. O, Niero R, Dal Magro J. Insecticidal and growth inhibiting action of the supercritical extracts of Melia azedarach on Spodoptera frugiperda . Rev Bras Eng Agríc Ambient 2014; 18: 866-872
    CrossrefPubMedGoogle Scholar
  • 31 Huang RC, Okamura H, Iwagawa T, Suenaga H, Nakatani M. Limonoid antifeedants from the root bark of Chinese Melia azedarach L. Rep Fac Sci Kagoshima Univ 1994; 27: 45-52
    PubMedGoogle Scholar
  • 32 Ware WR, Schutzman H, Lee BR, Knight MW. Chinaberry poisoning in two dogs. J Am Vet Med Assoc 1997; 210: 1638-1640
    PubMedGoogle Scholar
  • 33 Méndez MC, Aragão M, Elias F, Riet-Correa F, Gimeno EJ. Experimental intoxication by the leaves of Melia azedarach (Meliaceae) in cattle. Pesquisa Vet Brasil 2002; 22: 19-24
    PubMedGoogle Scholar
  • 34 Mendez MC, Elias F, Riet-Correa F, Gimeno EJ, Portiansky EL. Experimental poisoning by fruits of Melia azedarach (Meliaceae) in pigs. Pesquisa Vet Brasil 2006; 26: 26-30
    PubMedGoogle Scholar
  • 35 Cortinovis C, Caloni F. Epidemiology of intoxication of domestic animals by plants in Europe. Vet J 2013; 197: 163-168
    CrossrefPubMedGoogle Scholar
  • 36 Defagó MT, Valladares G, Banchio E, Carpinella C, Palacios S. Insecticide and antifeedant activity of different plant parts of Melia azedarach (Meliaceae) on Xanthogaleruca luteola (Coleoptera: Chrysomelidae). Fitoterapia 2006; 77: 500-505
    CrossrefPubMedGoogle Scholar
  • 37 Ferreiro D, Orozco JP, Mirón C, Real T, Hernández-Moreno D, Soler F, Pérez-López M. Chinaberry tree (Melia azedarach) poisoning in dog: A case report. Top Companion Anim Med 2010; 25: 64-67
    CrossrefPubMedGoogle Scholar
  • 38 Gimenez N, Guitart R. Melia azedarach as an example of avoidable accidental poisoning. Med Clin (Barc) 2011; 137: 519-520
    CrossrefPubMedGoogle Scholar
  • 39 Phua DH, Tsai WJ, Ger J, Deng JF, Yang CC. Human Melia azedarach poisoning. Clin Toxicol (Phila) 2008; 46: 1067-1070
    CrossrefPubMedGoogle Scholar
  • 40 Oelrichs PB, Hill MW, Vallely PJ, MacLeod JK, Molinski TF. Toxic tetranortriterpenes of the fruit of Melia azedarach . Phytochemistry 1983; 22: 531-534
    CrossrefPubMedGoogle Scholar
  • 41 Nakatani M, Huang RC, Okamura H, Iwagawa T, Tadera K, Naoki H. Three new antifeedant meliacarpinins from Chinese Melia azedarach Linn. Tetrahedron 1995; 51: 11731-11736
    CrossrefPubMedGoogle Scholar
  • 42 Karas M, Hillenkamp F. Laser desorption ionization of proteins with molecular masses exceeding 10,000 daltons. Anal Chem 1988; 60: 2299-2301
    CrossrefPubMedGoogle Scholar