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 JACEN  Vol.5 No.4 , November 2016
Natural and Derivatized Acetogenins Promising for the Control of Spodoptera frugiperda Smith
Abstract: Annonaceous acetogenins (ACG), belonging to the family Annonaceae, represent a class of bioactive compounds whose toxic effects have been reported for several spe-cies of insects. Given their insecticidal properties, we first carried out the isolation of the ACG from a Brazilian collection of the seeds of Annona squamosa (Annonaceae) and prepared their methoxy methylated (MOM) and acetylated (OAc) derivatives by chemical methods. ACG analogues were semi-synthesized and characterized by spec-troscopic techniques (1H and 13C-NMR). We isolated ten natural acetogenins: squamo-cin, molvizarin, motrilin, rolliniastatin-2, almunequin, cherimolin-1, cherimolin-2, an-nonacin, squamocin D and asiminecin. The main objective of this study is to report the antifeedant, toxic and nutritional effects of three of those natural acetogenins and their acetylated and methoxy methylated derivatives on Spodoptera frugiperda Smith (Lep-idoptera: Noctuidae). The natural ACGs squamocin and molvizarin killed 100% of S. frugiperda larvae, followed by motrilin (80%). Acetylated derivatives had less toxic and nutritional effects that led to pupal mortality and adult fatal malformations. The addition of MOM derivatives to the larval diet has not toxic effects on larvae, but significantly reduces growth rate and efficiency in conversion of ingested food into biomass, affecting adult survival.
Cite this paper: Hidalgo, J. , Parellada, E. , Blessing, L. , Bardón, A. , Ameta, K. , Vera, N. and Neske, A. (2016) Natural and Derivatized Acetogenins Promising for the Control of Spodoptera frugiperda Smith. Journal of Agricultural Chemistry and Environment, 5, 200-210. doi: 10.4236/jacen.2016.54021.
References

[1]   Bermejo, A., Figadere, B., Zafra-Polo, M.C., Barrachina, I., Estornell, E. and Cortes, D. (2005) Acetogenins from Annonaceae: Recent Progress in Isolation, Synthesis and Mechanisms of Action. Natural Product Reports, 22, 269-303.

http://dx.doi.org/10.1039/B500186M

[2]   Alali, F., Liu, X. and McLaughlin, J. (1999) Annonaceous Acetogenins: Recent Progress. Journal of Natural Products, 62, 504-540.

http://dx.doi.org/10.1021/np980406d

[3]   Murray, B. and Leatemia, J. (2004) Toxicity and Antifeedant Activity of Crude Seed Extracts of Annona squamosa (Annonaceae) against Lepidopteran Pests and Natural Enemies. International Journal of Insect Science, 24, 150-158.

[4]   Cortes, D., Myint, S., Dupont, B. and Davoust, D. (1993) Bioactives Acetogenins from Seeds of Annona cherimolia. Phytochemistry, 32, 1475-1482.

http://dx.doi.org/10.1016/0031-9422(93)85162-K

[5]   Alkofahi, A., Rupprecht, J.K., Anderson, J.E., McLaughlin, J.L., Mikolajczak, K. and Scott, B. (1989) Search for New Pesticides from Higher Plants. In: Arnason, J.T., Philogene, B. and Morand, A., Eds., Insecticides of Plant Origin, American Chemical Society, Washington DC, 25-43.

http://dx.doi.org/10.1021/bk-1989-0387.ch003

[6]   Cole, M.D. (1994) Key Antifungal, Antibacterial and Anti-Insect Assays—A Critical Review. Biochemical Systematics and Ecology, 22, 837-856.

http://dx.doi.org/10.1016/0305-1978(94)90089-2

[7]   Moeschler, H., Pfluger, W. and Wendish, D. (1986) Annonin Insecticide. German Patent DE 3438763 A1.

[8]   Moeschler, H., Pfluger, W. and Wendish, D. (1987) Pure Annonin and Process for the Preparation. US Patent 4689232.

[9]   Mikolajczak, K., McLaughlin, J. and Rupprecht, J. (1988) Control of Pests with Annonaceous Acetogenins. US Patent 4721727.

[10]   Mikolajczak, K., McLaughlin, J. and Rupprecht, J. (1989) Control of Pests with Annonaceous Acetogenins. US Patent 4855319.

[11]   Raynaud, S., Fourneau, Ch., Laurens, A., Hocquemiller, R., Loiseau, Ph. and Bories, Ch. (2000) Squamocin and Benzyl Benzoate, Acaricidal Components of Uvaria. Planta Medica, 66, 173-175.

http://dx.doi.org/10.1055/s-0029-1243125

[12]   Shimada, H., Kozlowski, J.F. and McLaughlin, J.L. (1998) The Localisations in Liposomal Membranas of Thetetrahydrofuran Ring Moieties of the Annonaceous Acetogenins, Annonacin and Sylvaticin, as Determined by 1HNMR Spectroscopy. Pharmacological Research, 37, 357-363.

http://dx.doi.org/10.1006/phrs.1998.0314

[13]   Shimada, H., Grutzner, J.B., Kozlowski, J.F. and McLaughlin, J.L. (1998) Membrane Conformation and Their Relation to Cytotoxicity of Asimicin and Its Analogues. Biochemistry, 37, 854-866.

http://dx.doi.org/10.1021/bi972348l

[14]   Di Toto Blessing, L., Budeguer, F., Ramos, J., Diaz, S., Bardón, A., Brovetto, M., Seoane, G. and Neske, A. (2015) Structural Factors of Annonaceous Acetogenins and Their Semisynthetic Analogues Related with Their Toxicity on Spodoptera frugiperda. Journal of Agricultural Chemistry and Environment, 4, 56-61.

http://dx.doi.org/10.4236/jacen.2015.42006

[15]   Guadano, A., Gutiérrez, C., De La Pena, E., Cortes, D. and González-Coloma, A. (2000) Insecticidal and Mutagenic Evaluation of Two Annonaceous Acetogenins. Journal of Natural Products, 63, 773-776.

http://dx.doi.org/10.1021/np990328+

[16]   Alvarez Colom, O., Neske, A., Popich, S. and Bardón, A. (2007) Toxic Effects of Annonaceous Acetogenins from Annona cherimolia (Magnoliales: Annonaceae) on Spodoptera frugiperda. Journal Pest Science, 80, 63-67.

http://dx.doi.org/10.1007/s10340-006-0149-2

[17]   Di Toto Blessing, L., Alvarez Colom, O., Popich, S., Neske, A. and Bardón, A. (2010) Antifeedant and Toxic Effects of Acetogenins from Annona montana on Spodoptera frugi- perda. Journal Pest Science, 83, 307-310.

http://dx.doi.org/10.1007/s10340-010-0299-0

[18]   Alvarez Colom, O., Neske, A., Barrachina, I., Ayala Mingol, I., Moya Sanz, P. and Bardón, A. (2008) Toxic Effects of Annonaceous Acetogenins on Oncopeltus fasciatus. Journal Pest Science, 81, 85-89.

http://dx.doi.org/10.1007/s10340-007-0189-2

[19]   Alvarez Colom, O., Salvatore, A., Willink, E., Ordónez, R., Isla, M.I., Neske, A. and Bardón, A. (2010) Insecticidal, Mutagenic and Genotoxic Evaluation of Annonaceous Acetogenins. Natural Product Communications, 5, 391-394.

[20]   Ramos, J.C., Bracco, P., Mazzini, M., Gamenara, D., Brovetto, M. and Seoane, G. (2010) XIV Antonio González Scientific Week. Universidad de la Laguna, Tenerife.

[21]   Villafane, E., Tolosa, D., Bardón, A. and Neske, A. (2011) Toxic Effects of Citrus aurantium and C. lemon Essential Oils on Spodoptera frugiperda (Lepidoptera: Noctuidae). Natural Product Communications, 6, 1389-1392.

[22]   Statistix 7.1 (2000) Analytical Software.

[23]   Kawasu, K., Alcántara, J. and Kobayashi, A. (1989) Isolation and Structure of Neoannonin, a Novel Insecticidal Compound from the Seeds of Annona squamosa. Agricultural and Biological Chemistry, 53, 2719-2722.

http://dx.doi.org/10.1271/bbb1961.53.2719

[24]   Cortes, D., Myint, S. and Hocquemiller, R. (1991) Molvizarin and Motrilin: Two Novel Cytotoxic Bis-Tetrahydro-Furanic γ-Lactone Acetogenins from Annona cherimolia. Tetrahedron, 47, 8195-8202.

http://dx.doi.org/10.1016/S0040-4020(01)91014-2

[25]   Pettit, G.R., Riensen, R., Leet, J.E., Polonsky, J., Smith, C.R., Schmidt, J.M., Dufresne, C., Schaufelberger, D. and Moretti, C. (1989) Isolation and Structure of Rolliniastatin-2, a New Cell Growth Inhibitory Acetogenin from Rollinia mucosa. Heterocycles, 28, 213-217.

http://dx.doi.org/10.3987/COM-88-S6

[26]   Fujimoto, Y., Murasaki, C., Shimada, H., Nishioka, S., Kakinuma, K., Singh, S., Singh, M., Gupta, Y.K. and Sahai, M. (1994) Annonaceous Acetogenins from the Seeds of Annona squamosa. Non-Adjacent Bis-Tetrahydrofuranic Acetogenins. Chemical and Pharmaceutical Bulletin, 42, 1175-1184.

http://dx.doi.org/10.1248/cpb.42.1175

[27]   McCloud, T.G., Smith, D.L., Chang, C.J. and Cassady, J.M. (1987) Annonacin, a Novel, Biologically Active Polyketide from Annona densicoma. Experiencia, 43, 947-949.

http://dx.doi.org/10.1007/BF01951681

[28]   Sahai, M., Singh, S., Singh, M., Gupta, Y.K., Akashi, S., Yuji, R., Asaki, H., Araya, H., Hara, N., Eguchi, T., Kakinuma, K. and Fujimoto, Y. (1994) Annonaceous Acetogenins from the seeds of Annona squamosa. Adjacent bis-Tetrahydrofuranic Acetogenins. Chemical and Pharmaceutical Bulletin, 42, 1163-1174.

http://dx.doi.org/10.1248/cpb.42.1163

[29]   Zhao, G.X., Miesbauer, L.R., Smith, D.L. and McLaughlin, J. (1994) Asimin, Asiminacin and Asiminecin: Novel Highly Cytotoxic Asimicin Isomers from Asimina triloba. Journal of Medicinal Chemistry, 37, 1971-1076.

http://dx.doi.org/10.1021/jm00039a009

 
 
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