Abstract
Permethrin, cypermethrin and cyfluthrin are three important pyrethroids with similar structures and contain four, eight and eight stereoisomers, respectively. All the stereoisomers were completely resolved by a combination of achiral and chiral high-performance liquid chromatography with hexane/isopropanol as the mobile phase. The absolute configurations for the stereoisomers were also assigned on the basis of enantioselective resolution of permethrinic acid. For cypermethrin and cyfluthrin, although there is the only difference being one F atom substitution in cyfluthrin, the cis-I diastereomer exhibited a reversal of enantiomer order. Three specific stereoisomers were further isolated to investigate the photolysis and chiral stability of synthetic pyrethroids at the enantiomeric level. The results clearly revealed that significant isomerization occurred along with the photolysis process. The isomerization occurred at chiral 1-C position, 3-C position or both in the cyclopropyl ring, and the chiral 3-C exhibited a higher inversion tendency.
Similar content being viewed by others
References
Diao JL, Xu P, Liu DH, Zhou ZQ (2011) Enantiomer-specific toxicity and bioaccumulation of alpha-cypermethrin to earthworm Eisenia fetida. J Hazard Mater 192:1072–1078
Dondi M, Flieger M, Olsovska J, Polcaro CM, Sinibaldi M (1999) High-performance liquid chromatography study of the enantiomer separation of chrysanthemic acid and its analogous compounds on terguride-based stationary phase. J Chromatogr A 859:133–142
Holmstead RL, Casida JE, Ruzo LO, Fullmer DG (1978) Pyrethroid photodecomposition: permethrin. J Agric Food Chem 26:590–595
Jin YX, Wang WY, Xu C, Fu ZW, Liu WP (2008) Induction of hepatic estrogen-responsive gene transcription by permethrin enantiomers in male adult zebrafish. Aquat Toxicol 88:146–152
Lee W, Kim BH (1998) Liquid chromatographic resolution of pyrethroic acids and their esters on chiral stationary phases. J High Resolut Chromatogr 21:189–192
Leicht W, Fuchs R, Londershausen M (1996) Stability and biological activity of cyfluthrin isomers. Pestic Sci 48:325–332
Li ZY, Zhang ZC, Zhang L, Leng L (2008) Stereo and enantioselective degradation of β-cypermethrin and β-cyfluthrin in soil. Bull Environ Contam Toxicol 81:335–339
Liu WP, Gan JJ, Qin SJ (2005a) Separation and aquatic toxicity of enantiomers of synthetic pyrethroid insecticides. Chirality 17:S127–S133
Liu WP, Qin SJ, Gan JY (2005b) Chiral stability of synthetic pyrethroid insecticides. J Agric Food Chem 53:3814–3820
Ôi N, Kitahara H, Kira R (1990) Elution orders in the separation of enantiomers by high-performance liquid chromatography with some chiral stationary phases. J Chromatogr 535:213–227
Pérez-Fernández V, García M, Marina ML (2010) Characteristics and enantiomeric analysis of chiral pyrethroids. J Chromatogr A 1217:968–989
Ruzo LO, Holmstead RL, Casida JE (1977) Pyrethroid photodecomposition: decamethrin. J Agric Food Chem 25:1385–1394
Sakata A, Mikami N, Yamada H (1992) Degradation of pyrethroid optical isomers in soils. J Pestic Sci 17:169–180
Shishovska M, Trajkovska V (2010) HPLC-method for determination of permethrin enantiomers using chiral β-cyclodextrin-based stationary phase. Chirality 22:527–533
Yang GS, Vazquez PP, Frenich AG, Vidal JLM, Aboul-Enein HY (2004) Separation and simultaneous determination of enantiomers of tau-fluvalinate and permethrin in drinking water. Chromatographia 60:523–526
Acknowledgments
This study was supported by Natural Science Foundation of Hebei Province, China (No. B2014208075).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Li, Z.Y., Luo, X.N., Li, Q.L. et al. Stereo and Enantioselective Separation and Identification of Synthetic Pyrethroids, and Photolytical Isomerization Analysis. Bull Environ Contam Toxicol 94, 254–259 (2015). https://doi.org/10.1007/s00128-014-1405-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00128-014-1405-4