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Development of ultrasound-assisted dispersive liquid–liquid microextraction–large volume injection–gas chromatography–tandem mass spectrometry method for determination of pyrethroid metabolites in brain of cypermethrin-treated rats

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Abstract

3-Phenoxybenzoic acid (3-PBA) and 4-hydroxy-3-phenoxybenzoic acid (OH-PBA) are the two common metabolites for most pyrethroid insecticides. A rapid, sensitive, and eco-friendly method has been developed based on ultrasound-assisted dispersive liquid–liquid microextraction (DLLME) coupled to large volume injection–gas chromatography–tandem mass spectrometry for the simultaneous determination of pyrethroid metabolites in rat brain treated with cypermethrin (CYP). Brain samples were homogenized in methanol (disperser solvent) followed by derivatization with methyl chloroformate (MCF) and extraction using DLLME. Factors that influence the extraction and derivatization efficiency such as type and volume of extraction and disperser solvent, sonication time, pH, ionic strength, and volumes of MCF and pyridine were optimized. Under optimized conditions, the limits of detection were 1 and 4 ng/g for 3-PBA and OH-PBA, respectively. Mean recoveries of pyrethroid metabolites in rat brain were in the range of 83–95 %. The developed method was successfully applied for determination of 3-PBA and OH-PBA in brain samples of CYP-treated rats. The developed method can be adopted for rapid and sensitive analysis of pyrethroid metabolites in toxicological and forensic laboratories.

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Abbreviations

3-PBA:

3-Phenoxybenzoic acid

ACFs:

Alkyl chloroformates

CB:

Chlorobenzene

CSIR-IITR:

Council of Industrial Research-Indian Institute of Toxicology Research

CYP:

Cypermethrin

DCM:

Dichloromethane

DLLME:

Dispersive liquid–liquid microextraction

ELISA:

Enzyme-linked immunosorbent assay

GC–ECD:

Gas chromatography–electron capture detection

GC–MS:

Gas chromatography–mass spectrometry

GC–MS/MS:

Gas chromatography–tandem mass spectrometry

HPLC:

High-performance liquid chromatography

LLE:

Liquid–liquid extraction

LOD:

Limit of detection

LOQ:

Limit of quantification

LVI:

Large volume injection

MCF:

Methyl chloroformate

NIST:

National Institute of Standards and Technology

OH-PBA:

4-Hydroxy-3-phenoxybenzoic acid

PFBBr:

Pentafluorobenzyl bromide

PTV–LVI:

Programmable temperature vaporization–large volume injection

PYRs:

Pyrethroids

RSD:

Relative standard deviation

SPE:

Solid-phase extraction

SPME:

Solid-phase microextraction

SRM:

Selected reaction monitoring

TCE:

Trichloroethylene

UA:

Ultrasound-assisted

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Acknowledgments

The authors thank Dr. K. C. Gupta, Director, CSIR-IITR, for support in providing the necessary facilities to carry out this work. RJ is thankful to UGC for providing a research fellowship to carry out this research work. AS is thankful to CSIR for providing a research fellowship. All authors are indebted to CSIR, New Delhi, for financial support through the INDEPTH (BSC0111) scheme.

Conflict of interest

There are no financial or other relations that could lead to a conflict of interest.

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Authors and Affiliations

  1. Analytical Chemistry Section, CSIR-Indian Institute of Toxicology Research, PO Box 80, M G Marg, Lucknow, 226 001, Uttar Pradesh, India

    Mohana Krishna Reddy Mudiam & Rajeev Jain

  2. Developmental Toxicology Division, CSIR-Indian Institute of Toxicology Research, Lucknow, India

    Anshuman Singh & Devendra Parmar

  3. Department of Medical Elementology and Toxicology, Jamia Hamdard, New Delhi, India

    Rajeev Jain & Haider A. Khan

Authors
  1. Mohana Krishna Reddy Mudiam
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  2. Rajeev Jain
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  3. Anshuman Singh
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  4. Haider A. Khan
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  5. Devendra Parmar
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Corresponding author

Correspondence to Mohana Krishna Reddy Mudiam.

Additional information

M. K. R. Mudiam and R. Jain contributed equally to this work.

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Mudiam, M.K.R., Jain, R., Singh, A. et al. Development of ultrasound-assisted dispersive liquid–liquid microextraction–large volume injection–gas chromatography–tandem mass spectrometry method for determination of pyrethroid metabolites in brain of cypermethrin-treated rats. Forensic Toxicol 32, 19–29 (2014). https://doi.org/10.1007/s11419-013-0196-3

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