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Synthesis of trans-4,5-epoxy-(E)-2-decenal and its deuterated analog used for the development of a sensitive and selective quantification method based on isotope dilution assay with negative chemical ionization

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Lipids

Abstract

The volatile compound trans-4,5-epoxy-(E)-2-decenal (1) was synthesized in two steps with good overall yields. The newly developed method is based on trans-epoxidation of (F)-2-octenal with alkaline hydrogen peroxide followed by a Wittig-type chain elongation with the ylide formylmethylene triphenylphosphorane. For the synthesis of [4,5-2H2]-trans-4,5-epoxy-(E)-2-decenal (d-1), [2,3-2H2]-(E)-2-octenal was prepared by reduction of 2-octyn-1-ol with lithium aluminum deuteride and subsequent oxidation of [2,3-2H2]-(E)-2-octen-1-ol with manganese oxide. Compound d-1 was used as internal standard for the quantification of 1 by isotope dilution assay. Among various mass spectrometry (MS) ionization techniques tested, negative chemical ionization with ammonia as reagent gas gave best results with respect to both sensitivity and selectivity. The detection limit was found to be at about 1 pg of the analyte introduced into the gas chromatography-MS system.

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Abbreviations

CC:

column chromatography

COSY:

homonuclear correlation spectroscopy

EI:

electron ionization

GC:

gas chromatography

HETCOR:

heteronuclear correlation spectra

IDA:

isotope dilution assay

MS:

mass spectrometry

NCI:

negative chemical ionization

NMR:

nuclear magnetic resonance

NOE:

nuclear Overhauser effect

PC:

phosphatidylcholine

PCI:

positive chemical ionization

PE:

phosphatidylethanolamine

RI:

retention index

SIM:

selected ion monitoring

THF:

tetrahydrofuran

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Authors and Affiliations

  1. Nestlé Research Center, Nestec Ltd., Vers-chez-les-Blanc, P.O. Box 44, CH-1000, Lausanne 26, Switzerland

    Jianming Lin, Laurent B. Fay, Dieter H. Welti & Imre Blank

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  1. Jianming Lin
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  2. Laurent B. Fay
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  3. Dieter H. Welti
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  4. Imre Blank
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Correspondence to Imre Blank.

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Lin, J., Fay, L.B., Welti, D.H. et al. Synthesis of trans-4,5-epoxy-(E)-2-decenal and its deuterated analog used for the development of a sensitive and selective quantification method based on isotope dilution assay with negative chemical ionization. Lipids 34, 1117–1126 (1999). https://doi.org/10.1007/s11745-999-0463-8

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  • DOI: https://doi.org/10.1007/s11745-999-0463-8

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