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Lipids of the Tail Gland, Body and Muzzle Fur of the Red Fox, Vulpes vulpes

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Lipids

Abstract

The tail gland of the red fox (Vulpes vulpes) secretes lipids containing volatile terpenes used in social communication. We have analysed lipids extracted from fur of the tail gland, body (flanks) and muzzle of foxes. GC–MS showed a novel group of iso-valerate and tiglate monoesters of alkane-1,2-diols (C18:0–22:0). There was also a larger group of Type II diesters in which a second, longer chain, fatty acid (FA) was attached to the free alcohol group. LC–MS showed the full range of diol diesters, mostly C36:0–50:0, with smaller amounts of the corresponding mono-unsaturated tiglate esters. An additional group of diesters with higher MW (C49:0–62:0) containing two long-chain FA was present in the lipids of body and muzzle fur. After saponification and GC–MS, 98 fatty acids were characterized as their methyl esters. Apart from the C5 FA, most were saturated n-, iso-, anteiso- or other methyl-branched FA (C12:0–28:0) whose structures were determined by a combination of their mass spectra and Kovats retention indices. Several FA have not previously been found in nature or in vertebrates. Thirty-four alkane-1,2-diols were found as their TMS derivatives, mostly n-, iso- or anteiso-isomers of C16:0–25:0. The tail gland had the greatest amount of wax esters, from a greater variety of FA and diols, but lacked the esters with two long-chain FA. These findings show that fox skin lipids comprise mono- and di-esters of alkane-1,2-diols, and exhibit enormous complexity due to the diversity of their constituent FA, diols and the many possible isomers of their esters.

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Notes

  1. FA are described as their methyl esters, in which the carbon number refers to the parent FA, before methylation. However, the masses of ions and KI values are for the FAME derivatives from which experimental data were derived. Similarly, alcohols are described as their TMS ethers. Compounds are named by the number of carbon atoms and double bonds, and abbreviated positions of methyl branches. For example, iso-valeric acid is FA 5:0, i. Esters of alkane-1,2-diols are named by the Cn of FA in positions 1 and 2 followed by the Cn of the diol (FA1/FA2/diol). For example 2-heptadecanoyloxy-octadecyl iso-valerate, diol diester (DD) 40:0 is 5:0, i/17:0/18:0. There is evidence that FA 5 occupies position 1 in the monoesters, but this evidence is lacking for the diesters. However, as it seems most probable that diesters are formed by the addition of a second FA at position 2, this structure has been provisionally assigned.

Abbreviations

CID:

Collision induced dissociation

Cn:

Number of carbons in a molecule

COM:

Carbomethoxy

DCM:

Dichloromethane

DD:

Alkane-1,2-diol diester(s)

Diols:

Alkane-1,2-diols

DM:

Alkane-1,2-diol monoester(s)

EI:

Electron ionisation

ESM:

Electronic supplementary material

FA:

Fatty acid(s); FA1 (or 2) at position 1 (or 2) on 1,2-diol

FAME:

Fatty acid methyl ester(s)

FCL:

Fractional chain length

GC:

Gas chromatography

GE:

1-O-alkyl glycerol ether(s)

KI:

Kovats Index (Indices)

LC:

Liquid chromatography

MHC:

Major histocompatibility complex

MS:

Mass spectrum (spectra), mass spectrometry

NL:

Neutral loss

RT:

Retention time

TIC:

Total ion current

TMS:

Trimethylsilyl (derivative)

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Acknowledgements

We thank Stuart Murphy and Dr Duncan Sutherland of Phillip Island Nature Parks, and members of the Anderson Peninsula Fox Hunting Club, Victoria, for assistance in obtaining fox samples. We are also grateful to the Tasmanian Department of Primary Industries, Parks, Water and Environment for issuing a special authority for the importation of fox material. We thank Dr Richard Wilson of the Central Science Laboratory, University of Tasmania, for the accurate mass data. We also thank the anonymous reviewers for their comments which considerably improved this article.

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Authors and Affiliations

  1. Division of Pharmacy, School of Medicine, University of Tasmania, Private Bag 26, Hobart, 7001, Australia

    Stuart McLean

  2. Central Science Laboratory, University of Tasmania, Private Bag 74, Hobart, 7001, Australia

    Noel W. Davies & David S. Nichols

Authors
  1. Stuart McLean
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  2. Noel W. Davies
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  3. David S. Nichols
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Correspondence to Stuart McLean.

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McLean, S., Davies, N.W. & Nichols, D.S. Lipids of the Tail Gland, Body and Muzzle Fur of the Red Fox, Vulpes vulpes . Lipids 52, 599–617 (2017). https://doi.org/10.1007/s11745-017-4270-1

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  • DOI: https://doi.org/10.1007/s11745-017-4270-1

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