The volatile components of the anal gland secretion of an adult, male, Ictonyx striatus were separated and identified by dynamic solvent effect sampling, capillary gas-liquid chromatography, and mass spectrometry. The major component was 2-ethylthiacyclobutane. Nine other sulphur compounds, a ketone, and a hydrocarbon were also identified. Some of these occur in the anal gland secretions of other mustelids

Apps, P.J.

Pretorius, V

Rohwer, E.R.

Viljoen, H.W.

English

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136 Volatile components of the anal gland secretion of the striped polecat lctonyx striatus P.J. Apps, H.W. Viljoen, V. Pretorius* and E.R. Rohwer Institute for Chromatography, University of Pretoria, Pretoria, 0002 Republic of South Africa Received 13 March 1987; accepted 11 December 1987 The volatile components of the anal gland secretion of an adult, male, Ictonyx striatus were separated and identified by dynamic solvent effect sampling, capillary gas-liquid chroma-tography, and mass spectrometry. The major component was 2-ethylthiacyclobutane. Nine other sulphur compounds, a ketone, and a hydrocarbon were also identified. Some of these occur in the anal gland secretions of other mustelids. Die vlugtige komponente van die anale klierafskeiding van die volwasse, manlike Ictonyx striatus is geskei en ge"identifiseer deur dinamiese oplosmiddeleffek-monsterneming, gas-chromatografie, en massaspectrometrie. Die hoofkomponent was 2-etieltiasiklobutaan. Nege ander swaelverbindings, 'n ketoon, en 'n koolwaterstof is ook ge"identifiseer. Van hierdie verbindings kom oak in die anale klierafskeiding van ander mustelidae voor. ·To whom correspondence should be addressed The striped polecat Ictonyx striatus is a small, African mustelid which in appearance, habits and ecology resem-bles the skunks of North America. Its biology has been authoritatively reviewed by Smithers (1983). Like the North American skunks Mephitis mephitis and SpiJogaJe interrupta, Ictonyx is equipped with a well developed 2 7 3 1 S.-Afr. Tydskr. Dierk. 1988,23(2) anal gland whose foul-smelling secretion is used for defence. The chemistry of this secretion has not previously been reported. We deal here with the identification of the major volatile components which give the secretion its defensive properties. Anal gland secretion was taken from an adult male Ictonyx obtained as a fresh road casualty in the northern Cape Province, South Africa and kept deep-frozen until analysis. The anal gland was excised and its secretion expelled into a 10 ml glass tube. Volatiles were accumulated from 10 ml of the head space above the secretion by dynamic, off-line, solvent effect sampling (Apps, Pretorius, Lawson, Rohwer, Centner, Viljoen & Hulse 1987) using n-hexane as solvent at 25°C. Table 1 Volatile components of the anal gland secretion of a male Ictonyx striatus Peak 1 Identification Criterion2 1 2-methylthiacyclobutane L 2 2,2-dimethylthiacyclobutane Pa 3 3-methyl-l-butanethiol L 4 l-pentanethiol L 5 2-ethylthiacyclobutane P b,d 6 2-ethyl-3-methylthiacyclobutane Pc 7 4-methyl-3-heptanone Pe 8 propylthiacyclobutane isomer I 9 methyldithiacyclopentane isomer I 10 a ketone I 11 1 ,2-dithiacycloheptane Pb 12 2-methyl-l-decene L 13 ethyldithiacyclopentane isomer I 14 a ketone I 15 a ketone I 1 Peak numbers correspond to Figure 1. 2L = found in mass spectra library, P = published spectrum: a, Brinck et al. 1983; b, Brinck et al. 1978; c, Crump & Moors 1985; d, Sokolov et aI. 1980; e, Stenhagen et aI. 1974, I = mass spectrum interpretation. 13 11 14 J 15 .},.~,J\~~ . .J LJ~ ... w,J.~9 JiJ~.~..J t .. _.jjL.,_~ ___ L_--' 1'· .... '· .. 1·" ...... ·1' .... ·"'·1"··' .. "'1 .. ·· .. "'·1·' .. ' .. '·'1', .. '·' .. ·1"· .. ' .. "1· .. ' .. " .. 1·"'·' .. ·'1· .. · .. ··'·1· .. ·······1·····'·'··1 .... ,. ·1 .. · .... '··1"··"' .. '1·'·······'1······ .. ·'1·· .. ' .. ·'·1 .. ' .. ' .... Figure 1 Total ion chromatogram of volatiles from 10 ml of headspace above the anal gland secretion of a male lctonyx striatus sampled by dynamic solvent effect. For analytical conditions see text. Reproduced by Sabinet Gateway under licence granted by the Publisher (dated 2010). S. Afr. J. Zoo\. 1988,23(2) 137 Table 2 Occurrence among Mustelidae of compounds found in anal gland secretion of Ictonyx striatus 1. 2-methylthiacyclobutane 2. 2,2-dimethylthiacyclobutane 3. 3-methyl-l-butanethiol 4. I-pentanethiol 5. 2-ethylthiacyclobutane 6. 2-ethyl-3-methylthiacyclobutane 7. 4-methyl-3-heptanone 8. propyldithiacyclobutane isomer 9. methyldithiacyclopentane isomer 11. 1,2-dithiacycloheptane 12. 2-methyl-l-decene 13. ethyldithiacyclopentane Mustela ermined' o x o Mustela Mustela Mustela putorius nivalis" putorius" furoD Mustela Mephitis visonD mephitisb o o o x x x o o o x o o x = same isomer; 0 = different isomer (based on published mass spectral); "Brink et al. (1983); bAndersen & Bernstein 1975. Accumulated volatiles were separated and identified by high resolution gas-liquid chromatography - mass spectrometry. A dynamic solvent effect inlet (Apps et al. 1987) was used to transfer the volatiles to a 25 m x 0,3 mm x 0,4 I-Lm methylpolysiloxane capillary column in a Varian 1400 gas chromatograph. The carrier gas was helium with a linear flow rate of 30 cm/s. The injector was held at 40°C for 7 min then heated ballistically to 220°C. The column was held at 40°C for 10 min then programmed at 4°C / min to 180°C. The column was coupled by an open-split interface to a Micromass 16 F mass spectrometer operating in the electron impact mode with an electron energy of 70 e V. Components were identified by comparison of their mass spectra with library material or with published spectra, or by mass spectral interpretation. Where possible chromatographic retention data were used for confirmation. The anal gland secretion of the male Ictonyx striatus consisted of a light, mobile, yellow oil and a colourless, translucent aqueous phase. The secretion emitted a strong, penetrating, metallic odour. Fifteen clearly resolved peaks appeared on the total ion chromatogram (Figure 1), of which 12 were identi-fied (Table 1). The occurrence in other mustelids of the compounds identified in Ictonyx striatus is summarized in Table 2. The presence of sulphur compounds conforms to expectation since these are usually strong-smelling and are important components of the anal gland secretions of other mustelids. The major, volatile component of the Ictonyx secretion; 2-ethylthiacyclobutane, made up 90% of the headspace volatiles. This compound was found as a minor component of the anal gland secretion of mink (Mustela vison) by Sokolov et al. (1980 compound V) but was then incorrectly identified as a dimethylthiacy-clobutane isomer (compare Brinck, Erlinge & Sandell 1983 compound 5). The offensive, odorous compounds of the anal gland of the striped skunk are trans-2-butene-I-thiol, 3-methyl-l-butanethiol and trans-2-butenyl-methyIOisulphide (Andersen & Bernstein 1975). Of these only 3-methyl-l-butanethiol was found in the striped polecat where it was a minor component. The presence of ketones is unusual among the mustelidae (Brinck et al. 1983) although they are important components of fox (Vulpes vulpes) urine (Jorgenson et al. 1978). Acknowledgements K. Lawson and M. Centner are thanked for useful suggestions. Mrs A. de Klerk made the column. References APPS, P.J., PRETORIUS; V., LAWSON, K.H., ROHWER, E.R., CENTNER, M.R., VILJOEN, H.W. & HULSE, G. 1987. Trace analysis of complex organic mixtures using capillary gas-liquid chromatography and the dynamic solvent effect. 1. High Resolut. Chromatogr. Chromatogr. Commun. 10: 122-127. ANDERSEN, K.K. & BERNSTEIN, D.T. 1975. Some chemical constituents of the scent of the striped skunk Mephitis mephitis. 1. Chem. Ecol. 1: 493-499. BRINCK, C., ERLINGE, S. & SANDELL, M. 1983. Anal sac secretion in mustelids. A comparison. 1. Chem. Ecol. 9: 727-745. BRINCK, C., GERELL, R. & ODHAM, G. 1978. Anal pouch secretion in mink Mustela vison. Oikos: 6S-75. CRUMP, D.R. & MOORS, P.J. 1985. Anal gland secretions of the stoat (Mustela erminea) and the ferret (Mustela putorius forma furo) some additional thietane compounds. 1. Chem. Ecol. 11: 1037-1043. JORGENSON, J.W., NOVOTNY, M., CARMACK, M., COPLAND, G.B., WILSON, S.R., KATANA, S. & WHITTEN, W.K. 1978. Chemical scent constituents in the urine of the red fox (Vulpes vulpes L.) during the winter season. Science: 796-798. SMITHERS, R.H.N. 1983. The Mammals of the Southern African Subregion. University of Pretoria, Pretoria. SOKOLOV, V.E., ALBONE, E.S., FLOOD, P.F., HEAP, P.F., KAGAN, M.Z., VASILIEVE, V.S., ROZNOV, V.V. & ZINKEVICH, E.P. 1980. Secretion and secretory tissues of the anal sac of the mink. Chemical and histological studies. 1. Chem. £COl. 6: 805--825. STENHAGEN, E., ABRAHAMSSON, S. & MCLAFFERTY, F.W. 1974. (eels) Registry of Mass Spectral Data. John Wiley & Sons, New York. Reproduced by Sabinet Gateway under licence granted by the Publisher (dated 2010). 

Volatile components of the anal gland secretion of the striped polecat Ictonyx striatus

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Volatile components of the anal gland secretion of the striped polecat Ictonyx striatus

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