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Ionic liquid phases with comprehensive two-dimensional gas chromatography of fatty acid methyl esters

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Abstract

New generation inert ionic liquid (iIL) GC columns IL60i, IL76i and IL111i, comprising phosphonium or imidazolium cationic species, were investigated for separation of fatty acid methyl esters (FAME). In general, the iIL phases provide comparable retention times to their corresponding conventional columns, with only minor selectivity differences. The average tailing factors and peak widths were noticeably improved (reduced) for IL60i and IL76i, while they were slightly improved for IL111i. Inert IL phase columns were coupled with conventional IL columns in comprehensive two-dimensional GC (GC × GC) with a solid-state modulator which offers variable modulation temperature (TM), programmable TM during analysis and trapping stationary phase material during the trap/release (modulation) process, independent of oven T and column sets. Although IL phases are classified as polar, relative polarity of the two phases comprising individual GC × GC column sets permits combination of less-polar IL/polar IL and polar IL/less-polar IL column sets; it was observed that a polar/less-polar column set provided better separation of FAME. A higher first dimension (1D) phase polarity combined with a lower 2D phase polarity, for instance 1D IL111i with 2D IL59 gave the best result; the greater difference in 1D/2D phase polarity results in increasing occupancy of peak area in the 2D space. The IL111i/IL59 column set was selected for analysis of fatty acids in fat and oil products (butter, margarine, fish oil and canola oil). Compared with the conventional IL111, IL111i showed reduced column bleed which makes this more suited to GC × GC analysis of FAME. The proposed method offers a fast profiling approach with good repeatability of analysis of FAME.

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References

  1. Dettmer K. Assessment of ionic liquid stationary phases for the GC analysis of fatty acid methyl esters. Anal Bioanal Chem. 2014;406(20):4931–9.

    Article  CAS  PubMed  Google Scholar 

  2. Poole CF, Lenca N. Gas chromatography on wall-coated open-tubular columns with ionic liquid stationary phases. J Chromatogr A. 2014;1357:87–109.

    Article  CAS  PubMed  Google Scholar 

  3. Kulsing C, Nolvachai Y, Hügel HM, Marriott PJ. Developments in gas chromatography using ionic liquid stationary phases. LCGC Europe. 2015;28(8):434–40.

    Google Scholar 

  4. Nolvachai Y, Kulsing C, Marriott PJ. In silico modeling of hundred thousand experiments for effective selection of ionic liquid phase combinations in comprehensive two-dimensional gas chromatography. Anal Chem. 2016;88(4):2125–31.

    Article  CAS  PubMed  Google Scholar 

  5. Yoshinaga K, Asanuma M, Mizobe H, Kojima K, Nagai T, Beppu F, et al. Characterization of cis- and trans-octadecenoic acid positional isomers in edible fat and oil using gas chromatography–flame ionisation detector equipped with highly polar ionic liquid capillary column. Food Chem. 2014;160:39–45.

    Article  CAS  PubMed  Google Scholar 

  6. Delmonte P, Fardin Kia A-R, Kramer JKG, Mossoba MM, Sidisky L, Rader JI. Separation characteristics of fatty acid methyl esters using SLB-IL111, a new ionic liquid coated capillary gas chromatographic column. J Chromatogr A. 2011;1218(3):545–54.

    Article  CAS  PubMed  Google Scholar 

  7. Kulsing C, Nolvachai Y, Zeng AX, Chin S-T, Mitrevski B, Marriott PJ. From molecular structures of ionic liquids to predicted retention of fatty acid methyl esters in comprehensive two-dimensional gas chromatography. Chem Plus Chem. 2014;79(6):790–7.

    CAS  Google Scholar 

  8. Tyburczy C, Delmonte P, Fardin-Kia AR, Mossoba MM, Kramer JKG, Rader JI. Profile of trans fatty acids (FAs) including trans polyunsaturated fas in representative fast food samples. J Agr Food Chem. 2012;60(18):4567–77.

    Article  CAS  Google Scholar 

  9. Delmonte P, Fardin-Kia AR, Kramer JKG, Mossoba MM, Sidisky L, Tyburczy C, et al. Evaluation of highly polar ionic liquid gas chromatographic column for the determination of the fatty acids in milk fat. J Chromatogr A. 2012;1233:137–46.

    Article  CAS  PubMed  Google Scholar 

  10. Guo Q, Jiang F, Jin J, Li Q, Wang F, Wang Q, et al. Highly sensitive method for the quantification of trans-linolenic acid isomers in trilinolenin of edible oils using an ionic liquid capillary column. J Sci Food Agric. 2017:4697–703.

  11. Fan H, Smuts J, Bai L, Walsh P, Armstrong DW, Schug KA. Gas chromatography–vacuum ultraviolet spectroscopy for analysis of fatty acid methyl esters. Food Chem. 2016;194:265–71.

    Article  CAS  PubMed  Google Scholar 

  12. Gómez-Cortés P, Rodríguez-Pino V, Juárez M, de la Fuente MA. Optimization of milk odd and branched-chain fatty acids analysis by gas chromatography using an extremely polar stationary phase. Food Chem. 2017;231:11–8.

    Article  CAS  PubMed  Google Scholar 

  13. Weatherly CA, Zhang Y, Smuts JP, Fan H, Xu C, Schug KA, et al. Analysis of long-chain unsaturated fatty acids by ionic liquid gas chromatography. J Agr Food Chem. 2016;64(6):1422–32.

    Article  CAS  Google Scholar 

  14. Fardin-Kia AR, Delmonte P, Kramer JKG, Jahreis G, Kuhnt K, Santercole V, et al. Separation of the fatty acids in menhaden oil as methyl esters with a highly polar ionic liquid gas chromatographic column and identification by time of flight mass spectrometry. Lipids. 2013;48(12):1279–95.

    Article  CAS  PubMed  Google Scholar 

  15. Shimizu K, Ando Y. Gas chromatographic separation of docosenoic acid positional isomers on an SLB-IL100 ionic liquid column. J Oleo Sci. 2012;61(8):421–6.

    Article  CAS  PubMed  Google Scholar 

  16. Nolvachai Y, Kulsing C, Marriott PJ. Thermally sensitive behavior explanation for unusual orthogonality observed in comprehensive two-dimensional gas chromatography comprising a single ionic liquid stationary phase. Anal Chem. 2015;87(1):538–44.

    Article  CAS  PubMed  Google Scholar 

  17. Nosheen A, Mitrevski B, Bano A, Marriott PJ. Fast comprehensive two-dimensional gas chromatography method for fatty acid methyl ester separation and quantification using dual ionic liquid columns. J Chromatogr A. 2013;1312:118–23.

    Article  CAS  PubMed  Google Scholar 

  18. Delmonte P, Fardin-Kia AR, Rader JI. Separation of fatty acid methyl esters by GC-online hydrogenation × GC. Anal Chem. 2013;85(3):1517–24.

    Article  CAS  PubMed  Google Scholar 

  19. Villegas C, Zhao Y, Curtis JM. Two methods for the separation of monounsaturated octadecenoic acid isomers. J Chromatogr A. 2010;1217(5):775–84.

    Article  CAS  PubMed  Google Scholar 

  20. Zeng AX, Chin S-T, Marriott PJ. Integrated multidimensional and comprehensive 2D GC analysis of fatty acid methyl esters. J Sep Sci. 2013;36(5):878–85.

    Article  CAS  PubMed  Google Scholar 

  21. Kulsing C, Nolvachai Y, Rawson P, Evans DJ, Marriott PJ. Continuum in MDGC technology: from classical multidimensional to comprehensive two-dimensional gas chromatography. Anal Chem. 2016;88(7):3529–38.

    Article  CAS  PubMed  Google Scholar 

  22. Poole CF, Poole SK. Ionic liquid stationary phases for gas chromatography. J Sep Sci. 2011;34(8):888–900.

    Article  CAS  PubMed  Google Scholar 

  23. Cagliero C, Bicchi C, Cordero C, Liberto E, Sgorbini B, Rubiolo P. Room temperature ionic liquids: new GC stationary phases with a novel selectivity for flavor and fragrance analyses. J Chromatogr A. 2012;1268:130–8.

    Article  CAS  PubMed  Google Scholar 

  24. Zeng AX, Chin S-T, Nolvachai Y, Kulsing C, Sidisky LM, Marriott PJ. Characterisation of capillary ionic liquid columns for gas chromatography–mass spectrometry analysis of fatty acid methyl esters. Anal Chim Acta. 2013;803:166–73.

    Article  CAS  PubMed  Google Scholar 

  25. Amaral MSS, Marriott PJ, Bizzo HR, Rezende CM. Ionic liquid capillary columns for analysis of multi-component volatiles by gas chromatography-mass spectrometry: performance, selectivity, activity and retention indices. Anal Bioanal Chem. 2018. https://doi.org/10.1007/s00216-017-0718-7.

  26. Cagliero C, Bicchi C, Cordero C, Liberto E, Rubiolo P, Sgorbini B. Analysis of essential oils and fragrances with a new generation of highly inert gas chromatographic columns coated with ionic liquids. J Chromatogr A. 2017;1495:64–75.

    Article  CAS  PubMed  Google Scholar 

  27. Harynuk J, Górecki T. Flow model for coupled-column gas chromatography systems. J Chromatogr A. 2005;1086(1):135–40.

    Article  CAS  PubMed  Google Scholar 

  28. Luong J, Guan X, Xu S, Gras R, Shellie RA. Thermal independent modulator for comprehensive two-dimensional gas chromatography. Anal Chem. 2016;88(17):8428–32.

    Article  CAS  PubMed  Google Scholar 

  29. Kittirattanapiboon K, Krisnangkura K. Separation of acylglycerols, FAME and FFA in biodiesel by size exclusion chromatography. Eur J Lipid Sci Tech. 2008;110(5):422–7.

    Article  CAS  Google Scholar 

  30. Zeng Z-D, Hugel HM, Marriott PJ. A modeling approach for orthogonality of comprehensive two-dimensional separations. Anal Chem. 2013;85(13):6356–63.

    Article  CAS  PubMed  Google Scholar 

  31. Eder K. Gas chromatographic analysis of fatty acid methyl esters. J Chromatogr B. 1995;671(1):113–31.

    Article  CAS  Google Scholar 

  32. Harynuk J, Wynne PM, Marriott PJ. Evaluation of new stationary phases for the separation of fatty acid methyl esters. Chromatographia. 2006;63(13):S61–S6.

    Article  CAS  Google Scholar 

  33. Mondello L, Casilli A, Tranchida PQ, Dugo P, Dugo G. Detailed analysis and group-type separation of natural fats and oils using comprehensive two-dimensional gas chromatography. J Chromatogr A. 2003;1019(1):187–96.

    Article  CAS  PubMed  Google Scholar 

  34. Iverson JL, Sheppard AJ. Determination of fatty acids in butter fat using temperature-programmed gas chromatography of the butyl esters. Food Chem. 1986;21(3):223–34.

    Article  CAS  Google Scholar 

  35. Wood R, Kubena K, O'Brien B, Tseng S, Martin G. Effect of butter, mono- and polyunsaturated fatty acid-enriched butter, trans fatty acid margarine, and zero trans fatty acid margarine on serum lipids and lipoproteins in healthy men. J Lipid Res. 1993;34(1):1–11.

    CAS  PubMed  Google Scholar 

  36. Warner K, Mounts TL. Frying stability of soybean and canola oils with modified fatty acid compositions. J Am Oil Chem Soc. 1993;70(10):983–8.

    Article  CAS  Google Scholar 

  37. Barceló-Coblijn G, Murphy EJ, Othman R, Moghadasian MH, Kashour T, Friel JK. Flaxseed oil and fish-oil capsule consumption alters human red blood cell n–3 fatty acid composition: a multiple-dosing trial comparing 2 sources of n–3 fatty acid. Am J Clin Nutr. 2008;88(3):801–9.

    Article  PubMed  Google Scholar 

  38. Ong RCY, Marriott PJ. A review of basic concepts in comprehensive two-dimensional gas chromatography. J Chromatogr Sci. 2002;40(5):276–91.

    Article  CAS  PubMed  Google Scholar 

  39. Xie L, Marriott PJ, Adams M. Chemometric analysis of comprehensive two-dimensional gas chromatography data using cryogenic modulation. Anal Chim Acta. 2003;500(1):211–22.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by a grant from the Thailand Research Fund through the Royal Golden Jubilee Ph.D. program (grant no. PHD/0048/2556). The authors acknowledge the Australian Research Council Linkage Grant support and partner PerkinElmer, LP150100465. Contribution of modulation facilities from J&X Technologies, Shanghai, China is appreciated. The authors appreciate the provision of the ionic liquid phase columns by Supelco. 

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Correspondence to Philip J. Marriott.

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Published in the topical collection Ionic Liquids as Tunable Materials in (Bio)Analytical Chemistry with guest editors Jared L. Anderson and Kevin D. Clark.

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Pojjanapornpun, S., Nolvachai, Y., Aryusuk, K. et al. Ionic liquid phases with comprehensive two-dimensional gas chromatography of fatty acid methyl esters. Anal Bioanal Chem 410, 4669–4677 (2018). https://doi.org/10.1007/s00216-018-0944-7

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