Skip to main content
SpringerLink
Log in

Selective Separation of Polar Unsaturated Organics Using a Water Stationary Phase in Gas Chromatography

  • Original
  • Published:
Chromatographia Aims and scope Submit manuscript

Abstract

A water stationary phase is explored as a novel means of selectively separating unsaturated analytes in gas chromatography. Several unsaturated/saturated analyte pairs consisting mainly of carboxylic acids and alcohols were examined using both a 30-m conventional non-polar HP-5 column and an 11-m water phase column. For most investigated on the HP-5 column, analytes often eluted very close to each other (~ 6–12 s apart) with poor resolution. By comparison, the shorter water phase column well separated each of the analogue pairs by about 3–8 min or more. As well on the water phase, analytes with a triple bond were much more retained than those with two double bonds, which in turn were much more retained than those with one double bond. Conversely, on the HP-5 column these were poorly separated if at all. Additionally, cis/trans isomers were baseline resolved on the water phase but co-eluted on a 30-m conventional polar Carbowax column. Similarly, positional isomers varying the location of the double bond were found to separate with a selectivity value near 1.1 on the Carbowax column, whereas on the water phase column they yielded a value of 1.3 and eluted in the reverse order. Addition of various metal ion salts to the water phase was explored. While Ca2+ ion produced modest increases in selectivity, the addition of Ag+ ion was most influential and further increased the original water phase selectivity by a factor of 2.3. The mechanistic implications of OH–-pi bonding in the water phase was discussed as a potential origin for the selectivity observed. The method was applied to gasoline, essential oil, and food stuff analysis. Results indicate that this method could be a very useful means of selectively separating such unsaturated analytes.

Graphical abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Dewulf J, Van Langenhove H (2002) Analysis of volatile organic compounds using gas chromatography. Trac-Trend Anal Chem 21:637–646

    Article  CAS  Google Scholar 

  2. Poster DL, Schantz MM, Sander LC, Wise SA (2006) Analysis of polycyclic aromatic hydrocarbons (PAHs) in environmental samples: a critical review of gas chromatographic (GC) methods. Anal Bioanal Chem 386:859–881

    Article  CAS  PubMed  Google Scholar 

  3. Medeiros PM, Simoneit BRT (2007) Gas chromatography coupled to mass spectrometry for analysis of organic compounds and biomarkers as tracers for geological, environmental, and forensic research. J Sep Sci 30:1516–1536

    Article  CAS  PubMed  Google Scholar 

  4. Anderson HE, Santos IC, Hildenbrand ZL, Schug KA (2019) A review of the analytical methods used for beer ingredient and finished product analysis and quality control. Anal Chim Acta 1085:1–20

    Article  CAS  PubMed  Google Scholar 

  5. Wang Y, Han Y, Hu W, Fu D, Wang G (2020) Analytical strategies for chemical characterization of bio-oil. J Sep Sci 43:360–371

    Article  CAS  PubMed  Google Scholar 

  6. de Zeeuw J, Luong J (2002) Developments in stationary phase technology for gas chromatography. Trac-Trend Anal Chem 21:594–607

    Article  Google Scholar 

  7. Mansour FR, Zhou L, Danielson ND (2015) Applications of poly(ethylene)glycol (PEG) in separation science. Chromatographia 78:1427–1442

    Article  CAS  Google Scholar 

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

    Article  CAS  PubMed  Google Scholar 

  9. Li X, Cui Y-Y, Yang C-X (2021) Covalent coupling fabrication of microporous organic network bonded capillary columns for gas chromatographic separation. Talanta 224:121914

    Article  CAS  PubMed  Google Scholar 

  10. Xu L, Bai J, Du A, Yang Z, Wu B (2020) 1,4-Diphenyltriphenylene grafted polysiloxane as a stationary phase for gas chromatography. New J Chem 44:695–703

    Article  CAS  Google Scholar 

  11. Nan H, Zhang C, Venkatesh A, Rossini AJ, Anderson JL (2017) Argentation gas chromatography revisited: separation of light olefin/paraffin mixtures using silver-based ionic liquid stationary phases. J Chromatogr A 1523:316–320

    Article  CAS  PubMed  Google Scholar 

  12. Anselmi C, Centini M, Fedeli P, Paoli ML, Sega A, Scesa C, Pelosi P (2000) Unsaturated hydrocarbons with fruity and floral odors. J Agric Food Chem 48(1285):1289

    Google Scholar 

  13. Aponte JC, Dillon JT, Tarozo R, Huang Y (2012) Separation of unsaturated organic compounds using silver-thiolate chromatographic material. J Chromatogr A 1240:83–89

    Article  CAS  PubMed  Google Scholar 

  14. Nikolava-Damyanova B (2009) Retention of lipids in silver ion high-performance liquid chromatography: facts and assumptions. J Chromatogr A 1216:1815–1824

    Article  Google Scholar 

  15. Ushikubo T, Nakamura H, Koyasu Y, Wajiki S (1995) Method for producing an unsaturated carboxylic acid. US Patent US5380933 A

  16. Farajzadeh MA, Yadeghari A, Khoshmaram L, Ghorbanpour H (2014) Gas chromatographic determination of some phenolic compounds in fuels and engine oil after simultaneous derivatization and microextraction. J Sep Sci 37:2966–2973

    Article  CAS  PubMed  Google Scholar 

  17. Sato S, Sato F, Gotoh H, Yamada Y (2013) Selective dehydration of alkanediols into unsaturated alcohols over rare earth oxide catalysts. ACS Catal 3:721–734

    Article  CAS  Google Scholar 

  18. Momchilova S, Nikolova-Damyanova B (2003) Stationary phases for silver ion chromatography of lipids: preparation and properties. J Sep Sci 26:261–270

    Article  CAS  Google Scholar 

  19. Correa RA, Ferraz V, Medvedovici A, Sandra P, Cerne K, David F (1999) Positional and configurational separation of fatty acid isomers by micro reversed-phase liquid chromatography with an Ag+-containing mobile phase. J Chromatogr A 848:83–93

    Article  CAS  Google Scholar 

  20. Gallant JA, Thurbide KB (2014) Properties of water as a novel stationary phase in capillary gas chromatography. J Chromatogr A 1359:247–254

    Article  CAS  PubMed  Google Scholar 

  21. Darko E, Thurbide KB (2016) Capillary gas chromatographic separation of organic bases using a pH-adjusted basic water stationary phase. J Chromatogr A 1465:184–189

    Article  CAS  PubMed  Google Scholar 

  22. Darko E, Thurbide KB (2017) Capillary gas chromatographic separation of carboxylic acids using an acidic water stationary phase. Chromatographia 80:1225–1232

    Article  CAS  Google Scholar 

  23. Darko E, Thurbide KB (2019) Dynamic control of gas chromatographic selectivity during the analysis of organic bases. Anal Chem 91:6682–6688

    Article  CAS  PubMed  Google Scholar 

  24. Darko E, Thurbide KB (2020) Active control of selectivity in organic acid analysis by gas chromatography. Anal Chim Acta 1106(216):223

    Google Scholar 

  25. Christie WW (1987) A stable silver-loaded column for the separation of lipids by high performance liquid chromatography. J High Res Chromatogr 10:148–150

    Article  CAS  Google Scholar 

  26. Christie WW (1995) In: Sebedio J-L, Perkins EG (ed) New trends in lipid and lipoprotein analysis. Champaign, IL

  27. Murakami JN, Thurbide KB (2015) Coating properties of a novel water stationary phase in capillary supercritical fluid chromatography. J Sep Sci 38:1618–1624

    Article  CAS  PubMed  Google Scholar 

  28. Huie CW (2003) Effects of organic solvents on sample pretreatment and separation performances in capillary electrophoresis. Electrophoresis 24:1508–1529

    Article  CAS  PubMed  Google Scholar 

  29. Christie WW, Dobson G, Adlof RO (2007) A practical guide to the isolation, analysis and identification of conjugated linoleic acid. Lipids 42:1073–1084

    Article  CAS  PubMed  Google Scholar 

  30. Quehenberger O, Armando AM, Dennis EA (2011) High sensitivity quantitative lipidomics analysis of fatty acids in biological samples by gas chromatography-mass spectrometry. Biochim Biophys Acta 1811:648–656

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  31. Anslyn EV, Dougherty DA (2005) Modern physical organic chemistry. Sausalito, CA

  32. Jain A, Ramanathan V, Sankararamakrishnan R (2009) Lone pair center dot center dot center dot pi interactions between water oxygens and aromatic residues: quantum chemical studies based on high-resolution protein structures and model compounds. Protein Sci 18:595–605

    CAS  PubMed  PubMed Central  Google Scholar 

  33. Andersen J, Heimdal NB, Larsen RW (2017) Competition between weak OH···π and CH···O hydrogen bonds: THz spectroscopy of the C2H2–H2O and C2H4–H2O complexes. J Chem Phys 146:194302

    Article  CAS  PubMed  Google Scholar 

  34. Yalkowsky SH, He Y (2003) Handbook of aqueous solubility data. Florida, Boca Raton

    Book  Google Scholar 

  35. Gierszal KP, Davis JG, Hands MD, Wilcox DS, Slipchenko LV, Ben-Amotz D (2011) π-hydrogen bonding in liquid water. J Phys Chem Lett 2:2930–2933

    Article  CAS  Google Scholar 

  36. DuPre DB, Yappert MC (2002) Cooperative hydrogen- and pi H-bonded interactions involving water and the ethylenic double bond. J Phys Chem A 106:567–574

    Article  CAS  Google Scholar 

  37. Zhang T, Chen X, Liang P, Liu C (2006) Determination of phenolic compounds in wastewater by liquid-phase microextraction coupled with gas chromatography. J Chromatogr Sci 44:619–624

    Article  CAS  PubMed  Google Scholar 

  38. Koe LCC, Shen W (1997) High resolution GC-MS analysis of VOCs in wastewater and sludge. Environ Monit Assess 44:549–561

    Article  CAS  Google Scholar 

  39. Nigiz FU, Hilmioglu ND (2017) Removal of acetone from wastewater by POSS loaded PDMS membrane. Period Polytech Chem 61:163–170

    Article  CAS  Google Scholar 

  40. Turkmenoglu A, Ozmen D (2021) Allergenic components, biocides, and analysis techniques of some essential oils used in food products. J Food Sci 86:2226–2241

    Article  Google Scholar 

  41. Do TKT, Hadji-Minaglou F, Antoniotti S, Fernandez X (2015) Authenticity of essential oils. TRAC-Trend Anal Chem 66:146–157

    Article  CAS  Google Scholar 

  42. Marriott PJ, Shellie R, Cornwell C (2001) Gas chromatographic technologies for the analysis of essential oils. J Chromatogr A 936:1–22

    Article  CAS  Google Scholar 

  43. Yun SS, Kim J, Lee SJ, So JS, Lee MY, Lee G, Lim HS, Kim M (2019) Naturally occurring benzoic, sorbic, and propionic acid in vegetables. Food Addit Contam B 12:167–174

    Article  CAS  Google Scholar 

  44. Tungkijanansin N, Alahmad W, Nhujak T, Varanusupakul P (2020) Simultaneous determination of benzoic acid, sorbic acid, and propionic acid in fermented food by headspace solid-phase microextraction followed by GC-FID. Food Chem 329:127161

    Article  CAS  PubMed  Google Scholar 

  45. List of permitted preservatives (2021) Government of Canada https://www.canada.ca. Accessed 2 Sep 2021

  46. McKenzie DL (1988) Physical and chemical properties of apple juice and apple juice particulate. MSc Thesis. Dept Food Sci Univ of British Columbia

Download references

Acknowledgements

The authors are grateful to the Natural Sciences and Engineering Research Council of Canada (NSERC) for a Discovery Grant in support of this project.

Funding

This study was funded by an NSERC Discovery Grant.

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Calgary, 2500 University Drive, NW, Calgary, AB, T2N 1N4, Canada

    Amberley R. Marno & Kevin B. Thurbide

Authors
  1. Amberley R. Marno
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Kevin B. Thurbide
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Kevin B. Thurbide.

Ethics declarations

Conflict of Interest

The authors declare no conflict of interest.

Ethical Approval

This study does not involve any human or animal participants.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Marno, A.R., Thurbide, K.B. Selective Separation of Polar Unsaturated Organics Using a Water Stationary Phase in Gas Chromatography. Chromatographia 85, 105–113 (2022). https://doi.org/10.1007/s10337-021-04125-9

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10337-021-04125-9

Keywords

Search

Navigation