A New Stationary Phase for Capillary Gas Chromatography: Calix[4]resorcinarene Functionalized with Imidazolium Cationic Units


In this work, a novel calix[4]resorcinarene-based ionic liquid (C4RA-2IL) was synthesized, structurally characterized, and statically coated on capillary column as stationary phase for capillary gas chromatography (GC). The column efficiency of the C4RA-2IL column is 3345 plates m−1, which are determined by n-dodecane at 120 °C. Based on its McReynolds constants, the C4RA-2IL column showed moderate polarity. Particularly, the C4RA-2IL column show high separation performance for a wide range of analytes and some difficult separation of meta/para-isomers. Moreover, it exhibited excellent selectivity for critical aromatic isomers of chloroaniline, bromaniline, iodoaniline, toluidine and xylidine isomers and shows advantageous separation capability over the commercial polysiloxane stationary phase. This work presents a promising future of calixarene-based ionic liquid as a new type of stationary phase in GC separations.

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  1. 1.

    Farmani Z, Schrader W (2019) Energies 12:3455–3466

    CAS  Google Scholar 

  2. 2.

    Qian JN, Zhang YD, Liu XH, Xia JB (2019) Talanta 204:592–601

    CAS  PubMed  Google Scholar 

  3. 3.

    García-Valcárcel AI, Martínez-Ferrer MT, Campos-Rivela JM, Guil MDH (2019) Talanta 204:153–162

    PubMed  Google Scholar 

  4. 4.

    Ortega-Gavilán F, Valverde-Som L, Rodríguez-García FP, Cuadros-Rodríguez L, Bagur-González MG (2020) Food Chem 322:126743

    PubMed  Google Scholar 

  5. 5.

    Rivera-Pérez A, López-Ruiz R, Romero-González R, Garrido Frenich A (2020) Food Chem 321:126727

    PubMed  Google Scholar 

  6. 6.

    Zhang CY, Li MH, Guo MQ (2020) J Chromatogr A 1621:461024–461030

    PubMed  Google Scholar 

  7. 7.

    He XX, Han X, Wang H, Wang B, Wu B (2016) RSC Adv 6:76514–76523

    CAS  Google Scholar 

  8. 8.

    Han X, Liu JC, Wang B, Du AQ, Xu L, Wu B (2018) J Chromatogr A 1578:76–82

    CAS  PubMed  Google Scholar 

  9. 9.

    Sun T, Shuai XM, Ren KX, Jiang XX, Chen YJ, Zhao XY, Song QQ, Hu SQ, Cai ZQ (2019) Molecules 24:3158

    CAS  PubMed Central  Google Scholar 

  10. 10.

    Nan H, Zhang C, O’Brien RA, Benchea A, Davis JH, Anderson JL (2017) J Chromatogr A 1481:127–136

    CAS  PubMed  Google Scholar 

  11. 11.

    Nan H, Anderson JL (2018) TrAC Trends Anal Chem 105:367–379

    CAS  Google Scholar 

  12. 12.

    Fan J, Wang ZZ, Li Q, Qi ML, Shao SJ, Fu RN (2014) J Chromatogr A 1362:231–240

    CAS  PubMed  Google Scholar 

  13. 13.

    Zhang P, Qin SJ, Qi ML, Fu RN (2014) J Chromatogr A 1334:139–148

    CAS  PubMed  Google Scholar 

  14. 14.

    Xie SM, Zhang XH, Wang BJ, Zhang M, Zhang JH, Yuan LM (2014) Chromatographia 77:1359–1365

    CAS  Google Scholar 

  15. 15.

    Xie SM, Zhang M, Fei ZX, Yuan LM (2014) J Chromatogr A 1363:137–143

    CAS  PubMed  Google Scholar 

  16. 16.

    Zhang WF, Zhang YH, Zhang YM, Lan C, Miao Y, Deng ZF, Ba X, Zhao WD, Zhang SS (2019) Talanta 193:56–63

    CAS  PubMed  Google Scholar 

  17. 17.

    Lu J, Zhang W, Zhang Y, Zhao W, Hu K, Yu A, Liu P, Wu Y, Zhang S (2014) J Chromatogr A 1350:61–67

    CAS  PubMed  Google Scholar 

  18. 18.

    Sun T, Li B, Li Y, Zhao XY, Song QQ, Jiang XX, Shuai XM, Li YY, Cai ZQ, Hu SQ (2019) Chromatographia 82:1697–1708

    CAS  Google Scholar 

  19. 19.

    Zátopková R, Aturki Z, Bednář P (2020) J Sep Sci 43:3382–3390

    PubMed  Google Scholar 

  20. 20.

    Sun WY, Jin Y, Wang CY, Zhao SS, Wang X, Luo M, Yan JZ, Tong SQ (2020) J Chromatogr A 1617:460834–460843

    CAS  PubMed  Google Scholar 

  21. 21.

    Feng H, Ye X, Liu Y, Wang Z, Gao T, Cheng A, Wang X, Chen J (2020) J Chromatogr A 1624:461234

    CAS  PubMed  Google Scholar 

  22. 22.

    Shinkai S (1993) Tetrahedron 49:8933–8968

    CAS  Google Scholar 

  23. 23.

    Kim H, Lee MH, Mutihac L, Vicens J, Kim JS (2012) Chem Soc Rev 41:1173–1190

    CAS  PubMed  Google Scholar 

  24. 24.

    Yilmaz M, Erdemir S (2013) Turk J Chem 37:558–585

    CAS  Google Scholar 

  25. 25.

    Edwards NY, Possanza AL (2013) Supramol Chem 25:446–463

    CAS  Google Scholar 

  26. 26.

    Zhao BT, Zhu XM, Chen XH, Yan ZN, Zhu WM (2013) Chin Chem Lett 24:573–577

    CAS  Google Scholar 

  27. 27.

    Zhao BT, Peng QM, Zhu XM, Yan ZN, Zhu WM (2015) J Org Chem 80:1052–1058

    CAS  PubMed  Google Scholar 

  28. 28.

    Yan Z, Lu Y, Wang H, Wu S, Zhao B (2013) J Mol Liq 183:72–78

    CAS  Google Scholar 

  29. 29.

    Yang BC, Wang CB, Zhao BT, Zhang SS, Ye BX (2012) Int J Environ Anal Chem 92:1776–1785

    CAS  Google Scholar 

  30. 30.

    Liu M, Liao W, Hu C, Du S, Zhang H (2012) Angew Chem Int Ed 51:1585–1588

    CAS  Google Scholar 

  31. 31.

    Mokhtari B, Pourabdollah K (2012) J Incl Phenom Macrocycl Chem 73:1–15

    CAS  Google Scholar 

  32. 32.

    Mokhtari B, Pourabdollah K, Dalali N (2011) J Incl Phenom Macrocycl Chem 69:1–55

    CAS  Google Scholar 

  33. 33.

    Mokhtari B, Pourabdollah K, Dalali N (2011) Chromatographia 73:829–847

    CAS  Google Scholar 

  34. 34.

    Śliwka-Kaszyńska M, Ślebioda M (2014) J Sep Sci 37:543–550

    PubMed  Google Scholar 

  35. 35.

    Delahousse G, Lavendomme R, Jabin I, Agasse V, Cardinael P (2015) Curr Org Chem 19:2237–2249

    CAS  Google Scholar 

  36. 36.

    Hu K, Zhao W, Wen F, Liu J, Zhao X, Xu Z, Niu B, Ye B, Wu Y, Zhang S (2011) Talanta 85:317–324

    CAS  PubMed  Google Scholar 

  37. 37.

    Hu K, Deng Z, Wang B, Cui Y, Miao M, Liu W, Jiang Q, Zhao W, Huang Y, Zhang S (2015) J Sep Sci 38:60–66

    CAS  PubMed  Google Scholar 

  38. 38.

    Zadmard R, Tabar-Heydar K, Imani M (2014) J Chromatogr Sci 53:702–707

    PubMed  Google Scholar 

  39. 39.

    Poole CF, Lenca N (2014) J Chromatogr A 1357:87–109

    CAS  PubMed  Google Scholar 

  40. 40.

    Pashirova TN, Gibadullina EM, Burilov AR, Kashapov RR, Zhiltsova EP, Syakaev VV, Habicher WD, Rümmeli MH, Latypov SK, Konovalov AI, Zakharova LY (2014) RSC Adv 4:9912–9919

    CAS  Google Scholar 

  41. 41.

    Padnya PL, Andreyko EA, Gorbatova PA, Parfenov VV, Rizvanov IK, Stoikov II (2017) RSC Adv 7:1671–1686

    CAS  Google Scholar 

  42. 42.

    Sun T, Jiang XX, Song QQ, Shuai XM, Chen YJ, Zhao XY, Cai ZQ, Li K, Qiao XG, Hu SQ (2019) RSC Adv 9:28783–28792

    CAS  Google Scholar 

  43. 43.

    Peng J, Sun T, Wu L, Qi M, Huang X (2017) RSC Adv 7:45408–45415

    CAS  Google Scholar 

  44. 44.

    Sun T, Chen H, Qiao X, Ma L, Hu S, Liu X (2018) RSC Adv 8:34102–34109

    CAS  Google Scholar 

  45. 45.

    Lv Q, Zhang Q, Qi M, Bai H, Ma Q, Meng X, Fu R (2015) J Chromatogr A 1404:89–94

    CAS  PubMed  Google Scholar 

  46. 46.

    Zhang YF, Qi ML, Fu RN (2016) Chin Chem Lett 27:88–90

    Google Scholar 

  47. 47.

    Roeleveld K, David F, Lynen F (2016) J Chromatogr A 1451:135–144

    CAS  PubMed  Google Scholar 

  48. 48.

    Shashkov MV, Sidelnikov VN (2013) J Chromatogr A 1309:56–63

    CAS  PubMed  Google Scholar 

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The work was supported by the National Natural Science Foundation of China (No. 21705072), Natural Science Foundation of Liaoning Province (20180550016), Scientific Research Fund Liaoning Provincial Education Department of China (LJGD2020015), Henan Province Science and Technology Attack Plan Foundation (No. 202102310485).

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Correspondence to Zhiqiang Cai or Tao Sun.

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Shuai, X., Cai, Z., Zhao, X. et al. A New Stationary Phase for Capillary Gas Chromatography: Calix[4]resorcinarene Functionalized with Imidazolium Cationic Units. Chromatographia 84, 325–333 (2021). https://doi.org/10.1007/s10337-021-04018-x

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  • Calix[4]resorcinarene
  • Ionic liquid
  • Gas chromatography
  • Stationary phase
  • Aromatic isomers