System Maps for the Retention of Neutral Compounds on an Electrostatic-Shielded Reversed-Phase Column

  • Sanka N. Atapattu
  • Kevin R. D. Johnson
  • Colin F. PooleEmail author


The system constants of the solvation parameter model are used to prepare system maps for the retention of small neutral compounds on an octadecylsiloxane-bonded positive shield porous silica stationary phase (Luna Omega PS C18) for aqueous mobile phases containing 10–70% (v/v) methanol or acetonitrile. Electrostatic interactions (cation exchange) for weak bases were observed using acetonitrile–water but not methanol–water mobile phases at a similar level to a sterically shielded octadecylsiloxane-bonded silica column (Kinetex XB-C18). The system constants of the solvation parameter model and retention factor correlation plots for varied compounds indicated that the Luna Omega PS C18 stationary phase was (near) selectivity equivalent to the diisobutyloctadecylsiloxane-bonded superficially porous silica column Kinetex XB-C18. No specific interactions related to the embedded charged/chargeable functional group were observed compared with other high-purity type-B silica octadecylsiloxane-bonded stationary phases for typical reversed-phase separation conditions with unbuffered mobile phases.


Reversed-phase liquid chromatography Retention Selectivity Solvation parameter model System maps Octadecylsiloxane-bonded silica stationary phase Positive shield Electrostatic shield Steric shield 


Compliance with Ethical Standards

Conflict of interest

The authors declare that external funding was not received for this study and the study protocols were not influenced by commercial considerations. The authors have no conflict of interest.

Supplementary material

10337_2019_3714_MOESM1_ESM.docx (127 kb)
Supplementary material 1 (DOCX 126 kb)


  1. 1.
    Fanali S, Haddad PR, Poole CF, Riekkola ML (eds) (2017) Liquid chromatography: fundamentals and instrumentation, 2nd edn. Elsevier, AmsterdamGoogle Scholar
  2. 2.
    Snyder LR, Kirkland JJ, Dolan JW (2009) Introduction to modern liquid chromatography, 3rd edn. Wiley, HobokenCrossRefGoogle Scholar
  3. 3.
    Unger KK, Liapis AI (2012) Adsorbents and columns in analytical high-performance liquid chromatography: a perspective with regard to development and understanding. J Sep Sci 35:1201–1212CrossRefGoogle Scholar
  4. 4.
    Wang L, Wei W, Xia Z, Ju X, Xia ZZ (2016) Recent advances in materials for stationary phases of mixed-mode high-performance liquid chromatography. Trends Anal Chem 80:495–506CrossRefGoogle Scholar
  5. 5.
    Poole CF (2018) Chromatographic test methods for characterizing alkylsiloxane-bonded silica columns for reversed-phase liquid chromatography. J Chromatogr B 1092:207–219CrossRefGoogle Scholar
  6. 6.
    Sykora D, Vozka J, Tesarova E (2016) Chromatographic methods enabling the characterization of stationary phases and retention prediction in high-performance liquid chromatography and supercritical fluid chromatography. J Sep Sci 39:115–131CrossRefGoogle Scholar
  7. 7.
    Snyder LR, Dolan JW, Marchand DA, Carr PW (2015) The hydrophobic subtraction model of reversed-phase column selectivity. Adv Chromatogr 50:297–376Google Scholar
  8. 8.
    Lesellier E, West C (2007) Description and comparison of chromatographic methods for packed column classification. J Chromatogr A 1158:329–360CrossRefGoogle Scholar
  9. 9.
    Poole CF, Lenca N (2017) Applications of the solvation parameter model in reversed-phase liquid chromatography. J Chromatogr A 1486:2–19CrossRefGoogle Scholar
  10. 10.
    Poole CF, Poole SK (2002) Column selectivity from the perspective of the solvation parameter model. J Chromatogr A 965:263–299CrossRefGoogle Scholar
  11. 11.
    Zhang K, Liu X (2016) Mixed-mode chromatography in pharmaceutical and biopharmaceutical applications. J Pharm Biomed Anal 128:73–88CrossRefGoogle Scholar
  12. 12.
    Yang Y, Geng X (2011) Mixed-mode chromatography and its applications to biopolymers. J Chromatogr A 1218:8813–8825CrossRefGoogle Scholar
  13. 13.
    Zhang L, Dai Q, Qiao X, Yu C, Qin X, Yan H (2016) Mixed-mode chromatographic stationary phases: recent advancements and its applications for high-performance liquid chromatography. Trends Anal Chem 82:143–163CrossRefGoogle Scholar
  14. 14.
    Gritti F, Guiochon G (2013) Effect of the pH and the ionic strength on overloaded band profiles of weak bases onto neutral and charged surface hybrid stationary phases in reversed-phase liquid chromatography. J Chromatogr A 1282:113–126CrossRefGoogle Scholar
  15. 15.
    Wang C, Guo Z, Long Z, Zhang X, Liang X (2013) Overloading study of basic compounds with positively charged C18 column in liquid chromatography. J Chromatogr A 1281:60–66CrossRefGoogle Scholar
  16. 16.
    Zimmermann A, Horak J, Sanchez-Munoz OL, Lammerhofer M (2015) Surface charge fine tuning of reversed-phase/weak anion-exchange type mixed-mode stationary phases for milder elution conditions. J Chromatogr A 1409:189–200CrossRefGoogle Scholar
  17. 17.
    Dores-Sousa JL, De Vos J, Kok WT, Eeltink S (2018) Probing selectivity of mixed-mode reversed-phase/weak anion-exchange liquid chromatography to advance method development. J Chromatogr A 1570:75–81CrossRefGoogle Scholar
  18. 18.
    Chu S, Letcher RJ (2018) A mixed-mode chromatographic separation method for the analysis of dialkyl phosphates. J Chromatogr A 1535:63–71CrossRefGoogle Scholar
  19. 19.
    Abraham MH, Ibrahim A, Zissmos AM (2004) Determination of sets of solute descriptors from chromatographic measurements. J Chromatogr A 1037:29–47CrossRefGoogle Scholar
  20. 20.
    Vitha MF, Carr PW (2006) The chemical interpretation and practice of linear solvation energy relationships in chromatography. J Chromatogr A 1126:143–194CrossRefGoogle Scholar
  21. 21.
    Poole CF, Atapattu SN, Poole SK, Bell AN (2009) Determination of solute descriptors by chromatographic methods. Anal Chim Acta 652:32–53CrossRefGoogle Scholar
  22. 22.
    Poole CF, Ariyasena TC, Lenca N (2013) Estimation of the environmental properties of compounds from chromatographic measurements and the solvation parameter model. J Chromatogr A 1317:85–104CrossRefGoogle Scholar
  23. 23.
    Wang J, Wang C, Guo Z, Dong X, Xiao Y, Xue X, Zhang X, Liang X (2014) A novel method for characterization and comparison of reversed-phase selectivity LSER column characterization using gradient elution. J Chromatogr A 1361:153–161CrossRefGoogle Scholar
  24. 24.
    Chu Y, Poole CF (2003) Possibility of calculating system maps using gradient elution reversed-phase liquid chromatography. Chromatographia 58:683–690Google Scholar
  25. 25.
    Lemasson E, Richer Y, Bertin S, Henning P, West C (2018) Characterization of retention mechanisms in mixed-mode HPLC with a bimodal reversed-phase/cation-exchange stationary phase. Chromatographia 81:387–399CrossRefGoogle Scholar
  26. 26.
    Poole CF, Poole SK (2009) Foundations of retention in partition chromatography. J Chromatogr A 1216:1530–1550CrossRefGoogle Scholar
  27. 27.
    Abraham MH (1993) Hydrogen-bonding. 31. Construction of a scale of solute effective or summation hydrogen-bonding basicity. J Phys Org Chem 6:660–684CrossRefGoogle Scholar
  28. 28.
    Smith RJ, Nieass CS, Wainwright NS (1986) A review of methods for determination of hold-up volume in modern liquid chromatography. J Liq Chromatogr 9:1387–1430CrossRefGoogle Scholar
  29. 29.
    Atapattu SN, Poole CF, Praseuth MB (2017) System maps for retention of small neutral compounds on a superficially porous ethyl-bridged octadecylsiloxane-bonded silica stationary phase in reversed-phase liquid chromatography. Chromatographia 80:1279–1286CrossRefGoogle Scholar
  30. 30.
    Poole CF, Ahmed H, Kiridena W, DeKay C, Koziol WW (2005) Contribution of steric repulsion to retention on an octadecylsiloxane-bonded silica stationary phase in reversed-phase liquid chromatography. Chromatographia 62:553–561CrossRefGoogle Scholar
  31. 31.
    Carr PW, Dolan JW, Neue UD, Snyder LR (2011) Contributions to reversed-phase column selectivity. 1. Steric interaction. J Chromatogr A 1218:1724–1742CrossRefGoogle Scholar
  32. 32.
    Walter TH, Iraneta P, Capparella P (2005) Mechanism of retention loss when C8 and C18 HPLC columns are used with highly aqueous mobile phases. J Chromatogr A 1075:177–183CrossRefGoogle Scholar
  33. 33.
    Atapattu SN, Poole CF, Praseuth MB (2018) Insights into the retention mechanism of small neutral compounds on octadecylsiloxane-bonded and diisobutyloctadecylsiloxane-bonded silica stationary phases in reversed-phase liquid chromatography. Chromatographia 81:373–385CrossRefGoogle Scholar
  34. 34.
    Poole CF (2019) Influence of solvent effects on retention of small molecules in reversed-phase liquid chromatography. Chromatographia 82:49–64CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.CanAm Bioresearch Inc.WinnipegCanada
  2. 2.Department of ChemistryWayne State UniversityDetroitUSA

Personalised recommendations