, Volume 75, Issue 1–2, pp 47–54 | Cite as

Effect of Tetrabutylammonium Cation on Solid-Phase Analytical Derivatization as a Function of Analyte Lipophilicity

  • Sanka N. Atapattu
  • Jordan N. Fortuna
  • Jack M. RosenfeldEmail author


Analytical derivatizations (AD) can increase the sensitivity of analyses—including those with mass spectrometric detection—by as much as three orders of magnitude. The extra steps required, however, are a possible impediment to their use. To simplify AD we investigated solid-phase analytical derivatization (SPAD) of compounds with diverse structures by using pentafluorobenzyl bromide (PFBBr) as the reagent. Model compounds were organic acids (e.g. phenols, chlorophenols and carboxylic acids) which were simultaneously extracted and derivatized from 0.1 M NaOH onto a polystyrene–divinylbenzene resin (XAD-4) as their pentafluorobenzyl (PFB) derivatives. Test analytes ranged in molecular weight from 94 for phenol to 266 for pentachlorophenol and octanol–water partition coefficients (log P) values ranged from 1.48 for phenol to 7.15 for hexadecanoic acid. Under SPAD conditions, reaction rates rapidly increased with log P, but yields for less lipophilic compounds, although precise, were unacceptably low. Use of the tetrabutylammonium (TBA) cation as a phase transfer catalyst increased the yield of compounds with low log P; but, unexpectedly, as the log P of the analyte increased, the phase transfer catalyst caused a decrease in yield. The data from this study define the log P range of compounds that require TBA for optimal yield and the log P range of compounds for which TBA compromises yield. This insight led to a simple, two-step, one-pot technique that gave high yields of the PFB derivatives for the entire range of analytes studied. SPAD first extracted/derivatized the lipophilic analytes from aqueous solution onto the solid phase. Extraction/derivatization of the polar analytes followed upon addition of TBA to the reaction mixture. The PFB ethers and esters of the entire range of analytes were then eluted from the XAD-4. The two-step procedure was faster, used less reagent and required lower temperature than comparable methods in the literature. With the two-step procedure, pentafluorobenzylation of phenols and carboxylic acids from water gave yields in excess of 88% with the exception of phenol and pentachlorophenol which were recovered in 57 and 44%, respectively. For all analytes, relative standard deviations were below 15%. The effect of matrix on yield varied between zero and a decline in recoveries of approximately 20–30% depending on the analyte and concentrations of NaCl or humic acid. In the presence of matrix components relative standard deviations remained below 20%.


Solid-phase analytical derivatizations Extractive alkylation Tetrabutylammonium cation Effects of analyte structure 



We thank the Best-In-Science Program from Ministry of the Environment of Ontario for their support. We also wish to thank Dr. Vince Taguchi of the Ministry of the Environment of Ontario for his guidance and contribution of the GC–MS instrumentation.


  1. 1.
    Rosenfeld JM (ed) (2011) Special issue on analytical derivatizations. J Chromatogr B 879(17–18):1157–1496Google Scholar
  2. 2.
    Blair IA (2010) Steroids 75:297–306CrossRefGoogle Scholar
  3. 3.
    Griffiths WJ, Sjovall J (2010) Biochem Biophys Res Commun 396:80–84CrossRefGoogle Scholar
  4. 4.
    Higashi T, Ichikawa T, Inagaki S, Min JZ, Fukushima T, Toyo’oka T (2010) J Pharm Biomed Anal 52:809–818CrossRefGoogle Scholar
  5. 5.
    Honda A, Miyazaki T, Ikegami T, Iwamoto J, Yamashita K, Numazawa M, Matsuzaki Y (2010) J Steroid Biochem Mol Biol 121:556–564CrossRefGoogle Scholar
  6. 6.
    Santa T (2011) Biomed Chromatogr 25:1–10CrossRefGoogle Scholar
  7. 7.
    Tsai SJ, Zhong YS, Weng JF, Huang HH, Hsieh PY (2011) J Chromatogr A 1218:524–533CrossRefGoogle Scholar
  8. 8.
    Bai L, Sun M, An J, Liu DQ, Chen TK, Kord AS (2010) J Chromatogr A 1217:302–306CrossRefGoogle Scholar
  9. 9.
    Banos CE, Silva M (2010) J Chromatogr B 878:653–658CrossRefGoogle Scholar
  10. 10.
    Croyal M, Dauvilliers Y, Labeeuw O, Capet M, Schwartz JC, Robert P (2011) Anal Biochem 409:28–36CrossRefGoogle Scholar
  11. 11.
    Fiamegos YC, Karatapanis A, Stalikas CD (2010) J Chromatogr A 1217:614–621CrossRefGoogle Scholar
  12. 12.
    Xu L, Basheer C, Lee HK (2009) J Chromatogr A 1216:701–707CrossRefGoogle Scholar
  13. 13.
    Fiamegos YC, Stalikas CD (2006) J Chromatogr A 1110:66–72CrossRefGoogle Scholar
  14. 14.
    Fiamegos YC, Stalikas CD (2005) Anal Chim Acta 550:1–12CrossRefGoogle Scholar
  15. 15.
    Starks CM (1971) J Am Chem Soc 93:195–199CrossRefGoogle Scholar
  16. 16.
    Lord HL, Rosenfeld J, Volovich V, Kumbhare D, Parkinson B (2009) J Chromatogr B 877:1292–1298CrossRefGoogle Scholar
  17. 17.
    Lord HL, Rosenfeld J, Raha S, Hamadeh MJ (2008) J Sep Sci 31:387–401CrossRefGoogle Scholar
  18. 18.
    Rosenfeld J, Kim M, Rullo A (2006) J Chromatogr Sci 44:333–339Google Scholar
  19. 19.
    Mateo-Vivaracho L, Cacho J, Ferreira V (2008) J Chromatogr A 1185:9–18CrossRefGoogle Scholar
  20. 20.
    Jonsson G, Cavcic A, Stokke TU, Beyer J, Sundt RC, Brede C (2008) J Chromatogr A 1183:6–14CrossRefGoogle Scholar
  21. 21.
    Rosenfeld JM (1999) J Chromatogr A 843:19–27CrossRefGoogle Scholar
  22. 22.
    Kojima M, Matsui N, Tsunoi S, Tanaka M (2005) J Chromatogr A 1078:1–6CrossRefGoogle Scholar
  23. 23.
    Kojima M, Tsunoi S, Tanaka M (2004) J Chromatogr A 1042:1–7CrossRefGoogle Scholar
  24. 24.
    Kojima M, Tsunoi S, Tanaka M (2003) J Chromatogr A 984:237–243CrossRefGoogle Scholar
  25. 25.
    Fiamegos YC, Konidari CN, Stalikas CD (2003) Anal Chem 75:4034–4042CrossRefGoogle Scholar
  26. 26.
    Kuklenyik Z, Ekong J, Cutchins CD, Needham LL, Calafat AM (2003) Anal Chem 75:6820–6825CrossRefGoogle Scholar
  27. 27.
    Sanchez-Avila N, Mata-Granados JM, Ruiz-Jimenez J, Luque dC (2009) J Chromatogr A 1216:6864–6872CrossRefGoogle Scholar
  28. 28.
    Trufelli H, Famiglini G, Termopoli V, Cappiello A (2011) Anal Bioanal Chem 400:2933–2941CrossRefGoogle Scholar
  29. 29.
    Rosenfeld J, Mureika-Russell M, Yeroushalmi S (1986) J Chromatogr A 358:137–146CrossRefGoogle Scholar
  30. 30.
    Fiamegos YC, Nanos CG, Pilidis GA, Stalikas CD (2003) J Chromatogr A 983:215–223CrossRefGoogle Scholar
  31. 31.
    Scheyer A, Morville S, Mirabel P, Millet M (2005) Anal Bioanal Chem 381:1226–1233CrossRefGoogle Scholar
  32. 32.
    Wang X, Luo L, Ouyang G, Lin L, Tam NF, Lan C, Luan T (2009) J Chromatogr A 1216:6267–6273CrossRefGoogle Scholar
  33. 33.
    Setkova L, Risticevic S, Pawliszyn J (2007) J Chromatogr A 1147:213–223CrossRefGoogle Scholar
  34. 34.
    Fiamegos YC, Kefala AP, Stalikas CD (2008) J Chromatogr A 1190:44–51CrossRefGoogle Scholar
  35. 35.
    Saaid M, Saad B, Ali AS, Saleh MI, Basheer C, Lee HK (2009) J Chromatogr A 1216:5165–5170CrossRefGoogle Scholar
  36. 36.
    Li N, Lee HK (1997) Anal Chem 69:5193–5199CrossRefGoogle Scholar
  37. 37.
    Maurice PA, Pullin MJ, Cabaniss SE, Zhou Q, Namjesnik-Dejanovic K, Aiken GR (2002) Water Res 36:2357–2371CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Sanka N. Atapattu
    • 1
  • Jordan N. Fortuna
    • 1
  • Jack M. Rosenfeld
    • 1
    Email author
  1. 1.Department of Pathology and Molecular MedicineMcMaster UniversityHamiltonCanada

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