Abstract
The effect of organic modifier concentration on retention and selectivity of two piperazine diastereomers in a typical n-octadecyl-bonded silica (ODS) column was investigated at pH 6.4 and pH 3.0 using phosphate-buffered acetonitrile (MeCN/H2O) and methanol (MeOH/H2O) mobile phases. The results show the logarithmic retention factors decrease with increasing organic concentration in a less rectilinear fashion in the MeCN/H2O system than in the MeOH/H2O system at high organic concentrations at both pHs. At pH 6.4, the MeOH/H2O system provided significantly higher diastereomer selectivity than the MeCN/H2O system, which can be ascribed to the hydrogen bonding interaction of methanol (as a hydrogen donor) with the piperazine amine moiety of the solute (as a hydrogen acceptor). At pH 3.0, both mobile phases provided high selectivity, in which both acetonitrile and methanol acted as hydrogen acceptors, while the protonated amine acted as the hydrogen donor. The effect of temperature on retention and selectivity was also studied in the two mobile phase systems at both pHs. It was found that at pH 6.4 the retention and selectivity were enthalpically driven in the MeOH/H2O system, while entropically driven in the MeCN/H2O system. However, the retention was entropically driven and the selectivity enthalpically driven in both systems at pH 3.0. Locally preferential solvating and hydrogen bonding effects are proposed to explain the “anomalous” retention and selectivity behaviors.
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Wysocki J (2001) LC•GC 19:1151–1159
Horávth Cs, Melander W, Molnar I (1976) J Chromatogr 125:129–156
Karger BL, Gant JR, Hartkopf A, Weiner PH (1976) J Chromatogr 128:65–78
Kikta EJ, Grushka E (1976) Anal Chem 48:1098–1104
Colin H, Diez-Mesa JC, Guiochon G, Czajkowska T, Miedziak I (1978) J Chromatogr 167:41–65
Melander WR, Chen B, Horváth Cs (1979) J Chromatogr 185:99–109
Sander LC, Field LR (1980) Anal Chem 52:2009–2013
Grushka E, Colin H, Guiochon G (1982) J Chromatogr 248:325–339
Melander W R, Mannan C A, Horváth Cs (1982) Chromatographia 15:611–615
Tchapla A, Colin H, Guiochon G (1984) Anal Chem 56:621–625
Melander WR, Chen BK, Horváth Cs (1985) J Chromatogr 318:1–10
Jaroniec M, Martire DE (1986) J Chromatogr 351:1–16
Tchapla A, Heron S, Colin H, Guiochon G (1988) Anal Chem 60:1443–1448
Sentell KB, Dorsey JG (1989) Anal Chem 61:930–934
Cheong WJ, Carr PW (1990) J Chromatogr 499:373–393
Alvarez-Zepeda A, Barman BN, Martire DE (1992) Anal Chem 64:1978–1984
Guillaume YC, Guinchard C (1998) Anal Chem 70:608–615
Ranatunga RPJ, Carr PW (2000) Anal Chem 72:5679–5692
Guillaume YC, Guinchard C (1997) Anal Chem 69:183–189
Nigam S, Juan A de, Stubbs RJ, Rutan SC (2000) Anal Chem 72:1956–1963
Cole LA, Dorsey JG, Dill KA (1992) Anal Chem 64:1324–1327
Park JH, Dallas AJ, Chau P, Carr PW (1994) J Phy Org Chem 7:757–769
Cole LA, Dorsey JG (1992) Anal Chem 64:1317–1323
Tchapla A, Heron S, Lesellier E, Colin H (1993) J Chromatogr A 656:81—112
Carr PW, Li J, Dallas AJ, Eikens DI, Tan LC (1993) J Chromatogr A 656:113–133
Carr PW, Tan LC, Park JH (1996) J Chromatogr A 724:1–12
Park JH, Lee YK, Weon YC, Tan LC, Li J, Evans JF, Carr PW (1997) J Chromatogr A 767:1–10
Sander LC, Wise SA (1987) CRC Crit Rev Anal Chem 18:299–415
Schoenmakers PJ, Tijssen R (1993) J Chromatogr 656:577–590
Lopes Marques RM, Schoenmakers PJ (1992) J Chromatogr 592:157–182
Lewis JA, Lommen DC, Raddatz WD, Dalan JW, Snyder R, Molnar I (1992) J Chromatogr 592:197–208
Horváth Cs, Melander W, Molnár I (1977) Anal Chem 49:142–154
LoBrutto R, Jones A, Kazakevich YV, McNair HM (2001) J Chromatogr 913:173–187
Mao Y, Carr PW (2001) Anal Chem 73:4478–4485
McCalley DV (2000) J Chromatogr 902:311–321
Greibrokk T, Anderson T (2001) J Sep Sci 24:899–909
Clausen A, Dowling T, Bicker G (2002) Liq Chromatogr & Rel Technol 25:705–715
Vervoort RJM, Ruyter E, Debets AJJ, Claessens HA, Cramers CA, de Jone GJ (2002) J Chromatogr 964:67–76
Snyder LR, Dolan JW, Gant JR (1979) J Chromatogr 165:31–58
Snyder LR (1980) In: High Performance Liquid Chromatography – Advances and Perspectives, Vol. 1, Horváth Cs (ed), Academic Press, New York, pp. 207–320
Snyder LR, Stadalius MA (1986) In: High Performance Liquid Chromatography – Advances and Perspectives, Vol. 4, Horváth Cs (ed), Academic Press, New York, pp.193–318
Stalcup AM, Martire DE, Wise SA (1988) J Chromatogr 442:1–14
Loewenschuss A, Yellin N (1975) Spectrochim Acta 31A:207–212
Rowlen KL, Harris JM (1991) Anal Chem 63:964–969
Albert A, Serjeant EP (1984) The Determination of Ionisation Constants, 3rd ed, Chapman and Hall, London
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Wu, N., Yehl, P., Gauthier, D. et al. Retention and Thermodynamic Studies of Piperazine Diastereomers in Reversed-Phase Liquid Chromatography. Chromatographia 59, 189–195 (2004). https://doi.org/10.1365/s10337-003-0159-7
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DOI: https://doi.org/10.1365/s10337-003-0159-7