Retention behavior of ginsenosides on a poly(vinyl alcohol)-bonded stationary phase in hydrophilic interaction chromatography |
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Authors: | Noel S Quiming Nerissa L Denola Azamjon B Soliev Yoshihiro Saito Kiyokatsu Jinno |
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Institution: | (1) School of Materials Science, Toyohashi University of Technology, Toyohashi 441-8580, Japan;(2) Department of Physical Sciences and Mathematics, College of Arts and Sciences, University of the Philippines Manila, Manila, Philippines;(3) Department of Pharmaceutical Chemistry, College of Pharmacy, University of the Philippines Manila, Manila, Philippines;(4) The Institute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, Tashkent, Republic of Uzbekistan |
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Abstract: | The influences of the organic component of the mobile phase and the column temperature on the retention of ginsenosides on
a poly(vinyl alcohol) (PVA) bonded stationary phase operated under hydrophilic interaction chromatographic mode were investigated.
The retention of the ginsenosides was found to increase with increasing amount of acetonitrile (MeCN) in the mobile phase,
which is typical of hydrophilic interaction chromatographic behavior. It was also found that the retention of the analytes
was highly affected by the type of the organic modifier used. Aqueous MeCN (75–90%) gave the most satisfactory retention and
separation of ginsenosides Rf, Rg1, Rd, Re, Rc, Rb2 and Rb1 compared with aqueous methanol, isopropyl alcohol or tetrahydrofuran
at the same composition levels. The effects of the different types of organic modifiers on the retention of the analytes were
attributed to their solvent strength and hydrogen-bond accepting/donating properties. The effect of temperature on the retention
of ginsenoside on the PVA-bonded phase was assessed by constructing van’t Hoff plots for two temperature ranges: subambient
(273–293 K) and ambient-elevated (298–333 K) temperatures. van’t Hoff plots for all analytes were linear at the two temperature
intervals; however, the slopes of the lines corresponding to ginsenosides Rg1 and Re were completely different from those
for the rest of the analytes especially in the subambient temperature range. Enthalpy-entropy compensation (EEC) studies were
conducted to verify the difference in thermodynamics observed for ginsenosides Rg1 and Re compared with the other analytes.
EEC plots showed that Rf, Rd, Rc, Rb2 and Rb1 were possibly retained by the same retention mechanism, which was completely
different from that of Rg1 and Re at subambient temperatures. Retention prediction models were derived using multiple linear
regression to identify solute attributes that affected the retention of the analytes on the PVA-bonded phase. The mathematical
models derived revealed that the number of hydrogen-bond donors and the ovality of the molecules are important molecular properties
that govern the retention of the compounds on the chromatographic system. |
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Keywords: | Ginsenosides Enthalpy-entropy compensation Hydrophilic interaction chromatography Poly(vinyl alcohol)-bonded phase Van’ t Hoff plot |
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