Binding forces contributing to reversed-phase liquid chromatographic retention on a β-cyclodextrin bonded phase

doi:10.1016/0021-9673(95)00455-6

Journal of Chromatography A

Volume 722, Issues 1–2, 26 January 1996, Pages 41-46

https://doi.org/10.1016/0021-9673(95)00455-6 Get rights and content

Abstract

Reversed-phase liquid chromatographic (RPLC) capacity factors for a number of organic solutes on a β-cyclodextrin (β-CD) bonded phase column in pure water mobile phase (k_w) were compared with formation constants of inclusion complexes (k′_f) between β-CD and the solutes based on the linear solvation energy relationship (LSER) in order to understand the types and relative strengths of various intermolecular forces between CD and the guest solute affecting the stability of inclusion complexes and hence retention in RPLC. A close fit of capacity factors (k′w) with complexation constants indicated that inclusion complexation is the major driving force in retention on the β-CD-bonded phase in RPLC. Comparison of LSERs for K_f and k′_w showed that an increasing guest molecular size stabilizes the complex by virtue of increasing dispersive interactions between the hydrophobic interior of CD cavity and the guest and hence increases the RPLC retention, and that increasing guest dipolarity and hydrogen bond (HB) acceptor basicity lead to a decrease in the stability of the complex due to the stronger dipolar and HB interactions with water, and hence decrease the retention.

References (40)

A. Nag et al.
Chem. Phys. Lett.
(1988)
A. Nag et al.
Chem. Phys. Lett.
(1989)
J.H. Park et al.
J. Chromatogr.
(1992)
M. Yoshinaga et al.
J. Chromatogr. A
(1994)
R.W. Taft et al.
J. Pharm. Sci.
(1985)
M.J. Kamlet et al.
J. Pharm. Sci.
(1986)
J.H. Park et al.
Chemosphere
(1993)
J.H. Park et al.
J. Chromatogr.
(1989)
J. Szejtli
Cyclodextrin Technology
(1988)
W. Saenger
Angew. Chem., Int. Ed. Engl.
(1980)

W.L. Hinze

Sep. Purif, Methods

(1981)

D.W. Armstrong et al.

J. Chromatogr. Sci.

(1984)

D.W. Armstrong et al.

J. Inclus. Phenom.

(1984)

K.W. Street

J. Liq. Chromatogr.

(1987)

J.H. Park et al.

J. Chem. Soc., Perkin Trans.

(1994)

M.J. Kamlet et al.

Acta Chem. Scand., Ser. B

(1985)

R.W. Taft et al.

J. Solution Chem.

(1985)

D.W. Armstrong

J. Liq. Chromatogr.

(1984)

D.W. Armstrong et al.

Science

(1985)

E.N. Arnold et al.

J. Liq. Chromatogr.

(1989)

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Binding forces contributing to reversed-phase liquid chromatographic retention on a β-cyclodextrin bonded phase

Abstract

Chem. Phys. Lett.

Chem. Phys. Lett.

J. Chromatogr.

J. Chromatogr. A

J. Pharm. Sci.

J. Pharm. Sci.

Chemosphere

J. Chromatogr.

Cyclodextrin Technology

Angew. Chem., Int. Ed. Engl.

Sep. Purif, Methods

J. Chromatogr. Sci.

J. Inclus. Phenom.

J. Liq. Chromatogr.

J. Chem. Soc., Perkin Trans.

Acta Chem. Scand., Ser. B

J. Solution Chem.

J. Liq. Chromatogr.

Science

J. Liq. Chromatogr.