Enantiomer separations by preparative gas chromatography : theory and practice /

Gas chromatography was investigated as a preparative method

Bibliographic Details
Main Author: Staerk, Daniel U., 1969-
Format: Thesis Book
Language:English
Published: [Place of publication not identified] : [publisher not identified] ; 1995.
Subjects:
Online Access:Link to OAKTrust copy
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Description
Summary:Gas chromatography was investigated as a preparative method
for the production of pure volatile enantiomers. Two classes
of enantiomeric compounds were studied: fluoroether
anesthetics, represented by enflurane and isoflurane, were
separated using trifluoroacetyl pentyl y-cyclodextrin as
stationary phase, and the chiral synthon methyl 2-
chloropropionate was separated using trichloroacetyl pentyl
@-cyclodextrin as stationary phase. These separations
required a custom-designed preparative gas chromatograph.
The instrument developed allowed independent temperature
control of the injector, the preparative column, the
detector, as well as the interface to the analytical column,
the analytical column, and another detector. The support
type and particle size, the stationary phase concentration
and the separation conditions were varied to improve product
purity and the production rate in overloaded elution mode
separations. The calculation of purity, recovery and
production rates for the separations was accomplished by
periodically sampling the effluent of the preparative column
followed by on-line enantiomeric analysis of the eluting
enantiomer bands. Aggressive yet safe fraction pooling
schemes result from this near real-time procedure. The gas-
liquid partition isotherms of the enantiomers of methyl 2
chloropropionate on the trichloroacetyl pentyl @-cyclodextrin
stationary phase were determined using the elution by
characteristic points method. The isotherms were described
using the single component and competitive biLangmuir
isotherm equations. The measured and calculated isotherms as
well as the retention factor and separation selectivity data
agreed, indicating that the isotherms might be suitable for
the modeling of the preparative-scale gas chromatographic
separation of the enantiomers. The equilibrium-dispersive
model of nonlinear chromatography was used to simulate the
band profiles of both the single-component as well as
competitive separations of methyl 2-chloropropionate on the
trichloroacetyl pentyl @-cyclodextrin stationary phase. The
model uses a mass balance equation for each analyte and for
the mobile phase, and is completed by the calculated
partition isotherm and the integrated Darcy equation for the
column pressure profile. The measured and simulated band
profiles are compared, and the behavior of both systems
discussed.
Item Description:Vita.
"Major Subject: Chemistry".
Physical Description:xiii, 128 leaves : illustrations ; 28 cm.
Issued also on microfiche from University Microfilms Inc.
Bibliography:Includes bibliographical references.