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Time-resolved cryogenic modulation reveals isomer interconversion profiles in dynamic chromatography


Marriott, PJ and Trapp, O and Shellie, RA and Schurig, V, Time-resolved cryogenic modulation reveals isomer interconversion profiles in dynamic chromatography, Journal of Chromatography A, 919, (1) pp. 115-126. ISSN 0021-9673 (2001) [Refereed Article]

DOI: doi:10.1016/S0021-9673(01)00778-6


The dynamic chromatographic study of interconversion of E and Z forms of oximes has been investigated by using a novel cryogenic modulation method in a two-dimensional gas chromatographic array. The primary column is a conventional capillary GC column on which the molecular interconversion proceeds. In this case, the molecular dynamical process leads to a peak profile describing the kinetics and thermodynamics of the interconverting molecules during its chromatographic elution. Thus an interconversion region intercedes the elution of the individual stereoisomers of the reaction. Since the molecules are isomers, classical molecular identification methods such as gas chromatography-mass spectrometry are unable to study the individual instantaneous amounts of each of the compounds. Hence the infinitesimal profiles of interconversion along the entire column have never been experimentally observed; rather the total profile is normally subjected to mathematical modelling studies in order to match experiment with theory, and to gain the kinetic parameters of the process. In the present study, an instantaneous ratio of the individual isomers can be found during the chromatographic elution by direct measurement. This is achieved by using a cryogenic zone focussing process, with rapid longitudinal modulation of a cold trap and continual pulsing of collected zones into a fast-analysis high-resolution capillary column on which isomer interconversion is minimized. The data can be displayed as a two-dimensional contour plot to demonstrate the individual isomer profiles. The two-dimensional analysis also allows easy measurement of the peak ratios of the two isomers which is an indicator of the extent of interconversion that has taken place. Two model systems, acetaldoxime and butyraldoxime, were chosen to illustrate the use of the cryogenic modulation procedure. It is anticipated that the procedure could be applied to other molecules which exhibit gas-phase isomerizations or reactions. © 2001 Elsevier Science B.V.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Analytical chemistry
Research Field:Separation science
Objective Division:Manufacturing
Objective Group:Instrumentation
Objective Field:Scientific instruments
UTAS Author:Shellie, RA (Associate Professor Robert Shellie)
ID Code:36270
Year Published:2001
Web of Science® Times Cited:31
Deposited By:Chemistry
Deposited On:2007-11-02
Last Modified:2007-11-02

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