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Peak modeling approach to accurate assignment of first-dimension retention times in comprehensive two-dimensional chromatography
journal contribution
posted on 2009-07-23, 00:00 authored by Jacqui AdcockJacqui Adcock, M Adams, B Mitrevski, P MarriottModeling of first-dimension retention of peaks based on modulation phase and period allows reliable prediction of the modulated peak distributions generated in the comprehensive two-dimensional chromatography experiment. By application of the inverse process, it is also possible to use the profile of the modulated peaks (their heights or areas) to predict the shape and parameters of the original input chromatographic band (retention time, standard deviation, area) for the primary column dimension. This allows an accurate derivation of the firstdimension retention time (RSD 0.02%) which is equal to that for the non-modulated experiment, rather than relying upon the retention time of the major modulated peak generated by the modulation process (RSD 0.16%). The latter metric can produce a retention time that differs by at least the modulation period employed in the experiment, which displays a discontinuity in the retention time vs modulation phase plot at the point of the 180° out-ofphase modulation. In contrast, the new procedure proposed here gives a result that is essentially independent of modulation phase and period. This permits an accurate value to be assigned to the first-dimension retention. The proposed metric accounts for the time on the seconddimension, the phase of the distribution, and the holdup time that the sampled solute is retained in the modulating interface. The approach may also be based on the largest three modulated peaks, rather than all modulated peaks. This simplifies the task of assigning the retention time with little loss of precision in band standard deviation or retention time, provided that these peaks are not all overloaded in the first or second dimension.
History
Journal
Analytical chemistryVolume
81Issue
16Pagination
6797 - 6804Publisher
American Chemical SocietyLocation
Washington, D.C.Publisher DOI
ISSN
0003-2700eISSN
1520-6882Language
engPublication classification
C1.1 Refereed article in a scholarly journalCopyright notice
2009, American Chemical SocietyUsage metrics
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