A simple, fast, and accurate thermodynamic-based approach for transfer and prediction of gas chromatography retention times between columns and instruments Part III: Retention time prediction on target column.
This is the third part of a three-part series of papers. In Part I, we presented a method for determining the actual effective geometry of a reference column as well as the thermodynamic-based parameters of a set of probe compounds in an in-house mixture. Part II introduced an approach for estimating the actual effective geometry of a target column by collecting retention data of the same mixture of probe compounds on the target column and using their thermodynamic parameters, acquired on the reference column, as a bridge between both systems. Part III, presented here, demonstrates the retention time transfer and prediction from the reference column to the target column using experimental data for a separate mixture of compounds. To predict the retention time of a new compound, we first estimate its thermodynamic-based parameters on the reference column (using geometric parameters determined previously). The compound's retention time on a second column (of previously determined geometry) is then predicted. The models and the associated optimization algorithms were tested using simulated and experimental data. The accuracy of predicted retention times shows that the proposed approach is simple, fast, and accurate for retention time transfer and prediction between gas chromatography columns.
Comprehensive two-dimensional gas chromatography thermodynamic modeling and selectivity evaluation for the separation of polychlorinated dibenzo-p-dioxins and dibenzofurans in fish tissue matrix.
Comprehensive two-dimensional gas chromatography (GC×GC) is a powerful tool for complex separations. The selectivity and sensitivity benefits from thermally modulated GC×GC were applied to the analysis of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Thermodynamic indices of 50 PCDD/Fs, including the 17 toxic 2378-substituted congeners, were collected and used to model one-dimensional and two-dimensional separations with the Rtx-Dioxin2 and Rxi-17SilMS capillary GC columns. Thermodynamic modeling was used to determine the optimal conditions to take advantage of the selectivity differences between the Rxi-17SilMS and Rtx-Dioxin2 to separate all PCDD/Fs congeners from the 2378-substituted compounds by GC×GC. The modeled elution order patterns closely matched the experimental elution order in 40 of the 45 tetrachlorinated through hexchlorinated compounds analyzed. The heptachlorinated and octachlorinated congeners were not included in the elution order modeling as they are readily resolved from other dioxin congeners. The Rxi-17SilMS crossed with the Rtx-Dioxin2 was able to separate all 2378-substituted compounds in a single separation in a fish matrix. Thirty-three additional PCDD/F congeners were added to the fish matrix that coelute with the 2378-substituted congeners. The Rxi-17SilMS crossed with the Rtx-Dioxin2 was able to fully resolve 11 of the 2378-substituted congeners with the other six congeners exhibiting coelutions with only one other congener.
Sterol metabolism. XLI. Cholesterol A-ring autoxidations
Abstract Chromatographic and spectral evidence is adduced for the presence of cholest-5-en-3-one, cholest-4-en-3-one, and cholest-4-ene-3,6-dione in samples of cholesterol aged naturally in air or subjected to irradiation in air by 60 Co gamma radiation. These findings establish an additional mode of air oxidation of cholesterol to A-ring 3-ketones. Moreover, the oxidation by air of cholest-5-en-3-one induced by 60 Co gamma radiation yielded cholest-4-en-3-one, cholest-4-ene-3,6-dione, and the epimeric 3-oxocholest-4-ene-6-hydroperoxides. Cholest-4-en-3-one was not altered by irradiation in air, nor was cholesterol isomerized to cholest-4-en-3β-ol upon irradiation. From these observations it is deduced that the radiation-induced A-ring dehydrogenation of cholesterol yields initially cholest-5-en-3-one which upon isomerization yields cholest-4-en-3-one not further oxidized and which by a second oxidation yields the epimeric 3-oxocholest-4-ene-6-hydroperoxides which decompose to cholest-4-ene-3,6-dione.