A multifunction flow channel switching module for multi-column capillary gas chromatography using silicon pneumatic microvalves.

Decades ago, multi-column GC was developed for separating analytes which cannot be separated with a single column by switching the flow channels and introducing them into multiple columns. Formerly, a channel switching system consisted of stainless-tube-type packed columns and multi-port switching valves which were connected by stainless-steel pipes. These systems utilizing packed columns are still widely used today, mainly for gas analysis, especially for refinery gas analysis and natural gas analysis related to oil refining. However, there have been no new development updates in terms of hardware for decades. Since multi-port switching valves are used, there are problems such as the high frequency of valve replacements due to wear of seals, high running costs as well as long downtimes. In recent years, a heart-cutting multidimensional capillary GC using pressure switching devices such as the Deans switch has been put into practical use. Compared to the switching valves, the pressure switching devices have no wearing parts and are maintenance-free. Multi-dimensional capillary GC using the pressure-switching method cannot be applied to the analysis of low-boiling-point gasses because the retention capacity of the capillary column is low and the column inlet pressure is far from the optimum value for switching. Because of this another related factors, it has not been able to completely replace the traditional methods. In this study, an ON/OFF type silicon pneumatic microvalve was designed and fabricated by semiconductor manufacturing technology, and a flow channel switching module was developed by mounting microvalves on a metallic channel plate which is made by diffusion bonding. The flow channel switching module using silicon pneumatic microvalves has a heat resistance of up to 310 °C, can withstand pressures up to 1.5 MPA or more, and a durability that can withstand over 2 million opening and closing operations. In addition, the reproducibility of the gas sample analysis showed good reproducibility values of RSD 0.1% or less for peak areas and RSD 0.01 to 0.04% for retention time. Flow path switching without the use of pressure switching simplifies method development in several ways. For instance, by incorporating the use of valves that can be opened and closed independently, it was possible to integrate several methods such as heart cut, precut, column switching, and backflushing flow path layouts.

Preparation of Dimethyl Disulfide Adducts from the Mono-Trans Octadecadienoic Acid Methyl Esters.

The dimethyl disulfide (DMDS) adduct method is one of the more effective methods for determining double bond positions of dienoic acid. The DMDS method can be simply used to obtain the characteristic ions in which cleavage occurs between the methylthio group-added double-bond carbons as can be seen in the mass spectrum obtained using gas chromatography/electron ionization-mass spectrometry. In the case of the methylene-interrupted di-cis type and di-trans type dienoic acid, the DMDS addition reaction only occurs at one double-bond position, and cannot occur at the remaining double-bond position due to steric hindrance. As a result, two types of adducts are produced in the addition reaction. However, in the case of the methylene-interrupted mono-trans (mono-cis) type dienoic acid, the DMDS addition reaction only occurs at the cis-double bond. As a result, one type of adduct is produced in the addition reaction. In this report, we investigate the cause of the reaction selectivity by focusing on the addition reaction time.

Determination of Double Bond Positions and Geometry of Methyl Linoleate Isomers with Dimethyl Disulfide Adducts by GC/MS.

The dimethyl disulfide (DMDS) adduct method is one of the convenient and effective methods for determining double bond positions of unsaturated fatty acid methyl esters (FAME) except conjugated FAME. When analyzed using gas chromatography/electron ionization-mass spectrometry (GC/EI-MS), unsaturated FAME with DMDS added to the double bonds yields high intensity MS spectra of characteristic ions. The MS spectra of characteristic ions can then be used to easily confirm double bond positions. Here we explore the GC/EI-MS analysis of the DMDS adducts of methyl linoleate geometrical isomers isolated by high performance liquid chromatography (HPLC) with a silver nitrate column. For C18:2-c9, c12 and C18:2-t9, t12, DMDS randomly formed adducts with double bonds at either carbon 9-10 or carbon 12-13, but not both at the same time due to steric hindrance. For C18:2-c9, t12 and C18:2-t9, c12, however, DMDS only formed adducts with the double bond in the cis configuration. Consequently, when analyzing fatty acids with methylene interrupted double bonds, with one double bond in the cis and one in the trans configuration, double bond positions cannot be completely confirmed.

Separation behavior of octadecadienoic acid isomers and identification of cis- and trans-isomers using gas chromatography.

Using a strongly polar cyanopropyl capillary column we have investigated the gas chromatography (GC) separation behaviors of 24 octadecadienoic acid methyl ester (18:2ME) isomers compared against saturated methyl stearate (18:0ME) and arachidic acid methyl ester (20:0ME), and the dependency on the GC column temperature. The 24 isomers were obtained by performing cis-to trans-isomerization of six regioisomers: five of the 18:2ME isomers were prepared by the partial reduction of methyl α-linolenate and methyl γ-linolenate C18 trienoic acids with different double bond positions, whereas the sixth isomer, 18:2ME (c5, c9), was obtained from a raw constituent fatty acid methyl ester (FAME) sample extracted from Japanese yew seeds. There are no reference standards commercially available for 18:2ME isomers, and in elucidating the elution order of these isomers this study should help the future identification of cis- and trans-type of 18:2ME. We also report the identification method of cis- and trans-type of FAME using equivalent chain lengths and attempt the identification of cis- and trans-type of 18:2ME isomers from partially hydrogenated canola oil.