Insights into Dodecenes Produced from Olefin Oligomerization Based on Two-Dimensional Gas Chromatography-Photoionization-Time of Flight Mass Spectrometry and Multivariate Statistics.

Catalyzed light olefin oligomerization is widely used in petrochemical industries to produce fuels and chemicals. Light olefins such as propene and butenes are commonly selected as feedstocks. Solid phosphoric acid (SPA) and zeolite are representative acidic catalysts. Both the feedstocks and catalysts have an impact on the product composition. In this study, state-of-the-art instrumentation two-dimensional gas chromatography (GC × GC) coupled photoionization-time of flight mass spectrometry was employed to investigate the composition of dodecene products produced from olefin oligomerization. Information such as the olefin congener distribution, dodecene structural subgroup distribution, and individual dodecene isomers was obtained and utilized in the statistical analyses. By using specific data sets of the product composition, the distinguishment between SPA and zeolite catalysts as well as among the feedstocks was achieved by applying the unsupervised screening approaches (principal component analysis and hierarchical clustering analysis). The potential indicators of catalysts and feedstocks were selected by the feature selection methods (univariate analysis: analysis of variance and multivariate analysis: partial least squares-discriminant analysis).

Unraveling the Complex Olefin Isomer Mixture Using Two-Dimensional Gas Chromatography-Photoionization-Time of Flight Mass Spectrometry.

Commercial dodecenes are a complex chemical mixture with a majority of C12 olefins and minority of C8-18 olefins. Structurally, dodecene products may consist of straight-chain alkenes, branched alkenes, as well as cyclic hydrocarbons. Due to the difference of feeds and catalysts used in the oligomerization reaction, the composition of the dodecenes is complex and their properties are very different. Knowing the complex composition of dodecenes can help tune the production process and select the appropriate products according to their end use. To reveal the complex profile of dodecenes, an analytical method using two-dimensional gas chromatography (GC×GC) coupled photoionization (PI) - time of flight mass spectrometry (TOFMS) was developed in this study. A conventional (nonpolar × polar) column combination (non-polar column as 1st dimension and mid-polar column as 2nd dimension) was selected. The analytical condition of GC was optimized using fractional factorial experimental design (DoE). Olefin congener grouping by carbon chain length and double bond equivalent (DBE) was achieved based on the detection of molecular ions by PI-TOFMS. Grouping of dodecenes by linear, mono-branched, di- and tri-branched subgroups was achieved based on branching index (BI) under the assumption of no retention time (RT) overlap among subgroups. Certain dodecene isomers were identified by retention index (RI) and further confirmed by PI mass spectra. The information altogether provided a multimodal characterization possibility to be used with statistical tools. Principal component analysis (PCA) and hierarchical clustering analysis (HCA) of seventeen dodecene samples explained the composition variance between catalysts solid phosphoric acid and zeolite, as well as between feeds with C4 and without C4.

Flow modulation comprehensive two-dimensional gas chromatography-mass spectrometry using ≈4 mL min(-1) gas flows.

The main objective of the herein described research was focused on performing satisfactory flow modulation (FM), in comprehensive two-dimensional gas chromatography-mass spectrometry (GC×GC-MS), using an MS-compatible second-dimension gas flow of approx. 4 mL min(-1). The FM model used was based on that initially proposed by Seeley et al. [3]. The use of limited gas flows was enabled through fine tuning of the FM parameters, in particular the duration of the re-injection (or flushing) process. Specifically, the application of a long re-injection period (i.e., 700 ms) enabled efficient accumulation-loop flushing with gas flows of about 4 mL min(-1). It was possible to apply such extended re-injection periods by using different restrictor lengths in the connections linking the modulator to the auxiliary pressure source. FM GC×GC-MS applications were performed on a mixture containing C9-10 alkanes, and on a sample of essential oil. GC×GC-MS sensitivity was compared with that attained by using conventional GC-MS analysis, in essential oil applications. It was observed that signal intensities were, in general, considerably higher in the FM GC×GC-MS experiments.

Four-stage (low-)flow modulation comprehensive gas chromatography-quadrupole mass spectrometry for the determination of recently-highlighted cosmetic allergens.

The present research is based on the development and use of a flow-modulation (FM) comprehensive two-dimensional gas chromatography-quadrupole mass spectrometry (GC×GC-qMS) method for the determination of recently-highlighted (by the Scientific Committee on Consumer Safety) fragrance allergens (54) in cosmetics. FM GC×GC-qMS conditions were finely tuned to generate flow conditions (≈7 mL min(-1)) compatible with the qMS system used. Six-point calibration curves, over the range 1, 5, 10, 20, 50, 100 mg L(-1), were constructed for the 54 target allergens, with satisfactory linearity observed in all cases. Absolute quantification was performed by using extracted ions; target analyte identification was performed through measurement of ion ratios (qualifier/quantifier), full-scan MS database matching and the use of linear retention indices. Additional analytical figures of merit subjected to measurement were intra-day repeatability, accuracy at the 25 and 5 mg L(-1) levels, and limits of detection and quantification. The number of data points per peak, along with mass spectral skewing, was also subjected to evaluation. Finally, the FM GC×GC-qMS method was used not only for the quantification of target allergens in five commercial perfumes, but also for general qualitative profiling.

Impact of comprehensive two-dimensional gas chromatography with mass spectrometry on food analysis.

Comprehensive two-dimensional gas chromatography with mass spectrometry has been on the separation-science scene for about 15 years. This three-dimensional method has made a great positive impact on various fields of research, and among these that related to food analysis is certainly at the forefront. The present critical review is based on the use of comprehensive two-dimensional gas chromatography with mass spectrometry in the untargeted (general qualitative profiling and fingerprinting) and targeted analysis of food volatiles; attention is focused not only on its potential in such applications, but also on how recent advances in comprehensive two-dimensional gas chromatography with mass spectrometry will potentially be important for food analysis. Additionally, emphasis is devoted to the many instances in which straightforward gas chromatography with mass spectrometry is a sufficiently-powerful analytical tool. Finally, possible future scenarios in the comprehensive two-dimensional gas chromatography with mass spectrometry food analysis field are discussed.

Performance evaluation of a versatile multidimensional chromatographic preparative system based on three-dimensional gas chromatography and liquid chromatography-two-dimensional gas chromatography for the collection of volatile constituents.

The present research deals with the multi-collection of the most important sesquiterpene alcohols belonging to sandalwood essential oil, as reported by the international regulations: (Z)-α-santalol, (Z)-α-trans bergamotol, (Z)-ß-santalol, epi-(Z)-ß-santalol, α-bisabolol, (Z)-lanceol, and (Z)-nuciferol. A versatile multidimensional preparative system, based on the hyphenation of liquid and gas chromatography techniques, was operated in the LC-GC-GC-prep or GC-GC-GC-prep configuration, depending on the concentration to be collected from the sample, without any hardware or software modification. The system was equipped with a silica LC column in combination with polyethylene glycol-poly(5% diphenyl/95% dimethylsiloxane)-medium polarity ionic liquid or ß-cyclodextrin based GC stationary phases. The GC-GC-GC-prep configuration was exploited for the collection of four components, by using a conventional split/splitless injector, while the LC-GC-GC-prep approach was applied for three low abundant components (<5%), in order to increase the quantity collected within a single run, by the LC injection of a high sample amount. All target compounds, whose determination is hampered by the unavailability of commercial standards, were collected at milligram levels and with a high degree of purity (>87%).

Evaluation of a novel helium ionization detector within the context of (low-)flow modulation comprehensive two-dimensional gas chromatography.

The present research is focused on the use and evaluation of a novel helium ionization detector, defined as barrier discharge ionization detector (BID), within the context of (low-)flow modulation comprehensive two-dimensional gas chromatography (FM GC×GC). The performance of the BID device was compared to that of a flame ionization detector (FID), under similar FM GC×GC conditions. Following development and optimization of the FM GC×GC method, the BID was subjected to fine tuning in relation to acquisition frequency and discharge flow. Moreover, the BID performance was measured and compared to that of the FID, in terms of extra-column band broadening, sensitivity and dynamic range. The comparative study was carried out by using standard compounds belonging to different chemical classes, along with a sample of diesel fuel. Advantages and disadvantages of the BID system, also within the context of FM GC×GC, are critically discussed. In general, the BID system was characterized by a more limited dynamic range and increased sensitivity, compared to the FID. Additionally, BID and FID contribution to band broadening was found to be similar under the operational conditions applied. Particular attention was devoted to the behaviour of the FM GC×GC-BID system toward saturated and aromatic hydrocarbons, for a possible future use in the field of mineral-oil food contamination research.