Development of a Gas Chromatography with High-Resolution Time-of-Flight Mass Spectrometry Methodology for BDNPA/F.

Analysis of thermally labile compounds such as bis(2,2-dinitropropyl) acetal/formal (BDNPA/F), an energetic plasticizer, is usually performed via liquid chromatography (LC) as opposed to gas chromatography (GC) due to thermal decomposition in the inlet or the analytical column. While LC is a powerful technique, the analysis of volatile and semivolatile compounds is best suited to GC. Herein, a method was developed for a gas chromatograph coupled to high-resolution mass spectrometer (GC-HRMS), utilizing a programmable temperature vaporizer (PTV) inlet. A subset of the native compounds and several produced by the thermal decomposition of BDNPA/F in the inlet were evaluated by using multiple PTV inlet parameters to determine the optimal ramp rate and final temperature of the inlet (60 °C/min from 60 to 325 °C). The optimized GC-HRMS method nearly reduced all thermal decomposition, allowing for an excellent separation to be obtained. Furthermore, multiple ionization methods, including electron impact (EI), negative chemical ionization (NCI), and positive chemical ionization (PCI), were used to explore the many chemical differences between the BDNPA/F samples. A preliminary investigation of the benefits of using GC-HRMS to evaluate the chemical differences between unaged and aged BDNPA/F samples for unique insight was evaluated.

Comprehensive two-dimensional gas chromatography under low-pressure conditions.

The analysis of thermally labile and high-boiling point compounds by gas chromatography (GC) can be a challenge. One technique to overcome these challenges is low-pressure GC, which uses the vacuum produced from the mass spectrometer and wide-bore columns to elute compounds at significantly lower temperatures. While GC-MS is a powerful technique, comprehensive two-dimensional gas chromatography (GC × GC), allows for resolution of compounds that would typically coelute using GC. In this study, a pesticide standard mixture (8270 MegaMix Standard) was analyzed using a conventional GC × GC-TOFMS configuration (0.25 mm inner diameter (i.d.) to a 0.18 mm i.d. column) and low-pressure GC × GC-TOFMS configuration (0.53 mm i.d. to a 0.53 mm i.d. column). Elution temperatures, sensitivity, and peak capacity were investigated for both configurations. Compounds eluted an average of 30 °C less on the low-pressure GC × GC-TOFMS configuration compared to the conventional GC × GC-TOFMS configuration. Moreover, the compounds were separated in ∼13 min on the low-pressure GC × GC-TOFMS as opposed to 33 min for conventional GC × GC-TOFMS. However, due to the wide-bore columns and faster runtimes the low-pressure GC × GC-TOFMS had a lower, ß corrected 2D peak capacity, nc,ß,2D, of 1260 while the conventional GC × GC-TOFMS was 3588. Interestingly, both configurations yielded a similar peak capacity production of 93 peaks/min and 107 peaks/min for low-pressure and conventional GC × GC-TOFMS, respectively. A "real world" sample of diesel fuel was tested on the low-pressure and conventional GC × GC-TOFMS configurations and similar results were obtained compared to the pesticide standard mix except the peak capacity production of the low-pressure GC × GC-TOFMS configuration was higher than that of the conventional GC × GC-TOFMS method.

Radiolytic degradation of dodecane substituted with common energetic functional groups.

Explosives exist in and are expected to withstand a variety of harsh environments up to and including ionizing radiation, though little is known about the chemical consequences of exposing explosives to an ionizing radiation field. This study focused on the radiation-induced chemical changes to a variety of common energetic functional groups by utilizing a consistent molecular backbone. Dodecane was substituted with azide, nitro, nitrate ester, and nitramine functional groups and γ-irradiated with 60Co in order to study how the functional group degraded along with what the relative stability to ionizing radiation was. Chemical changes were assessed using a combination of analysis techniques including: nuclear magnetic resonance (NMR) spectroscopy, gas chromatography of both the condensed and gas phases, Raman spectroscopy, and Fourier transform infrared (FTIR) spectroscopy. Results revealed that much of the damage to the molecules was on the energetic functional group and often concentrated on the trigger linkage, also known as the weakest bond in the molecule. The general trend from most to least susceptible to radiolytic damage was found to be D-ONO2 → D-N3 → D-NHNO2 → D-NO2. These results also appear to be in line with the relative stability of these functional groups to things such as photolysis, thermolysis, and explosive insults.

Evaluation of different getter substrates using two-dimensional gas chromatography with time of flight mass spectrometry.

While understanding hydrogen uptake by organic based getters such as 1,4-bis(phenylethynyl)benzene (DEB) combined with a palladium(0)bis(dibenzylideneacetone) (Pd(dba)2) catalyst is essential, another crucial element to understand is the decomposition of the DEB, Pd(dba)2, and/or substrate material. The breakdown of these materials may create unwanted volatiles, which may interact with and lead to deterioration of sensitive materials. Moreover, it is critical to understand if different substrates cause the getter and/or catalyst to degrade in different manners. Utilizing comprehensive two-dimensional gas chromatography (GC×GC) with time-of-flight mass spectrometry (TOFMS), the presence of volatiles located in the headspace of various DEB/Pd(dba)2 getter substrates is examined. These samples include a getter infused silicone foam, a hydrogenated getter infused silicone foam, an activated carbon getter pellet, and a hydrogenated activated carbon getter pellet. Application of Fisher ratio (F-ratio) analyses lead to the identification of several compounds that are generated or consumed through the hydrogenation process. These include benzene derivatives such as bibenzyl, benzaldehyde, and vinyl benzoate in the activated carbon pellets and 1,5-diphenyl-3-pentanone, toluene, styrene, and 1-1'(2-pentene 1,5-diyl)bis benzene in the silicone foams, and alkane/alkene derivatives such undecane, 4-tridecene, and decane in the activated carbon pellets and 2,6-dimethyl undecane in the silicone foams. Further comparison of the different hydrogenated getter substrates (e.g. activated carbon pellet and silicone foam) indicates that the different substrates alter the decomposition products created from the degradation of the DEB and Pd(dba)2.

Microstructural and Sensitivity Changes of Neat, Spray-Dried RDX.

Spray drying has recently gained interest in the high explosives (HE) community for the production of novel nanocomposites and well-controlled particle size distributions. However, there is a dearth of information on spray-dried, neat energetic materials. In this work, we correlate the spray drying production parameters to the resulting microstructure and handling sensitivity properties of neat RDX. We demonstrate the capability to fine-tune the particle size distributions for "nanopowder" spray-dried RDX, as well as larger particle size distributions by simply changing the spray dryer setup. We also investigate other physical and chemical changes that RDX undergoes after being processed with spray drying. We characterize these changes with scanning electron microscopy, X-ray diffraction, ultrahigh-performance liquid chromatography, and small-scale sensitivity tests. Interestingly, although the phase and chemical properties are similar before and after spray drying, small-scale sensitivity testing reveals that size reduction of RDX does not follow the typical HE desensitization trends, generally observed for other energetic materials.

Optimization of Parameters for ROI Data Compression for Nontargeted Analyses Using LC-HRMS.

Nontargeted analyses of low-concentration analytes in the information-rich data collected by liquid chromatography with high-resolution mass spectrometry detection can be challenging to accomplish in an efficient and comprehensive manner. The aim of this study is to demonstrate a workflow involving targeted parameter optimization for entire chromatograms using region of interest (ROI) data compression uncoupled from a subsequent tile-based Fisher ratio (F-ratio) analysis, a supervised discovery-based method, for the discovery of low-concentration analytes. Soil samples spiked with 18 pesticides at nominal concentrations ranging from 0.1 to 50 ppb for a total of six sample classes served as challenging samples to demonstrate the overall workflow. Optimization of two parameters proved to be the most critical for ROI data compression: the signal threshold parameter and the admissible mass deviation parameter. The parameter optimization method workflow we introduce is based upon spiking known analytes into a representative sample and determining the number of detectable spikes and the Δppm for various combinations of the signal threshold and admissible mass deviation, where Δppm is the absolute value of the difference between the theoretical m/z and the ROI m/z. Once optimal parameters are determined providing the lowest average Δppm and the greatest number of detectable analytes, the optimized parameters can be utilized for the intended analysis. Herein, tile-based F-ratio analysis was performed on the ROI compressed data of all spiked soil samples first by applying ROI parameters recommended in the literature, referred to herein as the initial ROI parameters, and finally by the combination of the two optimized parameters. Using the initial ROI parameters, three pesticides were discovered, whereas all 18 spiked pesticides were discovered by optimizing both ROI parameters.

Investigation into the Decomposition Pathways of an Acetal-Based Plasticizer.

Until now, it has been assumed that the primary decomposition pathway for the liquid plasticizer bis(2,2-dinitropropyl)acetal and bis(2,2-dinitropropyl)formal (BDNPA/F) was nitrous acid elimination (NAE). An ultrahigh-performance liquid chromatography (UHPLC) coupled to quadrupole time-of-flight mass spectrometry (QTOF) methodology was developed to discover and identify the degradation products of BDNPA/F. No evidence of NAE was found. However, two other degradation pathways were found: (1) hydrolysis of the acetal/formal functional group and (2) radical-based homolysis of the C-N bond, followed by hydrogen atom abstraction. Hydrolysis of BDNPA/F proceeds by the formation of 2,2-dinitropropanol (DNPOH) and 2,2-dinitropropyl hemiacetal/hemiformal, which further decompose into DNPOH and ethanal/methanal, respectively. Hydrolysis is the dominant decomposition pathway in all samples; however, at higher temperatures, C-N homolysis becomes more significant. Also, the solid PBX 9501 has different ratios of decomposition products than the liquid BDNPA/F due to the slower rate of diffusion through solids than liquids.

Chemical Evaluation and Performance Characterization of Pentaerythritol Tetranitrate (PETN) under Melt Conditions.

Pentaerythritol tetranitrate (PETN) is a nitrate ester explosive commonly used in commercial detonators. Although its degradation properties have been studied extensively, very little information has been collected on its thermal stability in the molten state due to the fact that its melting point is only ∼20 °C below its onset of decomposition. Furthermore, studies that have been performed on PETN thermal degradation often do not fully characterize or quantify the decomposition products. In this study, we heat PETN to melt temperatures and identify thermal decomposition products, morphology changes, and mass loss by ultrahigh-pressure liquid chromatography coupled to quadrupole time of flight mass spectrometry, scanning electron microscopy, nuclear magnetic resonance spectroscopy, and differential scanning calorimetry. For the first time, we quantify several decomposition products using independently prepared standards and establish the resulting melting point depression after the first melt. We also estimate the amount of decomposition relative to sublimation that we measure through gas evolution and evaluate the performance behavior of the molten material in commercial detonator configurations.

Non-targeted discovery-based analysis for gas chromatography with mass spectrometry: A comparison of peak table, tile, and pixel-based Fisher ratio analysis.

The ability to discover minute differences between samples or sample classes for gas chromatography coupled to mass spectrometry (GC-MS) can be a challenging endeavor, especially when those differences are not a priori. Fisher ratio (F-ratio) analysis is an apt technique to probe the differences between GC-MS chromatograms. F-ratio analysis is a supervised, non-targeted, discovery-based method that compares two different samples (or sample classes) to reduce the GC-MS dataset into a hit list composed of class distinguishing compounds. Three different F-ratio techniques, peak table, tile, and pixel-based were used to "discover" nine non-native analytes that were spiked into gasoline at four different nominal concentrations of 250, 85, 25, 5 parts-per-million (ppm). For the tile and pixel-based F-ratio calculations, a novel methodology is introduced to improve the sensitivity of the F-ratio calculations while reducing false positives. Furthermore, we use a combinatorial technique using null class comparisons, termed null distribution analysis, to determine a statistical F-ratio cutoff for analysis of the hit lists. The pixel-based algorithm was the most sensitive method and was able to "discover" all nine spiked analytes at a nominal concentration of 250 ppm albeit with one false positive interspersed towards the bottom of the hit list. The pixel-based software was also able to "discover" more of the spiked analytes at the lower concentrations with seven of the spiked analytes "discovered" at 85 ppm, four of the spiked analytes "discovered" at 25 ppm, and one analyte "discovered" at 5 ppm.

Development of comprehensive two-dimensional liquid chromatography for investigating aging of plastic bonded explosives.

The feasibility of measuring the aging and degradation of PBX 9501 via online two dimensional liquid chromatography (LC × LC) is investigated, and a preliminary instrumental setup and method is developed. Plastic-Bonded eXplosive (PBX) 9501 is nominally composed of 94.9 wt% HMX, 2.5 wt% Estane® 5703 (poly (ester urethane)), 2.5 wt% BDNPA/F (nitroplasticizer), 0.1 wt% Irganox 1010 and PBNA (N-phenyl-naphthylamine) at low concentrations. When exposed to various environmental conditions, PBX 9501 will degrade through different pathways. Because PBX 9501 is composed of both low molecular weight compounds (BDNPA/F, Irganox 1010, PBNA, and potential degradation products) and high molecular weight compounds (Estane® 5703), analysis is normally performed via two independent analyses. The low molecular weight species are analyzed via high pressure liquid chromatography (HPLC) and the high molecular weight species via size exclusion chromatography (SEC). While these individual techniques yield information about the aging of PBX 9501, the combination of HPLC and SEC (i.e. HPLC × SEC) can simplify and streamline the analyses while also providing additional chemical information. A simplified sample preparation method is proposed for LC × LC analysis. Various SEC columns and HPLC column selection, flow rate, and gradient ramps were investigated for their application of measuring aged PBX 9501. Finally, two LC × LC separations of a library standard of PBX 9501 and a sample of aged PBX 9501 are compared.

Comprehensive two-dimensional gas chromatography and time-of-flight mass spectrometry detection with a 50 ms modulation period.

An ultrafast flow modulation period, PM of 50 ms, for comprehensive two-dimensional (2D) gas chromatography (GC × GC) with time-of-flight mass spectrometry (TOFMS) detection is demonstrated, producing narrow peak widths, 2W (4σ width-at-base on the 2D dimension), demonstrating the potential for ultrafast (2D) separations with high peak capacity. The modulator is a pulse flow valve that injects a narrow pulse of carrier gas at a user defined PM, at the union between the 1D and 2D columns. The raw data produced combines the properties of vacancy chromatography and frontal analysis. Deconvolution of the raw data using unconstrained multivariate curve resolution alternating least squares (MCR-ALS) analysis facilitates identification and quantification for overlapped analyte peaks. The peak profile loadings obtained from MCR-ALS are converted into traditional appearing GC × GC data through a process commonly used with frontal analysis. An 18-component test mixture at seven different injected mass levels was studied. The 2D peaks generated ranged from an 2W of 16 to 36 ms with an average of 26 ms. At an on-column injected mass of 14 ng per analyte, an average mass spectral match value, MV, of 822 was achieved using in-house collected spectra for comparison, with an average match value RSD of 7.1%. Calibration of overlapped test analytes was evaluated using the areas of the MCR-ALS loadings, with excellent quantification demonstrated. The advancement demonstrated in modulation performance for GC × GC represents a significant decrease in PM as most commercial modulators have a minimum PM of 1 s, while maintaining the benefits of a duty cycle of essentially 1.0, which promises to enable new chemical analyzer designs, compatible with the vacuum requirements of the TOFMS detector.

Ultrafast separations via pulse flow valve modulation to enable high peak capacity multidimensional gas chromatography.

Ultrafast modulation with a modulation period PM ≥ 50ms via a pulse flow valve is demonstrated for comprehensive two-dimensional gas chromatography (GC×GC) and comprehensive three-dimensional (3D) gas chromatography (GC3). Significant increases in peak capacity and peak capacity production are achieved for GC×GC and GC3 relative to previous studies due to using pulse flow valve modulation. Due to the nature of the "partial" modulation process, the separation dimension following pulse flow valve modulation is not a traditional chromatogram, rather requires data processing to convert the data to expose the encoded chromatographic information, producing "apparent" chromatographic peaks. In the GC×GC mode, a 115-component test mixture was evaluated using a PM of 500ms, creating an apparent 2D peak width-at-base 2W with an average of 25ms, producing a 2nc of 20. Based on the average 1W of 1.0s for the 6min first dimension 1D separation, an ideal peak capacity nc,2D of 7200 is achieved (1,200/min peak production). For a high-speed GC×GC separation (30s run), a PM of 75ms produced apparent 2W of 8ms, ideal for the third dimension of a GC3 instrument. Using the knowledge gained from this high-speed GC×GC experiment, the pulse flow valve was implemented as the second modulator in GC3. Three samples were evaluated in the GC3 mode: a simple mixture containing 18 compounds (to illustrate basic concepts), the 115-component test mixture (to determine peak capacity figures-of-merit), and a diesel spiked with 8 polar compounds (to illustrate chemical selectivity benefits of GC3). For the 115-component test mixture with a 1PM of 1.2s and a 2PM of 60ms, average 1W of 3.2s, 2W of 130ms, and apparent 3W of 13ms were produced, resulting in a 1nc of 210, 2nc of 9.2, and 3nc of 5, respectively. Hence, an ideal peak capacity, nc,3D of ∼10,000 for GC3 was achieved for the 11min 1D separation window of the 115-component test mixture.

Enhancing the chemical selectivity in discovery-based analysis with tandem ionization time-of-flight mass spectrometry detection for comprehensive two-dimensional gas chromatography.

The complementary information provided by tandem ionization time-of-flight mass spectrometry (TI-TOFMS) is investigated for comparative discovery-based analysis, when coupled with comprehensive two-dimensional gas chromatography (GC × GC). The TI conditions implemented were a hard ionization energy (70 eV) concurrently collected with a soft ionization energy (14 eV). Tile-based Fisher ratio (F-ratio) analysis is used to analyze diesel fuel spiked with twelve analytes at a nominal concentration of 50 ppm. F-ratio analysis is a supervised discovery-based technique that compares two different sample classes, in this case spiked and unspiked diesel, to reduce the complex GC × GC-TI-TOFMS data into a hit list of class distinguishing analyte features. Hit lists of the 70 eV and 14 eV data sets, and the single hit list produced when the two data sets are fused together, are all investigated. For the 70 eV hit list, eleven of the twelve analytes were found in the top thirteen hits. For the 14 eV hit list, nine of the twelve analytes were found in the top nine hits, with the other three analytes either not found or well down the hit list. As expected, the F-ratios per m/z used to calculate each average F-ratio per hit were generally smaller fragment ions for the 70 eV data set, while the larger fragment ions were emphasized in the 14 eV data set, supporting the notion that complementary information was provided. The discovery rate was improved when F-ratio analysis was performed on the fused data sets resulted in eleven of the twelve analytes being at the top of the single hit list. Using PARAFAC, analytes that were "discovered" were deconvoluted in order to obtain their identification via match values (MV). Location of the analytes and the "F-ratio spectra" obtained from F-ratio analysis were used to guide the deconvolution. Eight of the twelve analytes where successfully deconvoluted and identified using the in-house library for the 70 eV data set. PARAFAC deconvolution of the two separate data sets provided increased confidence in identification of "discovered" analytes. Herein, we explore the limit of analyte discovery and limit of analyte identification, and demonstrate a general workflow for the investigation of key chemical features in complex samples.

Comprehensive two-dimensional gas chromatography using partial modulation via a pulsed flow valve with a short modulation period.

Partial modulation via a pulsed flow valve for comprehensive two-dimensional (2D) gas chromatography (GC × GC) is demonstrated, producing narrow peak widths, 2Wb, on the secondary separation dimension, 2D, coupled with short modulation periods, PM, thus producing a high peak capacity on the 2D dimension, 2nc. The GC × GC modulator is a pulse flow valve that injects a pulse of carrier gas at the specified PM, at the connection between the primary, 1D, column and the 2D column. Using a commercially available pulse flow valve, this injection technique performs a combination of vacancy chromatography and frontal analysis, whereby each pulse disturbance in the analyte concentration profile as it exits the 1D column results in data that is readily converted into a 2D separation. A three-step process converts the raw data into a format analogous to a GC × GC separation, incorporating signal differentiation, baseline correction and conversion to a GC × GC chromatogram representation. A 115-component test mixture with a wide range of boiling points (36-372°C) of nine compound classes is demonstrated using modulation periods of PM = 50, 100, 250, and 500ms, respectively. For the test mixture with a PM of 250ms, peak shapes on 2D are symmetric with apparent 2Wb ranging from 12 to 45ms producing a 2nc of ~ 10. Based on the average peak width of 0.93s on the 1D separation for a time window of 400s, the 1D peak capacity is 1nc ∼ 430. Thus, the ideal 2D peak capacity nc,2D is 4300 or a peak capacity production of 650 peaks/min using the PM of 250ms. Additionally, for a PM of 50, 100 and 500ms, the 2nc are 4, 7, and 12, respectively. Retention times on 2D, 2tR, are reproducible having standard deviations less than 1ms. Finally, the processed data is shown to be quantitative, with an average RSD of 4.7% for test analytes.

High temperature diaphragm valve-based comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry.

A high temperature diaphragm valve-based two-dimensional (2D) gas chromatography (GC×GC) with time-of-flight mass spectrometry (TOFMS) instrument, with the valve mounted directly in the GC oven, is demonstrated with separations up to 325°C. Use of the diaphragm valve allowed for the use of uncoupled carrier gas flows for 1D (first column dimension) and 2D (second column dimension), with a 1D flow rate of 1ml/min, and a 2D flow rate 3ml/min. The 3ml/min flow rate on 2D was selected to ensure compatibility with most TOFMS detectors. For valve-based modulation, a 5µl sample loop coupled with a 60ms pulse width was selected, providing sufficient sensitivity concurrent with an acceptable 2D peak capacity. A 44-component mixture of alkanes, alcohols, and polyaromatic hydrocarbons (including n-alkanes of heptane to triacontane) whose boiling points range from 98°C to 450°C was used to initially study instrument performance. For a 120min separation and a modulation period PM of 2s, average peak widths-at-base of 10s and 94ms were achieved for the alkanes on the 1D and 2D dimensions, respectively. Hence, the 1D peak capacity is 1nc~700, and the 2D peak capacity can in principle be 2nc~20. Thus the ideal 2D peak capacity could in principle approach nc,2D~14,000 using the 120min 1D run time. The limit of detection (LOD) for docosane, a representative analyte, was determined to be 1.5ppm injected concentration when 2µl of liquid sample was injected with a 20:1 split. A separation of diesel fuel demonstrated the practical utility of the instrument with this complex sample using a relatively fast run time of 20min and a short modulation period PM of 1s. Average peak widths-at-base of 5.4s and 166ms were achieved on the 1D and 2D dimensions, respectively. This yielded a 1nc~220 and a 2nc~ 6. Therefore, the 2D peak capacity is nc,2D~1320 with the 20min diesel separation.

Partial least squares analysis of rocket propulsion fuel data using diaphragm valve-based comprehensive two-dimensional gas chromatography coupled with flame ionization detection.

The chemical composition and several physical properties of RP-1 fuels were studied using comprehensive two-dimensional (2D) gas chromatography (GC×GC) coupled with flame ionization detection (FID). A "reversed column" GC×GC configuration was implemented with a RTX-wax column on the first dimension ((1)D), and a RTX-1 as the second dimension ((2)D). Modulation was achieved using a high temperature diaphragm valve mounted directly in the oven. Using leave-one-out cross-validation (LOOCV), the summed GC×GC-FID signal of three compound-class selective 2D regions (alkanes, cycloalkanes, and aromatics) was regressed against previously measured ASTM derived values for these compound classes, yielding root mean square errors of cross validation (RMSECV) of 0.855, 0.734, and 0.530mass%, respectively. For comparison, using partial least squares (PLS) analysis with LOOCV, the GC×GC-FID signal of the entire 2D separations was regressed against the same ASTM values, yielding a linear trend for the three compound classes (alkanes, cycloalkanes, and aromatics), yielding RMSECV values of 1.52, 2.76, and 0.945 mass%, respectively. Additionally, a more detailed PLS analysis was undertaken of the compounds classes (n-alkanes, iso-alkanes, mono-, di-, and tri-cycloalkanes, and aromatics), and of physical properties previously determined by ASTM methods (such as net heat of combustion, hydrogen content, density, kinematic viscosity, sustained boiling temperature and vapor rise temperature). Results from these PLS studies using the relatively simple to use and inexpensive GC×GC-FID instrumental platform are compared to previously reported results using the GC×GC-TOFMS instrumental platform.

High temperature diaphragm valve-based comprehensive two-dimensional gas chromatography.

A high-temperature diaphragm valve-based comprehensive two-dimensional gas chromatography (GC×GC) instrument is demonstrated which readily allows separations up to 325°C. Previously, diaphragm valve-based GC×GC was limited to 175°C if the valve was mounted in the oven, or limited to 265°C if the valve was faced mounted on the outside of the oven. A new diaphragm valve has been commercially developed, in which the temperature sensitive O-rings that previously limited the separation temperatures have been replaced with Kalrez O-rings, a perfluoroelastomer, allowing for significantly higher temperatures permitting a greater range of volatile and semi-volatile compounds to be readily separated. In the current investigation, a separation temperature up to 325°C is demonstrated with the valve mounted directly in the oven. Since the temperature limit for most commonly used GC columns is at or below 325°C, the scope of diaphragm valve-based GC×GC is now dramatically broadened to encompass a majority of all column stationary phase chemistries. A 44-component mixture of alkanes, alcohols, and polyaromatic hydrocarbons is used to study this new configuration whose boiling points range from 98°C (n-heptane) to 450°C (n-triacontane). For the test mixture using a modulation period PM of 1.0s, peak shapes on second dimension separations, (2)D, are symmetric with average widths at base of 79.4ms, producing a (2)D peak capacity of (2)nc∼12. Based on the average peak width of 2.4s for the first dimension separation with a run time of 32.5min, the (1)D peak capacity is (1)nc∼800. Thus, the ideal two-dimensional peak capacity [Formula: see text] is 9600. Little variation in within-analyte (2)D peak width was observed with an average %RSD of less than 3.0%. Furthermore, retention time on (2)D was very reproducible with an average %RSD less than 0.5%. Measured peak areas (sum of all (2)D peaks for given analyte) had an average %RSD of 4.4%. The transfer fraction from (1)D to (2)D was experimentally determined to be ∼30%, while the detection sensitivity for valve-based GC×GC was ∼8 times higher than one dimensional GC due to zone compression. After a year of use with temperatures consistently up to 325°C, there has been no deterioration of the valve or its performance for GC×GC. Separations of vacuum pump oil and orange oil are also reported to demonstrate practical utility.

Surface enhanced Raman scattering imaging of developed thin-layer chromatography plates.

A method for hyphenating surface enhanced Raman scattering (SERS) and thin-layer chromatography (TLC) is presented that employs silver-polymer nanocomposites as an interface. Through the process of conformal blotting, analytes are transferred from TLC plates to nanocomposite films before being imaged via SERS. A procedure leading to maximum blotting efficiency was established by investigating various parameters such as time, pressure, and type and amount of blotting solvent. Additionally, limits of detection were established for test analytes malachite green isothiocyanate, 4-aminothiophenol, and Rhodamine 6G (Rh6G) ranging from 10(-7) to 10(-6) M. Band broadening due to blotting was minimal (∼10%) as examined by comparing the spatial extent of TLC-spotted Rh6G via fluorescence and then the SERS-based spot size on the nanocomposite after the blotting process. Finally, a separation of the test analytes was carried out on a TLC plate followed by blotting and the acquisition of distance × wavenumber × intensity three-dimensional TLC-SERS plots.