Open Probe fast GC-MS - combining ambient sampling ultra-fast separation and in-vacuum ionization for real-time analysis.

An Open Probe inlet was combined with a low thermal mass ultra-fast gas chromatograph (GC), in-vacuum electron ionization ion source and a mass spectrometer (MS) of GC-MS for obtaining real-time analysis with separation. The Open Probe enables ambient sampling via sample vaporization in an oven that is open to room air, and the ultra-fast GC provides ~30-s separation, while if no separation is required, it can act as a transfer line with 2 to 3-s sample transfer time. Sample analysis is as simple as touching the sample, pushing the sample holder into the Open Probe oven and obtaining the results in 30 s. The Open Probe fast GC was mounted on a standard Agilent 7890 GC that was coupled with an Agilent 5977A MS. Open Probe fast GC-MS provides real-time analysis combined with GC separation and library identification, and it uses the low-cost MS of GC-MS. The operation of Open Probe fast GC-MS is demonstrated in the 30-s separation and 50-s full analysis cycle time of tetrahydrocannabinol and cannabinol in Cannabis flower, sub 1-min analysis of trace trinitrotoluene transferred from a finger onto a glass surface, vitamin E in canola oil, sterols in olive oil, polybrominated flame retardants in plastics, alprazolam in Xanax drug pill and free fatty acids and cholesterol in human blood. The extrapolated limit of detection for pyrene is <1 fg, but the concentration is too high and the software noise calculation is untrustworthy. The broad range of compounds amenable for analysis is demonstrated in the analysis of reserpine. The possible use with alternate standard GC-MS and Open Probe fast GC-MS is demonstrated in the analysis of heroin in its street drug powder. The use of Open Probe with the fast GC acting as a transfer line is demonstrated in <10-s analysis without separation of ibuprofen and estradiol. Copyright © 2017 John Wiley & Sons, Ltd.

Supersonic gas chromatography/mass spectrometry.

A new gas chromatography/mass spectrometry (GC/MS) system was designed and evaluated which we have named 'Supersonic GC/MS'. It is based on a modification of a commercially available GC/MS system to include a supersonic molecular beam (SMB) MS interface. In this system the standard electron ionization (EI) ion source was replaced with a fly-through EI ion source mounted in the path of the SMB. A hyperthermal surface ionization (HSI) ion source combined with a 90 degrees ion mirror (for the EI-produced ions) was also added, and placed inside the quadrupole mass analyzer in place of its original EI ion source. The 'Supersonic GC/MS' system requires 18 cm added bench space plus the addition of an air-cooled 60 L/s diffusion pump and a 537 L/min rotary pump. The system is user friendly since all the gas flow rates, heated zones, sampling and data analysis are performed the same way as the original system and are computer-controlled via the original software. Similar EI sensitivity was obtained as with the original system for hexachlorobenzene and octafluoronaphthalene, while improved EI detection limits were demonstrated for methyl stearate and eicosane due to the significant enhancement of their molecular ion abundances. A GC/MS detection limit of 500 ag for pyrene was demonstrated using HSI. Good supersonic expansion cooling was achieved with large alkanes, despite the use of a rotary pump at the nozzle chamber instead of a diffusion pump. High temperature GC/MS analysis was demonstrated for large polycyclic aromatic hydrocarbons (PAHs) including ovalene and decacyclene (ten rings). Library searches with EI mass spectra are demonstrated, and it is explained why the enhancement of the molecular ion actually improves the library search in most cases. The analysis of large phthalate esters is also described, and the improvement obtained is shown to originate from their enhanced molecular and high mass fragment ions.

Liquid chromatography mass spectrometry with supersonic molecular beams

A new approach for liquid chromatography mass spectrometry (LC-MS) is described, based on achieving soft thermal vaporization followed by supersonic expansion and direct sample compound ionization, while in a supersonic molecular beam (SMB). The soft molecular vaporization step utilizes spray formation that is continued by fast thermal vaporization inside a channel supersonic nozzle, followed by ultrafast supercooling in a supersonic expansion. The short time (several microseconds) spent by the vaporized compound in the heated nozzle prior to its expansion cooling may result in incomplete vibrational equilibrium and thus reduced degree of dissociation. In addition, even if vibrational equilibrium at the nozzle temperature is obtained, the sample compounds have significantly reduced time for their dissociation, which is thus further minimized (kinetic consideration). As soon as the molecules expand and form a SMB, they are supercooled and any further dissociation is avoided. While in the SMB, the sample molecules can be ionized either by electron ionization as described in this paper or by hyperthermal surface ionization. The major goal of this method is to obtain high quality library searchable electron ionization mass spectra, for a broad range of thermally labile compounds, with higher sensitivity than that achievable by particle beam LC-MS. The soft thermal vaporization nozzle is described and mass spectral results with corticosterone are demonstrated. The potential advantageous features of this new method are discussed.

SnifProbe: new method and device for vapor and gas sampling.

SnifProbe is based on the use of 15 mm short pieces of standard 0.53 mm I.D. capillary or porous layer open tubular columns for sampling airborne, headspace, aroma or air pollution samples. A miniaturized frit-bottomed packed vial named MicroSPE was also prepared which served for the sampling of solvent vapors and gases as well as liquid water. The short (15 mm) trapping column is inserted into the SnifProbe easy-insertion-port and the SnifProbe is located or aimed at the sample environment. A miniature pump is operated for pumping 10-60 ml/min of the air sample through the short piece of column to collect the sample. After a few seconds up to a few minutes of pumping, the short column is removed from the SnifProbe with tweezers (or gloved hands) and placed inside a glass vial of a direct sample introduction device (ChromatoProbe) having a 0.5 mm hole at its bottom. The ChromatoProbe sample holder with its glass vial and sample in the short column are introduced into the GC injector as usual. The sample is then quickly and efficiently desorbed from the short sample column and is transferred into the analytical column for conventional GC and/or GC-MS analysis. We have explored the various characteristics of SnifProbe and demonstrated its applicability and effectiveness in many applications. These applications include: the analysis of benzene, toluene and o-xylene in air, SO2 in air, perfume aroma on hand, beer headspace, wine aroma, coffee aroma, cigarette smoke, trace chemical warfare agent simulants, explosives vapors, ethanol in human breath and odorants in domestic cooking gas. SnifProbe can be operated in the field or at a chemical process. The sample columns can be plugged and stored in a small union storage device, placed in a small plastic bag, marked and brought to the laboratory for analysis with the full power of GC and/or GC-MS. Accordingly, we feel that the major and most significant feature of SnifProbe is that it brings the field and process to the laboratory. Thus, SnifProbe can extend the "arm" of the GC and GC-MS laboratory and enable high-quality field and process analysis.

Fast analysis of drugs in a single hair.

A new method for the fast screening of cocaine and 6-monoacetylmorphine (6-MAM) in a single hair, using gas chromatography/mass spectrometry (GC/MS), is described. The analyses are conducted in less than 10 min with minimal sample preparation. The novel method combines the ChromatoProbe direct sample introduction device for intrainjector thermal extraction, fast GC separation, a supersonic molecular beam GC/MS interface and hyperthermal surface ionization (HSI). The technique has been successfully employed for the detection of cocaine in as little as a 1-mm section of hair using selected ion monitoring (SIM). Unambiguous full scan mass spectra of cocaine and 6-MAM were obtained on a single hair for cocaine and heroin users, respectively. HSI was found to be almost 3 orders of magnitude more selective than electron impact ionization for cocaine compared with the major hair constituents, with a minimum detected concentration of approximately 10 ppb in the SIM mode. Results obtained for 12 drugs users showed full qualitative agreement with similar results using rigorous solvent extraction followed by electrospray-liquid chromatography/mass spectrometry analysis. However, quantitative studies showed only partial agreement. No false positives were observed for 10 drugs free subjects. This method enables fast drug monitoring along the hair length which permits time correlation studies.

Simultaneous pulsed flame photometric and mass spectrometric detection for enhanced pesticide analysis capabilities.

Analysis of pesticides by simultaneous pulsed flame photometric detection (PFPD) and mass spectrometric (MS) detection was performed with column-effluent splitting between these two detectors. The resulting PFPD chromatograms were always much simpler due to the PFPD selectively and were further characterized by better sensitivity than that of MS. Accordingly, the PFPD chromatogram served as a marker for the exact elution time of the suspected pesticide. At this exact elution time, the resulting mass spectra were examined of unique high-mass peaks and a precise background subtraction was performed for improved library identification. If no definite identification was achieved, reconstructed mass chromatograms were performed, inspected for suspected major ions and confirmed with the PFPD chromatogram. A sequential search was then performed with the NIST library. The presence of P or S atoms was introduced into the search algorithm and two of the major suspected fragment mass peaks were included with an estimate of their minimum relative abundance. Under these conditions, the library search provided the correct pesticide identification, at a considerably lower concentration than achievable with standard GC-MC analysis. If only information on a single ion was available, such as with very pronounced matrix interferences, or with single-ion monitoring MS analysis, the NIST library sequential search was operated with this single-on information and PFPD provided information on both P and S (the majority of organophosphorus pesticides contain both P and S). The incorporation of one major ion and two heteroatoms' (P and S) information enabled an effective library identification, at an even further reduced pesticide concentration. The simultaneous PFPD-MS analysis approach is demonstrated and discussed with several examples of authentic pesticides in vegetable and spices. The merits of this method are analyzed and discussed with an emphasis on the unique suitability of PFPD for combination with MS.

Laser desorption fast gas chromatography-mass spectrometry in supersonic molecular beams.

A novel method for fast analysis is presented. It is based on laser desorption injection followed by fast gas chromatography-mass spectrometry (GC-MS) in supersonic molecular beams. The sample was placed in an open air or purged laser desorption compartment, held at atmospheric pressure and near room temperature conditions. Desorption was performed with a XeCl Excimer pulsed laser with pulse energy of typically 3 mJ on the surface. About 20 pulses at 50 Hz were applied for sample injection, resulting in about 0.4 s injection time and one or a few micrograms sample vapor or small particles. The laser desorbed sample was further thermally vaporized at a heated frit glass filter located at the fast GC inlet. Ultrafast GC separation and quantification was achieved with a 50-cm-long megabore column operated with a high carrier gas flow rate of up to 240 mL/min. The high carrier gas flow rate provided effective and efficient entrainment of the laser desorbed species in the sweeping gas. Following the fast GC separation, the sample was analyzed by mass spectrometry in supersonic molecular beams. Both electron ionization and hyperthermal surface ionization were employed for enhanced selectivity and sensitivity. Typical laser desorption analysis time was under 10 s. The laser desorption fast GC-MS was studied and demonstrated with the following sample/matrices combinations, all without sample preparation or extraction: (a) traces of dioctylphthalate plasticizer oil on stainless steel surface and the efficiency of its cleaning; (b) the detection of methylparathion and aldicarb pesticides on orange leaves; (c) water surface analysis for the presence of methylparathion pesticide; (d) caffeine analysis in regular and decaffeinated coffee powder; (e) paracetamol and codeine drug analysis in pain relieving drug tablets; (f) caffeine trace analysis in raw urine; (g) blood analysis for the presence of 1 ppm lidocaine drug. The features and advantages of the laser desorption fast GC-MS are demonstrated and discussed.

Pesticide analysis with the pulsed-flame photometer detector and a direct sample introduction device.

New methods for fast, sensitive, and informative pesticide analysis in food products are described. These methods are based on sampling with a novel direct sample introduction device (DSI), gas chromatographic analysis, and pesticide detection with the pulsed flame photometric detector (PFPD). Sampling with the DSI is based on introduction of blended fruit or vegetable in a small glass vial that retains the harmful nonvolatile residue and is disposed of after the analysis. The DSI-GC-PFPD combination provides several new features that are demonstrated and discussed: (a) Extract-free analysis is achieved with the DSI, which serves as an effective alternative to sample extraction and cleanup methods. (b) Faster analysis is achieved through the use of the DSI due to the reduction of the upper GC program temperature, since the low-volatility compounds are retained in the sample vial. (c) Relatively efficient and uniform DSI thermal extraction and PFPD detection can be achieved, allowing the use of internal standards for pesticide calibration. (d) Higher sensitivity is provided by the PFPD as well as through the use of the DSI for sampling larger volumes of extract solutions. (e) Sulfur interference is eliminated with the PFPD in its phosphorus-selective detection mode, using software exploiting differences in S and P delayed pulsed flame emission time dependence. (f) Sulfur pesticides are effectively analyzed by the PFPD in its sulfur-selective detection mode at the usual required levels and with less matrix interference than with NPD in the nitrogen mode. (g) Simultaneous sulfur and phosphorus pesticide analysis is demonstrated, including heteroatom identification and the provision of P and S atom ratio information in the analyzed pesticide.

Cluster chemical ionization and deuterium exchange mass spectrometry in supersonic molecular Beams.

A cluster-based chemical ionization method has been developed that produces protonated molecular ions from molecules introduced through a supersonic molecular beam interface. Mixed clusters of the analyte and a clustering agent (water or methanol) are produced in the expansion region of the beam, and are subsequently ionized by "fly through" electron impact (EI) ionization, which results in a mass spectrum that is a combination of protonated molecular ion peaks together with the conventional EI fragmentation pattern. The technique is presented and discussed as a tool complementary to electron impact ionization in supersonic molecular beams. Surface-induced dissociation on a rhenium oxide surface is also applied to simplify the mass spectra of clusters and reveal the analyte spectrum. The high gas flow rates involved with the supersonic molecular beam interface that enable the easy introduction of the clustering agents also have been used to introduce deuterating agents. An easy-to-use, fast, and routine on-line deuterium exchange method was developed to exchange active hydrogens (NH, OH). This method, combined with electron impact ionization, is demonstrated and discussed in terms of the unique information available through the EI fragmentation patterns, its ability to help in isomer identification, and possible applications with fast gas chromatography-mass spectrometry in supersonic molecular beams.

Fast, very fast, and ultra-fast gas chromatography-mass spectrometry of thermally labile steroids, carbamates, and drugs in supersonic molecular beams.

Gas chromatography-mass spectrometry (GC-MS) analyses of thermally labile compounds have been studied by using a short column fast gas chromatograph, coupled with fly-through electron ionization in supersonic molecular beams. Thirty-two compounds, which include steroids, carbamate pesticides, antibiotic drugs, and other pharmaceutical compounds, have been analyzed and the details of their GC-MS analysis are provided. The ability to analyze thermally labile compounds is discussed in relation to the speed of analysis. A new term, "speed enhancement factor" (SEF), is defined as the product of column length reduction and the carrier gas linear velocity increase, as compared with normal GC-MS conditions. Fast, very fast, and ultra-fast GC-MS are defined with a SEF in the ranges of 5-30, 30-400, and 400-4000, respectively. Trade-offs in the degree of dissociation, speed, gas chromatograph resolution, and sensitivity were studied and examined with thermally labile molecules. The experimental factors that affect the dissociation are described with emphasis on its reduction. We claim that the use of supersonic molecular beams for sampling and ionization provides the ultimate capability in the GC-MS of thermally labile compounds. The obtained 70-eV electron ionization mass spectra are shown, and an enhanced relative abundance of the molecular ion is demonstrated together with library search capability of these mass spectra, which is better than that reported with particle beam liquid chromatography-mass spectrometry. The performance of fast GC-MS in supersonic molecular beams is compared with other methods of fast GC-MS and with particle beam liquid chromatography-mass spectrometry.

Electron impact mass spectrometry of alkanes in supersonic molecular beams.

The electron impact mass spectrometry of straight chain alkanes C8H18-C40H82, squalane, methylstearate, 1-chlorohexadecane, 1-bromohexadecane, and dioctylphthalate was studied by sampling them with supersonic molecular beams. A fly-through Brink-type electron impact ion source was used, utilizing a vacuum background ion filtration technique based on differences between the kinetic energy of the supersonic beam species and that of thermal molecules. The 70-eV electron impact mass spectra of all the alkanes were characterized by a pronounced or dominant molecular weight peak together with all the fragment ions normally exhibited by the standard thermal 70-eV EI mass spectra. In contrast, the NIST library of most of these molecules did not show any molecular weight peak. By eliminating tile intramolecular thermal vibrational energy we gained control over the degree of molecular ion fragmentation by the electron energy. At an electron energy of 18 eV the molecular ion dissociation was further reduced considerably, with only a small absolute reduction in the peak height by less than a factor of 2. The effect of vibrational cooling increased with the molecular size and number of atoms. Pronounced differences were observed between the mass spectra of the straight chain triacontane and its branched isomer squalane. Similar mass spectra of octacosane (C28H58) achieved with 70-eV EI in a supersonic molecular beam were obtained with a magnetic sector mass spectrometer by using an electron energy of 14 eV and an ion source temperature of 150 °C. However, this ion source temperature precluded the gas chromatography-mass spectrometry (GC-MS) of octacosane. The GC-MS of alkanes was studied with an ion trap gas chromatograph-mass spectrometer at an ion source temperature of 230 °C. Thermal peak tailing was observed for C20H42 and heavier alkanes, whereas for C28H58 and heavier alkanes the severe peak tailing made quantitative GC-MS impractical. In contrast, no peak tailing existed even with C40H82 for GC-MS in supersonic molecular beams. The minimum detected amount of eicosane (C20, H42) was shown to be 60 fg. This was demonstrated by using single ion monitoring with the quadrupole mass analyzer tuned to the molecular weight peak of 282 u. The coupling of electron impact mass spectrometry in supersonic molecular beams with hyperthermal surface ionization and a fast GC-MS inlet is briefly discussed.

High-efficiency surface-induced dissociation on a rhenium oxide surface.

We report on the high-efficiency surface-induced dissociation of benzene and cyclohexane polyatomic ions after scattering from a rhenium oxide surface with a kinetic energy of 5-290 eV. Rhenium oxide was prepared by directly heating a rhenium metal foil, under 10(-5) mbar partial oxygen pressure, at about 1000 K.Rhenium oxide is characterized by a very high work function of 6.4 eV and thus minimizes ion reneutralization probabilities. The catalytic combustion of surface organic impurities with oxygen ensures good long-term stability.We found that the surface-induced dissociation ion current is 70 times larger on rhenium oxide than on bare rhenium or stainless steel. Absolute scattered ion yields of about 50% were measured. The implications of surface-induced dissociation on mass spectrometry in supersonic molecular beams are mentioned.