Analytical Instrument Documents

Comprehensive two‐dimensional gas chromatography (GC × GC) coupled to time‐of‐flight mass spectrometry is a powerful separation tool for complex petroleum product analysis. However, the most commonly used electron ionization (EI) technique often makes the identification of the majority of hydrocarbons impossible due to the exhaustive fragmentation and lack of molecular ion preservation, prompting the need of soft‐ionization energies. In this study, three different soft‐ionization techniques including photo ionization (PI), chemical ionization (CI), and field ionization (FI) were compared against EI to elucidate their relative capabilities to reveal different base oil hydrocarbon classes. Compared with EI (70 eV), PI (10.8 eV) retained significant molecular ion (M+·) information for a large number of isomeric species including branched‐alkanes and saturated monocyclic hydrocarbons along with unique fragmentation patterns. However, for bicyclic/polycyclic naphthenic and aromatic compounds, EI played upper hand by retaining molecular as well as fragment ions to identify the species, whereas PI exhibited mainly molecular ion signals. On the other hand, CI revealed selectivity towards different base oil groups, particularly for steranes, sulfur‐containing thiophenes, and esters, yielding protonated molecular ions (M + H)+ for unsaturated and hydride abstracted ions (M‐H+) for saturated hydrocarbons. FI, as expected, generated intact molecular ions (M+·) irrespective to the base oil chemical classes. It allowed elemental composition by TOFMS with a mass resolving power up to 8000 (FWHM) and a mass accuracy of 1 mDa, leading to the calculation of heteroatomic content, double bond equivalency, and carbon number of the compounds. The qualitative and quantitative results presented herein offer a unique perspective into the detailed comparison of different ionization techniques corresponding to several hydrocarbon classes.

The introduction of DART and DESI sources approximately seven years ago led to the development of a new series of atmospheric pressure ion sources referred to as “ambient ionization” sources. These fall into two major categories: spray techniques like DESI or plasma techniques like DART. The selectivity of “direct ionization,” meaning analysis without chromatography and with little or no sample preparation, depends on the mass spectrometer selectivity. Although high resolution and tandem mass spectrometry are valuable tools, rapid and simple sample preparation methods can improve the utility of ambient ionization methods. The concept of ambient ionization has led to the realization that there are many more ways to form ions than might be expected. An interesting example is the use of a flint-and-steel spark source to generate ions from compounds such as phenolphthalein and Gramicidin S.

Fentanyl and fentanyl analogues represent a current and emerging threat in the United States as pure illicit narcotics and in mixtures with heroin. Because of their extreme potency, methods to safely and rapidly detect these compounds are of high interest. This work investigates the use of thermal desorption direct analysis in real time mass spectrometry (TD-DART-MS) and ion mobility spectrometry (IMS) as tools for the rapid and sensitive (nanogram to picograms) detection of fentanyl, 16 fentanyl analogues, and five additional opioids. Competitive ionization studies highlight that detection of these compounds in the presence of heroin is readily achievable, down to 0.1% fentanyl by mass with TD-DART-MS. With IMS, detection of nanogram levels of fentanyl in a binary fentanyl and heroin mixture is possible but can be complicated by decreased resolution in certain commercial instrument models. Modifications to the alarm windows can be used to ensure detection of fentanyl in binary mixtures. Additionally, three complex background matrices (fingerprint residue, dirt, and plasticizers) are shown to have a minimal effect of the detection of these compounds. Wipe sampling of the exterior of bags of questioned powders is shown to be a safe alternative method for field screening and identification, removing the need to handle potentially lethal amounts of material.

The roots of the shy plant Mimosa pudica emit a cocktail of small organic and inorganic sulfur compounds and reactive intermediates into the environment, including SO2, methanesulfinic acid, pyruvic acid, lactic acid, ethanesulfinic acid, propanesulfenic acid, 2-aminothiophenol, S-propyl propane 1-thiosulfinate, phenothiazine, and thioformaldehyde, an elusive and highly unstable compound that, to our knowledge, has never before been reported to be emitted by a plant. When soil around the roots is dislodged or when seedling roots are touched, an odor is detected. The perceived odor corresponds to the emission of higher amounts of propanesulfenic acid, 2-aminothiophenol, S-propyl propane 1-thiosulfinate, and phenothiazine. The mechanosensitivity response is selective. Whereas touching the roots with soil or human skin resulted in odor detection, agitating the roots with other materials such as glass did not induce a similar response. Light and electron microscopy studies of the roots revealed the presence of microscopic sac-like root protuberances. Elemental analysis of these projections by energy-dispersive x-ray spectroscopy revealed them to contain higher levels of K+ and Cl− compared with the surrounding tissue. Exposing the protuberances to stimuli that caused odor emission resulted in reductions in the levels of K+ and Cl− in the touched area. The mechanistic implications of the variety of sulfur compounds observed vis-à-vis the pathways for their formation are discussed.

Determining the species source of logs and planks suspected of being Araucaria araucana (Molina) K.Koch (CITES Appendix I) using traditional wood anatomy has been difficult, because its anatomical features are not diagnostic. Additionally, anatomical studies of Araucaria angustifolia (Bertol.) Kuntze, Araucaria heterophylla (Salisb.) Franco, Agathis australis (D.Don) Lindl., and Wollemia nobilis W.G.Jones, K.D.Hill & J.M.Allen have reported that these taxa have similar and indistinguishable anatomical characters from A. araucana. Transnational shipments of illegal timber obscure their geographic provenance, and therefore identification using wood anatomy alone is insufficient in a criminal proceeding. In this study we examine the macroscopic appearance of selected members of the Araucariaceae and investigate whether analysis of heartwood chemotypes using Direct Analysis in Real Time (DART) Time-of-Flight Mass Spectrometry (TOFMS) is useful for making species determinations. DART TOFMS data were collected from 5 species (n =75 spectra). The spectra were analyzsed statistically using supervised and unsupervised classification algorithms. Results indicate that A. araucana can be distinguished from the look-alike taxa. Another statistical inference of the data suggests that Wollemia nobilis is more similar and within the same clade as Agathis australis. We conclude that DART TOFMS spectra can help in making species determination of the Araucariaceae even when the geographic provenance is unknown.

A ionization technique in mass spectrometry called Direct Analysis in Real Time Mass Spectrometry (DART TOF-MS) coupled with a Direct Binding Assay was used to identify and characterize anti-viral components of an elderberry fruit (Sambucus nigra L.) extract without either derivatization or separation by standard chromatographic techniques. The elderberry extract inhibited Human Influenza A (H1N1) infection in vitro with an IC(50) value of 252+/-34 microg/mL. The Direct Binding Assay established that flavonoids from the elderberry extract bind to H1N1 virions and, when bound, block the ability of the viruses to infect host cells. Two compounds were identified, 5,7,3',4'-tetra-O-methylquercetin (1) and 5,7-dihydroxy-4-oxo-2-(3,4,5-trihydroxyphenyl)chroman-3-yl-3,4,5-trihydroxycyclohexanecarboxylate (2), as H1N1-bound chemical species. Compound 1 and dihydromyricetin (3), the corresponding 3-hydroxyflavonone of 2, were synthesized and shown to inhibit H1N1 infection in vitro by binding to H1N1 virions, blocking host cell entry and/or recognition. Compound 1 gave an IC(50) of 0.13 microg/mL (0.36 microM) for H1N1 infection inhibition, while dihydromyricetin (3) achieved an IC(50) of 2.8 microg/mL (8.7 microM). The H1N1 inhibition activities of the elderberry flavonoids compare favorably to the known anti-influenza activities of Oseltamivir (Tamiflu; 0.32 microM) and Amantadine (27 microM).

Elemental compositions are commonly determined from the exact m/z of the monoisotopic peak, which is often the lightest isotope. However, the lightest isotope peak is often weak or absent and the monoisotopic peak can be difficult to identify for organometallics, polyhalogenated compounds, or large molecules. An alternative approach using the abundant isotope for elemental composition determinations is presented here.

To ensure food safety, rapid detection of adulterated and counterfeit food products is critical. One such method, Direct Analysis in Real Time-Mass Spectrometry (DART-MS) (IonSense, Saugus, Mass.), quickly screens and analyzes a wide array of samples for mass spectral information and does not require sample preparation. As an example, several recent studies detail the analysis of cinnamon, mostly using chromatographic methods. High concentrations of coumarin in cinnamon have prompted numerous investigations as well, as its presence is suspected of being harmful. All of these studies require sample derivatization and long analysis times. In the current study, DART-MS was used to analyze cinnamon and detect the presence of coumarin.

DART-MS spectra were acquired under CID conditions to rapidly differentiate among  five synthetic cannabinoids contained within  ’herbal’ products purchased locally in New York State (USA). The spectra exhibited [M+H]+ ions and product ions unique to each cannabinoid that corresponded to major structural features. Five different cannabinoid analogs, alone and as mixtures of at least two cannabinoids, were identified in six herbal products and differentiated by their CID product ion patterns.

The blue lotus flower (Nymphea caerulea) is an Egyptian water lily containing apomorphine and nuciferine. Apomorphine has been described as a psychoactive alkaloid and is a non-selective dopamine agonist primarily used to treat Parkinson’s disease as it stimulates dopamine receptors and improves motor function. Nuciferine is an alkaloid associated with dopamine receptor blockade. Today, blue lotus flower is used as a sleep aid and anxiety reliever. The rebuildable dripping atomizer (RDA) is an electronic cigarette that allows direct application of an e-liquid onto the coil in the atomizer for aerosolization, compared to a typical electronic cigarette where the e-liquid is wicked from a storage vessel to the coil. Our laboratory received a dark-brown resin material from a concerned parent. The resin had been confiscated from an adolescent who had a reported history of marijuana use. The resin was later identified as blue lotus flower (N. caerulea). This resin, together with four commercially available blue lotus products, was analyzed for content. Apomorphine was detected in two samples, and nuciferine was detected in all five samples. The confiscated resin was determined to contain no apomorphine and 4300 ng/g of nuciferine. The nuciferine resin was shown to aerosolize using aRDA electric cigarette.