Analysis of synthetic phenethylamine street drugs using direct sample analysis coupled to accurate mass time of flight mass spectrometry.

Serious health complications and fatal overdoses have brought phenethylamine, otherwise known as 2C, drug abuse to the public's attention. These compounds are 2C-X series analogs of mescaline. The name "2C" results from the two carbons in the ethyl chain. The substituents on these emerging drugs are constantly changed in order to avoid listing as controlled substances. These synthetic drugs are marketed as having affects similar to LSD and MDMA and are typically consumed sublingually via blotter paper. Twenty-six commercially available standards were analyzed using a direct sample analysis technique coupled to accurate mass time of flight mass spectrometry. Direct sample analysis is an ambient ionization technique employing direct charge transfer from nitrogen reagent gas resulting in ionization and in-source collision induced dissociation. Mass spectral analysis was used to determine the fragmentation patterns of the 2C compounds. While the mass spectral data for the compounds are similar in fragmentation, they also display differences that allow the analyst to distinguish which compound is present. The fragmentation patterns, high-resolution mass spectral data, and isotope ratios are used to qualitatively identify two blotter paper street samples that were extracted together. As these drugs are emerging substances of abuse, there are no generally accepted protocols for this analysis. Additionally, presumptive, or screening, tests have not been widely developed for these materials. Direct sample analysis allows for a quick screening of seized compounds resulting in a preliminary identification, which can then be analyzed and confirmed using other analytical techniques.

Systems analysis in Cellvibrio japonicus resolves predicted redundancy of ß-glucosidases and determines essential physiological functions.

Degradation of polysaccharides forms an essential arc in the carbon cycle, provides a percentage of our daily caloric intake, and is a major driver in the renewable chemical industry. Microorganisms proficient at degrading insoluble polysaccharides possess large numbers of carbohydrate active enzymes (CAZymes), many of which have been categorized as functionally redundant. Here we present data that suggests that CAZymes that have overlapping enzymatic activities can have unique, non-overlapping biological functions in the cell. Our comprehensive study to understand cellodextrin utilization in the soil saprophyte Cellvibrio japonicus found that only one of four predicted ß-glucosidases is required in a physiological context. Gene deletion analysis indicated that only the cel3B gene product is essential for efficient cellodextrin utilization in C. japonicus and is constitutively expressed at high levels. Interestingly, expression of individual ß-glucosidases in Escherichia coli K-12 enabled this non-cellulolytic bacterium to be fully capable of using cellobiose as a sole carbon source. Furthermore, enzyme kinetic studies indicated that the Cel3A enzyme is significantly more active than the Cel3B enzyme on the oligosaccharides but not disaccharides. Our approach for parsing related CAZymes to determine actual physiological roles in the cell can be applied to other polysaccharide-degradation systems.

Visualization of Ambient Mass Spectrometry with the Use of Schlieren Photography.

This manuscript outlines how to visualize mass spectrometry ambient ionization sources using schlieren photography. In order to properly optimize the mass spectrometer, it is necessary to characterize and understand the physical principles of the source. Most commercial ambient ionization sources utilize jets of nitrogen, helium, or atmospheric air to facilitate the ionization of the analyte. As a consequence, schlieren photography can be used to visualize the gas streams by exploiting the differences in refractive index between the streams and ambient air for visualization in real time. The basic setup requires a camera, mirror, flashlight, and razor blade. When properly configured, a real time image of the source is observed by watching its reflection. This allows for insight into the mechanism of action in the source, and pathways to its optimization can be elucidated. Light is shed on an otherwise invisible situation.

Molecular Ionization-Desorption Analysis Source (MIDAS) for Mass Spectrometry: Thin-Layer Chromatography.

Molecular ionization-desorption analysis source (MIDAS), which is a desorption atmospheric pressure chemical ionization (DAPCI) type source, for mass spectrometry has been developed as a multi-functional platform for the direct sampling of surfaces. In this article, its utility for the analysis of thin-layer chromatography (TLC) plates is highlighted. Amino acids, which are difficult to visualize without staining reagents or charring, were detected and identified directly from a TLC plate. To demonstrate the full potential of MIDAS, all active ingredients from an analgesic tablet, separated on a TLC plate, were successfully detected using both positive and negative ion modes. The identity of each of the compounds was confirmed from their mass spectra and compared against standards. Post separation, the chemical signal (blue permanent marker) as reference marks placed at the origin and solvent front were used to calculate retention factor (Rf) values from the resulting ion chromatogram. The quantitative capabilities of the device were exhibited by scanning caffeine spots on a TLC plate of increasing sample amount. A linear curve based on peak are, R2 = 0.994, was generated for seven spots ranging from 50 to 1000 ng of caffeine per spot.

Characterization of a Direct Sample Analysis (DSA) Ambient Ionization Source.

Water cluster ion intensity and distribution is affected by source conditions in direct sample analysis (DSA) ionization. Parameters investigated in this paper include source nozzle diameter, gas flow rate, and source positions relative to the mass spectrometer inlet. Schlieren photography was used to image the gas flow profile exiting the nozzle. Smaller nozzle diameters and higher flow rates produced clusters of the type [H + (H(2)O)(n)](+) with greater n and higher intensity than larger nozzles and lower gas flow rates. At high gas flow rates, the gas flow profile widened compared with the original nozzle diameter. At lower flow rates, the amount of expansion was reduced, which suggests that lowering the flow rate may allow for improvements in sampling spatial resolution.