This work presents the direct coupling of a custom-made smoking machine (SM) to fast gas chromatography combined with single-photon ionization mass spectrometry (GC × SPI-MS) utilizing a six-port, two-position valve for online puff-resolved comprehensive two-dimensional investigation of cigarette smoke. The innovative electron-beam pumped rare gas excimer light source (EBEL) filled with argon provided vacuum ultraviolet (VUV) photons of 9.8 ± 0.4 eV (126 ± 9 nm) for SPI. Puff-by-puff quantification of 14 hazardous volatile organic smoke constituents from the 2R4F Kentucky research cigarette was enabled for two smoking regimes, i.e., ISO and Canadian Intense, after determination of photoionization cross sections. The investigated analytes comprised NO, acetaldehyde, butadiene, acrolein, propanal, acetone, isoprene, furan, crotonaldehyde, isobutanal, butanal, 2-butanone, benzene, and toluene. The determined amounts of these compounds in cigarette smoke agreed excellently with the literature values. Furthermore, the two well-known patterns of puff-by-puff behaviors for these different smoke constituents were obtained for both whole smoke and gas-phase measurements.

This document is confidential and is proprietary to the American Chemical Society and its authors. Do not copy or disclose without written permission. If you have received this item in error, notify the sender and delete all copies. Complete group-type quantification of petroleum middle distillates based on comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC×GC-TOFMS) and visual basic scripting

The performance of microfluidic glass devices with a monolithically integrated nanospray tip have been evaluated. The nanospray tip is generated directly on the edge of a microfluidic glass chip by a pulling step followed by HF-etching for directed formation of a sharp tip with defined emitter area. For a fair judgment of the MS-detection sensitivity, we compared the detection performance with commercial nanospray needles. For that purpose the effect of the emitter opening on the sensitivity was studied in detail for different microfluidic chips as well as for commercial nanospray needles. A comparison of the chip-nanospray device with commercial nanospray needles revealed that a comparable spray performance is obtained at similar emitter diameters. A stable electrospray could be generated at such tapered tips without any need for hydrodynamic or electroosmotic pumping. The nanospray chips were successfully applied for coupling microchip electrophoresis and mass spectrometry. For improved performance, the separation channel of the microdevice was flushed with hydroxypropylmethylcellulose (HPMC) in order to reduce analyte-wall interactions and electroosmotic flow.

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