Pulsed Discharge Helium Ionization Detector for Highly Sensitive Aquametry.

Trace moisture quantitation is crucial in medical, civilian and military applications. Current aquametry technologies are limited by the sample volume, reactivity, or interferences, and/or instrument size, weight, power, cost, and complexity. We report for the first time on the use of a pulsed discharge helium ionization detector (PDHID-D2) (∼196 cm(3)) for the sensitive (limit of detection, 0.047 ng; 26 ppm), linear (r(2) >0.99), and rapid (< 2 min) quantitation of water using a small (0.2 - 5.0 µL) volume of liquid or gas. The relative humidity sensitivity was 0.22% (61.4 ppmv) with a limit of detection of less than 1 ng moisture with gaseous samples. The sensitivity was 10 to 100 to fold superior to competing technologies without the disadvantages inherent to these technologies. The PDHID-D2, due to its small footprint and low power requirement, has good size, weight, and power-portability (SWAPP) factors. The relatively low cost (∼$5000) and commercial availability of the PDHID-D2 makes our technique applicable to highly sensitive aquametry.

Development of a Mesoscale Pulsed Discharge Helium Ionization Detector for Portable Gas Chromatography.

Miniaturization of gas chromatography (GC) instrumentation enables field detection of volatile organic compounds (VOCs) for chembio-applications such as clandestine human transport and disease diagnostics. We fabricated a mesoscale pulsed discharge helium ionization detector (micro-PDHID) for integrating with our previously described mini-GC hardware. Stainless steel electrodes fabricated by photochemical etching and electroforming facilitated rapid prototyping and enabled nesting of inter-electrode insulators for self-alignment of the detector core during assembly. The prototype was ∼10 cm(3) relative to >400 cm(3) of a commercial PDHID, but with a comparable time to sweep a VOC peak from the detector cell (170 ms and 127 ms, respectively). Electron trajectory modeling, gas flow rate, voltage bias, and GC outlet location were optimized for improving sensitivity. Despite 40-fold miniaturization, the micro-PDHID detected 18 ng of the human emanation, 3-methyl-2-hexenoic acid with <3-fold decrease in sensitivity relative to the commercial detector. The micro-PDHID was rugged and operated for 9 months without failure.

Diagnostic potential of the pulsed discharged helium ionization detector (PDHID) for pathogenic Mycobacterial volatile biomarkers.

Pathogenic Mycobacteria cause diseases in animals and humans with significant economic and societal consequences. Current methods for Mycobacterial detection relies upon time- and labor-intensive techniques such as culturing or DNA analysis. Using gas chromatography and mass spectrometry, four volatile compounds (methyl phenylacetate, methyl p-anisate, methyl nicotinate and o-phenyl anisole) were recently proposed as potential biomarkers for Mycobacteria. We demonstrate for the first time the capabilities of a field-deployable, pulsed discharge helium ionization detector (PDHID) for sensing these volatiles. We determined the analytical performance of the PDHID toward these Mycobacterial volatiles. Detector performance was moderately affected over the temperature range of 150 to 350 °C. The linear dynamic range for all four analytes exceeded three orders of magnitude. The limits of detection (LOD) and quantitation (LOQ) were calculated as 150 and 450 pg respectively, for all compounds, except methyl phenylacetate (LOD and LOQ, 90 and 270 pg, respectively). Control charts revealed that the PDHID detection system was generally stable, and deviations could be traced to common causes and excluded special causes. Grob tests and ionization potential data suggest that the PDHID is capable of detecting Mycobacterial volatiles in a complex milieu such as culture headspace or breath samples from tuberculosis patients. The diagnostic potential of the PDHID is critical to our goal of a handheld, field-deployable 'sniffer' system for biological pathogens and chemical warfare agents.

Nature and kinetic analysis of carbon-carbon bond fragmentation reactions of cation radicals derived from SET-oxidation of lignin model compounds.

Features of the oxidative cleavage reactions of diastereomers of dimeric lignin model compounds, which are models of the major types of structural units found in the lignin backbone, were examined. Cation radicals of these substances were generated by using SET-sensitized photochemical and Ce(IV) and lignin peroxidase promoted oxidative processes, and the nature and kinetics of their C-C bond cleavage reactions were determined. The results show that significant differences exist between the rates of cation radical C1-C2 bond cleavage reactions of 1,2-diaryl-(ß-1) and 1-aryl-2-aryloxy-(ß-O-4) propan-1,3-diol structural units found in lignins. Specifically, under all conditions C1-C2 bond cleavage reactions of cation radicals of the ß-1 models take place more rapidly than those of the ß-O-4 counterparts. The results of DFT calculations on cation radicals of the model compounds show that the C1-C2 bond dissociation energies of the ß-1 lignin model compounds are significantly lower than those of the ß-O-4 models, providing clear evidence for the source of the rate differences.