Microfluidic ion mobility chromatograph
This paper describes the development of a microfluidic ion mobility chromatograph for small inorganic ion analysis.
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This paper describes the development of a microfluidic ion mobility chromatograph for small inorganic ion analysis.
A detailed knowledge of the history and abundances of the biogenic elements and their compounds throughout the solar system can provide the exobiologists with a basis for understanding the conditions necessary for chemical evolution and the origin of life. The Ion Mobility Drift Spectrometer is an ion molecule reactor coupled with an ion drift spectrometer. Sample molecules are ionized to form product ions in the reactant region. An electric field moves the ions through a drift region against the flow of a drift gas where they are separated according to their size and structure producing an ion mobility spectrum. These spectra provide the IMDS with virtually universal sample identification capability. To conform to the rigid limits of weight, volume and consumables placed on flight instrumentation, several aspects of the IMDS must be studied and redesigned for flight use. In addition to miniaturization of the instrument, a reduction in the high flow rates used for the drift gas is an obvious necessary consideration. The effect of drastically reduced drift flow rates on IMDS spectra was investigated by lowering flow rates from 500ml/min to 50ml/min. Changes in peak shape, drift time and total spectra were studied at each flow rate.
In this paper we focus our attention on ion mobility spectrometers (IMSs) as a potential candidate to be incorporated with SIM.
A planar high field asymmetric waveform ion mobility spectrometer (PFAIMS) with a micro-machined drift tube was characterized as a detector for capillary gas chromatography. The performance of the PFAIMS was compared directly to that of a flame ionization detector (FID) for the separation of a ketone mixture from butanone to decanone. Effluent from the column was continuously sampled by the detector and mobility scans could be obtained throughout the chromatographic analysis providing chemical inforrmation in mobility scans orthogonal to retention time. Limits of detection were approximately I ng for measurement of positive ions and were comparable or slightly better than those for the FID. Direct comparison of calibration curves for the FAIMS and the FID was possible over four orders of magnitude with a semi-log plot. The concentration dependence of the PFAIMS mobility scans showed the dependence between ion intensity and ion clustering, evident in other mobility spectrometers and atmospheric pressure ionization technologies. Ions were identified using mass spectrometry as the protonated monomer and the proton bound dimer of the ketones. Residence time for column effluent in the PFAIMS was calculated as approximately 1 ms and a 36% increase in extra-column broadening versus the FID occurred with the PFAIMS.
Total scattering and charge exchange cross sections and ion mobility for cesium ion-neutral atom interaction
Hydrazine (HZ) and monomethylhydrazine (MMH) in air were monitored continuously using a hand-held ion mobility spectrometer equipped with membrane inlet, 63Ni ion source, acetone reagent gas, and ambient temperature drift tube. Response characteristics included detection limit, 6 ppb; linear range, 10-600 ppb; saturated response, >2 ppm; and stable response after 15-30 min. Ammonia interfered in hydrazines detection through a product ion with the same drift time as that for MMH and HZ. Acetone reagent gas was replaced with 5-nonanone to alter drift times of product ions and separate ammonia from MMH and HZ. Patterns in mobility spectra, ion identifications from mass spectra, and fragmentation cross-sections from collisional-induced dissociations suggest that drift times are governed by ion-cluster equilibria in the drift region of the mobility spectrometer. Practical aspects including calibration, stability, and reproducibility are reported from the use of a hand-held mobility spectrometer on the space shuttle Atlantis during mission STS-37.
Signal processing techniques for systems based upon Ion Mobility Spectrometry will be discussed in the light of 10 years of experience in the design of real-time IMS. Among the topics to be covered are compensation techniques for variations in the number density of the gas - the use of an internal standard (a reference peak) or pressure and temperature sensors. Sources of noise and methods for noise reduction will be discussed together with resolution limitations and the ability of deconvolution techniques to improve resolving power. The use of neural networks (either by themselves or as a component part of a processing system) will be reviewed.
Astrobiology flight experiments require highly sensitive instrumentation for in situ analysis of volatile chemical species and minerals present in the atmospheres and surfaces of planets, moons, and asteroids. The complex mixtures encountered place a heavy burden on the analytical instrumentation to detect and identify all species present. The use of land rovers and balloon aero-rovers place additional emphasis on miniaturization of the analytical instrumentation. In addition, smaller instruments, using tiny amounts of consumables, allow the use of more instrumentation and/or ionger mission life for stationary landers/laboratories. The miniCometary Ice and Dust Experiment (miniCIDEX), which combined Gas Chromatography (GC) with helium Ion Mobility Spectrometry (IMS), was capable of providing the wide range of analytical information required for Astrobiology missions. The IMS used here was based on the PCP model 111 IMS. A similar system, the Titan Ice and Dust Experiment (TIDE), was proposed as part of the Titan Orbiter Aerorover Mission (TOAM). Newer GC systems employing Micro Electro- Mechanical System (MEMS) based technology have greatly reduced both the size and resource requirements for space GCs. These smaller GCs, as well as the continuing miniaturization of Astrobiology analytical instruments in general, has highlighted the need for smaller, dry helium IMS systems. We describe here the development of a miniature, MEMS GC-IMS system (MEMS GC developed by Thorleaf Research Inc.), employing the MiniCell Ion Mobility Spectrometer (IMS), from Ion Applications Inc., developed through NASA's Astrobiology Science and Technology Instrument Development (ASTID) Program and NASA s Small Business Innovative Research (SBIR) Program.
A simple procedure to analyze ammonia in ethylene by ion mobility spectrometry is described. The spectrometer is operated with a silane polymer membrane., 63Ni ion source, H+ (H2O)n reactant ion, and nitrogen drift and source gas. Ethylene containing parts per billion (ppb) (v/v) concentrations of ammonia is pulled across the membrane and diffuses into the spectrometer. Preconcentration or preseparation is unnecessary, because the ethylene in the spectrometer has no noticeable effect on the analytical results. Ethylene does not polymerize in the radioactive source. Ethylene's flammability is negated by the nitrogen inside the spectrometer. Response to ammonia concentrations between 200 ppb and 1.5 ppm is near linear, and a detection limit of 25 ppb is calculated.
Resonance charge exchange effect on gaseous ions mobility, noting cross sections structure due to resonance and wave interference
By utilizing the combination of a unique electronic ion injection control circuit in conjunction with a particularly designed drift cell construction, the instantly disclosed ion mobility spectrometer achieves increased levels of sensitivity, while achieving significant reductions in size and weight. The instant IMS is of a much simpler and easy to manufacture design, rugged and hermetically sealed, capable of operation at high temperatures to at least 250.degree. C., and is uniquely sensitive, particularly to explosive chemicals.
By utilizing the combination of a unique electronic ion injection control circuit in conjunction with a particularly designed drift cell construction, the instantly disclosed ion mobility spectrometer (IMS) achieves increased levels of sensitivity, while achieving significant reductions in size and weight. The instant IMS is of a much simpler and easy to manufacture design, rugged and hermetically sealed, capable of operation at high temperatures to at least 250 degrees Centigrade, and is uniquely sensitive, particularly to explosive chemicals.
When a positive detection of a narcotic occurs during the search of a vessel, a decision has to be made whether further intensive search is warranted. In terms of unwarranted delays of vessels and possible property damage, the accuracy of the analytical determination is very important. Analytical accuracy becomes critical when the data may be used in court actions as evidence. For this purpose, the U.S. Coast Guard has been investigating several confirmatory ion mobility spectrometry (IMS) field methods for the detection and identification of cocaine. This paper presents the findings of our investigations on the use of catalytic pyrolysis and base hydrolysis as confirmatory methods. The catalytic effects of various metals on the pyrolysis reaction are reported. In addition, the effects of several different ion mobility spectrometer sample transfer mediums and varying laboratory conditions on the base hydrolysis of the cocaine molecule are also be reported.
Results are presented from a comparison between two ion-mobility-spectrometer (IMS) methods of sample ionisation: a conventional IMS with very dry helium and an IMS using metastable helium ionization. As one of the tests, a mixture of several hydrocarbons expected to be the components of Titan's atmosphere (made of ethane, ethylene, acetylene, propane, n-butane, isobutane, and propyne in concentrations from 20 to 200 ppm) was analyzed by both methods. Results from the dry-He IMS showed that the dry-helium approach was more adequate for the analysis of these gases than the metastable-helium IMS approach. In the metastable-He approach, in which several versions of He ionization reaction were tested, the spectra produced were not as clear as the conventional IMS spectra, due to the fact that the strong electric field introduced in the reaction region to generate metastable helium affected the gating, resolution, and collection of the ions.
Atmospheric pressure chemical ionization (APCI)-mass spectrometry (MS) for fluorinated phenols (C6H5-xFxOH Where x = 0-5) in nitrogen with Cl- as the reagent ion yielded product ions of M Cl- through ion associations or (M-H)- through proton abstractions. Proton abstraction was controllable by potentials on the orifice and first lens, suggesting that some proton abstraction occurs through collision induced dissociation (CID) in the interface region. This was proven using CID of adduct ions (M Cl-) with Q2 studies where adduct ions were dissociated to Cl- or proton abstracted to (M-H)-. The extent of proton abstraction depended upon ion energy and structure in order of calculated acidities: pentafluorophenol > tetrafluorophenol > trifluorophenol > difluorophenol. Little or no proton abstraction occurred for fluorophenol, phenol, or benzyl alcohol analogs. Ion mobility spectrometry was used to determine if proton abstraction reactions passed through an adduct intermediate with thermalized ions and mobility spectra for all chemicals were obtained from 25 to 200 degrees C. Proton abstraction from M Cl- was not observed at any temperature for phenol, monofluorophenol, or difluorophenol. Mobility spectra for trifluorophenol revealed the kinetic transformations to (M-H)- either from M Cl- or from M2 Cl- directly. Proton abstraction was the predominant reaction for tetra- and penta-fluorophenols. Consequently, the evidence suggests that proton abstraction occurs from an adduct ion where the reaction barrier is reduced with increasing acidity of the O-H bond in C6H5-xFxOH.
The IMS (Ion Mobility Spectroscopy) instrument 'Ionscan' takes advantage of the fact that trace quantities of illicit drugs are adsorbed on dust particles on clothes, in cars and on other items of evidence. The dust particles are collected on a membrane filter by a special attachment on a vacuum cleaner. The sample is then directly inserted into the spectrometer and can be analyzed immediately. We show casework applications of a forensic chemistry and toxicology laboratory. One new application of IMS in forensic chemistry is the detection of psilocybin in dried mushrooms without any further sample preparation.
Wind tunnel calibration study to correlate measurements with ion mobility spectrometer and mass spectral measurements
A hand-held, portable gas chromatography-ion mobility spectrometer (GC-IMS) device was used to detect the presence of volatile amine compounds in the headspace of decomposing fish. The Food and Drug Administration (FDA) largely relies on olfactory discrimination with respect to fresh and spoiled, frozen and unfrozen fish. The fish are delivered at ship docks on pallets, and each pallet of fish can range from 30-40 thousand dollars in value. Fresh fish were placed in a teflon bag and the direct headspace was interrogated. In the first three days, only low molecular weight volatile amines were detected. On the fourth day, a number of spectral signatures were observed which indicated the presence of 1,5-diaminopentane, cadaverine. Analyses typically took from 0.5-1 minute.