Evgeny Krylov

Chemical effects in the separation process of a differential mobility/mass spectrometer system.

In differential mobility spectrometry (also referred to as high-field asymmetric waveform ion mobility spectrometry), ions are separated on the basis of the difference in their mobility under high and low electric fields. The addition of polar modifiers to the gas transporting the ions through a differential mobility spectrometer enhances the formation of clusters in a field-dependent way and thus amplifies the high- and low-field mobility difference, resulting in increased peak capacity and separation power. Observations of the increase in mobility field dependence are consistent with a cluster formation model, also referred to as the dynamic cluster-decluster model. The uniqueness of chemical interactions that occur between an ion and cluster-forming neutrals increases the selectivity of the separation, and the depression of low-field mobility relative to high-field mobility increases the compensation voltage and peak capacity. The effect of a polar modifier on the peak capacity across a broad range of chemicals has been investigated. We discuss the theoretical underpinnings which explain the observed effects. In contrast to the result with a polar modifier, we find that using mixtures of inert gases as the transport gas improves the resolution by reducing the peak width but has very little effect on the peak capacity or selectivity. The inert gas helium does not cluster and thus does not reduce low-field mobility relative to high-field mobility. The observed changes in the differential mobility alpha parameter exhibited by different classes of compounds when the transport gas contains a polar modifier or has a significant fraction of inert gas can be explained on the basis of the physical mechanisms involved in the separation processes.

Miniature radio-frequency mobility analyzer as a gas chromatographic detector for oxygen-containing volatile organic compounds, pheromones and other insect attractants.

A high electric field, radio-frequency ion mobility spectrometry (RF-IMS) analyzer was used as a small detector in gas chromatographic separations of mixtures of volatile organic compounds including alcohols, aldehydes, esters, ethers, pheromones, and other chemical attractants for insects. The detector was equipped with a 2 mCi 63Ni ion source and the drift region for ion characterization was 5 mm wide, 15 mm long and 0.5 mm high. The rate of scanning for the compensation voltages was 60 V s(-1) and permitted four to six scans to be obtained across a capillary chromatographic elution profile for each component. The RF-IMS scans were characteristic of a compound and provided a second dimension of chemical identity to chromatographic retention adding specificity in instances of co-elution. Limits of detection were 1.6-55 x 10(-11) g with an average detection limit for all chemicals of 9.4 x 10(-11) g. Response to mass was linear from 2-50 x 10(-10) g with an average sensitivity of 4 pA ng(-1). Separations of pheromones and chemical attractants for insects illustrated the distinct patterns obtained from gas chromatography with RF-IMS scans in real time and suggest an analytical utility of the RF-IMS as a small, advanced detector for on-site gas chromatographs.

Comparison of the planar and coaxial field asymmetrical waveform ion mobility spectrometer (FAIMS)

Abstract A method and apparatus for ion separation in gases using the dependence of ion mobility coefficient on electric field strength are briefly described (including effect of ion focusing in apparatus with coaxial design of separation chamber). A mathematical model described ions transition for both coaxial and planar separation chamber design is proposed. The model has been verified by our own and published experimental data. Using the proposed model comparative analysis of the planar and coaxial apparatus is conducted by comparison of ion diffusion losses (sensitivity) and response time (speed of operation). Qualitative and quantitative advantages and disadvantages of both variants are considered.

Micro-machined planar field asymmetric ion mobility spectrometer as a gas chromatographic detector.

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.

DMS-IMS2, GC-DMS, DMS-MS: DMS hybrid devices combining orthogonal principles of separation for challenging applications

Sionex Differential Mobility Spectrometer (DMS) sensors can be used as standalone detectors in many applications because of their outstanding sensitivity and selectivity. However, in applications like field screening for toxic chemicals and explosives, the number of possible interferents may be so high that additional separation becomes useful for identification and for quantitative measurement. For these cases, we have developed several different hybrid technologies. (1) DMS-IMS2 integrates bipolar differential mobility ion filtration with IMS drift time measurement in IMS drift tubes, one tube for each ion polarity. (2)The Sionex GC-DMS (microAnalyzer) combines a pre-concentrator, a rapid and selective GC column that operates at high temperature in an air recirculation loop, and DMS ion filtration and detection. (3) Sionex DMS-MS interfaces have been developed for several types of mass spectrometers, and dramatically improve mass spec performance by filtering out unwanted species to reduce chemical noise and improve measurement accuracy. The Sionex DMS-IMS2 first uses DMS to select positive and negative ions based on ion mobility variation with field (the α(E) function), then uses paired IMS sections to measure the low field mobility (K(0)). DMS separation depends on many properties including the distribution of internal charges, rigidity, and clustering. The IMS drift times depend on molecular size and conformation at low fields. A number of applications of this technology will be described, including CWAs, TIC/TIM, and explosives. The Sionex microAnalyzer GC-DMS system combines sophisticated preconcentration, thermal desorption, GC temperature ramping, and DMS separation and detection in a compact, portable and field-deployable package. The list of applications for this technology is growing rapidly, currently including CWAs, BTEX, H2S and mercaptans, and others. Sionex DMS-MS interfaces are being used to make quantitative measurements of biomarkers, including breath markers, biofluid markers, and cancer-linked agents. DMS-MS improves the performance / cost tradeoff for the mass spectrometer, greatly speeds analysis compared to LC-MS, and maintains measurement accuracy.

Planar Drift Tube for Ion Mobility Spectrometry

Abstract The drift tube in ion mobility spectrometry is the component of central importance, where sample vapors are ionized and where ions are separated on the basis of gaseous mobility in a comparatively weak electric field. Construction of drift tubes is labor intensive and costly when built with precision machined components and an alternative design, fabricated using photolithography methods with planar drift plates, is described. Diagnostics of performance including response toward electric fields, peak shape of mobility spectra, determined values for reduced mobility coefficients, and patterns of response to changing vapor concentrations were consistent with conventional drift tubes. Neither ion losses nor band broadening were unexpectedly large though ultimate measures of performance were limited by the unavailability of drift tube components with rectangular profiles and by an imperfect reaction region design. The cost of making drift tubes is calculated as roughly 10% of that for conventional designs.

High Performance Micromachined Planar Field-Asymmetric Ion Mobility Spectrometers for Chemical and Biological Compound Detection

The micromachined Planar High Field Asymmetric Waveform Ion Mobility Spectrometer (PFAIMS) is a novel detector for chemical and biological sensing applications. This detector fills an unmet market need, providing spectrometer capabilities and extremely high sensitivity, at a cost comparable to stand-alone sensors. The PFAIMS is quantitative, and has detection limits down to the parts-per-trillion. The performance of the PFAIMS in a number of applications ranging from industrial to biomedical, where it is used as both a stand alone sensor, and as a gas chromatographic detector are demonstrated. These applications include the detection of xylene isomers and non-invasive medical diagnosis through breath analysis.

DMS-prefiltered mass spectrometry for the detection of biomarkers

Technologies based on Differential Mobility Spectrometry (DMS) are ideally matched to rapid, sensitive, and selective detection of chemicals like biomarkers. Biomarkers linked to exposure to radiation, exposure to CWAs, exposure to toxic materials (TICs and TIMs) and to specific diseases are being examined in a number of laboratories. Screening for these types of exposure can be improved in accuracy and greatly speeded up by using DMS-MS instead of slower techniques like LC-MS and GC-MS. We have performed an extensive series of tests with nanospray-DMS-mass spectroscopy and standalone nanospray-DMS obtaining extensive information on chemistry and detectivity. DMS-MS systems implemented with low-resolution, low-cost, portable mass-spectrometry systems are very promising. Lowresolution mass spectrometry alone would be inadequate for the task, but with DMS pre-filtration to suppress interferences, can be quite effective, even for quantitative measurement. Bio-fluids and digests are well suited to ionization by electrospray and detection by mass-spectrometry, but signals from critical markers are overwhelmed by chemical noise from unrelated species, making essential quantitative analysis impossible. Sionex and collaborators have presented data using DMS to suppress chemical noise, allowing detection of cancer biomarkers in 10,000-fold excess of normal products1,2. In addition, a linear dynamic range of approximately 2,000 has been demonstrated with accurate quantitation3. We will review the range of possible applications and present new data on DMS-MS biomarker detection.