Drift Tube Ion Mobility Spectrometer Research Articles

Reliable Detection of Chemical Warfare Agents Using High Kinetic Energy Ion Mobility Spectrometry.

High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) ionize and separate ions at reduced pressures of 10-40 mbar and over a wide range of reduced electric field strengths E/N of up to 120 Td. Their reduced operating pressure is distinct from that of conventional drift tube ion mobility spectrometers that operate at ambient pressure for trace compound detection. High E/N can lead to a field-induced fragmentation pattern that provides more specific structural information about the analytes. In addition, operation at high E/N values adds the field dependence of ion mobility as an additional separation dimension to low-field ion mobility, making interfering compounds less likely to cause a false positive alarm. In this work, we study the chemical warfare agents tabun (GA), sarin (GB), soman (GD), cyclosarin (GF) and sulfur mustard (HD) in a HiKE-IMS at variable E/N in both the reaction and the drift region. The results show that varying E/N can lead to specific fragmentation patterns at high E/N values combined with molecular signals at low E/N. Compared to the operation at a single E/N value in the drift region, the variation of E/N in the drift region also provides the analyte-specific field dependence of ion mobility as additional information. The accumulated data establish a unique fingerprint for each analyte that allows for reliable detection of chemical warfare agents even in the presence of interfering compounds with similar low-field ion mobilities, thus reducing false positives.

Ion Mobility Separations Using Cocentric Architecture.

Ion mobility separations, especially using drift tube ion mobility spectrometers, are usually performed in linear channels, which can have a large footprint when extended to achieve higher resolving powers. In this work, we explored the performance of an ion mobility device with a curved architecture, which can have a more compact form. The cocentric ion mobility spectrometer (CoCIMS) manipulates ions between two cocentric surfaces containing a serpentine track. The mobility separation inside the CoCIMS is achieved using traveling waveforms (TWs). We initially evaluated the device using ion trajectory simulations using SIMION, which indicated that when ions traveled circularly inside the CoCIMS they resulted in similar resolving powers and transmitted m/z range as traveling in a straight path. We then performed experimental validation of the CoCIMS in conjunction with a TOF MS. The CoCIMS was made of two flexible printed circuit board materials folded into cocentric cylinders separated by a gap of 2.8 mm. The device was about 50 mm diameter ×152 mm long and provided 1.846 m of serpentine path length. Three sets of mixtures (Agilent tune mixture, tetraalkylammonium salts, and an eight-peptide mixture) and four traveling waveform profiles (square, sine, triangle, and sawtooth) were used. The sawtooth TW profile produced a slightly higher resolving power for the Agilent tuning mixture and tetraalkylammonium ions. The average resolving power for Agilent tune mixture ions ranged from 37 (using sawtooth TW) to 27 (using square TW). The average resolving powers ranged from 45 (sawtooth TW) to 31 (square TW) for tetraalkylammonium ions. The resolving power of the peptide mixture ions was similar among the four TW profiles and ranged from 51 to 56. The average percent error in TWCCS for the peptide mixture ions was about 0.4%. The new device showed promising results, but improvements are needed to further increase the resolving power.

Development of a Modular, Open-Source, Reduced-Pressure, Drift Tube Ion Mobility Spectrometer.

Toward the goal of minimizing construction costs while maintaining high performance, a new, reduced-pressure, drift tube ion mobility system is coupled with an ion trap mass analyzer through a custom ion shuttle. The availability of reduced-pressure ion mobility systems remains limited due to comparatively expensive commercial options and limited shared design features in the open literature. This report details the complete design and benchmarking characteristics of a reduced-pressure ion mobility system. The system is constructed from FR4 PCB electrodes and encased in a PTFE vacuum enclosure with custom torque-tightened couplers to utilize standard KF40 bulkheads. The PTFE enclosure directly minimizes the overall system expenses, and the implementation of threaded brass inserts allows for facile attachments to the vacuum enclosure without damaging the thermoplastic housing. Front and rear ion funnels maximize ion transmission and help mitigate the effects of radial ion diffusion. A custom planar ion shuttle transports ions from the exit of the rear ion funnel into the ion optics of an ion trap mass analyzer. The planar ion shuttle can couple the IM system to any contemporary Thermo Scientific ion trap mass analyzer. Signal stability and ion intensity remain unchanging following the implementation of the planar ion shuttle when compared to the original stacked ring ion guide. The constructed IM system showed resolving powers up to 85 for various small molecules and proteins using the Fourier transform from a ∼1 m drift tube. Recorded mobilities derived from first principles agree with published literature results with an average error of 1.1% and an average error toward literature values using single field calibration of <1.3%.

Evaluation of Fourier deconvolution ion mobility spectrometer as high-performance gas chromatography detector for the analysis of plant extract flavors

The Fourier deconvolution ion mobility spectrometer (FDIMS) offers multiplexing and improves the resolving power and signal-to-noise ratio. To evaluate the FDIMS as a detector for gas chromatography for the analysis of complex samples, we connected a drift tube ion mobility spectrometer to a commercial gas chromatograph and compared the performance including resolving power, sensitivity, and linear range using 2,6-di‑tert-butylpyridine. Mixed standards were also injected into the tandem system to evaluate the performance under optimized conditions. A complex plant extract sample used as natural flavoring was investigated using the resulting system. The results show that the instrument implemented with the Fourier deconvolution multiplexing method demonstrated higher performance over the traditional signal averaging method including higher resolving power, better limit of detection, and wider linear range for a variety of compounds and natural plant extract flavorings.

Influence of ionization volume and sample gas flow rate on separation power in gas chromatography-ion mobility spectrometry

In this work, the influence of the sample gas flow rate and the ionization region volume of an ion mobility spectrometer (IMS) used as a detector in gas chromatography (GC) on GC-IMS peak shape has been investigated. Therefore, a drift tube IMS with a field-switching ion shutter, a defined ionization region volume and an ultra-violet radiation source was used. To identify the influence of the sample gas flow rate entering the ionization region (equals the GC carrier gas flow rate if no further make-up gas is used) and the ionization region volume on peak broadening and signal intensity, different sample volumes as they would elute from a GC were tested at a variety of sample gas flow rates at a given ionization region volume. The results clearly show that for low sample gas flow rates a depletion of sample molecules in the ionization region leads to a significant decrease in effective detector volume but also to reduced signal intensities. Therefore, for optimal performance of a GC-IMS, the optimal operating point of the GC should match the flow range, where the IMS provides the best compromise between signal-to-noise ratio and peak broadening.

Non-destructive, solvent-free quantification of wood preservatives in wood flour and wooden objects using GC-DTIMS

Qualitative and quantitative on-site detection methods for wood preservatives are of high value for the recycling industry and the occupational health and safety. Wood preservatives revealed as toxic to human and environment after decades of use. For the detection of contaminated wood and for processing of matured timber to particle boards a versatile detection method is needed. Especially historical wooden objects were treated with preservatives like pentachlorophenol, lindane or dichlorodiphenyltrichloroethane. This requires a non-destructive on-site detection method, that does not require specialized personnel. In this publication two methods are presented utilizing headspace sampling by solid-phase microextraction, subsequent separation using gas chromatography and detection by a drift tube ion mobility spectrometer (SPME–HS–GC-DTIMS). One method enables the quantitative detection of pentachlorophenol in wood flour and wood chips as they are used in wood processing industries. A limit of detection of 0.1 mg/kg was achieved using DIN 32645, which can be even more lowered. The second method enables non-destructive detection of pentachlorophenol, lindane, dichlorodiphenyltrichloroethane and other preservatives in wooden objects. Therefore, samples were prepared, which show a significantly lower concentration than typical treated objects, and used next to real samples for method validation. With the method contamination of the real samples and of the prepared samples of low concentration were proven.

How to Improve the Resolving Power of Compact Electrospray Ionization Ion Mobility Spectrometers.

Every drift tube ion mobility spectrometer (IMS) has an optimum drift voltage to reach maximum resolving power. This optimum depends, among other things, on the temporal and spatial width of the injected ion packet and the pressure within the IMS. A reduction of the spatial width of the injected ion packet leads to improved resolving power, higher peak amplitudes when operating the IMS at optimum resolving power, and thus a better signal-to-noise ratio despite the reduced number of injected ions. Hereby, the performance of electrospray ionization (ESI)-IMS can be considerably improved. By setting the ion shutter opening time to just 5 μs and slightly increasing the pressure, a high resolving power RP > 150 can be achieved with a given drift length of just 75 mm. At such high resolving power, even a mixture of the herbicides isoproturon and chlortoluron having similar ion mobility can be well separated despite short drift length.

Highly Efficient Ion Manipulator for Tandem Ion Mobility Spectrometry: Exploring a Versatile Technique by a Study of Primary Alcohols

In this work, we present a tandem ion mobility spectrometer (IMS) utilizing a highly efficient ion manipulator allowing to store, manipulate, and analyze ions under high electric field strengths and controlled ion-neutral reactions at ambient conditions. The arrangement of tandem drift regions and an ion manipulator in a single drift tube allows a sequence of mobility selection of precursor ions, followed by storage and analysis, mobility separation, and detection of the resulting product ions. In this article, we present a journey exploring the capabilities of the present instrument by a study of eight different primary alcohols characterized at reduced electric field strengths E/N of up to 120 Td with a water vapor concentration ranging from 40 to 540 ppb. Under these conditions, protonated alcohol monomers up to a carbon number of nine could be dissociated, resulting in 18 different fragmented product ions in total. The fragmentation patterns revealed regularities, which can be used for assignment to the chemical class and improved classification of unknown substances. Furthermore, both the time spent in high electrical field strengths and the reaction time with water vapor can be tuned precisely, allowing the fragment distribution to be influenced. Thus, further information regarding the relations of the product ions can be gathered in a standalone drift tube IMS for the first time.

Probing Colossal Carbon Rings.

Carbon aggregates containing between 10 and 30 atoms preferentially arrange themselves as planar rings. To learn more about this exotic allotrope of carbon, electronic spectra are measured for even cyclo[n]carbon radical cations (-) using two-color photodissociation action spectroscopy. To eliminate spectral contributions from other isomers, the target cyclo[n]carbon radical cations are isomer-selected using a drift tube ion mobility spectrometer prior to spectroscopic interrogation. The electronic spectra exhibit sharp transitions spanning the visible and near-infrared spectral regions with the main absorption band shifting progressively to longer wavelength by ≈100 nm for every additional two carbon atoms. This behavior is rationalized with a Hückel theory model describing the energies of the in-plane and out-of-plane π orbitals. Photoexcitation of smaller carbon rings leads preferentially to neutral C3 and C5 loss, whereas rings larger than tend to also decompose into two smaller rings, which, when possible, have aromatic stability. Generally, the observed charged photofragments correspond to low energy fragment pairs, as predicted by density functional theory calculations (CAM-B3LYP-D3(BJ)/cc-pVDZ). Using action spectroscopy it is confirmed that and photofragments from rings have cyclic structures.

Detection of Chemical Warfare Agents with a Miniaturized High-Performance Drift Tube Ion Mobility Spectrometer Using High-Energetic Photons for Ionization.

A growing demand for low-cost gas sensors capable of detecting the smallest amounts of highly toxic substances in air, including chemical warfare agents (CWAs) and toxic industrial chemicals (TICs), has emerged in recent years. Ion mobility spectrometers (IMS) are particularly suitable for this application due to their high sensitivity and fast response times. In view of the preferred mobile use of such devices, miniaturized ion drift tubes are required as the core of IMS-based lightweight, low-cost, hand-held gas detectors. Thus, we evaluate the suitability of a miniaturized ion mobility spectrometer featuring an ion drift tube length of just 40 mm and a high resolving power of Rp = 60 for the detection of various CWAs, such as nerve agents sarin (GB), tabun (GA), soman (GD), and cyclosarin (GF), as well as the blister agent sulfur mustard (HD), the blood agent hydrogen cyanide (AC) and the choking agent chlorine (CL). We report on the limits of detection reaching minimum concentration levels of, for instance, 29 pptv for sarin (GB) within an averaging time of only 1 s. Furthermore, we investigate the effects of precursors, simulants, and other common interfering substances on false positive alarms.

Simulation study of inverse diffusion counterbalance method for super-resolution ion mobility spectrometry.

Ion mobility spectrometer (IMS) is a powerful chemical composition analysis tool working at atmospheric pressure that can be used to separate complex samples and study molecular structures. Resolution is a key parameter for evaluating the performance of IMS. However, for the pulsed sampling technique used by drift tube IMS, there is an upper limit to the resolution due to the diffusion between ions and the drift gas. In this work, an inverse diffusion counterbalance method is proposed to break the resolution limit. The method is inspired by the stimulated emission depletion (STED). In optical microscopy systems, STED is used to break the optical diffraction limit by a ring of depleted light to counteract diffraction effects of the excited light. We modified this strategy and applied it to an IMS system for counteracting the diffusion effect of the pulsed ion packet. The method can increase the resolution up to 1.55 times through theoretical analysis, and the improvement is verified by simulations. The simulation results find that the initial width of the ion packet has an influence on the effectiveness of the method, and the narrower the initial width, the better the effect. The proposed inverse counterbalance strategy may also be applied to other spectral analysis instruments to break the resolution limit.

Miniaturized Photo-Ionization Fourier Deconvolution Ion Mobility Spectrometer for the Detection of Volatile Organic Compounds.

Because of its simplicity, reliability, and sensitivity, the drift tube ion mobility spectrometer (IMS) has been recognized as the equipment of choice for the on-site monitoring and identification of volatile organic compounds (VOCs). However, the performance of handheld IMS is often limited by the size, weight, and drift voltage, which heavily determine the sensitivity and resolving power that is crucial for the detection and identification of VOCs. In this work, we present a low-cost, miniaturized drift tube ion mobility spectrometer incorporated with a miniaturized UV ionization lamp and a relatively low drift voltage. The sensitivity and resolving power are boosted with the implementation of Fourier deconvolution multiplexing compared to the conventional signal averaging data acquisition method. The drift tube provides a high resolving power of up to 52 at a drift length of 41 mm, 10 mm ID dimensions, and a drift voltage of 1.57 kV. Acetone, benzene, dimethyl methyl phosphonate, methyl salicylate, and acetic acid were evaluated in the developed spectrometer and showed satisfactory performance.

Ultrasensitive Ion Source for Drift Tube Ion Mobility Spectrometers Combining Optimized Sample Gas Flow with Both Chemical Ionization and Direct Ionization.

Efficient ionization of analyte molecules is a crucial step for the outstanding sensitivity of ion mobility spectrometers (IMS) used for trace gas detection. Here, we present a new ion source that combines the previously published extended field switching ion shutter with two switchable ionization sources and an optimized sample gas flow that leads to a focused laminar stream through the reaction region of the ion source. The X-ray ionization source allows for chemical gas phase ionization of analyte molecules, while the UV ionization source allows for direct ionization of analyte molecules. The optimized sample gas flow not only allows for quickly washing out analyte molecules from the reaction region but also has improved sensitivity by a factor of about 5 for protonated monomers, 20 for proton-bound dimers, and over 100 for the proton-bound trimer of 1-octanol. The resulting limits of detection using chemical X-ray ionization are in the subpptv-range for protonated monomers and in the low pptv-range for proton-bound dimers, while the limits of detection using direct UV ionization are in the subppbv-range. Especially, a direct comparison between chemical and direct ionization of ketones using this ultrasensitive ion source reveals a stepwise conversion from directly ionized monomers to proton-bound dimers via protonated monomers during direct UV ionization.

High voltage pulser for ion shutters in ion mobility spectrometry based on an optocoupler.

A novel high voltage pulser for an ion shutter used in drift-tube ion-mobility spectrometers is described. The simple design suitable for the in-house construction of these spectrometers relies on a special optocoupler to isolate the triggering circuitry from the high voltage at the ion shutter. The device was tested with an electrospray-ionization ion-mobility device with a 10cm drift tube operated at 4kV into which a standard test mixture of four tetraalkylamines was injected with a negative going gating pulse of about 50V on top of 4kV. A fall time of 15.7 µs and a rise time of 2.0 µs were determined for the pulse, which was adequate for the required injection pulse width of 450 µs. Resolving powers between 61 and 81 were determined for the four quaternary amines, which were found to be comparable to the performance obtained with a previously reported pulser circuitry of a different design used as a reference.

An ion mobility mass spectrometer coupled with a cryogenic ion trap for recording electronic spectra of charged, isomer-selected clusters.

Infrared and electronic spectra are indispensable for understanding the structural and energetic properties of charged molecules and clusters in the gas phase. However, the presence of isomers can potentially complicate the interpretation of spectra, even if the target molecules or clusters are mass-selected beforehand. Here, we describe an instrument for spectroscopically characterizing charged molecular clusters that have been selected according to both their isomeric form and their mass-to-charge ratio. Cluster ions generated by laser ablation of a solid sample are selected according to their collision cross sections with helium buffer gas using a drift tube ion mobility spectrometer and their mass-to-charge ratio using a quadrupole mass filter. The mobility- and mass-selected target ions are introduced into a cryogenically cooled, three-dimensional quadrupole ion trap where they are thermalized through inelastic collisions with an inert buffer gas (He or He/N2 mixture). Spectra of the molecular ions are obtained by tagging them with inert atoms or molecules (Ne and N2), which are dislodged following resonant excitation of an electronic transition, or by photodissociating the cluster itself following absorption of one or more photons. An electronic spectrum is generated by monitoring the charged photofragment yield as a function of wavelength. The capacity of the instrument is illustrated with the resonance-enhanced photodissociation action spectra of carbon clusters (Cn +) and polyacetylene cations (HC2nH+) that have been selected according to the mass-to-charge ratio and collision cross section with He buffer gas and of mass-selected Au2 + and Au2Ag+ clusters.

Portable nanoelectrospray periodic focusing differential ion mobility spectrometer for the rapid screening of illicit drugs

The spread of illicit drug abuse is a major public health issue in most countries. Law enforcement personnel on drug abuse need a tool to confiscate and block illicit trade of illicit drug or monitoring drug impaired driving. Therefore, affordable and portable instruments for illegal drug detection are in critical need. In this study, we developed a portable periodic focusing differential ion mobility (PFDMA) spectrometer for in situ motoring illicit drugs. The device comprised an ionization source, drift cell, air blower, voltage divider board and electronic control board. In general, an ion mobility spectrometer (IMS) is able to work with air as a buffer gas at atmospheric pressure. There is no need to install heavy mechanical and/or expensive turbo molecular pumps. For our instrument, a small air blower was used to generate laminar counterflow. The whole device is compact with a size of 150 × 200 × 280 (WLH, mm) and a weight of 2.5 kg. In general, most commercial drift tube ion mobility spectrometers use radioactive or corona discharge ionization. In this work, we utilized a different approach to analyze liquid samples. The device was equipped with a nanoelectrospray ionization source. To avoid memory effects, a disposable micropipette was used. An aluminum-coated tip with an ID of 2 μm was applied with a high voltage to achieve nanoelectrospray ionization without sheath gas. Advantages of PFDMA are to isomer separation and better sensitivity compared to other types of ion mobility spectrometers. Most illicit drugs could be detected by this homemade device. The detection limit is lower than the level allowed by law. With our device, the detection limit of methamphetamine is ∼10 ng/ml.

Analysis of drugs including illicit and new psychoactive substances in oral fluids by gas chromatography-drift tube ion mobility spectrometry

In this study, a gas chromatograph (GC) has been coupled to a drift tube ion mobility spectrometer (IMS) in order to develop an analytical procedure for the determination of psychoactive substances in oral fluids. Working parameters, including the GC-IMS interface ones, were adjusted in order to obtain sensitive and robust signals. A volume of 500 μL of oral fluid was extracted with 250 μL chloroform and, after centrifugation, were injected into the GC-IMS system. Amphetamine, methylone, α-PVP, ketamine, lidocaine, MPHP, cocaine, THJ-2201, and 5F-ADB were employed as model compounds, providing limits of detection from 6 to 15 μg L−1 and recoveries from 70 to 115% for field oral fluids spiked with target analytes at 250, 500, and 600 μg L−1. Moreover, two oral fluid certified reference materials were analysed by the proposed GC-IMS based methodology with obtained relative percentage errors lower than 8.4%, being the proposed GC-IMS procedure a reliable, selective, and sensitive technique for the determination of psychoactive substances in oral fluids.

Studies on the Processes of Electron Capture and Clustering of Benzyl Chloride by Ion Mobility Spectrometry.

This paper presents the results of the study on the course of the benzyl chloride (BzCl) ionization process in a drift tube ion mobility spectrometer (DT IMS) in which nitrogen was used as the carrier gas. BzCl ionization follows the dissociative electron capture mechanism. The chloride ions produced in this process take part in the formation of cluster ions. Using DT IMS allows for estimation of the value of the electron attachment rate for BzCl and the equilibrium constant for the cluster ion formation. The basic experimental method used in this work was to analyze drift time spectra obtained for the introduction of the sample to the spectrometer with the drift gas. The theoretical interpretation of the results is based on the mathematical description of the ion transport. This description takes into account the phenomenon of diffusion, as well as the processes of formation and dissociation of ionic clusters occurring during the movement of ions in the drift section.

Detection of Triacetone Triperoxide (TATP) and Hexamethylene Triperoxide Diamine (HMTD) from the Gas Phase with Differential Ion Mobility Spectrometry (DMS)

One of the significant problems in the modern world is the detection of improvised explosives made of materials synthesized at home. Such compounds include triacetone triperoxide (TATP) and hexamethylene triperoxide diamine (HMTD). An attempt was made to construct an instrument allowing for the simultaneous detection of both compounds despite the large difference of vapor pressure: very high for TATP and very low for HMTD. The developed system uses differential ion mobility spectrometry (DMS) in combination with a specially designed gas sample injection system. The created system of detectors allowed for the detection of a high concentration of TATP and a very low concentration of HMTD. TATP detection was possible despite the presence of impurities—acetone remaining from the technological process and formed as a coproduct of diacetone diperoxide (DADP) synthesis. Ammonia added to the carrier gas improved the possibility of detecting the abovementioned explosives, reducing the intensity of the acetone signal. The obtained results were then compared with the detection capabilities of drift tube ion mobility spectrometer (DT-IMS), which has not made possible such detection as DMS.

Toward Compact High-Performance Ion Mobility Spectrometers: Ion Gating in Ion Mobility Spectrometry.

Printed circuit board (PCB) based drift tube ion mobility spectrometers enable the use of state-of-the-art production techniques to manufacture compact devices with excellent performance at minimum cost. The new PCB ion mobility spectrometer (PCB-IMS) presented here is equipped with either a 140 MBq tritium or a 95 MBq nickel-63 ionization source and consists of a combination of horizontally arranged 6-layer PCBs for the drift and reaction regions and vertically arranged PCBs for interfacing the ionization source, ion shutter, and detector. The design allows the reproducible manufacturing and thus comparison of different IMS topologies. Here, we investigate different ion shutters, field-switching, Bradbury-Nielsen, and tristate and their effects on resolving power and limits of detection considering two different ionization region geometries and ionization sources, tritium and nickel-63. It is shown that the high resolving power of RP > 80 at low drift voltage of 3 kV and short drift length of 50 mm can be achieved independent of the used ion shutter mechanism and reaction region geometry. While the resolving power of all ion shutters is excellent, the Bradbury-Nielsen shutter shows a pronounced discrimination of slow ion species when using short shutter opening times for small initial ion cloud widths, as required for high resolving power. Thus, the intensity of the proton-bound dimer of 2-pentanone is reduced by 30% compared to the signal intensity obtained with both the field-switching and tristate shutter. The detection limits employing the Bradbury-Nielsen shutter and a 50 mm reaction region as required for nickel-63 are 58 pptv for the protonated monomer and 3.4 ppbv for the proton-bound dimer of 2-pentanone. The detection limits achieved with the tristate shutter utilizing the same reaction region are slightly higher for the protonated monomer at 68 pptv, but lower for the proton-bound dimer at 2 ppbv due to the advanced ion shutter principle not discriminating slow ions. However, the lowest detection limits of 13 pptv and 301 pptv can be achieved with the field-switching shutter and a 2 mm reaction region, sufficient for a tritium ionization source.