Drift Gas Research Articles

Setting the Separation Factor α for Ketone Monomers and Dimers by the Use of Different Drift Gases.

This study investigates the influence of different drift gases on ion mobility in ion mobility spectrometry (IMS) using ketones as model substances within a custom-built drift tube spectrometer. Different binary mixtures of nitrogen, helium, and argon were used as drift gases to investigate the influence of mobility on the monomers and dimers of the different ketones. Experimental results reveal shifts in ion drift times and separation factors (α) with varying gas compositions, in accordance with Blanc's Law. Furthermore, the study underscores the device-independent nature of α and the device-dependent resolution, emphasizing the importance of comparative analyses. Employing 2-hexanone and 2-decanone in the same sample but with different drift gases is used to show the impact of different drift gases. By changing the drift gas composition, total alignment of drift times and therefore no possible resolution or baseline resolution could be achieved. Through different experiments and analyses, this research provides insights into the interactions between gas composition and ion mobility, offering implications for diverse analytical applications from environmental monitoring to chemical detection.

Time-Resolved Ion Mobility Spectrometry with a Stop Flow Confined Volume Reaction Region.

An ion source concept is described where the sample flow is stopped in a confined volume of an ion mobility spectrometer creating time-dependent patterns of ion patterns of signal intensities for ions from mixtures of volatile organic compounds and improved signal-to-noise rate compared to conventional unidirectional drift gas flow. Hydrated protons from a corona discharge were introduced continuously into the confined volume with the sample in air at ambient pressure, and product ions were extracted continuously using an electric field for subsequent mobility analysis. Ion signal intensities for protonated monomers and proton bound dimers were measured and computationally extracted using mobilities from mobility spectra and exhibited distinct times of appearance over 30 s or more after sample injection. Models, and experimental findings with a ternary mixture, suggest that the separation of vapors as ions over time was consistent with differences in the reaction rate for reactions between primary ions from hydrated protons and constituents and from cross-reactions that follow the initial step of ionization. The findings suggest that the concept of stopped flow, introduced here for the first time, may provide a method for the temporal separation of atmospheric pressure ions. This separation relies on ion kinetics and does not require chromatographic technology.

X-ray characterization of a bulk resistive MICROMEGAS operating at low gas pressure

In the last decades, interest has grown in the development of detectors that can accurately measure energy and track of low-energy (1–100 keV) charged particles. In this paper we present our effort to construct a resistive MICROMEGAS detector with a wide amplification gap (192μm), to achieve high gain with a low discharge probability, even when operating with a low-pressure gas down to 50mbar. The detector response (gain, energy resolution, relative primary charge collection efficiency) to X-rays from a 55Fe source was measured under different operating conditions of amplification and drift fields, gas pressure and gas mixture composition. The results obtained and their temporal stability demonstrate that the detector can be used for the measurement of low-energy radiation with good energy resolution.

Charge amplification in low pressure CF4:SF6:He mixtures with a multi-mesh ThGEM for directional dark matter searches

The CYGNO collaboration is developing next generation directional Dark Matter (DM) detection experiments, using gaseous Time Projection Chambers (TPCs), as a robust method for identifying Weakly Interacting Massive Particles (WIMPs) below the Neutrino Fog. SF6 is potentially ideal for this since it provides a high fluorine content, enhancing sensitivity to spin-dependent interactions and, as a Negative Ion Drift (NID) gas, reduces charge diffusion leading to improved positional resolution. CF4, although not a NID gas, has also been identified as a favourable gas target as it provides a scintillation signal which can be used for a complimentary light/charge readout approach. These gases can operate at low pressures to elongate Nuclear Recoil (NR) tracks and facilitate directional measurements. In principle, He could be added to low pressure SF6/CF4 without significant detriment to the length of 16S, 12C, and 19F recoils. This would improve the target mass, sensitivity to lower WIMP masses, and offer the possibility of atmospheric operation; potentially reducing the cost of a containment vessel. In this article, we present gas gain and energy resolution measurements, taken with a Multi-Mesh Thick Gaseous Electron Multiplier (MMThGEM), in low pressure SF6 and CF4:SF6 mixtures following the addition of He. We find that the CF4:SF6:He mixtures tested were able to produce gas gains on the order of 104 up to a total pressure of 100 Torr. These results demonstrate an order of magnitude improvement [1] in charge amplification in NID gas mixtures with a He component.

Open-set adversarial domain match for electronic nose drift compensation and unknown gas recognition

In practical applications, electronic noses (EN) must tackle not only sensor drift but also resist interference from unknown gases. In prolonged open environments, electronic noses often encounter unknown gases that cannot be predicted in advance. Current gas detection methods typically rely on prior knowledge of target analytes but struggle to comprehensively address sensor drift and interference from unknown gases. Such as indoor air quality monitoring, long-term stability is crucial, and not all relevant analytes can be predetermined. However, the recent research cannot solve both the sensor drift and unknown gas intrusion problem simultaneously well. In this work, we unify above problems in to the open-set risk boundary. We propose an open-set adversarial domain match (OSADM) model and introduce the considers of open-set domain adaptation (OSDA). OSDA trains a target classifier through matching the domain distribution to recognize the known and unknown gases. First, a binary adversarial loss divides the class boundary. Secondly, adversarial domain adaptation unifies the distribution of different domains. Compared with the metric methods, it avoids complex distribution computation and parameter adjustment to reduce negative transfer. Extensive experimental results on two benchmark datasets, Gas Sensor Array Drift and Twin gas sensor arrays Dataset show that OSADM outperformance of the existing open-set models.

Gas gains over 104 and optimisation using 55Fe X-rays in low pressure SF6 with a novel Multi-Mesh ThGEM for directional dark matter searches

The Negative Ion Drift (NID) gas SF6 has favourable properties for track reconstruction in directional Dark Matter (DM) searches utilising low pressure gaseous Time Projection Chambers (TPCs). However, the electronegative nature of the gas means that it is more difficult to achieve significant gas gains with regular Thick Gaseous Electron Multipliers (ThGEMs). Typically, the maximum attainable gas gain in SF6 and other Negative Ion (NI) gas mixtures, previously achieved with an 55Fe X-ray source or electron beam, is on the order of 103 [1,2,3,4]; whereas electron drift gases like CF4 and similar mixtures are readily capable of reaching gas gains on the order of 104 or greater [5,9,7,8,6]. In this paper, a novel two stage Multi-Mesh ThGEM (MMThGEM) structure is presented. The MMThGEM was used to amplify charge liberated by an 55Fe X-ray source in 40 Torr of SF6. By expanding on previously demonstrated results [10], the device was pushed to its sparking limit and stable gas gains up to ˜50000 were observed. The device was further optimised by varying the field strengths of both the collection and transfer regions in isolation. Following this optimisation procedure, the device was able to produce a maximum stable gas gain of ˜90000. These results demonstrate an order of magnitude improvement in gain with the NID gas over previously reported values and ultimately benefits the sensitivity of a NITPC to low energy recoils in the context of a directional DM search.

Coated Blade Spray Ion Mobility Spectrometry.

Coated blade spray (CBS) is a microextraction technology with blades that serve as both the extraction device and the electrospray ionization (ESI) emitter. CBS is designed for easy and rapid extraction of analytes in complex matrices as well as ESI directly from the blade. The technology selectively enriches the components of interest on a coated metal blade. The coating consists of a selective polymer. So far, CBS has only been coupled with mass spectrometry but never with ion mobility spectrometry (IMS), where ions are separated and detected based on their ion mobility in a drift gas under the influence of an electric field, while instrumentation is compact and easy to operate so that the advantages of CBS can be particularly well exploited. Therefore, this work focuses on coupling CBS with our previously described ESI-IMS. The ion mobility spectrometer has a drift length of only 75 mm and provides a high resolving power of RP = 100. In this work, preliminary measurements of CBS-IMS are presented. In particular, the detection of benzodiazepines and ketamine in drinks and the pesticide isoproturon in water samples is shown to demonstrate the feasibility of CBS-IMS.

Potential of measured relative shifts in collision cross section values for biotransformation studies.

Ion mobility spectrometry-mass spectrometry (IMS-MS) separates gas phase ions due to differences in drift time from which reproducible and analyte-specific collision cross section (CCS) values can be derived. Internally conducted in vitro and in vivo metabolism (biotransformation) studies indicated repetitive shifts in measured CCS values (CCSmeas) between parent drugs and their metabolites. Hence, the purpose of the present article was (i)to investigate if such relative shifts in CCSmeas were biotransformation-specific and (ii) tohighlight their potential benefits for biotransformation studies. First, mean CCSmeas values of 165 compounds were determined (up to n = 3) using a travelling wave IMS-MS device with nitrogen as drift gas (TWCCSN2, meas). Further comparison with their predicted values (TWCCSN2, pred, Waters CCSonDemand) resulted in a mean absolute error of 5.1%. Second, a reduced data set (n = 139) was utilized to create compound pairs (n = 86) covering eight common types of phase I and II biotransformations. Constant, discriminative, and almost non-overlapping relative shifts in mean TWCCSN2,meas were obtained for demethylation (- 6.5 ± 2.1 Å2), oxygenation (hydroxylation + 3.8 ± 1.4 Å2, N-oxidation + 3.4 ± 3.3 Å2), acetylation (+ 13.5 ± 1.9 Å2), sulfation (+ 17.9 ± 4.4 Å2), glucuronidation (N-linked: + 41.7 ± 7.5 Å2, O-linked: + 38.1 ± 8.9 Å2), and glutathione conjugation (+ 49.2 ± 13.2 Å2). Consequently, we propose to consider such relative shifts in TWCCSN2, meas (rather than absolute values) as well for metabolite assignment/confirmation complementing the conventional approach to associate changes in mass-to-charge (m/z) values between a parent drug and its metabolite(s). Moreover, the comparison of relative shifts in TWCCSN2, meas significantly simplifies the mapping of metabolites into metabolic pathways as demonstrated.

Ultra-Fast Ion Mobility Spectrometer for High-Throughput Chromatography.

Fast chromatography systems especially developed for high sample throughput applications require sensitive detectors with a high repetition rate. These high throughput techniques, including various chip-based microfluidic designs, often benefit from detectors providing subsequent separation in another dimension, such as mass spectrometry or ion mobility spectrometry (IMS), giving additional information about the analytes or monitoring reaction kinetics. However, subsequent separation is required at a high repetition rate. Here, we therefore present an ultra-fast drift tube IMS operating at ambient pressure. Short drift times while maintaining high resolving power are reached by several key instrumental design features: short length of the drift tube, resistor network of the drift tube, tristate ion shutter, and improved data acquisition electronics. With these design improvements, even slow ions with a reduced mobility of just 0.94 cm2/(V s) have a drift time below 1.6 ms. Such short drift times allow for a significantly increased repetition rate of 600 Hz compared with previously reported values. To further reduce drift times and thus increase the repetition rate, helium can be used as the drift gas, which allows repetition rates of up to 2 kHz. Finally, these significant improvements enable IMS to be used as a detector following ultra-fast separation including chip-based chromatographic systems or droplet microfluidic applications requiring high repetition rates.

On-chip gas reaction nanolab for in situ TEM observation.

The catalysis reaction mechanism at nano/atomic scale attracted intense attention in the past decades. However, most in situ characterization technologies can only reflect the average information of catalysts, which leads to the inability to characterize the dynamic changes of single nanostructures or active sites under operando conditions, and many micro-nanoscale reaction mechanisms are still unknown. The combination of in situ transmission electron microscopy (TEM) holder system with MEMS chips provides a solution for it, where the design and fabrication of MEMS chips are the key factors. Here, with the aid of finite element simulation, an ultra-stable heating chip was developed, which has an ultra-low thermal drift during temperature heating. Under ambient conditions within TEM, atomic resolution imaging was achieved during the heating process or at high temperature up to 1300 °C. Combined with the developed polymer membrane seal technique and nanofluidic control system, it can realize an adjustable pressure from 0.1 bar to 4 bar gas environment around the sample. By using the developed ultra-low drift gas reaction cells, the nanoparticle's structure evolution at atomic scale was identified during reaction.

Single-Molecule Pycnometry and Shape Analysis of Ions in the Gas Phase.

The analysis of ions and clusters by mobility-classified mass spectrometry provides information on the mobility of analytes in the drift gas and the analyte mass. Mass equivalent and mobility equivalent diameters of globular analytes, such as ions, poly(ethylene glycol) (PEG), and ionic liquid nanodroplets, can be correlated with good accuracy by the Stokes-Millikan mobility model. A prerequisite to such an analysis is, however, the assumption of a globular analyte shape, which then allows determination of material density for globular ions. We show that the analyte density can be evaluated with high precision, independent of any assumptions on the analyte shape, by careful analysis of analyte-PEG-cluster ions following the concept of classical pycnometry. In particular, the analyte is entrapped in a globular PEG-analyte droplet. Based on the now independently derived mobility diameter and volume equivalent diameter, it is possible to attribute two parameters, size and shape, to the analyte molecule. We demonstrate the approach for lysozyme, cyano-cobalamin (vitamin B12), and glucose, which cover two orders of magnitude in analyte mass (180···14 300 Da). The derived densities for these analytes are highly accurate, i.e., they deviate less than 1% from literature values. Our method can be applied to newly synthesized molecules, supramolecular assemblies, isolated biomolecules, and molecular clusters, where only minor amounts of materials are available. The obtained shape parameters of lysozyme and cyano-cobalamin agree well with the expected molecular shapes. Data evaluation relies only on locations of the species in the mass-mobility plane and is in principle independent of any mobility theory. Our approach is thus robust with respect to experimental uncertainties and produces identical results irrespective of the type of mobility classification and drift gas.

Directional dark matter readout with a novel multi-mesh ThGEM for SF6 negative ion operation

Abstract Direct searches for Weakly Interacting Massive Particle (WIMP) dark matter could greatly benefit from directional measurement of the expected induced nuclear recoils. Gas-based Time Projection Chambers (TPCs) offer potential for this, opening the possibility of measuring WIMP signals below the so-called neutrino floor but also of directional measurement of recoils induced by neutrinos from the Sun, for instance as proposed by the CYGNUS collaboration. Presented here for the first time are results from a Multi-Mesh Thick Gas Electron Multiplier (MM-ThGEM) using negative ion gases for operation with such a directional dark matter TPC. Negative ion drift gases are favoured for directionality due to their low diffusion characteristics. The multiple internal mesh structure is designed to provide a high gain amplification stage when coupled to future large area Micromegas, strip or pixel charge readout planes. Experimental results and simulations are presented of MM-ThGEM gain and functionality using low pressure pure CF4, SF6 and SF6:CF4 mixtures irradiated with alpha particles and 55Fe x-rays. The concept is found to work well, providing stable operation with gains over 103 in pure SF6.

Opioid cutting agents for use as internal standards in ion mobility spectrometry (IMS)

Opioids have become a serious public health concern over the last decade. These compounds are commonly found mixed, or cut, with safer compounds to make the opioids appear unadulterated while also enhancing the psychoactive effect on the user. Commercial benchtop and handheld IMS devices are capable of detection but published reduced ion mobility (K0) values, used to identify the target analytes with IMS instrumentation, have shown variability. This lack of agreement, even for compounds used for calibration, is often due to the effects of drift tube temperature, drift gas water vapor levels and the use in-house built instrumentation rather than commercial equipment. Multiple reports exist on assessment of IMS reference standards but a single, consensus universal standard does not exist. Assessment of opioid cutting agents as internal standards is a worthwhile pursuit if precise and accurate K0 values are obtained. The effects of drift gas water vapor content and drift tube temperature were used to evaluate the cutting agents. The K0 values of papaverine, a representative opioid with a similar K0 value to heroin and fentanyl, were calculated with respect to quinine and were in agreement with literature data. The use of quinine as an internal standard also improved precision relative to the instrument standard and shows promise in the application presented here.

Characterization of Bile Acid Isomers and the Implementation of High-Resolution Demultiplexing with Ion Mobility-Mass Spectrometry

Bile acids (BAs) are a complex suite of clinically relevant metabolites that include many isomers. Liquid chromatography coupled to mass spectrometry (LC-MS) is an increasingly popular technique due to its high specificity and sensitivity; nonetheless, acquisition times are generally 10–20 min, and isomers are not always resolved. In this study, the application of ion mobility (IM) spectrometry coupled to MS was investigated to separate, characterize, and measure BAs. A subset of 16 BAs was studied, including three groups of isomers belonging to unconjugated, glycine-conjugated, and taurine-conjugated BA classes. A variety of strategies were explored to increase BA isomer separation such as changing the drift gas, measuring different ionic species (i.e., multimers and cationized species), and enhancing the instrumental resolving power. In general, Ar, N2, and CO2 provided the best peak shape, resolving power (Rp), and separation, especially CO2; He and SF6 were less preferable. Furthermore, measuring dimers versus monomers improved isomer separation due to enhanced gas-phase structural differences. A variety of cation adducts other than sodium were characterized. Mobility arrival times and isomer separation were affected by the choice of adduct, which was shown to be used to target certain BAs. Finally, a novel workflow that involves high-resolution demultiplexing in combination with dipivaloylmethane ion-neutral clusters was implemented to improve Rp dramatically. A maximum Rp increase was observed with lower IM field strengths to obtain longer drift times, increasing Rp from 52 to 187. A combination of these separation enhancement strategies demonstrates great potential for rapid BA analysis.

Breath-by-breath measurement of exhaled ammonia by acetone-modifier positive photoionization ion mobility spectrometry via online dilution and purging sampling

Exhaled ammonia (NH3) is an essential noninvasive biomarker for disease diagnosis. In this study, an acetone-modifier positive photoionization ion mobility spectrometry (AM-PIMS) method was developed for accurate qualitative and quantitative analysis of exhaled NH3 with high selectivity and sensitivity. Acetone was introduced into the drift tube along with the drift gas as a modifier, and the characteristic NH3 product ion peak of (C3H6O)4NH4+ (K0 = 1.45 cm2/V·s) was obtained through the ion-molecule reaction with acetone reactant ions (C3H6O)2H+ (K0 = 1.87 cm2/V·s), which significantly increased the peak-to-peak resolution and improved the accuracy of exhaled NH3 qualitative identification. Moreover, the interference of high humidity and the memory effect of NH3 molecules were significantly reduced via online dilution and purging sampling, thus realizing breath-by-breath measurement. As a result, a wide quantitative range of 5.87–140.92 μmol/L with a response time of 40 ms was achieved, and the exhaled NH3 profile could be synchronized with the concentration curve of exhaled CO2. Finally, the analytical capacity of AM-PIMS was demonstrated by measuring the exhaled NH3 of healthy subjects, demonstrating its great potential for clinical disease diagnosis.

Real-time monitoring of atmospheric ammonia based on modifier-enhanced vacuum ultraviolet photoionization ion mobility spectrometry.

Ammonia (NH3) plays an important role in the atmospheric environment such as the formation of PM2.5, the concentration monitoring of which could hence help in the air quality assessment. In this study, a method for quantitative monitoring of atmospheric NH3 was developed based on modifier-enhanced selectivity detection using a homemade vacuum ultraviolet photoionization ion mobility spectrometry (VUV-PI-IMS). To enhance the resolution and sensitivity of measuring NH3, 2-butanone as the gas modifier was introduced into the drift tube with the drift gas. Atmospheric NH3 can be selectively detected, where the peak-to-peak resolution (RP-P) of 7.69 was obtained. The product ions were identified to be [C4H8O]2NH4+ by using a homemade time-of-flight mass spectrometer. The calculated limit of detection (LOD) was 0.39 ppbv improving about 10 times. For the most common concentration variation of atmospheric NH3 in the range of 10-100 ppbv, the linear curve was obtained with R2 of 0.997. Lastly, the VUV-PI-IMS was used to monitor the evolution of atmospheric NH3 near our laboratory and mounted on a car for monitoring the regional distribution of atmospheric NH3 in Dalian, China. The results also showed that VUV-PI-IMS has a promising application prospect in monitoring the concentration of atmospheric NH3 and supporting the air quality assessment.

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.

Negative Atmospheric Pressure Chemical Ionization of Chlorinated Hydrocarbons Studied by Ion Mobility Spectrometry (IMS) and IMS-MS Techniques

Negative polarity atmospheric pressure chemical ionization of selected chlorinated hydrocarbons (tetrachloromethane CCl4 and hexachloroethane C2Cl6, dichloromethane CH2Cl2, trichloromethane CHCl3, 1,1,1,2-tetrachloroethane 1,1,1,2-C2H2Cl4, 1,1,2,2-tetrachloroethane 1,1,2,2,-C2H2Cl4 1,1,2-trichloroethane 1,1,2-C2H3Cl3, and 1,1,2-trichloroethane 1,1,2-C2HCl3) was studied using ion mobility spectrometry (IMS) and IMS combined with time-of-flight mass spectrometer (IMS-TOF MS) techniques, in the dry air and at two different drift gas temperatures (323 and 373 K). The ionization was performed using the O2-CO2(H2O)0,1 reactant ions (RIs), and the dominant ionization reaction was the dissociative electron transfer. The ionization resulted in the appearance of Cl- ions for all substances and [O2H..Cl]- ions, which were absent in the case of perchlorinated substances. The quantum-chemical calculations at the density functional theory level of theory using the ωB97X-D/aug-cc-pVTZ method were performed to calculate the thermochemical data (heats of formations, electron affinities, reaction enthalpies) for RIs, neutral substances, neutral fragments, and the anionic fragments. The calculations supported the experimental observations regarding the endothermicity of the Cl- channel for all substances and the exothermicity of the [O2H..Cl]- channel for the tetrachloro- and trichloroethanes.

Determination of trace organic chlorides in hydrogen for fuel cell vehicles by gas chromatography coupled with ion mobility spectrometry.

A method for the determination of organic chlorides in hydrogen for fuel cell vehicles by gas chromatography coupled with ion mobility spectrometry was established. Organic chlorides were separated by a non-polar gas chromatography column and detected in the negative ion mode of the ion mobility spectrometer. The effect of operating parameters of ion mobility spectrometer including drift gas flow rate and drift tube temperature on sensitivity and resolution were evaluated. Under the optimized conditions, the detection limits of seven organic chlorides were from 0.65 to 6.73nmol/mol, which met the requirement of detection for the specification limit of 50nmol/mol of total halogen impurities in hydrogen for fuel cell vehicles. Compared with gas chromatography-mass spectrometry, and gas chromatography coupled with electron capture detector under the same gas chromatography conditions, gas chromatography coupled with ion mobility spectrometry method demonstrated higher sensitivity for detection of organic chlorides under study. Based on the portability of the device and its detection capabilities, gas chromatography coupled with ion mobility spectrometry has the potential to perform online detection of impurities in hydrogen for fuel cell vehicles.

Evaluating the Effects of Metal Adduction and Charge Isomerism on Ion-Mobility Measurements using m-Xylene Macrocycles as Models.

Gas-phase ion-mobility spectrometry provides a unique platform to study the effect of mobile charge(s) or charge location on collisional cross section and ion separation. Here, we evaluate the effects of cation/anion adduction in a series of xylene and pyridyl macrocycles that contain ureas and thioureas. We explore how zinc binding led to unexpected deprotonation of the thiourea macrocyclic host in positive polarity ionization and subsequently how charge isomerism due to cation (zinc metal) and anion (chloride counterion) adduction or proton competition among acceptors can affect the measured collisional cross sections in helium and nitrogen buffer gases. Our approach uses synthetic chemistry to design macrocycle targets and a combination of ion-mobility spectrometry mass spectrometry experiments and quantum mechanics calculations to characterize their structural properties. We demonstrate that charge isomerism significantly improves ion-mobility resolution and allows for determination of the metal binding mechanism in metal-inclusion macrocyclic complexes. Additionally, charge isomers can be populated in molecules where individual protons are shared between acceptors. In these cases, interactions via drift gas collisions magnify the conformational differences. Finally, for the macrocyclic systems we report here, charge isomers are observed in both helium and nitrogen drift gases with similar resolution. The separation factor does not simply increase with increasing drift gas polarizability. Our study sheds light on important properties of charge isomerism and offers strategies to take advantage of this phenomenon in analytical separations.