Rift-induced disruption of cratonic keels drives kimberlite volcanism.

Kimberlites are volatile-rich, occasionally diamond-bearing magmas that have erupted explosively at Earth's surface in the geologic past1-3. These enigmatic magmas, originating from depths exceeding 150 km in Earth's mantle1, occur in stable cratons and in pulses broadly synchronous with supercontinent cyclicity4. Whether their mobilization is driven by mantle plumes5 or by mechanical weakening of cratonic lithosphere4,6 remains unclear. Here we show that most kimberlites spanning the past billion years erupted about 30 million years (Myr) after continental breakup, suggesting an association with rifting processes. Our dynamical and analytical models show that physically steep lithosphere-asthenosphere boundaries (LABs) formed during rifting generate convective instabilities in the asthenosphere that slowly migrate many hundreds to thousands of kilometres inboard of rift zones. These instabilities endure many tens of millions of years after continental breakup and destabilize the basal tens of kilometres of the cratonic lithosphere, or keel. Displaced keel is replaced by a hot, upwelling mixture of asthenosphere and recycled volatile-rich keel in the return flow, causing decompressional partial melting. Our calculations show that this process can generate small-volume, low-degree, volatile-rich melts, closely matching the characteristics expected of kimberlites1-3. Together, these results provide a quantitative and mechanistic link between kimberlite episodicity and supercontinent cycles through progressive disruption of cratonic keels.

Novel Hybrid Quadrupole-Multireflecting Time-of-Flight Mass Spectrometry System.

A novel mass spectrometry system is described here comprising a quadrupole-multireflecting time-of-flight design. The new multireflecting time-of-flight analyzer has an effective path length of 48 m and employs planar, gridless ion mirrors providing fourth-order energy focusing resulting in resolving power over 200 000 fwhm and sub-ppm mass accuracy. We show how these attributes are maintained with relatively fast acquisition speeds, setting the system apart from other high resolution mass spectrometers. We have integrated this new system into both liquid chromatography-mass spectrometry and mass spectrometry imaging workflows to demonstrate how the instrument characteristics are of benefit to these applications.

High-resolution ion mobility spectrometry-mass spectrometry for isomeric separation of prostanoids after Girard's reagent T derivatization.

RATIONALE: Isomeric separation of prostanoids is often a challenge and requires chromatography and time-consuming sample preparation. Multiple prostanoid isomers have distinct in vivo functions crucial for understanding the inflammation process, including prostaglandins E2 (PGE2 ) and D2 (PGD2 ). High-resolution ion mobility spectrometry (IMS) based on linear ion transport in low-to-moderate electric fields and nonlinear ion transport in strong electric fields emerges as a broad approach for rapid separations prior to mass spectrometry. METHODS: Derivatization with Girard's reagent T (GT) was used to overcome inefficient ionization of prostanoids in negative ionization mode due to poor deprotonation of the carboxylic acid group. Three high-resolution IMS techniques, namely linear cyclic IMS, linear trapped IMS, and nonlinear high-field asymmetric waveform IMS, were compared for the isomeric separation and endogenous detection of prostanoids present in intestinal tissue. RESULTS: Direct infusion of GT-derivatized prostanoids proved to increase the ionization efficiency in positive ionization mode by a factor of >10, which enabled detection of these molecules in endogenous concentration levels. The high-resolution IMS comparison revealed its potential for rapid isomeric analysis of biologically relevant prostanoids. Strengths and weaknesses of both linear and nonlinear IMS are discussed. Endogenous prostanoid detection in intestinal tissue extracts demonstrated the applicability of our approach in biomedical research. CONCLUSIONS: The applied derivatization strategy offers high sensitivity and improved stereoisomeric separation for screening of complex biological systems. The high-resolution IMS comparison indicated that the best sensitivity and resolution are achieved by linear and nonlinear IMS, respectively.

Exploiting Self-Association to Evaluate Enantiomeric Composition by Cyclic Ion Mobility-Mass Spectrometry.

The characterization of enantiomers is an important analytical challenge in the chemical and life sciences. Thorough evaluation of the purity of chiral molecules is particularly required in the pharmaceutical industry where safety concerns are paramount. Assessment of the enantiomeric composition is still challenging and time-consuming, meaning that alternative approaches are required. In this study, we exploit the formation of dimers as diastereomeric pairs of enantiomers to affect separation by high resolution cyclic ion mobility-mass spectrometry. Using the example of (R/S)-thalidomide, we show that even though this is not an enantiomer separation, we can determine which enantiomer is in excess and obtain quantitative information on the enantiomer composition without the need for a chiral modifier. Further examples of the approach are presented, including d/l-tryptophan and (R/S)-propanolol, and demonstrate the need for mobility resolving power in excess of 400 (CCS/ΔCCS).

Mapping Isomeric Peptides Derived from Biopharmaceuticals Using High-Resolution Ion Mobility Mass Spectrometry.

The identification and localization of isomeric peptide modifications is a critical requirement of the biopharmaceutical industry. Despite the ability of liquid chromatography-mass spectrometry to identify many of the common post translational modifications, the identification of isobaric or racemized peptides is confounded by modern mass spectrometry-based techniques. Here, we present a novel approach combining liquid chromatography with a high-resolution ion mobility mass spectrometry system to differentiate peptide and peptide fragments based upon their mobility and mass.

A Novel Lab-on-Chip Spectrophotometric pH Sensor for Autonomous In Situ Seawater Measurements to 6000 m Depth on Stationary and Moving Observing Platforms.

We report a new, autonomous Lab-on-Chip (LOC) microfluidic pH sensor with a 6000 m depth capability, ten times the depth capability of the state of the art autonomous spectrophotometric sensor. The pH is determined spectrophotometrically using purified meta-Cresol Purple indicator dye offering high precision (<0.001 pH unit measurement reproducibility), high frequency (every 8 min) measurements on the total proton scale from the surface to the deep ocean (to 600 bar). The sensor requires low power (3 W during continuous operation or ∼1300 J per measurement) and low reagent volume (∼3 µL per measurement) and generates small waste volume (∼2 mL per measurement) which can be retained during deployments. The performance of the LOC pH sensor was demonstrated on fixed and moving platforms over varying environmental salinity, temperature, and pressure conditions. Measurement accuracy was +0.003 ± 0.022 pH units (n = 47) by comparison with validation seawater sample measurements in coastal waters. The combined standard uncertainty of the sensor in situ pHT measurements was estimated to be ≤0.009 pH units at pH 8.5, ≤ 0.010 pH units at pH 8.0, and ≤0.014 pH units at pH 7.5. Integrated on autonomous platforms, this novel sensor opens new frontiers for pH observations, especially within the largest and most understudied ecosystem on the planet, the deep ocean.

Investigations into pesticide charge site isomers using conventional IM and cIM systems.

A growing number of pesticides are being used around the world necessitating strict regulatory policies to guarantee consumer safety. Liquid Chromatography - Mass Spectrometry (LC-MS) is a highly sensitive method for pesticide screening, which provides retention time, mass/charge ratios and the relative abundances of characteristic product ions. Variability in the latter necessitates relatively large tolerances (±30%, SANCO/12682/2019, current EU regulation). One cause of this variability may stem from the presence of different charge-site isomers (charge carrier being a proton, sodium cation, potassium cation and alike); each yielding a set of different product ions, of which the relative ratios are influenced by solution and ion source conditions. Consequently, varying relative abundances may be observed for analyte ions produced from calibration standards, chemical residues in food matrices and across different instruments. Ion Mobility Spectrometry (IMS) is a fast, gas phase separation technique which can resolve charge-site isomers based on differences in their collisional cross sections (CCSs). We previously used the IM device embedded in LC-IM-MS geometry to generate a pesticide CCS database and subsequently focussed upon identification of pesticides which form charge-site isomers. Latterly, we applied this approach to screen food commodities for pesticide residues. In some instances, isomer separation was clear, however sometimes broad, unresolved distributions were observed. Using a high-resolution cyclic IM device (cIM) we resolved and determined CCS values of species of indoxacarb, spinosad, fenpyroximate, epoxiconazole, metaflumizone and avermectin. Furthermore, utilising novel cIM functionalities (tandem-IM) we discovered that two spinosyn sodimers can interconvert in the gas phase.

Combined Chemical Modification and Collision Induced Unfolding Using Native Ion Mobility-Mass Spectrometry Provides Insights into Protein Gas-Phase Structure.

Native mass spectrometry is now an important tool in structural biology. Thus, the nature of higher protein structure in the vacuum of the mass spectrometer is an area of significant interest. One of the major goals in the study of gas-phase protein structure is to elucidate the stabilising role of interactions at the level of individual amino acid residues. A strategy combining protein chemical modification together with collision induced unfolding (CIU) was developed and employed to probe the structure of compact protein ions produced by native electrospray ionisation. Tractable chemical modification was used to alter the properties of amino acid residues, and ion mobility-mass spectrometry (IM-MS) utilised to monitor the extent of unfolding as a function of modification. From these data the importance of specific intramolecular interactions for the stability of compact gas-phase protein structure can be inferred. Using this approach, and aided by molecular dynamics simulations, an important stabilising interaction between K6 and H68 in the protein ubiquitin was identified, as was a contact between the N-terminus and E22 in a ubiquitin binding protein UBA2.

Use of Cyclic Ion Mobility Spectrometry (cIM)-Mass Spectrometry to Study the Intramolecular Transacylation of Diclofenac Acyl Glucuronide.

1-ß-O-Acyl-glucuronides (AGs) are common metabolites of carboxylic acid-containing xenobiotics, including, e.g., many nonsteroidal anti-inflammatory drugs (NSAIDs). They are of concern to regulatory authorities because of the association of these metabolites with the hepatotoxicity that has resulted in drug withdrawal. One factor in assessing the potential risk posed by AGs is the rate of transacylation of the biosynthetic 1-ß-O-acyl form to the 2-, 3-, and 4-O-acyl isomers. While transacylation can be measured using 1H NMR spectroscopy or liquid chromatography-mass spectrometry (LC-MS), the process can be time consuming and involve significant method development. The separation of these positional isomers by ion mobility spectrometry (IMS) has the potential to allow their rapid analysis, but conventional instruments lacked the resolving power to do this. Prediction of the collision cross section (CCS) using a machine learning model suggested that greater IMS resolution might be of use in this area. Cyclic IMS was evaluated for separating mixtures of isomeric AGs of diclofenac and was compared with a conventional ultraperformance liquid chromatography (UPLC)-MS method as a means for studying transacylation kinetics. The resolution of isomeric AGs was not seen using a conventional traveling wave IMS device; however, separation was seen after several passes around a cyclic IMS. The cyclic IMS enabled the degradation of the 1-ß-O-acyl-isomer to be analyzed much more rapidly than by LC-MS. The ability of cyclic IMS to monitor the rate of AG transacylation at different pH values, without the need for a prior chromatographic separation, should allow high-throughput, real-time, monitoring of these types of reactions.

Exploring Complex Mixtures by Cyclic Ion Mobility High-Resolution Mass Spectrometry: Application Toward Petroleum.

The in-depth isomeric and isobaric description of ultra-complex organic mixtures remains one of the most challenging analytical tasks. In the last two decades, ion mobility coupled to high-performance mass spectrometry added an additional structural dimension. Despite tremendous instrumental improvements, commercial devices are still limited in ion mobility and mass spectrometric resolving power and struggle to resolve isobaric species and complex isomeric patterns. To overcome these limitations, we explored the capabilities of cyclic ion mobility high-resolution mass spectrometry with special emphasis on petrochemical applications. We could show that quadrupole-selected ion mobility mass spectrometry gives closer insights into the isomeric distribution. In combination with slicing the specific parts of the ion mobility dimension, isobaric interferences could be drastically removed. Collision-induced dissociation (CID) allowed separating structural groups of polycyclic aromatic hydrocarbons and heterocycles (PAH/PASH), deploying up to 10 passes in the cyclic ion mobility device. Finally, we introduce a data processing workflow to resolve the 3.4 mDa SH4/C3 mass split by combining ion mobility and mass spectrometric resolving power. Cyclic ion mobility with the intelligent design of experiments and processing routines will be a powerful approach addressing the isobaric and isomeric complexity of ultra-complex mixtures.

Cyclic Ion Mobility Spectrometry Coupled to High-Resolution Time-of-Flight Mass Spectrometry Equipped with Atmospheric Solid Analysis Probe for the Molecular Characterization of Combustion Particulate Matter.

Anthropogenic air pollution has a severe impact on climate and human health. The immense molecular complexity and diversity of particulate matter (PM) is a result of primary organic aerosol (POA) as well as secondary organic aerosols (SOAs). In this study, a direct inlet probe (DIP), i.e., atmospheric solids analysis probe (ASAP), with ion mobility high-resolution mass spectrometric detection is applied. Primary particulate matter emissions from three sources were investigated. Furthermore, photochemically aged emissions were analyzed. DIP introduction allowed for a direct analysis with almost no sample preparation and resulted in a complex molecular pattern. This pattern shifted through oxidation processes toward heavier species. For diesel emissions, the fuel's chemical characteristic is partially transferred to the particulate matter by incomplete combustion and characteristic alkylated series were found. Polycyclic aromatic hydrocarbons (PAHs) were identified as major contributors. Ion mobility analysis results in drift time profiles used for structural analysis. The apex position was used to prove structural changes, whereas the full-width-at-half-maximum was used to address the isomeric diversity. With this concept, the dominance of one or a few isomers for certain PAHs could be shown. In contrast, a broad isomeric diversity was found for oxygenated species. For the in-depth specification of fresh and aged spruce emissions, the ion mobility resolving power was almost doubled by allowing for three passes in the circular traveling wave design. The results prove that ASAP coupled with ion mobility spectrometry-mass spectrometry (IMS-MS) serves as a promising analytical approach for tackling the vast molecular complexity of PM.

A comparative study on the physicochemical characteristics of nanoparticles released in vivo from CoCrMo tapers and cement-stem interfaces of total hip replacements.

The good biocompatibility and corrosion resistance of the bulk CoCrMo alloy has resulted in it being used in the manufacture of implants and load bearing medical devices. These devices, however, can release wear and corrosion products which differ from the composition of the bulk CoCrMo alloy. The physicochemical characteristics of the particles and the associated in vivo reactivity are dictated by the wear mechanisms and electrochemical conditions at the sites of material loss. Debris released from CoCrMo hip bearings, taper junctions, or cement-stem interfaces can, therefore, have different chemical and morphological characteristics, which provide them with different in vivo toxicities. Here, we propose to assess and compare the characteristics of the particles released in vivo from CoCrMo tapers and cement-stem interfaces which have received less attention compared to debris originating from the hip bearings. The study uses state-of-art characterization techniques to provide a detailed understanding of the size, morphology, composition, and chemistry of the particles liberated from the wear and corrosion flakes from revised hip replacements, with an enzymatic treatment. The phase analyses identified Cr2 O3 nanoparticles released from tapers and cement-stem interfaces, whose composition did not vary with origin or particle morphology. The size distributions showed significantly smaller particles were released from the stems, compared to the particles originating from the corresponding tapers. The investigation demonstrates that the tribocorrosive processes occurring at the taper and stem interfaces both result in Cr2 O3 nanoparticle formation.

LESA Cyclic Ion Mobility Mass Spectrometry of Intact Proteins from Thin Tissue Sections.

Liquid extraction surface analysis (LESA) is an ambient surface sampling technique that allows the analysis of intact proteins directly from tissue samples via mass spectrometry. Integration of ion mobility separation to LESA mass spectrometry workflows has shown significant improvements in the signal-to-noise ratios of the resulting protein mass spectra and hence the number of proteins detected. Here, we report the use of a quadrupole-cyclic ion mobility-time-of-flight mass spectrometer (Q-cIM-ToF) for the analysis of proteins from mouse brain and rat kidney tissues sampled via LESA. Among other features, the instrument allows multiple pass cyclic ion mobility separation, with concomitant increase in resolving power. Single-pass experiments enabled the detection of 30 proteins from mouse brain tissue, rising to 44 when quadrupole isolation was employed. In the absence of ion mobility separation, 21 proteins were detected in rat kidney tissue including the abundant α- and ß-globin chains from hemoglobin. Single-pass cyclic ion mobility mass spectrometry enabled the detection of 60 additional proteins. Multipass experiments of a narrow m/z range (m/z 870-920) resulted in the detection of 24 proteins (one pass), 37 proteins (two passes) and 54 proteins (three passes), thus demonstrating the benefits of improved mobility resolving power.

Application of a novel cyclic ion mobility-mass spectrometer to the analysis of synthetic polymers: A preliminary evaluation.

RATIONALE: Mass spectrometry (MS) is often employed in the characterisation of synthetic polymers. As polymer architecture becomes more complex, ion mobility (IM) is increasingly being coupled with MS to provide an additional dimension of separation, along with structural information. In this study, we explore the use of a novel cyclic ion mobility (cIM) mass spectrometer for the analysis of a co-polymer sample. METHODS: A solution of poly(ethylene glycol)-poly(propylene glycol) random co-polymer (PEG-ran-PPG) was used as a representative polymer sample. The solution was infused into a cIM-enabled quadrupole time-of-flight mass spectrometer. An m/z region of interest, selected using the quadrupole, was passed around the cIM device multiple times. Subsequently, regions of an arrival time distribution were 'sliced' and subjected to tandem mass spectrometric (MS/MS) analysis. RESULTS: Typical, multiply charged series were observed for the polymer under electrospray ionisation. Multiple passes of the cIM device resulted in the separation of otherwise-overlapping charge states within a narrow m/z window (~3 m/z units), allowing individual selection of ions. These isolated ions were then subjected to post-mobility fragmentation resulting in clean, high-resolution product ion spectra, with a significant reduction in interference. CONCLUSIONS: Scalable IM separation (IMS), brought about by passing ions multiple times around the cIM device, was demonstrated to provide increased IM resolution for ions in the selected m/z window. After multiple passes, deconvoluted high-resolution MS/MS product ion spectra were successfully acquired for ions that previously had interfering overlapping species present.

High-resolution ion mobility spectrometry-mass spectrometry of isomeric/isobaric ribonucleotide variants.

In this report, we explored the benefits of cyclic ion mobility (cIM) mass spectrometry in the analysis of isomeric post-transcriptional modifications of RNA. Standard methyl-cytidine samples were initially utilized to test the ability to correctly distinguish different structures sharing the same elemental composition and thus molecular mass. Analyzed individually, the analytes displayed characteristic arrival times (tD ) determined by the different positions of the modifying methyl groups onto the common cytidine scaffold. Analyzed in mixture, the widths of the respective signals resulted in significant overlap that initially prevented their resolution on the tD scale. The separation of the four isomers was achieved by increasing the number of passes through the cIM device, which enabled to fully differentiate the characteristic ion mobility behaviors associated with very subtle structural variations. The placement of the cIM device between the mass-selective quadrupole and the time-of-flight analyzer allowed us to perform gas-phase activation of each of these ion populations, which had been first isolated according to a common mass-to-charge ratio and then separated on the basis of different ion mobility behaviors. The observed fragmentation patterns confirmed the structures of the various isomers thus substantiating the benefits of complementing unique tD information with specific fragmentation data to reach more stringent analyte identification. These capabilities were further tested by analyzing natural mono-nucleotide mixtures obtained by exonuclease digestion of total RNA extracts. In particular, the combination of cIM separation and post-mobility dissociation allowed us to establish the composition of methyl-cytidine and methyl-adenine components present in the entire transcriptome of HeLa cells. For this reason, we expect that this technique will benefit not only epitranscriptomic studies requiring the determination of identity and expression levels of RNA modifications, but also metabolomics investigations involving the analysis of natural extracts that may possibly contain subsets of isomeric/isobaric species.

Isolation of Crude Oil Peaks Differing by m/z ∼0.1 via Tandem Mass Spectrometry Using a Cyclic Ion Mobility-Mass Spectrometer.

Mass spectrometry is widely used in studying the structures of compounds present in crude oil. In this study, a novel mass spectrometer incorporating a cyclic ion mobility separator was used to obtain tandem mass spectra of crude oil compounds in a narrow mass-to-charge ratio (m/z) window. Isolation of specific peaks was performed by combining quadrupole and ion mobility separation. As a result, peaks differing by an m/z value of 0.1 could be isolated. Tandem mass spectrometry with collision-induced dissociation was successfully performed to study the chemical structures of the isolated ions. A series of ions ranging from m/z 374 to m/z 384, differing by two hydrogen atoms but with the same number of carbons, were isolated and tandem mass spectra were obtained. The higher m/z precursor ions produced smaller fragment ions; this is explained by the reduced aromaticity owing to an increased number of hydrogen atoms. The ions at m/z 388 and 374, differing by a CH2 group, produced very similar fragmentation patterns. Overall, the data obtained from this study clearly demonstrate that the novel cyclic ion mobility-mass spectrometer is a powerful instrument that can provide tandem mass spectra of individual compounds constituting complex mixtures such as crude oils.

Ion-Mobility Spectrometry Can Assign Exact Fucosyl Positions in Glycans and Prevent Misinterpretation of Mass-Spectrometry Data After Gas-Phase Rearrangement.

The fucosylation of glycans leads to diverse structures and is associated with many biological and disease processes. The exact determination of fucoside positions by tandem mass spectrometry (MS/MS) is complicated because rearrangements in the gas phase lead to erroneous structural assignments. Here, we demonstrate that the combined use of ion-mobility MS and well-defined synthetic glycan standards can prevent misinterpretation of MS/MS spectra and incorrect structural assignments of fucosylated glycans. We show that fucosyl residues do not migrate to hydroxyl groups but to acetamido moieties of N-acetylneuraminic acid as well as N-acetylglucosamine residues and nucleophilic sites of an anomeric tag, yielding specific isomeric fragment ions. This mechanistic insight enables the characterization of unique IMS arrival-time distributions of the isomers which can be used to accurately determine fucosyl positions in glycans.

Discrimination of Regioisomeric and Stereoisomeric Saponins from Aesculus hippocastanum Seeds by Ion Mobility Mass Spectrometry.

Modern mass spectrometry methods provide a huge benefit to saponin structural characterization, especially when combined with collision-induced dissociation experiments to obtain a partial description of the saponin (ion) structure. However, the complete description of the structures of these ubiquitous secondary metabolites remain challenging, especially since isomeric saponins presenting small differences are often present in a single extract. As a typical example, the horse chestnut triterpene glycosides, the so-called escins, comprise isomeric saponins containing subtle differences such as cis-trans ethylenic configuration (stereoisomers) of a side chain or distinct positions of an acetyl group (regioisomers) on the aglycone. In the present paper, the coupling of liquid chromatography and ion mobility mass spectrometry has been used to distinguish regioisomeric and stereoisomeric saponins. Ion mobility arrival time distributions (ATDs) were recorded for the stereoisomeric and regioisomeric saponin ions demonstrating that isomeric saponins can be partially separated using ion mobility on a commercially available traveling wave ion mobility (TWIMS) mass spectrometer. Small differences in the ATD can only be monitored when the isomeric saponins are separated with liquid chromatography prior to the IM-MS analysis. However, gas phase separation between stereoisomeric and regioisomeric saponin ions can be successfully realized, without any LC separation, on a cyclic ion mobility-enabled quadrupole time-of-flight (Q-cIM-oaToF) mass spectrometer. The main outcome of the present paper is that the structural analysis of regioisomeric and stereoisomeric natural compounds that represents a real challenge can take huge advantages of ion mobility experiments but only if increased ion mobility resolution is attainable.

Structure Determination of Large Isomeric Oligosaccharides of Natural Origin through Multipass and Multistage Cyclic Traveling-Wave Ion Mobility Mass Spectrometry.

Carbohydrate isomers with identical atomic composition cannot be distinguished by mass spectrometry. By separating the ions according to their conformation in the gas phase, ion mobility (IM) coupled to mass spectrometry is an attractive approach to overcome this issue and extend the limits of mass spectrometry in structural glycosciences. Recent technological developments have significantly increased the resolving power of ion mobility separators. One such instrument features a cyclic traveling-wave IM separator integrated in a quadrupole/time-of-flight mass spectrometer. This system allows for multipass ion separations and for pre-, intra-, and post-IM fragmentation. In the present study, we utilize this system to explore a complex mixture of oligoporphyrans derived from the enzymatic digestion of the cell wall of the red alga P. umbilicalis. We are able to deduce their complete structure using IM arrival times and the m/z of specific fragments. This approach was successfully applied for sequencing of oligoporphyrans of up to 1500 Da and included the positioning of the methyl ether and sulfate groups. The structures defined in this study by IM-MS/MS agree with those found in the past but use much more time-consuming analytical approaches. This study also revealed some so far undescribed structures, present at very low abundance. In addition, the results made it possible to compare the abundance of the different isomers released by the enzyme and to draw further conclusions on the specificity of ß-porphyranase and more particularly on its accommodation tolerance of anhydro-bridges in subsites. Finally, a separation of two isomers with very similar mobility was obtained after 58 passes around the cIM, with an estimated resolving power of 920 for these triply charged species, confirming the structures attributed to these two isomers.