Recommendations for reporting ion mobility mass spectrometry measurements

© 2019 The Authors. Mass Spectrometry Reviews Published by Wiley Periodicals, Inc. Here we present a guide to ion mobility mass spectrometry experiments, which covers both linear and nonlinear methods: what is measured, how the measurements are done, and how to report the results, including the uncertainties of mobility and collision cross section values. The guide aims to clarify some possibly confusing concepts, and the reporting recommendations should help researchers, authors and reviewers to contribute comprehensive reports, so that the ion mobility data can be reused more confidently. Starting from the concept of the definition of the measurand, we emphasize that (i) mobility values (K0) depend intrinsically on ion structure, the nature of the bath gas, temperature, and E/N; (ii) ion mobility does not measure molecular surfaces directly, but collision cross section (CCS) values are derived from mobility values using a physical model; (iii) methods relying on calibration are empirical (and thus may provide method-dependent results) only if the gas nature, temperature or E/N cannot match those of the primary method. Our analysis highlights the urgency of a community effort toward establishing primary standards and reference materials for ion mobility, and provides recommendations to do so. © 2019 The Authors. Mass Spectrometry Reviews Published by Wiley Periodicals, Inc

Open Source Ion Mobility Spectrometer

Source files to construction an Open Source Ion Mobility Spectromete

Implementation of a flexible, open-source platform for ion mobility spectrometry

When operated as a stand-alone device, an ion mobility spectrometer (IMS) routinely offers low limits of detection (pptv-range) for gas-phase analytes even for measurement times less than a second. Mass analyzers further enhance the analytical power of IMS separations, however, high performance drift-cell IMS instruments are often highly customized, relatively large, and require extensive expertise to operate. In this work we present an optimized, low cost IMS system that leverages an easy-to-assemble ion gating structure that enables IMS spectra with resolving powers exceeding 90 for a drift cell only 10 cm in length. The IMS presented in this work consists of stacked rings divided by spacers all fabricated from printed circuit boards (PCB). The rings are connected via a slotted PCB-board containing a surface mounted voltage divider that connects directly to the ring electrodes allowing a fast and easy assembly. This highly modular design enables e.g. the realization of variable drift tube lengths or single and dual gate setups. Instead of the commonly used Bradbury Nielsen gates, the IMS is equipped with a 3-grid ion gate allowing the generation of short (<50 μs) ion packets increasing the resolving power of the instrument. Keywords: Ion mobility spectrometry, Chemical instrumentation, Laboratory instrumentation, Trace analysi

Rapid Resolution of Carbohydrate Isomers by Electrospray Ionization Ambient Pressure Ion Mobility Spectrometry-Time-of-Flight Mass Spectrometry (ESI-APIMS-TOFMS)

Carbohydrates are an extremely complex group of isomeric molecules that have been difficult to analyze in the gas phase by mass spectrometry because (1) precursor ions and product ions to successive stages of MS n are frequently mixtures of isomers, and (2) detailed information about the anomeric configuration and location of specific stereochemical variants of monosaccharides within larger molecules has not been possible to obtain in a general way. Herein, it is demonstrated that gas-phase analyses by direct combination of electrospray ionization, ambient pressure ion mobility spectrometry, and time-of-flight mass spectrometry (ESI-APIMS-TOFMS) provides sufficient resolution to separate different anomeric methyl glycosides and to separate different stereoisomeric methyl glycosides having the same anomeric configuration. Reducing sugars were typically resolved into more than one peak, which might represent separation of cyclic species having different anomeric configurations and/or ring forms. The extent of separation, both with methyl glycosides and reducing sugars, was significantly affected by the nature of the drift gas and by the nature of an adducting metal ion or ion complex. The study demonstrated that ESI-APIMS-TOFMS is a rapid and effective analytical technique for the separation of isomeric methyl glycosides and simple sugars, and can be used to differentiate glycosides having different anomeric configurations

SLIM Tricks: Tools, Concepts, and Strategies for the Development of Planar Ion Guides

Traveling wave ion mobility experiments using planar electrode structures (e.g., structures for lossless ion manipulation, TW-SLIM) leverage the mature manufacturing capabilities of printed circuit boards (PCBs). With routine levels of mechanical precision below 150 μm, the conceptual flexibility afforded by PCBs for use as planar ion guides is expansive. To date, the design and construction of TW-SLIM platforms require considerable legacy expertise, especially with respect to simulation and circuit layout strategies. To lower the barrier of TW-SLIM implementation, we introduce Python-based interactive tools that assist in graphical layout of the core electrode footprints for planar ion guides with minimal user inputs. These scripts also export the exact component locations and assignments for direct integration into KiCad and SIMION for PCB finalization and ion flight simulations. The design concepts embodied in the set of scripts comprising SLIM Pickins (PCB CAD generation) and pigsim (SIMION workspace generation) build upon the lessons learned in the independent development of the research-grade TW-SLIM platforms in operation at WSU. Due to the inherent flexibility of the PCB manufacturing process and the time devoted to board layouts prior to manufacturing, both scripts serve to enable rapid, iterative design considerations. Because only a few predefined parameters are necessary (i.e., the TW-SLIM monomer width, x position following a TW Turn, and y position following a TW Turn) it is possible to design the exact component layouts and accompanying simulation space in a manner of minutes. There is no known limitation to the board layout capacities of the scripts, and the size of a designed layout is ultimately constrained by the abilities of the final PCB design and simulation tools, KiCad and SIMION, to accommodate the thousands of electrodes comprising the final design (i.e., RAM and software overhead). Toward removing the barriers to exploring new SLIM tracks and the likelihood of layout errors that require considerable revision and engineering time, the SLIM Pickins and pigsim tools (included as Supporting Information) allow the user to quickly design a length of planar ion guide, simulate its abilities to confine and transmit ions, compare hypothetical board outlines to given vacuum chamber dimensions, and generate a near-production ready PCB CAD file. In addition to these tools, this report outlines a series of cost-saving strategies with respect to vacuum feedthroughs and vacuum chamber design for TW ion mobility experiments using planar ion guides

Ion mobility-mass spectrometry analysis of isomeric carbohydrate precursor ions

The rapid separation of isomeric precursor ions of oligosaccharides prior to their analysis by mass spectrometry to the nth power (MS(n)) was demonstrated using an ambient pressure ion mobility spectrometer (IMS) interfaced with a quadrupole ion trap. Separations were not limited to specific types of isomers; representative isomers differing solely in the stereochemistry of sugars, in their anomeric configurations, and in their overall branching patterns and linkage positions could be resolved in the millisecond time frame. Physical separation of precursor ions permitted independent mass spectra of individual oligosaccharide isomers to be acquired to at least MS(3), the number of stages of dissociation limited only practically by the abundance of specific product ions. IMS-MS(n) analysis was particularly valuable in the evaluation of isomeric oligosaccharides that yielded identical sets of product ions in tandem mass spectrometry experiments, revealing pairs of isomers that would otherwise not be known to be present in a mixture if evaluated solely by MS dissociation methods alone. A practical example of IMS-MS(n) analysis of a set of isomers included within a single high-performance liquid chromatography fraction of oligosaccharides released from bovine submaxillary mucin is described

Systematic characterization of high mass accuracy influence on false discovery and probability scoring in peptide mass fingerprinting

Whereas the bearing of mass measurement error on protein identification is sometimes underestimated, uncertainty in observed peptide masses unavoidably translates to ambiguity in subsequent protein identifications. Although ongoing instrumental advances continue to make high accuracy mass spectrometry (MS) increasingly accessible, many proteomics experiments are still conducted with rather large mass error tolerances. In addition, the ranking schemes of most protein identification algorithms do not include a meaningful incorporation of mass measurement error. This article provides a critical evaluation of mass error tolerance as it pertains to false positive peptide and protein associations resulting from peptide mass fingerprint (PMF) database searching. High accuracy, high resolution PMFs of several model proteins were obtained using matrix-assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry (MALDI–FTICR–MS). Varying levels of mass accuracy were simulated by systematically modulating the mass error tolerance of the PMF query and monitoring the effect on figures of merit indicating the PMF quality. Importantly, the benefits of decreased mass error tolerance are not manifest in Mowse scores when operating at tolerances in the low parts-per-million range but become apparent with the consideration of additional metrics that are often overlooked. Furthermore, the outcomes of these experiments support the concept that false discovery is closely tied to mass measurement error in PMF analysis. Clear establishment of this relation demonstrates the need for mass error-aware protein identification routines and argues for a more prominent contribution of high accuracy mass measurement to proteomic science

Coulombic effects in ion mobility spectrometry

Ion mobility spectrometry (IMS) has been increasingly employed in a number of applications. When coupled to mass spectrometry (MS), IMS becomes a powerful analytical tool for separating complex samples and investigating molecular structure. Therefore, improvements in IMS-MS instrumentation, e.g., IMS resolving power and sensitivity, are highly desirable. Implementation of an ion trap for accumulation and pulsed ion injection to IMS based on the ion funnel has provided considerably increased ion currents and thus a basis for improved sensitivity and measurement throughput. However, large ion populations may manifest Coulombic effects contributing to the spatial dispersion of ions traveling in the IMS drift tube and reduction in the IMS resolving power. In this study, we present an analysis of Coulombic effects on IMS resolution. Basic relationships have been obtained for the spatial evolution of ion packets due to Coulombic repulsion. The analytical relationships were compared with results of a computer model that simulates IMS operation based on a first principles approach. Initial experimental results reported here are consistent with the computer modeling. A noticeable decrease in the IMS resolving power was observed for ion populations of >10,000 elementary charges. The optimum IMS operation conditions which would minimize the Coulombic effects are discussed

Dual polarity accurate mass calibration for electrospray ionization and matrix-assisted laser desorption/ionization mass spectrometry using maltooligosaccharides

In view of the fact that memory effects associated with instrument calibration hinder the use of many mass-to-charge ( m/ z) ratios and tuning standards, identification of robust, comprehensive, inexpensive, and memory-free calibration standards is of particular interest to the mass spectrometry community. Glucose and its isomers are known to have a residue mass of 162.05282 Da; therefore, both linear and branched forms of polyhexose oligosaccharides possess well-defined masses, making them ideal candidates for mass calibration. Using a wide range of maltooligosaccharides (MOSs) derived from commercially available beers, ions with m/z ratios from approximately 500 to 2500 Da or more have been observed using Fourier transform ion cyclotron resonance mass spectrometry (FT–ICR–MS) and time-of-flight mass spectrometry (TOF–MS). The MOS mixtures were further characterized using infrared multiphoton dissociation (IRMPD) and nano-liquid chromatography/mass spectrometry (nano-LC/MS). In addition to providing well-defined series of positive and negative calibrant ions using either electrospray ionization (ESI) or matrix-assisted laser desorption/ionization (MALDI), the MOSs are not encumbered by memory effects and, thus, are well-suited mass calibration and instrument tuning standards for carbohydrate analysis

Direct Real-Time Detection of RDX Vapors Under Ambient Conditions

The results in this manuscript represent a demonstration of RDX vapor detection in real time at ambient temperature without sample preconcentration. The detection of vapors from the low volatility explosive compound RDX was achieved through selective atmospheric pressure chemical ionization using nitrate reactant ions (NO₃^–) and NO₃^–·HNO₃ adducts generated in an electrical discharge source. The RDX vapors were ionized in a reaction region, which provided a variable (up to several seconds) reaction time. The reaction times were controlled either by flow in an atmospheric flow tube (AFT) or by an electric field in an atmospheric drift tube (ADT). Both AFT and ADT were interfaced to a quadrupole mass spectrometer for ion detection and identification. Recorded signals were observed for RDX concentrations below 25 ppq using selected ion monitoring (SIM) of the RDX-nitrate adduct at <i>m</i>/<i>z</i> 284