Uncovering the behaviour of ions in the gas-phase to predict the ion mobility separation of isomeric steroid compounds

Hadavi, Darya; Borzova, Marina; Siegel, Tiffany Porta; Honing, Maarten

doi:10.1016/j.aca.2022.339617

Cited by 11 publications

(18 citation statements)

References 35 publications

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“…Bile acids (BA) are steroids synthesised in the liver from cholesterol. The primary BA cholic acid, and its derivatives, exhibited measurable ion mobility differences upon investigation by DI-TWIMS ( Hadavi et al, 2022 ). A representative isomeric pair from this study is glycodeoxycholic acid (GDCA) and glycochenodeoxycholic acid (GCDCA), whose structural differences are related to the position of the hydroxyl group on C7 and C12, respectively.…”

Section: Ims-ms Approaches Towards the Separation Of Geometrical Lipi...mentioning

confidence: 99%

“…Conversely, multiple sodium monomers presented a bulky conformation with a poorer separation between isomers. Thus, the presence of multiple adducts does not necessarily increase their ΔCCS value ( Hadavi et al, 2022 ).…”

Section: Ims-ms Approaches Towards the Separation Of Geometrical Lipi...mentioning

confidence: 99%

“…An interesting alternative approach is to exploit the mobility of product ions when IMS is coupled directly after the collision cell. This strategy revealed different behaviours in TWIMS for eicosanoid oxylipins ( di Giovanni et al, 2018 ), as well as for isomeric BA ( Hadavi et al, 2022 ). Similarly, the use of a dual-stage CID (TAP fragmentation) together with TWIMS separation of fragment ions enabled the determination of PC and LPC species ( Castro-Perez et al, 2011 ).…”

Section: Ims-ms Approaches Towards the Structural Characterisation Of...mentioning

confidence: 99%

“…Sodium adduct formation has been more extensively used for steroid epimers. For instance, in the case of 25-hydroxy-vitamin D3 and its epimer in carbon 3, using DTIMS ( Chouinard et al, 2017b ; Oranzi et al, 2018 ), non-conjugated muricholic acids (α-, β-, ω- and γ-MCA) and taurine conjugated muricholic acids (Tα-, Tβ-, Tω- and Tγ-MCA) using TWIMS ( Hadavi et al, 2022 ), and androgenic steroid hormones (e.g., testosterone and epitestosterone), using TWIMS as well ( Rister et al, 2019 ).…”

Section: Ims-ms Approaches Towards the Separation And Characterisatio...mentioning

confidence: 99%

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Integrating the potential of ion mobility spectrometry-mass spectrometry in the separation and structural characterisation of lipid isomers

Camunas‐Alberca

Morán-Garrido

Sáiz

et al. 2023

Front. Mol. Biosci.

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It is increasingly evident that a more detailed molecular structure analysis of isomeric lipids is critical to better understand their roles in biological processes. The occurrence of isomeric interference complicates conventional tandem mass spectrometry (MS/MS)-based determination, necessitating the development of more specialised methodologies to separate lipid isomers. The present review examines and discusses recent lipidomic studies based on ion mobility spectrometry combined with mass spectrometry (IMS-MS). Selected examples of the separation and elucidation of structural and stereoisomers of lipids are described based on their ion mobility behaviour. These include fatty acyls, glycerolipids, glycerophospholipids, sphingolipids, and sterol lipids. Recent approaches for specific applications to improve isomeric lipid structural information using direct infusion, coupling imaging, or liquid chromatographic separation workflows prior to IMS-MS are also discussed, including: 1) strategies to improve ion mobility shifts; 2) advanced tandem MS methods based on activation of lipid ions with electrons or photons, or gas-phase ion-molecule reactions; and 3) the use of chemical derivatisation techniques for lipid characterisation.

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Section: Ims-ms Approaches Towards the Separation Of Geometrical Lipi...mentioning

confidence: 99%

Section: Ims-ms Approaches Towards the Separation Of Geometrical Lipi...mentioning

confidence: 99%

Section: Ims-ms Approaches Towards the Structural Characterisation Of...mentioning

confidence: 99%

Section: Ims-ms Approaches Towards the Separation And Characterisatio...mentioning

confidence: 99%

See 2 more Smart Citations

Integrating the potential of ion mobility spectrometry-mass spectrometry in the separation and structural characterisation of lipid isomers

Camunas‐Alberca

Morán-Garrido

Sáiz

et al. 2023

Front. Mol. Biosci.

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show abstract

“…19 Bile acids comprise a structurally challenging subclass, due to the presence of numerous hydroxyl group positional and stereochemical isomers, but further incorporation of complementary computational modeling could assist in identification. 20 IM-MS has even seen utility in identifying steroids in food safety applications. 21−23 Other steroid subclasses that have been profiled using IM-MS have included vitamin D metabolites, 24 glucorocorticoids, 11 and serum estrogens.…”

Section: ■ Introductionmentioning

confidence: 99%

Development of a Rapid, Targeted LC-IM-MS Method for Anabolic Steroids

Wedge,

Hoover,

Pettit-Bacovin

et al. 2023

J. Am. Soc. Mass Spectrom.

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Anabolic steroids are of high biological interest due to their involvement in human development and disease progression. Additionally, they are banned in sport due to their performance-enhancing characteristics. Analytical challenges associated with their measurement stem from structural heterogeneity, poor ionization efficiency, and low natural abundance. Their importance in a variety of clinically relevant assays has prompted the consideration of integrating ion mobility spectrometry (IMS) into existing LC-MS assays, due primarily to its speed and structure-based separation capability. Herein we have optimized a rapid (2 min) targeted LC-IM-MS method for the detection and quantification of 40 anabolic steroids and their metabolites. First, a steroid-specific calibrant mixture was developed to cover the full range of retention time, mobility, and accurate mass. Importantly, this use of this calibrant mixture provided robust and reproducible measurements based on collision cross section (CCS) with interday reproducibility of <0.5%. Furthermore, the combined separation power of LC coupled to IM provided comprehensive differentiation of isomers/isobars within 6 different isobaric groups. Multiplexed IM acquisition also provided improved limits of detection, which were well below 1 ng/mL in almost all compounds measured. This method was also capable of steroid profiling, providing quantitative ratios (e.g., testosterone/epitestosterone, androsterone/etiocholanolone, etc.). Lastly, phase II steroid metabolites were probed in lieu of hydrolysis to demonstrate the ability to separate those analytes and provide information beyond total steroid concentration. This method has tremendous potential for rapid analysis of steroid profiles in human urine spanning a variety of applications from developmental disorders to doping in sport.

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Ion mobility in gas and liquid phases: How much orthogonality is obtained in capillary electrophoresis–ion mobility–mass spectrometry?

Schairer,

Plathe,

Hudelmaier

et al. 2023

Electrophoresis

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Ion mobility–mass spectrometry (IM–MS) is an ever‐evolving tool to separate ions in the gas phase according to electrophoretic mobility with subsequent mass determination. CE is rarely coupled to IM–MS, possibly due to similar separation mechanisms based on electrophoretic mobility. Here, we investigate the orthogonality of CE and ion mobility (IM) by analyzing a complex peptide mixture (tryptic digest of HeLa proteins) with trapped ion mobility mass spectrometry (TIMS–MS). Using the nanoCEasy interface, excellent sensitivity was achieved by identifying thousands of peptides and achieving a peak capacity of 7500 (CE: 203–323 in a 150 cm long capillary, IM: 27–31). Plotting CE versus mass and CE versus (inverse) mobility, a clear grouping in curved striped patterns is observed according to the charge‐to‐size and mass‐to‐charge ratios. The peptide charge in the acidic background electrolyte can be estimated from the number of basic amino acids, with a few exceptions where neighboring effects reduce the positive charge. A surprisingly high orthogonality of CE and IM is observed, which is obviously caused by solvation effects leading to different charges and sizes in the liquid phase compared to the gas phase. A high orthogonality of CE and ion mobility is expected to be observed for other peptide samples as well as other substance classes, making CE–IM–MS a promising tool for various applications.

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Uncovering the behaviour of ions in the gas-phase to predict the ion mobility separation of isomeric steroid compounds

Cited by 11 publications

References 35 publications

Integrating the potential of ion mobility spectrometry-mass spectrometry in the separation and structural characterisation of lipid isomers

Integrating the potential of ion mobility spectrometry-mass spectrometry in the separation and structural characterisation of lipid isomers

Development of a Rapid, Targeted LC-IM-MS Method for Anabolic Steroids

Ion mobility in gas and liquid phases: How much orthogonality is obtained in capillary electrophoresis–ion mobility–mass spectrometry?

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