Spatial effects on electrospray ionization response

Janusson, Eric; Hesketh, Amelia V.; Bamford, Karlee L.; Hatlelid, Katherine; Higgins, Rehan; McIndoe, J. Scott

doi:10.1016/j.ijms.2015.07.016

Cited by 21 publications

(26 citation statements)

References 41 publications

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“…The ESI interface used in this study was the Waters ZSpray™ source. The geometry of the design of this ion source has an unique dual orthogonal pathway, making the ion beam follow a Z‐shaped path from the capillary to the analyser inlet (Figure A): the eluent from the LC column enters through the probe and is pneumatically converted into an electrostatically charged aerosol spray – through the capillary ; the solvent is then evaporated from the spray by means of desolvation heater; the resulting analyte and solvent gaseous ions are then drawn through the sample cone aperture (orthogonal to the capillary) into the ion block (an intermediate vacuum region), where they are then extracted into the analyser by the extraction cone, geometrically orthogonal to the sample cone aperture (Figures A and B) …”

Section: Methodsmentioning

confidence: 99%

“…the eluent from the LC column enters through the probe and is Figures 1A and 1B). 35,37 Thus, the LC system was interfaced with a Waters ZSpray™ ESI source ( Figure 1 capturing as much usable information as possible. 13,43 Furthermore, for semantic clarification, the term 'defined features' (specifically in this study) means recorded true MS signals, relevant ionised species (extracted from processing and data scrutiny stepsclean data matrices), which most likely represent 'detected' metabolites.…”

Section: Mass Spectrometry Analysesmentioning

confidence: 99%

“…the comprehensiveness of the analysis or the extent of the overall coverage of the metabolome under study. Thus, the most significant parameters include: (i) electronically: capillary voltage and the voltage between skimmer cones; (ii) thermally: the temperatures of the source and the desolvation gas; (iii) volumetrically: the desolvation gas flow rate as well as any auxiliary gas flows; and (iv) spatially: the position of the spray capillary which can be moved in two directions with respect to the skimmer cone …”

Section: Introductionmentioning

confidence: 99%

“…8,20,22,32 Surprisingly, despite nearly 50 years post the first development and introduction, ESI is still a technique with grey areas, and uncovering the intricacies of this process remains an active area of the desolvation gas flow rate as well as any auxiliary gas flows; and (iv) spatially: the position of the spray capillary which can be moved in two directions with respect to the skimmer cone. 34,37 Considering the ongoing conversation and efforts to maximise the value of untargeted LC/MS metabolomic data and the current bottlenecks of global metabolite profiling, this work investigated the impact of the ESI parameters (specifically the capillary and sample cone voltages) upon the collected data in an untargeted experiment.…”

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confidence: 99%

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Mass spectrometry in untargeted liquid chromatography/mass spectrometry metabolomics: Electrospray ionisation parameters and global coverage of the metabolome

Tugizimana

Steenkamp

Piater

et al. 2017

Rapid Comm Mass Spectrometry

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Rationale: Liquid chromatography coupled to mass spectrometry (LC/MS) is a dominant analytical platform in metabolomics, because of the high sensitivity and resolution, thus enabling large-scale coverage of metabolomes. Correspondingly, electrospray ionisation (ESI) is the favoured ionisation method in untargeted LC/MS metabolomics given the ability to produce large numbers of ions. In the workflow of LC/ESI-MS metabolomics, maximising the ionisation efficiency over a wide mass range is inevitably an essential and determining step, subsequently defining the extent of coverage of the metabolome under investigation. Thus in this study, electronic factors related to the functioning of the ESI source, namely the capillary and sample cone voltages, were explored to investigate the influence on the data acquired in metabolomic investigations.Methods: Hydromethanolic samples from an untargeted study (sorghum plants responding dynamically to fungal infection) were analysed on a high-resolution/definition LC/ESI-MS system.Here the capillary and sample cone voltages of the ZSpray™ ESI source were varied between 1.5-3.0 kV and 10.0-40.0 V, respectively. The acquired data were processed with MarkerLynx™ software and analysed using central composite design response surface methodology and chemometric approaches (principal component analysis and orthogonal projection latent structures-discriminant analysis). Results:The results evidently demonstrate that both capillary and sampling cone voltages not only significantly influence the recorded MS signals with regard to the number and abundance of features, but also the overall structure of the collected data. This consequently impacts on the information extracted from the data and thus affects coverage of the metabolome. Conclusions: | INTRODUCTIONUntargeted, global metabolite profiling, a scientific approach followed in metabolomics, is a rapidly growing and maturing research field, and has become an indispensable pillar for systems biology approaches, providing direct functional information for understanding biological systems. [1][2][3] Comprehensive analysis (qualitatively and quantitatively) of exo-and/or endo-metabolites, as readouts of cellular metabolism, is the focus of metabolomics. These small molecules (of molecular weight ≤ 1500 Da) represent functional entities that collectively define the developmental, physiological, or pathological status of a biological system. 4,5 Ideally, the holistic coverage of the metabolome in toto, in a given biosystem, is the ultimate aim of an untargeted metabolomic study.However, the realisation of such a goal is not yet possible at present, considering technological, analytical and algorithmic limitations.Another contributing factor is the inherent complexity of metabolomes due to the physicochemical diversity, instability, and rapid turnover of

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Section: Methodsmentioning

confidence: 99%

Section: Mass Spectrometry Analysesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

See 2 more Smart Citations

Mass spectrometry in untargeted liquid chromatography/mass spectrometry metabolomics: Electrospray ionisation parameters and global coverage of the metabolome

Tugizimana

Steenkamp

Piater

et al. 2017

Rapid Comm Mass Spectrometry

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“…16 The main disadvantage is the non-linear ion transfer response of ESI to the concentration of the given species in solution. 17 The concentration can be thus determined only using isotopically labelled standards. 18 For investigation of reaction intermediates, we have recently introduced a new method denoted as Delayed reactant labeling.…”

Section: Introductionmentioning

confidence: 99%

Palladium-Catalyzed C–H Activation: Mass Spectrometric Approach to Reaction Kinetics in Solution

et al. 2017

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We report a new method for determination of rate constants of processes in solution using electrospray ionization mass spectrometry (ESI-MS). The investigated reaction is C-H activation of acetanilides by palladium(II)trifluoroacetate leading to stable organopalladium complexes. The rate constants can be determined from an experiment with a couple of differently substituted acetanilides being in competition activated by the palladium salt. The formed organopalladium complexes can be detected by ESI-MS. The time dependence is achieved by adding one of the acetanilides to the reaction mixture with a time delay. The kinetics can be then evaluated from the evolution of the ratio of the ESI-MS signals of differently substituted complexes as a function of the time delay. The Hammett analysis of the rate constants obtained for a series of meta-and para-substituted acetanilides provides the ρ value of-1.5, which is in agreement with values reported for similar C-H activations. We have investigated the very same reaction also with UV-Vis spectroscopy that gave us about three times smaller rate constants, but the same trend with the ρ value of-1.6. The rate constants determined by ESI-MS are directly linked to the occurrence of organopalladium complexes, whereas the UV-Vis data are associated with an absorption spectra change that could involve more reaction steps. DFT calculations support the interpretation of the reaction mechanism as cyclopalladation and provide the ρ value in the same range. The rate determining step corresponds to the agostic C-H transition structure.

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Pressurized Sample Infusion

et al. 2021

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Pressurized sample infusion (PSI) is a simple and effective means of continuously introducing a solution to an electrospray ionization mass spectrometry (ESI‐MS) source. It allows for acquisition of real‐time data in an air‐ and moisture‐free environment and requires minimal additional infrastructure. It is applicable for use for any reaction in which one or more components are detectable by ESI‐MS and for which time‐course information is desired over a time scale of seconds to minutes. The strengths and weaknesses of the method are critically examined, and technique tips and tricks are provided to enable maximal effectiveness when employing this approach to continuous monitoring of complex reaction mixtures.

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Spatial effects on electrospray ionization response

Cited by 21 publications

References 41 publications

Mass spectrometry in untargeted liquid chromatography/mass spectrometry metabolomics: Electrospray ionisation parameters and global coverage of the metabolome

Mass spectrometry in untargeted liquid chromatography/mass spectrometry metabolomics: Electrospray ionisation parameters and global coverage of the metabolome

Palladium-Catalyzed C–H Activation: Mass Spectrometric Approach to Reaction Kinetics in Solution

Pressurized Sample Infusion

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