Comparison of isotope pattern deconvolution and calibration curve quantification methods for the determination of estrone and 17β-estradiol in human serum

Pitarch-Motellón, Jorge; Fabregat-Cabello, Neus; Goff, Caroline Le; Roig-Navarro, A.F.; Sancho, Juan V.; Cavalier, Étienne

doi:10.1016/j.jpba.2019.04.013

Cited by 5 publications

(5 citation statements)

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“…There are many challenges with current calibration practices in clinical mass spectrometry, as discussed above. Internal calibration is a novel approach, which obviates the use of external calibration curves [ 13 , 16 , 37 - 39 ]. Currently, an SIL-IS is commonly used to normalize instrumental responses and attenuate the overall analytical variation caused by random errors, matrix effects, poor recovery, or instrumental drift [ 16 ].…”

Section: Recommendationsmentioning

confidence: 99%

“…When an SIL-IS is added to the sample, the altered isotopic abundances represent a mixture of a linear combination of those from naturally occurring isotypes and those from the spiked labeled standards. Multiple linear regression is then used to deconvolute the resulting combined distribution of abundances to obtain their molar fractions [ 37 ]. The concentration of the measurand in the unknown sample is calculated from the ratio of the signals of the unknown analyte to the SIL-IS multiplied by the SIL-analyte concentration equivalent [ 16 ].…”

Section: Recommendationsmentioning

confidence: 99%

“…Experiments must also be performed during validation to examine the effects of the matrix and the time required for SIL standard equilibration with the sample (if any). This approach also requires full characterization of both the analyte and SIL compounds in terms of their isotopic distribution of abundances [ 37 ]. Similar to the SIL-IS used for external calibrations, these SILs should resemble the analyte in both physical and chemical properties and must co-elute chromatographically.…”

Section: Recommendationsmentioning

confidence: 99%

See 2 more Smart Citations

Calibration Practices in Clinical Mass Spectrometry: Review and Recommendations

et al. 2022

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Background: Calibration is a critical component for the reliability, accuracy, and precision of mass spectrometry measurements. Optimal practice in the construction, evaluation, and implementation of a new calibration curve is often underappreciated. This systematic review examined how calibration practices are applied to liquid chromatography-tandem mass spectrometry measurement procedures.Methods: The electronic database PubMed was searched from the date of database inception to April 1, 2022. The search terms used were "calibration," "mass spectrometry," and "regression." Twenty-one articles were identified and included in this review, following evaluation of the titles, abstracts, full text, and reference lists of the search results.Results: The use of matrix-matched calibrators and stable isotope-labeled internal standards helps to mitigate the impact of matrix effects. A higher number of calibration standards or replicate measurements improves the mapping of the detector response and hence the accuracy and precision of the regression model. Constructing a calibration curve with each analytical batch recharacterizes the instrument detector but does not reduce the actual variability. The analytical response and measurand concentrations should be considered when constructing a calibration curve, along with subsequent use of quality controls to confirm assay performance. It is important to assess the linearity of the calibration curve by using actual experimental data and appropriate statistics. The heteroscedasticity of the calibration data should be investigated, and appropriate weighting should be applied during regression modeling.Conclusions: This review provides an outline and guidance for optimal calibration practices in clinical mass spectrometry laboratories.

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Section: Recommendationsmentioning

confidence: 99%

Section: Recommendationsmentioning

confidence: 99%

Section: Recommendationsmentioning

confidence: 99%

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Calibration Practices in Clinical Mass Spectrometry: Review and Recommendations

et al. 2022

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“…Plug-in methods by manufacturers are making the field more robust and increasing its accessibility, and best practice for sampling handling and storage is being addressed formally [68]. However to fully mine the rich multi-profile datasets, engagement with new methods of data handling are needed, for example isotope deconvolution analysis to improve calibration [69]. Harvesting the concept of the "steroid metabolomic profile" [70] requires multi-variate statistical analysis and machine learning has recently been explored to exciting effect in diagnostics of adrenal cancer [15].…”

Section: Data Complexity Validation and Community Standardsmentioning

confidence: 99%

Mass spectrometry: Future opportunities for profiling and imaging steroids and steroid metabolites

Andrew

Homer

2020

Current Opinion in Endocrine and Metabolic Research

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Steroid hormone profiling has historically underpinned advances in endocrine investigation and research, crucially dependent on selective and sensitive hormone assays. Mining the "steroidome" by mass spectrometry (MS) provides greater specificity than immunoassays. Building on a 50 year legacy, gas and liquid chromatography-MS continue to evolve (e.g. sequential derivatisation, mobile phase modifiers). Exciting new technology (e.g. imaging, ion mobility, supercritical fluid), sample preparation (microextraction, molecular imprinted polymers) are advancing the field. Automated analysis of wider profiles of steroids is within reach, in smaller and more varied sample types, including molecular mapping of tissue sections. These new analytical dimensions require rigorous validation and advanced statistics. This review highlights that MS continues to open new windows of biochemical understanding in endocrinology.

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“…To improve laboratory efficiency and make endogenous metabolites’ analysis more accessible and attractive in a clinical environment, alternative calibration methodologies have been proposed. The most recent strategies include reducing the number of calibrants or restricting internal calibration to a limited number of analytes. − …”

Section: Introductionmentioning

confidence: 99%

Multitargeted Internal Calibration for the Quantification of Chronic Kidney Disease-Related Endogenous Metabolites Using Liquid Chromatography–Mass Spectrometry

Visconti,

de Figueiredo,

Strassel

et al. 2023

Anal. Chem.

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Accurate quantitative analysis in liquid chromatography−mass spectrometry (LC−MS) benefits from calibration curves generated in the same matrix as the study sample. In the case of endogenous compound quantification, as no blank matrix exists, the multitargeted internal calibration (MTIC) is an attractive and straightforward approach to avoid the need for extensive matrix similarity evaluation. Its principle is to take advantage of stable isotope labeled (SIL) standards as internal calibrants to simultaneously quantify authentic analytes using a within sample calibration. An MTIC workflow was developed for the simultaneous quantification of metabolites related to chronic kidney disease (CKD) using a volumetric microsampling device to collect 20 μL of serum or plasma, followed by a single-step extraction with acetonitrile/water and liquid chromatography−tandem mass spectrometry (LC−MS/MS) analysis. Since a single concentration of internal calibrant is necessary to calculate the study sample concentration, the instrument response function was investigated to determine the best SIL concentration. After validation, the trueness of 16 endogenous analytes in authentic human serum ranged from 72.2 to 116.0%, the repeatability from 1.9 to 11.3%, and the intermediate precision ranged overall from 2.1 to 15.4%. The proposed approach was applied to plasma samples collected from healthy control participants and two patient groups diagnosed with CKD. Results confirmed substantial concentration differences between groups for several analytes, including indoxyl sulfate and cortisone, as well as metabolite enrichment in the kynurenine and indole pathways. Multitargeted methodologies represent a major step toward rapid and straightforward LC−MS/MS absolute quantification of endogenous biomarkers, which could change the paradigm of MS use in clinical laboratories.

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Comparison of isotope pattern deconvolution and calibration curve quantification methods for the determination of estrone and 17β-estradiol in human serum

Cited by 5 publications

References 24 publications

Calibration Practices in Clinical Mass Spectrometry: Review and Recommendations

Calibration Practices in Clinical Mass Spectrometry: Review and Recommendations

Mass spectrometry: Future opportunities for profiling and imaging steroids and steroid metabolites

Multitargeted Internal Calibration for the Quantification of Chronic Kidney Disease-Related Endogenous Metabolites Using Liquid Chromatography–Mass Spectrometry

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