Challenges and applications of isotachophoresis coupled to mass spectrometry: A review

Melzer, Tanja; Wimmer, Benedikt; Bock, Stephanie; Posch, Tjorben Nils; Hühn, Carolin

doi:10.1002/elps.201900454

Cited by 14 publications

(9 citation statements)

References 89 publications

(212 reference statements)

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“…As demonstrated in reviews and articles dealing with recent developments of capillary and microchip ITP [104][105][106], this CE method is much more often used for the determination of small ions, for example, counterions or ionic admixtures of peptides [107,108] than for analyses of peptides themselves. However, ITP or t-ITP are frequently applied as preconcentration and/or preseparation steps [61,67,72,109] prior to CE analysis of cationic or anionic analytes including peptides present at low concentrations and/or in complex mixtures.…”

Section: Isotachophoresismentioning

confidence: 99%

Recent developments in capillary and microchip electroseparations of peptides (2019–mid 2021)

Kašička

2021

Electrophoresis

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The review provides a comprehensive overview of developments and applications of high performance capillary and microchip electroseparation methods (zone electrophoresis, isotachophoresis, isoelectric focusing, affinity electrophoresis, electrokinetic chromatography, and electrochromatography) for analysis, microscale isolation, and physicochemical characterization of peptides from 2019 up to approximately the middle of 2021. Advances in the investigation of electromigration properties of peptides and in the methodology of their analysis, such as sample preparation, sorption suppression, EOF control, and detection, are presented. New developments in the individual CE and CEC methods are demonstrated and several types of their applications are shown. They include qualitative and quantitative analysis, determination in complex biomatrices, monitoring of chemical and enzymatic reactions and physicochemical changes, amino acid, sequence, and chiral analyses, and peptide mapping of proteins. In addition, micropreparative separations and determination of significant physicochemical parameters of peptides by CE and CEC methods are described.

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Section: Isotachophoresismentioning

confidence: 99%

Recent developments in capillary and microchip electroseparations of peptides (2019–mid 2021)

Kašička

2021

Electrophoresis

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“…In beer samples, the most critical macrocomponent was phosphate (phosphorous content in beer in the range of 0.3-15 mmol/L [86]). Using disodium phosphate at a concentration of 75-100 mM for GLP extraction from soil, the transient ITP did not fully resolve and GLP was detected in the isotachophoretic stack (data shown elsewhere [82]). At the highest injection volume, poor resolution between GLP and phosphate led to quenching of the GLP signal; poor resolution between GLP and a near isobaric matrix compound (m/z 167.996) impaired accurate quantification (see ESM Fig.…”

Section: Online Preconcentrationmentioning

confidence: 97%

Capillary electrophoresis-mass spectrometry for the direct analysis of glyphosate: method development and application to beer beverages and environmental studies

et al. 2020

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In this study, we developed and validated a CE-TOF-MS method for the quantification of glyphosate (N-(phosphonomethyl)glycine) and its major degradation product aminomethylphosphonic acid (AMPA) in different samples including beer, media from toxicological analysis with Daphnia magna, and sorption experiments. Using a background electrolyte (BGE) of very low pH, where glyphosate is still negatively charged but many matrix components become neutral or protonated, a very high separation selectivity was reached. The presence of inorganic salts in the sample was advantageous with regard to preconcentration via transient isotachophoresis. The advantages of our new method are the following: no derivatization is needed, high separation selectivity and thus matrix tolerance, speed of analysis, limits of detection suitable for many applications in food and environmental science, negligible disturbance by metal chelation. LODs for glyphosate were < 5 μg/L for both aqueous and beer samples, the linear range in aqueous samples was 5-3000 μg/L, for beer samples 10-3000 μg/L. For AMPA, LODs were 3.3 and 30.6 μg/L, and the linear range 10-3000 μg/L and 50-3000 μg/L, for aqueous and beer samples, respectively. Recoveries in beer samples for glyphosate were 94.3-110.7% and for AMPA 80.2-100.4%. We analyzed 12 German and 2 Danish beer samples. Quantification of glyphosate and AMPA was possible using isotopically labeled standards without enrichment, purification, or dilution, only degassing and filtration were required for sample preparation. Finally, we demonstrate the applicability of the method for other strong acids, relevant in food and environmental sciences such as N-acetyl glyphosate, Nacetyl AMPA (present in some glyphosate resistant crop), trifluoroacetic acid, 2-methyl-4-chlorophenoxyacetic acid, glufosinate and its degradation product 3-(methylphosphinico)propionic acid, oxamic acid, and others.

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“…The display data were smoothed by a tenpoint moving average function. For maximum insight into the separation process, three optional openC 4 Ds were used [51], which were named according to the capillary ends, compare It was used to detect counterions possibly migrating into the BGE from the sheath liquid changing its composition [52] or a possible counter-ITP migrating from the MS to the chip interface [53]. Further details can be found in Section S4.…”

Section: Detection Setupmentioning

confidence: 99%

Picomolar detection limits for glyphosate by two‐dimensional column‐coupled isotachophoresis/capillary zone electrophoresis‐mass spectrometry

Graf

Rudisch

Ude

et al. 2022

J of Separation Science

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Capillary electrophoresis‐mass spectrometry often lacks sufficient limits of detection for trace substances in the environment due to its low loadability. To overcome this problem, we conducted a feasibility study for column‐coupling isotachophoresis to capillary electrophoresis‐mass spectrometry. The first dimension isotachophoresis preconcentrated the analytes. The column‐coupling of both dimensions was achieved by a hybrid capillary microfluidic chip setup. Reliable analyte transfer by voltage switching was enabled by an in‐chip capacitively coupled contactless conductivity detector placed around the channel of the common section between two T‐shaped crossings in the chip connecting both dimensions. This eliminated the need to calculate the moment of analyte transfer. A commercial capillary electrophoresis‐mass spectrometry instrument with easily installable adaptations operated the setup. Prior to coupling isotachophoresis with capillary zone electrophoresis‐mass spectrometry, both dimensions were optimized individually by simulations and verified experimentally. Both dimensions were able to stack/separate all degradation products of glyphosate, the most important herbicide applied worldwide. The first dimension isotachophoresis also removed phosphate, which is a critical matrix component in many environmental samples. Enrichment and separation of glyphosate and its main degradation product aminomethylphosphonic acid by the two‐dimensional setup provided an excellent limit of detection of 150 pM (25 ng/L) for glyphosate.

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Challenges and applications of isotachophoresis coupled to mass spectrometry: A review

Cited by 14 publications

References 89 publications

Recent developments in capillary and microchip electroseparations of peptides (2019–mid 2021)

Recent developments in capillary and microchip electroseparations of peptides (2019–mid 2021)

Capillary electrophoresis-mass spectrometry for the direct analysis of glyphosate: method development and application to beer beverages and environmental studies

Picomolar detection limits for glyphosate by two‐dimensional column‐coupled isotachophoresis/capillary zone electrophoresis‐mass spectrometry

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