Direct analysis of complex samples is demonstrated by the at-line coupling of hollow fiber liquid-phase microextraction (HF-LPME) to capillary electrophoresis (CE). The hyphenation of the preparative and the analytical technique is achieved through a 3D-printed microextraction device with an HF located in a sample vial of a commercial CE instrument. The internal geometry of the device guides the CE separation capillary into the HF and the CE injection of the HF-LPME extract is performed directly from the HF lumen. The 3D-printing process ensures uniform dimensions of the devices, their constant position inside the sample vial, and excellent repeatability of the HF-LPME as well as the CE injection. The devices are cheap (∼0.01 €) and disposable, thus eliminating any possible sample-carryover, moreover, the at-line CE analysis of the extract is performed fully autonomously with no need for operator's intervention. The developed HF-LPME/CE-UV method is applied to the determination of acidic drugs in dried blood spot and wastewater samples and is characterized by excellent repeatability (RSD, 0.6-9.6%), linearity (r2, 0.9991-0.9999), enrichment (EF, 29-97), sensitivity (LOD, 0.2-3.4 μg/L), and sample throughput (7 samples/h). A further improvement of selected characteristics of the analytical method is achieved by the at-line coupling of HF-LPME to capillary isotachophoresis (ITP) with electrospray ionization-mass spectrometry (ESI-MS). The HF-LPME/ITP-ESI-MS system facilitates enhanced selectivity, matrix-free analytical signals, and up to 34-fold better sensitivity due to the use of ESI-MS detection and additional on-capillary ITP preconcentration of the HF-LPME extracts.
Electrophoretic focusing on an inverse electromigration dispersion (EMD) profile is based on a principle different from those of other electrophoretic separation methods. It has already proved its applicability in analytical practice by offering competitive separation performance and sensitivity and specific selectivity. It can be classified as an intermediate between field-driven and equilibrium gradient methods and is therefore interesting from the viewpoint of theory of separation methods. This work presents a comprehensive theoretical description of electrophoretic focusing on an inverse EMD profile comprising properties of the electrolyte system, formed gradients, and focused analyte zones. The separation properties are described in terms of resolution and peak capacity and their dependence on system and analyte properties is discussed from the viewpoint of how the counteracting phenomena of electromigration and dispersion are affected by electric current, voltage, and hydrodynamic and electroosmotic flow. The overall performance of the present method is shown to be comparable with other electrophoretic separation methods like zone electrophoresis or isoelectric focusing.
This work extends the present working range of isotachophoresis (ITP) with electrospray-ionization mass-spectrometric (ESI-MS) detection and describes for the first time a functional cationic electrolyte system for analyses at medium-alkaline pH. So far no ITP-MS application was published on the analysis of medium strong bases although there is a broad spectrum of potential analytes like biogenic amines, alkaloids or drugs, where this technique promises interesting gains in both sensitivity and specificity. The presented results include a selection of suitable sufficiently volatile ESI-compatible system components, discussion of factors affecting system properties, and recommendations for functional ITP electrolyte systems. Theoretical conclusions based on calculations and computer simulations are confirmed by experiments with a model mixture of beta-blockers. Practical applicability of the method is demonstrated on the example of analysis of sotalol in dried blood spots where direct injection of aqueous extract, ITP stacking and MS detection provide a fast, simple and sensitive technique with limits of quantitation on the sub-nM level.
Chiral ITP of the weak base methadone using inverse cationic configurations with H+ as leading component and multiple isomer sulfated β-CD (S-β-CD) as leading electrolyte (LE) additive, has been studied utilizing dynamic computer simulation, a calculation model based on steady-state values of the ITP zones, and capillary ITP. By varying the amount of acidic S-β-CD in the LE composed of 3-morpholino-2-hydroxypropanesulfonic acid and the chiral selector, and employing glycylglycine as terminating electrolyte (TE), inverse cationic ITP provides systems in which either both enantiomers, only the enantiomer with weaker complexation, or none of the two enantiomers form cationic ITP zones. For the configuration studied, the data reveal that only S-methadone migrates isotachophoretically when the S-β-CD concentration in the LE is between about 0.484 and 1.113 mM. Under these conditions, R-methadone migrates zone electrophoretically in the TE. An S-β-CD concentration between about 0.070 and 0.484 mM results in both S- and R-methadone forming ITP zones. With >1.113 mM and < about 0.050 mM of S-β-CD in the LE both enantiomers are migrating within the TE and LE, respectively. Chiral inverse cationic ITP with acidic S-β-CD in the LE is demonstrated to permit selective ITP trapping and concentration of the less interacting enantiomer of a weak base.
Electrophoretic sample stacking comprises a group of capillary electrophoretic techniques where trace analytes from the sample are concentrated into a short zone (stack). This paper is a continuation of our previous reviews on the topic and brings a survey of more than 120 papers published approximately since the second quarter of 2016 till the first quarter of 2018. It is organized according to the particular stacking principles and includes chapters on concentration adjustment (Kohlrausch) stacking, on stacking techniques based on pH changes, on stacking in electrokinetic chromatography and on other stacking techniques. Where available, explicit information is given about the procedure, electrolyte(s) used, detector employed and sensitivity reached. Not reviewed are papers on transient isotachophoresis which are covered by another review in this issue.
This review brings a survey of studies on analytical ITP published since 2016 until the first quarter of 2018 and includes chapters about theory and principles, instrumentation and techniques, and analytical applications of ITP. It shows the position of analytical ITP among contemporary separation techniques, where particularly its unique concentrating capabilities keep the interest to include it into novel high-sensitivity analytical procedures. The reviewed papers are considered according to their nature, techniques used, and instrumentation employed. The significance of electrolyte system composition is emphasized by providing explicit values where possible.
- MeSH
- biologické markery analýza MeSH
- elektroforéza kapilární * MeSH
- izotachoforéza * MeSH
- lidé MeSH
- myši MeSH
- zvířata MeSH
- Check Tag
- lidé MeSH
- myši MeSH
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- přehledy MeSH
Electrophoretic focusing on inverse electromigration dispersion (EMD) gradient is a new analytical technique based on a unique separation principle where weak non-amphoteric ionogenic species are focused, separated and transported to the detector by an EMD profile of suitable properties. The present work extends the theoretical description of this method by introducing the concept of resolution and deriving the fundamental equation expressing resolution as function of basic system parameters. The results indicate that at constant current operation, resolution is proportional to the square root of time. For variable current regimes (e.g. constant voltage), the time variable is replaced by the product of electric current and passed electric charge. Computer simulations for a model pair of substances support the validity of the presented theory and confirm the theoretical conclusion that resolution can be increased by allowing longer electromigration of the gradient in terms of time or passed charge. The experimental example shown comprises an anionic electrolyte system based on maleic acid and 2,6-lutidine, combined with ESI-MS detection and operated in the reverse mode due to strong electroosmotic flow and ESI suction. The practical implementation of the proposed methodology is done by application of negative pressure at the inlet vial, resulting in very substantial resolution enhancement and baseline separation of otherwise unresolved substances. The performance and high sensitivity of the developed technique is demonstrated on the example of simultaneous analysis of four sulfonamides and three dichlorophenols in waters with limits of detection on the 1 nM level.
- MeSH
- chlorfenoly analýza MeSH
- elektroforéza kapilární MeSH
- elektrolyty chemie MeSH
- hmotnostní spektrometrie s elektrosprejovou ionizací * MeSH
- limita detekce MeSH
- maleáty chemie MeSH
- pitná voda analýza MeSH
- pyridiny chemie MeSH
- sulfonamidy analýza MeSH
- tlak MeSH
- Publikační typ
- časopisecké články MeSH
The term "sample stacking" comprises a relatively broad spectrum of techniques that already form an almost inherent part of the methodology of CZE. Their principles are different but the effect is the same: concentration of a diluted analyte into a narrow zone and considerable increase of the method sensitivity. This review brings a survey of papers on electrophoretic sample stacking published approximately since the second quarter of 2014 till the first quarter of 2016. It is organized according to the principles of the stacking methods and includes chapters aimed at the concentration adjustment principle (Kohlrausch stacking), techniques based on pH changes, micellar methods, and other stacking techniques. Not reviewed are papers on transient ITP that are covered by another review in this issue.
- MeSH
- analýza potravin MeSH
- anorganické látky analýza krev moč MeSH
- biologické markery analýza MeSH
- elektroforéza kapilární metody MeSH
- extrakce kapalina-kapalina metody MeSH
- koncentrace vodíkových iontů MeSH
- lidé MeSH
- micely MeSH
- nukleosidy analýza MeSH
- organické látky antagonisté a inhibitory krev moč MeSH
- Check Tag
- lidé MeSH
- Publikační typ
- časopisecké články MeSH
- přehledy MeSH
This review brings a survey of papers on analytical ITP published since 2014 until the first quarter of 2016. The 50th anniversary of ITP as a modern analytical method offers the opportunity to present a brief view on its beginnings and to discuss the present state of the art from the viewpoint of the history of its development. Reviewed papers from the field of theory and principles confirm the continuing importance of computer simulations in the discovery of new and unexpected phenomena. The strongly developing field of instrumentation and techniques shows novel channel methodologies including use of porous media and new on-chip assays, where ITP is often included in a preseparative or even preparative function. A number of new analytical applications are reported, with ITP appearing almost exclusively in combination with other principles and methods.
- MeSH
- anorganické látky analýza MeSH
- elektroforéza kapilární * přístrojové vybavení metody MeSH
- izotachoforéza * přístrojové vybavení metody MeSH
- mikročipové analytické postupy MeSH
- nanočástice analýza MeSH
- organické látky analýza MeSH
- počítačová simulace MeSH
- povrchové vlastnosti MeSH
- Publikační typ
- časopisecké články MeSH
- přehledy MeSH
Capillary isotachophoresis (ITP) is an electrophoretic technique offering high sensitivity due to permanent stacking of the migrating analytes. Its combination with electrospray-ionization mass-spectrometric (ESI-MS) detection is limited by the narrow spectrum of ESI-compatible components but can be compensated by experienced system architecture. This work describes a methodology for sensitive analysis of hydroxyderivatives of s-triazine herbicides, based on implementation of the concepts of moving-boundary isotachophoresis and of H+ as essential terminating component into cationic ITP with ESI-MS detection. Theoretical description of such kind of system is given and equations for zone-related boundary mobilities are derived, resulting in a much more general definition of the effective mobility of the terminating H+ zone than used so far. Explicit equations allowing direct calculation for selected simple systems are derived. The presented theory allows prediction of stacking properties of particular systems and easy selection of suitable electrolyte setups. A simple ESI-compatible system composed of acetic acid and ammonium with H+ and ammonium as a mixed terminator was selected for the analysis of 2-hydroxyatrazine and 2-hydroxyterbutylazine, degradation products of s-triazine herbicides. The proposed method was tested with direct injection without any sample pretreatment and provided excellent linearity and high sensitivity with limits of detection below 100ng/L (0.5nM). Example analyses of unspiked and spiked drinking and river water are shown.
- MeSH
- atrazin analogy a deriváty analýza chemie MeSH
- elektrolyty chemie MeSH
- herbicidy analýza chemie MeSH
- hmotnostní spektrometrie s elektrosprejovou ionizací * MeSH
- izotachoforéza * MeSH
- látky znečišťující životní prostředí analýza MeSH
- sladká voda chemie MeSH
- voda chemie MeSH
- Publikační typ
- časopisecké články MeSH
