A miniaturized electrospray interface consisting of a microfluidic nanosprayer and nanospray module is reported in the presented short communication. The nanosprayer was fabricated using silicon (Si) technology suitable for cost-efficient high-volume mass production. The nanospray module enabled the positioning of the nanosprayer in front of a mass spectrometry entrance and its coupling with capillary electrophoresis based on the liquid junction principle. A case study of top-down and bottom-up proteomic analyses of intact cytochrome c and its tryptic digest demonstrates the practical applicability of the developed interface.

• Klíčová slova
• capillary electrophoresis, electrospray ionization, mass spectrometry, microfabrication, proteomics,
• MeSH
• cytochromy c * analýza   chemie   MeSH
• design vybavení MeSH
• elektroforéza kapilární * metody   přístrojové vybavení   MeSH
• hmotnostní spektrometrie s elektrosprejovou ionizací * metody   přístrojové vybavení   MeSH
• miniaturizace * přístrojové vybavení   MeSH
• nanotechnologie * přístrojové vybavení   MeSH
• proteomika metody   MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• cytochromy c * MeSH

An HPLC method with UV and electrospray ionization - mass spectrometry (ESI-MS) detection was developed for the separation and determination of obeticholic acid (OBE) and its related compounds in development process and quality control. OBE and its related compounds were classified into three major group based on the mass spectra profiles: (A) those containing a hydroxyl group at position 3 and 7, (B) those containing a hydroxyl group and/or carbonyl group at position 3, hydrogen, ethyl or ethylidene group at position 6 and a hydroxyl group and/or carbonyl group at position 7, and (C) those containing carbonyl groups at position 3 and 7. ESI-MS ionization of OBE and its related compounds often produced intense adduct ions [M+H+98]+ and/or [M+H+196]+ that were identified as the adduct ions of phosphoric acid ([M+H+H3PO4]+ and [M+H+2H3PO4]+) originating from the mobile phase. The separation on HPLC system was accomplished using stationary phase based on XSelect CSH C18 (3.0×150mm×2.5μm) and a linear gradient elution using acetonitrile and 0.05% of o-phosphoric acid. The condition of chromatographic system was set as follows: flow rate 0.7mL/min, temperature 45°C and UV detection at 192nm. The separation of the 19 compounds was finished in less than 18min (including equilibration time). The HPLC/UV method was partially validated according to International Council for Harmonisation of Technical Requirements for Pharmaceuticals for Human Use (ICH) guidelines in terms of repeatability, selectivity, linearity and limit of quantification and detection.

• Klíčová slova
• LC separation, Mass adducts with phosphoric acid, Mass detection, Obeticholic acid,
• MeSH
• chemická frakcionace přístrojové vybavení   metody   MeSH
• chemie farmaceutická metody   MeSH
• hmotnostní spektrometrie s elektrosprejovou ionizací přístrojové vybavení   metody   MeSH
• kontaminace léku prevence a kontrola   MeSH
• kyselina chenodeoxycholová analogy a deriváty   analýza   chemie   MeSH
• limita detekce MeSH
• příprava léků přístrojové vybavení   metody   MeSH
• reprodukovatelnost výsledků MeSH
• řízení kvality * MeSH
• senzitivita a specificita MeSH
• spektrofotometrie ultrafialová přístrojové vybavení   metody   MeSH
• vysokoúčinná kapalinová chromatografie přístrojové vybavení   metody   MeSH
• Publikační typ
• časopisecké články MeSH
• validační studie MeSH
• Názvy látek
• kyselina chenodeoxycholová MeSH
• obeticholic acid MeSH Prohlížeč

This review focuses on the latest development of microseparation electromigration methods in capillaries and microfluidic devices coupled with MS for detection and identification of important analytes. It is a continuation of the review article on the same topic by Kleparnik (Electrophoresis 2015, 36, 159-178). A wide selection of 161 relevant articles covers the literature published from June 2014 till May 2016. New improvements in the instrumentation and methodology of MS interfaced with capillary or microfluidic versions of zone electrophoresis, isotachophoresis, and isoelectric focusing are described in detail. The most frequently implemented MS ionization methods include electrospray ionization, matrix-assisted desorption/ionization and inductively coupled plasma ionization. Although the main attention is paid to the development of instrumentation and methodology, representative examples illustrate also applications in the proteomics, glycomics, metabolomics, biomarker research, forensics, pharmacology, food analysis, and single-cell analysis. The combinations of MS with capillary versions of electrochromatography, and micellar electrokinetic chromatography are not included.

• Klíčová slova
• CE, Electrospray, MS, Microfluidic devices,
• MeSH
• analýza jednotlivých buněk metody   MeSH
• analýza potravin metody   MeSH
• biologické markery analýza   MeSH
• buněčné linie MeSH
• chromatografie metody   MeSH
• elektroforéza kapilární přístrojové vybavení   metody   MeSH
• glykomika MeSH
• hmotnostní spektrometrie s elektrosprejovou ionizací přístrojové vybavení   metody   MeSH
• hmotnostní spektrometrie metody   MeSH
• isoelektrická fokusace přístrojové vybavení   metody   MeSH
• laboratoř na čipu * MeSH
• lidé MeSH
• metabolomika metody   MeSH
• spektrometrie hmotnostní - ionizace laserem za účasti matrice přístrojové vybavení   metody   MeSH
• Check Tag
• lidé MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• přehledy MeSH
• Názvy látek
• biologické markery MeSH

We report a construction of a self-aligning subatmospheric hybrid liquid junction electrospray interface for CE eliminating the need for manual adjustment by guiding the capillaries in a microfabricated liquid junction glass chip at a defined angle. Both the ESI and separation capillaries are inserted into the microfabricated part until their ends touch. The distance between the capillary openings is defined by the angle between the capillaries. The microfabricated part contains channels for placement of the capillaries and connection of the external electrode reservoirs. It was fabricated using standard photolithographic/wet chemical etching techniques followed by thermal bonding. The liquid junction is connected to a subatmospheric electrospray chamber inducing the flow inside the ESI needle and helping the ion transport via aerodynamic focusing.

• Klíčová slova
• Capillary electrophoresis, Electrospray interfacing, Microfabrication,
• MeSH
• design vybavení MeSH
• dextrany MeSH
• elektroforéza kapilární přístrojové vybavení   MeSH
• hmotnostní spektrometrie s elektrosprejovou ionizací přístrojové vybavení   MeSH
• mikrofluidní analytické techniky přístrojové vybavení   MeSH
• peptidy MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• dextrany MeSH
• peptidy MeSH

The application of continuous flow-extractive desorption electrospray ionization (CF-EDESI), an ambient ionization source demonstrated previously for use with intact protein analysis, is expanded here for the coupling of reversed phase protein separations to mass spectrometry. This configuration allows the introduction of charging additives to enhance detection without affecting the chromatographic separation mechanism. Two demonstrations of the advantages of CF-EDESI are presented in this work. First, a proof-of- principle is presented to demonstrate the applicability of hyphenation of liquid chromatography (LC) to CF- EDESI. LC-CF-EDESI-MS has good sensitivity compared to LC-electrospray ionization (ESI)-mass spectrometry. Second, the supercharging mechanism investigated in CF-EDESI provides an insight into a highly debated supercharging process in ESI. The results indicate that the mechanism of protein charging seen in HPLC-CF-EDESI is different from supercharging phenomena in conventional ESI. The surface tension mechanism and binding mechanism may both contribute to protein supercharging in ESI.

• MeSH
• analýza selhání vybavení MeSH
• chromatografie s reverzní fází přístrojové vybavení   MeSH
• design vybavení MeSH
• hmotnostní spektrometrie s elektrosprejovou ionizací přístrojové vybavení   MeSH
• odběr biologického vzorku přístrojové vybavení   MeSH
• peptidové mapování přístrojové vybavení   MeSH
• proteiny analýza   chemie   MeSH
• statická elektřina MeSH
• vysokoúčinná kapalinová chromatografie přístrojové vybavení   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Research Support, U.S. Gov't, Non-P.H.S. MeSH
• Názvy látek
• proteiny MeSH

Capillary electrophoresis hyphenated with electrospray mass spectrometry (CE-ESI-MS) has emerged in the past decade as one of the most powerful bioanalytical techniques. As the sensitivity and efficiency of new CE-ESI-MS interface designs are continuously improving, numerical modeling can play important role during their development. In this review, different aspects of computer modeling and simulation of CE-ESI-MS interfaces are comprehensively discussed. Relevant essentials of hydrodynamics as well as state-of-the-art modeling techniques are critically evaluated. Sheath liquid-, sheathless-, and liquid-junction interfaces are reviewed from the viewpoint of multidisciplinary numerical modeling along with details of single and multiphase models together with electric field mediated flows, electrohydrodynamics, and free fluid-surface methods. Practical examples are given to help non-specialists to understand the basic principles and applications. Finally, alternative approaches like air amplifiers are also included. © 2014 Wiley Periodicals, Inc. Mass Spec Rev 34: 558-569, 2015.

• Klíčová slova
• CE-ESI-MS, CFD, interface design, modeling, simulation,
• MeSH
• algoritmy MeSH
• chemické modely MeSH
• elektroforéza kapilární přístrojové vybavení   metody   MeSH
• elektromagnetická pole MeSH
• hmotnostní spektrometrie s elektrosprejovou ionizací přístrojové vybavení   metody   MeSH
• hydrodynamika MeSH
• lidé MeSH
• počítačová simulace MeSH
• zvířata MeSH
• Check Tag
• lidé MeSH
• zvířata MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• přehledy MeSH

The capability of employing synthesized zwitterionic silica-based monolithic capillary columns (140 mm × 0.1mm) for separation of highly polar and hydrophilic nucleobases, nucleosides, and nucleotides in hydrophilic interaction chromatography is reported. The suitability of the columns for on-line conjunction with electrospray tandem mass spectrometry was explored. Our results show that the grafted layer of zwitterionic monomer ([2-(methacryloyloxy)ethyl]-dimethyl-(3-sulfopropyl)-ammonium hydroxide or 2-methacryloyloxyethyl phosphorylcholine) on the silica monolithic surface significantly improved the separation selectivity and reproducibility, as compared to the bare silica monolith. The stepwise elution from 90% to 70% of acetonitrile enabled separation of a complex sample mixture containing 21 compounds with a total analysis time less than 40 min.

• Klíčová slova
• ESI–MS, HILIC separation, Monolithic silica column, Nucleobase, Nucleoside, Nucleotide,
• MeSH
• hmotnostní spektrometrie s elektrosprejovou ionizací přístrojové vybavení   metody   MeSH
• hydrofobní a hydrofilní interakce MeSH
• nukleosidy chemie   izolace a purifikace   MeSH
• nukleotidy chemie   izolace a purifikace   MeSH
• oxid křemičitý chemie   MeSH
• povrchové vlastnosti MeSH
• reprodukovatelnost výsledků MeSH
• tandemová hmotnostní spektrometrie přístrojové vybavení   metody   MeSH
• vysokoúčinná kapalinová chromatografie metody   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• nukleosidy MeSH
• nukleotidy MeSH
• oxid křemičitý MeSH

DART (direct analysis in real time), a novel technique with wide potential for rapid screening analysis, coupled with high-resolution time-of-flight mass spectrometry (TOF-MS) has been used for quantitative analysis of 5-hydroxymethylfurfural (5-HMF), a typical temperature marker of food. The DART/TOF-MS method was optimised and validated. Quantification of 5-HMF was achieved by use of a stable isotope-labelled 5-HMF standard prepared from glucose. Formation of 5-HMF from saccharides, a potential source of overestimation of results, was evaluated. Forty-four real samples (honey and caramelised condensed sweetened milk) and 50 model samples of heated honey were analysed. The possibility of using DART for analysis of heated samples of honey was confirmed. HPLC and DART/TOF-MS methods for determination of 5-HMF were compared. The correlation equation between these methods was DART = 1.0287HPLC + 0.21340, R(2) = 0.9557. The DART/TOF-MS method has been proved to enable efficient and rapid determination of 5-HMF in a variety of food matrices, for example honey and caramel.

• MeSH
• 2-furaldehyd analogy a deriváty   analýza   MeSH
• analýza selhání vybavení MeSH
• design vybavení MeSH
• hmotnostní spektrometrie s elektrosprejovou ionizací přístrojové vybavení   metody   MeSH
• počítačové systémy MeSH
• reprodukovatelnost výsledků MeSH
• senzitivita a specificita MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• 2-furaldehyd MeSH
• 5-hydroxymethylfurfural MeSH Prohlížeč

A new method for the simultaneous separation of cocaine and four metabolites in urine by CE-ESI-MS via a pressurized nanoliquid junction interface was developed. The resolution of cocaine, cocaethylene, benzoylecgonine, norcocaine, and ecgonine methyl ester was achieved in a polyvinyl-alcohol-coated capillary with 75 μm id × 50 cm total length, using a 15 mM ammonium formate electrolyte solution (pH 9.5) in less than 15 min. In addition, to enhance sensitivity, a field-amplified sample injection (FASI) was evaluated in terms of injection time and sample solvent composition. The limits of detection achieved with the FASI method ranged from 1.5 to 10 ng/mL for all the compounds. The detection of the studied compounds was performed using an ion-trap mass spectrometer in a positive ionization mode. A mixture of methanol:water (80:20 v/v) containing 0.1% v/v of formic acid was employed as spray liquid and delivered at ~200 nL/min. Under optimal CE-MS conditions, linearity was assessed in the concentration range of interest for all analytes with correlation coefficients r² ≥ 0.9913. Intra- and inter-day precision provided a relative standard deviation lower than 1.54% for migration times and lower than 12.15% for peak areas. Finally, urine samples, spiked with the standard mixture, were extracted using a solid-phase extraction procedure and injected under FASI conditions, providing recoveries from 80% to 94% for all analytes.

• MeSH
• elektroforéza kapilární přístrojové vybavení   metody   MeSH
• hmotnostní spektrometrie s elektrosprejovou ionizací přístrojové vybavení   metody   MeSH
• kokain metabolismus   moč   MeSH
• koncentrace vodíkových iontů MeSH
• lidé MeSH
• nanotechnologie přístrojové vybavení   metody   MeSH
• reprodukovatelnost výsledků MeSH
• senzitivita a specificita MeSH
• Check Tag
• lidé MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• kokain MeSH

This review describes the current state of mass spectrometry imaging (MSI) in life sciences. A brief overview of mass spectrometry principles is presented followed by a thorough introduction to the MSI workflows, principles and areas of application. Three major desorption-ionization techniques used in MSI, namely, secondary ion mass spectrometry (SIMS), matrix-assisted laser desorption ionization (MALDI), and desorption electrospray ionization (DESI) are described, and biomedical and life science imaging applications of each ionization technique are reviewed. A separate section is devoted to data handling and current challenges and future perspectives are briefly discussed at the end.

• MeSH
• biologické vědy metody   MeSH
• biomedicínský výzkum metody   MeSH
• hmotnostní spektrometrie s elektrosprejovou ionizací přístrojové vybavení   metody   MeSH
• lidé MeSH
• spektrometrie hmotnostní - ionizace laserem za účasti matrice přístrojové vybavení   metody   MeSH
• spektrometrie hmotnostní sekundárních iontů přístrojové vybavení   metody   MeSH
• zvířata MeSH
• Check Tag
• lidé MeSH
• zvířata MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• přehledy MeSH