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At least 109 records · Page 6Linked to original sources

Capillary electrophoresis--electrospray ionization--mass spectrometry for the characterization of natural organic matter: an evaluation with free flow electrophoresis-off-line flow injection electrospray ionization-mass spectrometry.

The separation of Suwannee River natural organic matter (NOM) with capillary zone electrophoresis hyphenated to electrospray ionization-mass spectrometry (CZE-ESI-MS) is presented. The obtained electropherograms and signal distributions are comparable to the mobility distributions obtained with more classical UV detection. A direct comparison of the results was possible with free-flow electrophoresis (FFE), which allows an upscaling of the CZE method and the analysis of the collected fractions in an off-line modus with flow-injection electrospray ionization-mass spectrometry (FI-ESI-MS). The changes of the m/z distributions with mobility are very similar with both methods and show a decrease of the m/z with increasing electrophoretic mobility in the humic hump at alkaline pH; superimposed on this hump a low-molecular-weight fraction migrates at lower mobility. The analysis of benzene carboxylic acids, glycerrhycic acid as well as oligomers of polystyrene sulfonic acid and polyacrylic acid additionally illustrates possible fragmentation, formation of adducts and multiplicity of the charges of the molecules prior to MS detection. These hardly controllable difficulties add a challenge to the interpretation of the obtained m/z distributions of NOM in terms of charge and mass distributions of molecules present in the NOM mixture.

Acrylic Resins↗

Photoelectron resonance capture ionization mass spectrometry: a soft ionization source for mass spectrometry of particle-phase organic compounds.

Photoelectron resonance capture ionization (PERCI) is a soft and sensitive ionization method, based on the attachment of low-energy (<1 eV) photoelectrons to organic analyte molecules. PERCI has been developed in our laboratory for the real-time analysis of organic particles by mass spectrometry, and is employed here to monitor the heterogeneous reaction of ozone with oleic acid. Simplified identification of the reaction products is possible as a result of the soft nature of PERCI, giving predominantly the [M--H](-) ions. The major particle-phase products are identified as: 1-nonanal, nonanoic acid, 9-oxononanoic acid, and azelaic acid, consistent with proposed mechanisms. New insight into this well-studied heterogeneous reaction is gained as additional minor particle-phase products, consistent with the Criegee mechanism, are readily detected.

Electrons↗

Quantitative determination of polar and ionic compounds in petroleum fractions by atmospheric pressure chemical ionization and electrospray ionization mass spectrometry.

The capabilities of atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI) methods for quantitative analysis of polar and ionic compounds in petroleum fractions have been examined. The requirements of the analysis for sensitivity, linear dynamic range, and structural characterization have been discussed. ESI was found to be approximately two orders of magnitude more sensitive than APCI and is most suitable for the detection of analytes in weak concentrations. Equivalent relative linear dynamic ranges were observed by the two methods (at least three orders of magnitude). For the relatively high analyte concentrations examined here (e.g., 1-100 ppm or higher), the absolute area counts increased linearly with the analyte amount only in APCI, making this method more attractive for quantitative liquid chromatography/mass spectrometry (LC/MS) applications. Nevertheless, a wider range of ionic compounds can be detected by ESI than by APCI.

Air Pressure↗

Mass probe-assisted ionization method for total analysis of biomolecules with electrospray ionization-mass spectrometry.

In this paper, we review the mass probes used for the derivation of a variety of biomolecules efficiently detected by the electrospray ionization-mass spectrometry and mass probe-assisted ionization method for total analysis and determination by consecutive detection with a single instrument. We describe mass probes for a variety of molecules including proteins, nucleobases, metallic cations, and other small molecules.

Metals↗

Artifact-free quantification of free 3-chlorotyrosine, 3-bromotyrosine, and 3-nitrotyrosine in human plasma by electron capture-negative chemical ionization gas chromatography mass spectrometry and liquid chromatography-electrospray ionization tandem mass spectrometry.

Halogenation and nitration of biomolecules have been proposed as key mechanisms of host defense against bacteria, fungi, and viruses. Reactive oxidants also have the potential to damage host tissue, and they have been implicated in disease. In the current studies, we describe specific, sensitive, and quantitative methods for detecting three stable markers of oxidative damage: 3-chlorotyrosine, 3-bromotyrosine, and 3-nitrotyrosine. Our results indicate that electron capture-negative chemical ionization-gas chromatography/mass spectrometry (EC-NCI GC/MS) is 100-fold more sensitive than liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-MS/MS) for analyzing authentic 3-chlorotyrosine, 3-bromotyrosine, and 3-nitrotyrosine. Using an isotopomer of tyrosine to evaluate artifactual production of the analytes during sample preparation and analysis, we found that artifact generation was negligible with either technique. However, LC-MS/MS proved cumbersome for analyzing multiple samples because it required 1.5 h of run and equilibration time per analysis. In contrast, EC-NCI GC/MS required only 5 min of run time per analysis. Using EC-NCI GC/MS, we were able to detect and quantify attomole levels of free 3-chlorotyrosine, 3-bromotyrosine, and 3-nitrotyrosine in human plasma. Our results indicate that EC-NCI GC/MS is a sensitive and specific method for quantifying free 3-chlorotyrosine, 3-bromotyrosine, and 3-nitrotyrosine in biological fluids in a single, rapid analysis and that it avoids generating any of the analytes ex vivo.

Artifacts↗

Application of high-performance liquid chromatograph-electrospray ionization mass spectrometry and matrix-assisted laser-desorption ionization time-of-flight mass spectrometry in combination with selective enzymatic modifications in the characterization of glycosylation patterns in single-chain plasminogen activator.

The application of high-performance liquid chromatography (HPLC), electrospray ionization mass spectrometry (ESI-MS) and matrix-assisted laser-desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and selective enzymatic deglycosylation treatments is demonstrated in the analysis of glycosylation patterns in recombinant Desmodus salivary plasminogen activator, a heterogeneous glycoprotein. The sample was initially digested with a proteolytic enzyme (endoproteinase Lys-C) and then further treated with either PNGase F to remove N-linked carbohydrates or a combination of neuraminidase and O-glycosidase to remove sialic acid and O-linked carbohydrates. By comparison of the LC-ESI-MS peptide maps for the fully glycosylated and deglycosylated samples, it was possible to unambiguously identify the sites of N-linked glycosylation as well a number of N-linked glycopeptides. The O-link glycopeptides, which are present at low level ( < 1%), were not detected prior to the deglycosylation, nor could changes in peptide elution in the map following deglycosylation be correlated with potential O-linked glycosylation sites.

Amidohydrolases↗

Electrospray ionization and matrix-assisted laser desorption ionization mass spectrometry. Emerging technologies in biomedical sciences.

Tremendous progress in biomedical sciences has been made possible in part by recent advances in bioanalytical methods, in particular biological mass spectrometry. Since the introduction of electrospray ionization mass spectrometry (ESI-MS) in 1984 and matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) in 1988, the field of bioanalytical mass spectrometry has seen rapid growth. In concert with separation techniques such as capillary electrophoresis and high performance liquid chromatography, mass spectrometry allows characterization of a large array of small organic molecules, peptides, proteins, oligonucleotides, and RNA fragments. Thus, substantially more expedient and definitive determination of molecular weight is now possible by mass spectrometric analysis. In this commentary, general descriptions of ESI- and MALDI-MS are presented. Furthermore, several recent developments and applications in addressing difficult biological problems are discussed.

Forecasting↗

Identification of nitrate ester explosives by liquid chromatography-electrospray ionization and atmospheric pressure chemical ionization mass spectrometry.

Liquid chromatography-mass spectrometry (LC-MS) with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI), in the negative-ion mode, was investigated for the analyses of three widely used nitrate ester explosives, pentaerythritol tetranitrate, nitroglycerin and ethylene glycol dinitrate, as well as six additional nitrate esters, using post-column additives. In ESI, ammonium nitrate, sodium nitrite, propionic acid and ammonium chloride promoted formation of characteristic adduct ions of the respective nitrate esters. In APCI, chlorinated agents, dichloromethane, chloroform, carbon tetrachloride and ammonium chloride, were employed, fanning chloride attachment adduct ions. Three forensic samples, Booster DYNO, Semtex and Smokeless Powder, were analyzed to demonstrate the validity of the developed LC-MS methods.

Atmospheric Pressure↗

Fast C18 solid-phase desalting/delipidation of the human serum apolipoproteins for matrix-assisted laser desorption ionization and electrospray ionization mass spectrometric analysis.

A new method for the delipidation of human serum lipoproteins involving the use of a reversed-phase C18 solid-phase extraction (SPE) cartridge is introduced for use with matrix-assisted laser desorption ionization and electrospray ionization mass spectrometry. This method is compared with two other methods of lipoprotein delipidation. The SPE method of delipidation produces a higher and more reproducible protein yield than the conventional liquid-liquid methanol-diethyl ether delipidation technique. Furthermore, the SPE method implements a fast, sequential, desalting and delipidation of the lipoproteins for subsequent mass spectrometric analysis providing high quality spectra.

Apolipoproteins↗

Application of self-ionization for enhancing stereochemical and positional effects from arylglycosides under electron ionization conditions in an ion trap mass spectrometer.

Ion trap mass spectrometry has been used to structurally characterize and differentiate positional and stereo isomers of arylglycosides having potential antioxidant properties. The use of the self-ionization (SI) technique has allowed to evidence a strong reactivity of fragment ions produced from dissociations of the molecular ion towards the molecules introduced into the trap. Specific structural effects due to positional isomers and anomers have been also envisaged through the occurrence of bimolecular processes inside the ion trap analyzer. Under self-ionization conditions, even-electron ions are produced. The charge is retained on the sugar moiety, in agreement with its proton affinity higher than that of the substituted phenol moiety. Most of the fragmentation pathways involve elimination of acetic acid that protects the hydroxylic groups of the glycoside. SI also produces adduct ions, likely as covalent species, having higher m/z values than the molecular ion. The reaction site is mainly the double bond present in the pyranosidic ring. Even if some fragment ions have lost the initial stereochemistry, their formation can be related to the structure of the parent neutrals introduced into the cell. Collision-induced dissociation (CID) experiments, carried out on ions formed by ion-molecule reactions, have allowed to obtain further information on gas phase ion structures. The study of mass-selected ion-molecule reactions and their kinetics have evidenced a spectacularly different reactivity of the ion at m/z 111 towards the two anomers 2alpha and 2beta, with the latter showing a much more pronounced reactivity. The approach developed in this work revealed to be an useful tool in structural characterization, as well as in stereo and regiochemical differentiation of arylglycosides.

Alkylation↗

Characterization of phosphoantigens by high-performance anion-exchange chromatography-electrospray ionization ion trap mass spectrometry and nanoelectrospray ionization ion trap mass spectrometry.

New phosphorylated microbial metabolites referred to as phosphoantigens activate immune responses in humans. Although these molecules have leading applications in medical research, no direct method allows their rapid and unambiguous structural identification. Here, we interfaced online HPAEC (high performance anion-exchange chromatography) with ESI-ITMS (electrospray ionization ion trap mass spectrometry) to identify such pyrophosphorylated molecules. A self-regenerating anion suppressor located upstream of electrospray ionization enabled the simultaneous detection of pyrophosphoester by conductimetry, UV and MS. By HPAEC-ITMS and HPAEC-ITMS2, a single run permitted characterization of reference phosphoantigens and of related structures. Although all compounds were resolved by HPAEC, MS enabled their detection and identification by [M-H]- and fragment ions. Isobaric phosphoantigen analogues were also separated by HPAEC and distinguished by MS2. The relevance of this device was demonstrated for phosphoantigens analysis in human urine and plasma. Furthermore, identification of natural phosphoantigens by automatically generated 2D mass spectra from nano-ESI-ITMS is presented. This last technique permits the simultaneous performance of molecular screening of natural phosphoantigen extracts and their identification.

Antigens↗

Comparison of atmospheric pressure photoionization, atmospheric pressure chemical ionization, and electrospray ionization mass spectrometry for analysis of lipids.

In this work, we compare the quantitative accuracy and sensitivity of analyzing lipids by atmospheric pressure photoionization (APPI), atmospheric pressure chemical ionization (APCI), and electrospray ionization (ESI) LC/MS. The target analytes include free fatty acids and their esters, monoglyceride, diglyceride, and triglyceride. The results demonstrate the benefits of using LC/APPI-MS for lipid analysis. Analyses were performed on a Waters ZQ LC/MS. Normal-phase solvent systems were used due to low solubility of these compounds in aqueous reversed-phase solvent systems. By comparison, APPI offers lower detection limits, generally highest signal intensities, and the highest S/N ratio. APPI is 2-4 times more sensitive than APCI and much more sensitive than ESI without mobile-phase modifiers. APPI and APCI offer comparable linear range (i.e., 4-5 decades). ESI sensitivity is dramatically enhanced by use of mobile phase modifiers (i.e., ammonium formate or sodium acetate); however, these ESI adduct signals are less stable and either are nonlinear or have dramatically reduced linear ranges. Analysis of fish oils by APPI shows significantly enhanced target analyte intensities in comparison with APCI and ESI.

Atmospheric Pressure↗

Analysis of bitter limonoids in citrus juices by atmospheric pressure chemical ionization and electrospray ionization liquid chromatography-mass spectrometry.

Improved analytical techniques for bitter limonoids in citrus and citrus juices can expedite the evaluation of freeze-induced citrus damage for citrus growers and juice quality for citrus juice producers. Microbore normal-phase and reverse-phase chromatography coupled to a mass spectrometer operating in a positive ion atmospheric pressure chemical ionization and electrospray ionization modes were found to be rapid, selective, and sensitive methods for the analysis of the bitter limonoids limonin and nomilin in citrus juices. Analysis was performed on a chloroform extract of citrus juice to which an internal standard was added. The methods are capable of detecting citrus limonoids in citrus juice in the 60-200 picogram range and quantifying citrus juice limonoids in concentrations as low as 120 picograms. An accurate "total limonoid bitterness" in citrus juice, as represented by the combined occurrence of limonin and nomilin, is easily determined by these methods.

Atmospheric Pressure↗

Adverse cutaneous effects of ionizing and non-ionizing electromagnetic radiation.

Modern man is constantly exposed to many forms of electromagnetic radiation, both ionizing and non-ionizing. Although many uses of electromagnetic radiation artfully administered serve man well, injudicious exposure carries a potential for harm. Various types of electromagnetic radiation and possible hazards from them are discussed.

Aircraft↗

Ionization collection efficiencies of some ionization chambers in pulsed and continuous radiation beams.

The most commonly used method of calibrating high-energy photon or electron beams consists in converting cavity ionization to dose by the application of the appropriate Clambda or CE multipled by the 60Co correction factor. The correct interpretation of calibration data for pulsed photon or electron beams requires a knowledge of the charge collection efficiencies of the ionization chambers used. The results are presented of efficiency measurements for both pulsed and continuous beams made with these chambers: 0.6-cm3 Farmer, 0.5-cm3 Spokas, 3-cm3 Shonka, 1-cm3 PTW, and 1-cm3 Memorial pancake. The dependence of collection efficiency on collection voltage, dose rate, and dose per pulse is demonstrated. These results are shown to agree with Boag's formulas for collection efficiency. Attention is drawn to the fact that several kinds of dosimeters provide only minimal collection voltages for efficient collection of charge at high dose rates, especially in Linac electron beams. It is recommended to check the collection efficiency of chambers which are to be used at high dose rates, and a simple method for this purpose is described.

Cobalt Radioisotopes↗

Measurement of inclusion complex formation between cyclophane and biological relevant amino acids using electrospray ionization, cold-spray ionization and fast atom bombardment mass spectrometry.

The investigation of the host-guest complex formations between cyclophane (TGDMAP) (1) as a host and L-acidic amino acids such as L-glutamic acid (Glu) and L-aspartic acid (Asp) as guests was carried out using fast atom bombardment (FAB), electrospray ionization (ESI) and cold-spray ionization (CSI) mass spectrometry (MS). The stability constant (K(s)) values obtained by the three different MS methods almost agreed. However, the complex ion peaks of a novel cyclophane (CPCn) (2) with Glu and Asp were not observed in FAB-MS. Then, these host-guest complex formations by use of CSI-MS and ESI-MS was examined, as the results, these complex ion peaks were observed clearly and the measurement values by the two MS methods are mostly in agreement. It was concluded that ESI-MS and CSI-MS are available for the determination of K(s) value as well as FAB-MS.

Amino Acids↗

Chiral and isomeric analysis by electrospray ionization and sonic spray ionization using the fixed-ligand kinetic method.

The fixed-ligand version of the kinetic method has been used for chiral and for isomeric analysis by studying the dissociation kinetics of transition metal-bound trimeric cluster ions ([(M(II) + L(fixed)-H)(ref*)(An)](+), where M(II) is a transition metal, L fixed is a fixed (non-dissociating) ligand, ref* is a reference ligand and An is the analyte. The trimeric cluster ions are readily generated by electrospray ionization (ESI) or sonic spray ionization (SSI). The size of the fixed ligand, L- Phe-Gly-L-P he-Gly, is chosen based on previous results but with the inclusion of aromatic functionality to increase chiral recognition. Improved chiral/isomeric differentiation results from enhanced chiral/isomeric interactions (metal-ligand and ligand-ligand) due to the fixed ligand. As shown in the cases of chiral dipeptides (D-Ala-D-Ala/L-Ala-L-Ala), sugars (D/L-glucose, D/L-mannose) and isomeric tetrapeptides (L-Ala-Gly-Gly-Gly/Gly-Gly -Gly-L-Ala), improved chiral/isomeric discrimination by factors from three to six were obtained by the fixed ligand procedure. Chiral recognition is independent of the concentrations of the analyte, the reference ligand, the fixed ligand and the transition metal salt, a great advantage for practical applications. In addition to increased chiral distinction, the simplified dissociation kinetics also contribute to improved accuracy in chiral quantification, in comparison with data obtained by investigating the dissociation kinetics of simple trimeric cluster ions [M(II)(ref*)2(An) H](+). Accurate determination of enantiomeric excess (ee) is demonstrated by enantiomeric quantification of D-Ala-D-Ala/L-Ala-L-Ala down to 2% ee. Both ESI and SSI allow chiral quantification with similar accuracies. The performance of chiral analysis experiments is not limited to ion trapping devices such as quadrupole ion trap mass spectrometers by a hybrid quadrupole-time of flight (Q-ToF) mass spectrometer is shown to provide an alternative choice. The fixed-ligand kinetic method is not restricted to any particular kinds of isomers and, hence, represents a general procedure for improving molecular recognition and chiral analysis in the gas phase.

Carbohydrates↗

Resonance-enhanced multiphoton ionization time-of-flight mass spectrometry for detection of nitrogen containing aliphatic and aromatic compounds: resonance-enhanced multiphoton ionization spectroscopic investigation and on-line analytical application.

Resonance-enhanced multiphoton ionization (REMPI) combined with time-of-flight mass spectrometry (TOFMS) is an analytical method capable of on-line monitoring of trace compounds in complex matrices. A necessary prerequisite for substance selective detection is spectroscopic investigation of the target molecules. Several organic nitrogen compounds comprising aliphatic and aromatic amines, nitrogen heterocyclic compounds, and aromatic nitriles are spectroscopically investigated with a tunable narrow bandwidth optical parametric oscillator (OPO) laser system providing a scannable wavelength range between 220 and 340 nm. These species are known as possible precursors in fuel-NO formation from combustion of solid fuels such as biomass and waste. A newly conceived double inlet system was used in this study, which allows rapid change between effusive and supersonic molecular beams. The resulting REMPI spectra of the compounds are discussed with respect to electronic transitions that could be utilized for a selective ionization of these compounds in complex mixtures such as combustion and process gases. The practicability of this approach is demonstrated by wavelength selected on-line REMPI-TOFMS detection of aniline and cyanonaphthalene in the burning chamber of a waste incineration plant. REMPI mass spectra recorded at different excitation wavelengths as well as variations in time show the utilization of species-selective REMPI-TOFMS detection for on-line monitoring of crucial substances in pollutant formation.

Air Pollutants↗