Comparison of negative ion electrospray mass spectra measured by seven tandem mass analyzers towards library formation

A library of negative ion electrospray ionization mass spectra and tandem mass spectra (MS/MS) of sulfonated dyes has been developed for fast identification purposes. The uniform protocol has been elaborated and applied to the measurements of more than 50 anionic dyes. Three collision energies are selected in our protocol which ensures that at least one of them provides a suitable ratio of product ions to the precursor ion. The robustness is investigated with altered values of tuning parameters (e.g. the pressure of the nebulizing gas, the temperature and the flow rate of drying gas, and the mobile phase composition). The results of the inter-laboratory comparison of product ion mass spectra recorded on seven different tandem mass spectrometers (three ion traps, two triple quadrupoles and two hybrid quadrupole time of flight instruments) are presented for four representative anionic dyes--azo dye Acid Red 118, anthraquinone dye Acid Violet 43, triphenylmethane dye Acid Blue 1 and Al(III) metal-complex azo dye. The fragmentation patterns are almost identical for all tandem mass analyzers, only the ratios of product ions differ somewhat which confirms the possibility of spectra transfer among different mass analyzers with the goal of library formation.     

Synthesis of 8-bromo-, 8-methyl- and 8-phenyl-dATP and their polymerase incorporation into DNA

dATP derivatives bearing Br, Me or Ph groups in position 8 were prepared and tested as substrates for DNA polymerases to show that 8-Br-dATP and 8-Me-dATP were efficiently incorporated, while 8-Ph-dATP was a poor substrate due to its bulky Ph group.     

Toward the discovery of potent inhibitors of botulinum neurotoxin A: development of a robust LC MS based assay operational from low to subnanomolar enzyme concentrations

The development of a sensitive, yet reliable assay for the analysis of botulinum neurotoxin A (BoNT/A) inhibitors is described; using this assay a new protease inhibitor was characterized and found to be one of the most potent inhibitors reported to date.     

Magnetic techniques for the detection and determination of xenobiotics and cells in water

Magnetic techniques based on the application of magnetic nanoparticles and microparticles and films have been successfully used for the determination and detection of different types of xenobiotics (e.g. herbicides, insecticides, fungicides, aromatic and polyaromatic hydrocarbons, pentachlorophenol and heavy metal ions) as well as viruses, microbial pathogens and protozoan parasites in water samples. Preconcentration of xenobiotics from large volumes of samples can be performed using magnetic solid-phase extraction, stir-bar sorptive extraction and related procedures. This review provides basic information about these techniques. Published examples of successful applications document the importance of these simple and efficient procedures employing magnetic materials.     

Posttranslational modifications of collagen studied by off-line coupling of HPLC and CE

A typical example of non-enzymatic change of collagen is glycation (the Maillard reaction, formation of advanced glycation end products) resulting from the reaction of sugars with the epsilon-amino group of lysine. Posttranslational non-enzymatic modifications of collagen by sugars were studied. Collagenous tissues were incubated as a test protein separately with both glucose and ribose. The collagen mixture was digested by bacterial collagenase and separated by reversed-phase HPLC (in a Jupiter Proteo 90 A column). The eluate from this HPLC separation was collected as seven fractions and consecutively analysed by CE in a bare fused silica capillary (57/50 cm x 75 mm id) using 100 mM sodium 1-heptanesulfonate in 100 mM phosphate buffer, pH 2.5 (NaH2PO4 adjusted to pH by phosphoric acid). The chromatographic and electromigration behaviour of individual peptides varied considerably. This off-line HPLC-CE coupling made it possible to discover minor changes in the structure of collagen caused by posttranslational modifications. A new HPLC-CE technique for peptide analysis was developed, and applied to the identification of posttranslational modifications in slowly metabolised test proteins.     

Synthetic,structural and spectroscopic studies of complexes derived from the copper(II) perchlorate/fumaric acid/N,N′-chelates tertiary reaction systems

The synthetic investigation of the Cu(ClO₄)₂·6H₂O/fumaric acid (H₂fum)/N,N’-chelates (1,10-phen, 2,2′-bpy) tertiary reaction systems has yielded mononuclear, dinuclear and tetranuclear complexes, and three coordination polymers. The chemical and structural identity of the products depends on the solvent, the absence or presence of external hydroxides in the reaction mixtures and the N,N’-donor. Three fumarato(−2) complexes, i.e. compounds [Cu₂(fum)(phen)₄](ClO₄)₂·2H₂O (1·2H₂O), [Cu(fum)(phen)(H₂O)]_n (3) and [Cu₂(fum)(bpy)₂(H₂O)₂]_n(ClO₄)_2n (6), were isolated and structurally characterized, and four non-fumarato complexes, i.e. compounds [Cu₄(μ₃-ΟΗ)₂(μ₂-ΟΗ)₂(phen)₄(H₂O)₂](ClO₄)₄·2H₂O (2·2H₂O), [Cu(ClO₄)(phen) (MeCN)₂(H₂O)](ClO₄) (4), [Cu(ClO₄)(phen)(MeCN)₂]_n(ClO₄)_n (5) and [Cu(ClO₄)₂(bpy)(MeCN)₂] (7), were simultaneously obtained from the reaction systems investigated. The coordination versatility of the fumarato(−2) ligand is reflected to the three different coordination modes observed in 1·2H₂O, 3 and 6; the monodentate bridging μ₂-κO:κO′ mode in 3, the asymmetric chelating bridging μ₂-κO:κO′:κO′′:κO′′′ mode in 1·2H₂O and 3, and the syn,syn bridging μ₄-κO:κO′:κO′′:κO′′′ mode in 6. The crystal structures of the complexes are stabilized by intra- and inter-molecular hydrogen bonding and π–π stacking interactions leading to interesting supramolecular architectures. Characteristic IR bands of the complexes are discussed in terms of the known structures, and the coordination modes of the fum²⁻ ligands.     

Biomarkers of Aspergillus spores: Strain typing and protein identification

We applied both matrix-assisted laser desorption/ionization time of flight (MALDI-TOF) mass spectrometric and 1D sodium dodecylsulfate polyacrylamide gel electrophoretic (1D-PAGE) approaches for direct analysis of intact fungal spores of twenty four Aspergillus species. In parallel, we optimized various protocols for protein extraction from Aspergillus spores using acidic conditions, step organic gradient and variable sonication treatment. The MALDI-TOF mass spectra obtained from optimally prepared samples provided a reproducible fingerprint demonstrating the capability of the MALDI-TOF approach to type and characterize different fungal strains within the Aspergillus genus. Mass spectra of intact fungal spores provided signals mostly below 20 kDa. The minimum material amount represented 0.3 μg (10,000 spores). Proteins with higher molecular weight were detected by 1D-PAGE. Eleven proteins were identified from three selected strains in the range 5–25 kDa by the proteomic approach. Hemolysin and hydrophobin have the highest relevance in host–pathogen interactions.     

Oxygen evolution on nanocrystalline RuO2 and Ru0.9Ni0.1O2−δ electrodes – DEMS approach to reaction mechanism determination

The mechanism of the oxygen evolution on RuO₂ and Ru_0.9Ni_0.1O_2−δ anodes was studied in 0.1 M HClO₄ using ¹⁸labeling combined with differential electrochemical mass spectrometry (DEMS). It was shown that the mechanism of the oxygen evolution is potential sensitive. At potentials negative to 1.12 V vs. SCE all the evolved oxygen originates from the electrolyte solution. At higher potentials an additional mechanism involving an exchange of the oxygen between electrolyte and electrocatalyst starts to apply. The extent of this oxygen exchange mechanism reflects the chemical composition of the electrocatalyst and is significantly higher at Ru_0.9Ni_0.1O_2−δ electrodes.     

ChemInform Abstract: Formation and Stability of Gaseous Ternary Oxides of Group 14-16 Elements and Related Oxides of Group 15 Elements: Mass Spectrometric and Quantum Chemical Study.

The formation of the new compounds PbTeO₃, PbTe₂O₅, Pb₂TeO₄, and Pb₂Te₂O₆ is observed in the gas phase by heating a mixture of solid PbO and TeO₂ at 1063 K using a mass-spectrometric Knudsen-cell method.