Bestimmung des Zinkchlorids in impr?gnierten Holz

Ohne Zusammenfassung     

Quantitative-qualitative data acquisition using a benchtop orbitrap mass spectrometer

Current approaches to discovery-stage drug metabolism studies (pharmacokinetics, microsomal stability, etc. ) typically use triple-quadrupole-based approaches for quantitative analysis. This necessitates the optimization of parameters such as Q1 and Q3 m/z values, collision energy, and interface voltages. These studies detect only the specified compound and information about other components, such as metabolites, is lost. The ability to perform full-scan acquisition for quantitative analysis would eliminate the need for compound optimization while enabling the detection of metabolites and other non-drug-related endogenous components. Such an instrument would have to provide sensitivity, selectivity, dynamic range, and scan speed suitable for discovery-stage quantitative studies. In this study, a prototype benchtop Orbitrap-based mass analyzer was used to collect both quantitative and qualitative data from human microsomal incubation samples as well as rat plasma from pharmacokinetic studies. Instrumental parameters such as scan speed, resolution, and mass accuracy are discussed in relation to the requirements for a quantitative-qualitative workflow. The ability to perform highly selective quantitative analysis while simultaneously characterizing metabolites from both in vitro and in vivo studies is discussed.     

A parallel approach to post source decay MALDI-TOF analysis

We present a novel enhancement to matrix-assisted laser desorption ionization (MALDI) post-source decay (PSD) analysis whereby fragment ions from multiple precursor ions are acquired into the same spectrum without employing a timed ion gate to preselect each parent ion. Fragment ions are matched to their corresponding precursor ions by comparing spectra acquired at slightly different reflectron electric fields. By measuring the difference in time-of-flight (TOF) between the two spectra for each fragment, it is possible to calculate the mass of the fragment ion and its parent. This new "parallel PSD" technique reduces analysis time and consumes less sample than conventional PSD, which requires an ion gate for serial preselection of precursor ions.     

Ion dispersion near parallel wire grids in orthogonal acceleration time-of-flight mass spectrometry: predicting the effect of the approach angle on resolution

Ions experience small deflections in the vicinity of grids in accelerators and ion mirrors in time-of-flight (TOF) mass spectrometers. Recent experiments with an orthogonal acceleration (oa) TOF instrument have verified that the effect can significantly degrade resolution when ions approach grids at an angle deviating from 90 degrees. The phenomenon becomes significant only when ions have components of velocity at right angles to the wires of the grids. A model is presented in this study to predict this phenomenon for parallel wire grids. The fractional energy spread of ions (calculated in the static TOF-spectrometer frame of reference) scales directly with the approach angle of ions to the grid (as measured from normal approach). The energy spread also scales with the range of angles that is a consequence of the focusing effect in each gap between the wires of the grid. The equations imply that closely spaced parallel wire grids are best for deployment in oa-TOF systems where non-zero approach angles are unavoidable. Such grids are relatively impractical to manufacture and support but rectangular repeat cell grids with relatively few wires at right angles to the source axis are shown experimentally to introduce minimal energy spread. When these grids are rotated by 90 degrees, the resolution measured in a Q-TOF spectrometer is degraded in approximate agreement with the parallel wire model. A practical implication of this work is that grid transmissions in oa-TOF systems may be significantly increased without loss of resolution. Improvements of approximately 200% (V-mode) and approximately 400% (W-mode) in ion transmission were obtained in this study without compromising resolution. This was achieved with approximately 73% transmission grids and greater potential improvements in transmission are being realised since this study with approximately 89% transmission grids having similar geometry.     

Bacterial siderophores: unusual 3,4,5,6-tetrahydropyrimidine-based amino acids in pyoverdins frompseudomonas fluorescens

Two unusual natural amino acids have been identified in the pyoverdins occurring from two different strains ofPseudomonas fluorescens. They contain a 3,4,5,6-tetrahydropyrimidine moiety resulting from the condensation of 2,4-diaminobutyric acid with the car☐yl group of respectively serine and glutamine.     

Positive integers expressible as a sum of three squares in essentially only one way

The set S consisting of those positive integers n which are uniquely expressible in the form n = a² + b² + c², $\text{a ≧ b ≧ c ≧ 0}$, is considered. Since n ∈ S if and only if 4n ∈ S, we may restrict attention to those n not divisible by 4. Classical formulas and the theorem that there are only finitely many imaginary quadratic fields with given class number imply that there are only finitely many n ∈ S with n = 0 (mod 4). More specifically, from the existing knowledge of all the imaginary quadratic fields with odd discriminant and class number 1 or 2 it is readily deduced that there are precisely twelve positive integers n such that n ∈ S and n ≡ 3 (mod 8). To determine those n ∈ S such that n ≡ 1, 2, 5, 6 (mod 8) requires the determination of the imaginary quadratic fields with even discriminant and class number 1, 2, or 4. While the latter information is known empirically, it has not been proved that the known list of 33 such fields is complete. If it is complete, then our arguments show that there are exactly 21 positive integers n such that n ∈ S and n ≡ 1, 2, 5, 6 (mod 8).