Mass spectrometric and tandem mass spectrometric behavior of nitrocatechol glucuronides: A comparison of atmospheric pressure chemical ionization and electrospray ionization

The mass spectrometric (MS) and tandem mass spectrometric (MS/MS) behavior of six nitrocatechol-type glucuronides using atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI) was systematically studied, and the effect of operation parameters on the fragmentations are presented. The positive ion APCI- and ESI-MS spectra showed an intense protonated molecule and the respective negative ion spectra a deprotonated molecule with minimal fragmentation. The main fragment ions in the MS/MS spectra of the protonated and deprotonated molecules were [M + H - Glu]+ and [M - H - Glu]-, respectively, formed by the loss of the glucuronide moiety. The measured limits of detection indicated that ESI is a significantly more efficient ionization method than APCI in the negative and positive ion modes for the compounds studied. MS/MS was found to be less sensitive, but more reliable and simple than MS due to the absence of chemical noise.     

Current-density imaging using ultra-low-field MRI with zero-field encoding

Electric current density can be measured noninvasively with magnetic resonance imaging (MRI). Determining all three components of the current density, however, requires physical rotation of the sample or current injection from several directions when done with conventional methods. However, the emerging technology of ultra-low-field (ULF) MRI, in which the signal encoding and acquisition is conducted at a microtesla-range magnetic field, offers new possibilities. The low applied magnetic fields can even be switched off completely within the pulse sequence, increasing the flexibility of the available sequences. In this article, we present a ULF-MRI sequence designed for obtaining all three components of a current-density pattern without the need of sample rotations. The sequence consists of three steps: prepolarization of the sample, signal encoding in the current-density-associated magnetic field without applying any MRI fields, and spatial encoding in a microtesla-range field using any standard ULF-MRI sequence. The performance of the method is evaluated by numerical simulations. The method may find applications, e.g., in noninvasive conductivity imaging of tissue.     

Besicovitch-Federer projection theorem and geodesic flows on Riemann surfaces

We extend the Besicovitch-Federer projection theorem to transversal families of mappings. As an application we show that on a certain class of Riemann surfaces with constant negative curvature and with boundary, there exist natural 2D measures invariant under the geodesic flow having 2D supports such that their projections to the base manifold are 2D but the supports of the projections are Lebesgue negligible. In particular, the union of complete geodesics has Hausdorff dimension 2 and is Lebesgue negligible.     

The Reception of Frege''sBegriffsschrift

The topic of the paper is the public reception of Gottlob Frege's (1848–1925)Begriffsschriftright after its publication in 1879. According to a widespread conception, the reception of the book was “unfavorable” and even “tragic.” The aim of the paper is to correct this exaggerated and even false view. The arguments are based, above all, on the six journal reviews of Frege's book in 1879 and 1880, and on Leonhard Rabus's critical comment on it in his bookDie neuesten Bestrebungen auf dem Gebiete der Logik bei den Deutschen und die logische Frage(1880). The conclusion is that it is misleading to regard the reception of Frege's first work as unfair and hostile even though it is apparent thatsomereviewers of the book were rather poorly motivated to comment on theBegriffsschrift.Copyright 1998 Academic Press.Der Gegenstand dieses Beitrags ist die öffentliche Rezeption von Gottlob Freges (1848–1925)Begriffsschriftnach ihrer Publikation 1879. Nach einer weitverbreiteten Auffassung war die Rezeption “ungünstig,” sogar “tragisch.” Ziel des Beitrags ist es zu zeigen, dass solche Interpretationen überspannt, teilweise sogar falsch sind. Der Verfasser gründet seine Behauptung vor allem auf die Rezensionen, die in verschiedenen Zeitschriften in den Jahren 1879 und 1880 erschienen sind. Er benutzt auch den Kommentar von Leonhard RabusDie neuesten Bestrebungen auf dem Gebiete der Logik bei den Deutschen und Die logische Frage(1880). Die Untersuchung kommt zu dem Schluss, dass, obwohl offensichtlicheinigeRezensenten dem Buch eher ablehnend gegenüberstanden, es irreführend ist, von einer ungerechtfertigten oder abweisenden Rezeption der Fregeschen Begriffsschrift zu sprechenCopyright 1998 Academic Press.AMS subject classification: 00A30, 01A55, 03A05     

Fabrication of enclosed SU-8 tips for electrospray ionization-mass spectrometry

We describe a novel electrospray tip design for MS which is fabricated completely out of SU-8 photoepoxy. A three-layer SU-8 fabrication process provides fully enclosed channels and tips. The tip shape and alignment of all SU-8 layers is done lithographically and is therefore very accurate. Fabrication process enables easy integration of additional fluidic functions on the same chip. Separation channels can be made with exactly the same process. Fluidic inlets are made in SU-8 during the fabrication process and no drilling or other postprocessing is needed. Channels have been fabricated and tested in the size range of 10 microm x 10 microm-50 microm x 200 microm. Mass spectrometric performance of the tips has been demonstrated with both pressure-driven flow and EOF. SU-8 microtips have been shown to produce stable electrospray with EOF in a timescale of tens of minutes. With pressure driven flow stable spray is maintained for hours. Taylor cone was shown to be small in volume and well defined even with the largest channel cross section. The spray was also shown to be well directed with our tip design.     

A computational and experimental study of the structures and Raman and 77Se NMR spectra of SeX3+ and SeX2 (X = Cl, Br, I): FT-Raman spectrum of (SeI3)[AsF6

The ability of MP2, B3PW91 and PBE0 methods to produce reliable predictions in structural and spectroscopic properties of small selenium-halogen molecules and cations has been demonstrated by using 6-311G(d) and cc-pVTZ basis sets. Optimized structures and vibrational frequencies agree closely with the experimental information, where available. Raman intensities are also well reproduced at all levels of theory. Calculated GIAO isotropic shielding tensors yield a reasonable linear correlation with the experimental chemical shift data at each level of theory. The largest deviations between calculated and experimental chemical shifts are found for selenium-iodine species. The agreement between observed and calculated chemical shifts for selenium-iodine species can be improved by inclusion of relativistic effects using the ZORA method. The best results are achieved by adding spin-orbit correction terms from ZORA calculations to nonrelativistic GIAO isotropic shielding tensors. The calculated isotropic shielding tensors can be utilized in the spectroscopic assignment of the 77Se chemical shifts of novel selenium-halogen molecules and cations. The experimental FT-Raman spectra of (SeI3)[AsF6] in the solid state and in SO2(l) solution are also reported.     

High-performance liquid chromatographic determination of oligomeric procyanidins from dimers up to the hexamer in hawthorn

An HPLC method using UV diode array detection was developed for analysing procyanidins qualitatively and quantitatively up to the hexameric level in hawthorn samples. The analysed compounds included procyanidin dimers B-2, B-4 and B-5, procyanidin trimers C-1, epicatechin-(4beta-->8)-epicatechin-(4beta-->6)-epicatechin and epicatechin-(4beta-->6)-epicatechin-(4beta-->8)-epicatechin, a tetramer D-1 and a pentamer E-1 both consisting of (-)-epicatechin units linked through C-4beta/C-8 bonds. The concentrations of two unknown tetramers and a hexamer F were also quantified. The oligomeric procyanidins (OPs) were specifically determined due to the development of a method for isolating them from hawthorn during sample preparation. The pattern of oligomeric procyanidins in the leaves, flowers and fruits was similar, but the concentrations varied depending on the part of the plant. The concentration in leaves was 1.6%, in flowers 1.2% and in fruits 0.2% of the dry mass. The method was validated with respect to repeatability, recovery, linearity, and sensitivity. The repeatability for the quantitative analytical method of all the OPs in leaves was 7.7%, in flowers 8.8%, and in fruits 12.3%. The recovery of the main OPs ranged from 91 to 97%. The correlation coefficients of calibration curves were between 0.997 and 1.000. The limits of quantitation for different procyanidin standards were 0.05-0.12 mg/ml, when 10 microl of each standard solution was injected into the HPLC.     

Experimental and theoretical investigations of structural trends for selenium(IV) imides and oxides: X-ray structure of Se3(NAd)2

The thermal decomposition of Se(NAd)(2) (Ad = 1-adamantyl) in THF was monitored by (77)Se NMR and shown to give the novel cyclic selenium imide Se(3)(NAd)(2) as one of the products. An X-ray structural determination showed that Se(3)(NAd)(2) is a puckered five-membered ring with d(Se-Se) = 2.404(1) A and |d(Se-N)| = 1.873(4) A. On the basis of (77)Se NMR data, other decomposition products include the six-membered ring Se(3)(NAd)(3), and the four-membered rings AdNSe(micro-NAd)(2)SeO and OSe(micro-NAd)(2)SeO. The energies for the cyclodimerization of E(NR)(2) and RNEO (E = S, Se; R = H, Me, (t)Bu, SiMe(3)), and the cycloaddition reactions of RNSeO with E(NR)(2), RNSO(2) with Se(NR)(2), and S(NR)(2) with Se(NR)(2) have been calculated at MP2, CCSD, and CCSD(T) levels of theory using the cc-pVDZ basis sets and B3PW91/6-31G* optimized geometries. Sulfur(IV) and selenium(IV) diimide monomers are predicted to be stable, the sole exception being Se(NSiMe(3))(2) that shows a tendency toward cyclodimerization. The cyclodimerization energy for RNSeO and the cycloaddition reaction energies of RNSeO with Se(NR)(2) as well as that of RNSO(2) with Se(NR)(2) are negative, consistent with the observed formation of OSe(micro-N(t)Bu)(2)SeO, OSe(micro-N(t)Bu)(2)SeN(t)Bu, and O(2)S(micro-N(t)Bu)(2)SeN(t)Bu, respectively. Cycloaddition is unlikely when one of the reactants is a sulfur(IV) diimide.