Zur Kenntnis sterischer Einflüsse auf Ringschlußreaktionen

Ohne Zusammenfassung     

Use of capillary electrophoresis to monitor wheat maturation

Summary The maturation of wheat varieties with different harvest times has been examined by high-performance capillary electrophoresis. The unique proteins of the albumin, gliadin and glutenin fractions of Hungarian winter wheat cultivars Bánkúti 1201 (early harvest time), Martonvásári 23 (medium harvest time), and Martonvásári 15 (semi-late harvest time) were analysed. An acidic phosphate buffer containing a polymeric additive and organic modifiers was used in capillary zone electrophoresis mode. Formation of albumin followed the same time scale, and the patterns were quite similar, for all three cultivars. For gliadins and glutenins the time scale and patterns were different and some correlation was observed between harvest time and gliadin formation. Presented at Balaton Symposium '01 on High-Performance Separation Methods, Siófok, Hungary, September 2–4, 2001     

Beiträge zur Chemie der Pyrrolpigmente, 3. Mitt.1: Die NH-Tautomerie von substituierten Pyrromethenen: Protonenresonanzspektrometrische Untersuchungen

NMR-spectra of several pyrromethenes were measured at different temperatures, concentrations and in different solvents. The chemical shifts of all protons were assigned and long range coupling constants determined. This variation of temperature, concentration and solvent provided evidence forintra- andinter-molecular proton transfer. In all pyrromethenes investigated the tautomeric NH exchanges are too fast—even at –100°C—to be measured by NMR.

---

---

Mit 2 Abbildungen     

Application of variational reduced-density-matrix theory to organic molecules

Variational calculation of the two-electron reduced-density matrix (2-RDM), using a new first-order algorithm [D. A. Mazziotti, Phys. Rev. Lett. 93, 213001 (2004)], is applied to medium-sized organic molecules. The calculations reveal systematic trends in the accuracy of the energy with well-known chemical concepts such as hybridization, electronegativity, and atomic size. Furthermore, correlation energies from hydrocarbon chains indicate that the calculation of the 2-RDM subject to two-positivity conditions is size extensive, that is, the energy grows linearly with the number of electrons. Because organic molecules have a well-defined set of functional groups, we employ the trends in energy accuracy of the functional groups to design a correction to the 2-RDM energy for an arbitrary organic molecule. We apply the 2-RDM calculations with the functional-group correction to a large set of organic molecules with different functional groups. Energies with millihartree accuracy are obtained both at equilibrium and nonequilibrium geometries.     

Auger spectrometric studies on fracture surfaces of tool steel

The fracture surfaces of tool steel K-13 (Hungarian Standard) were studied by Auger electron spectroscopy. Notched specimens of 3 × 3 mm² were fractured in UHV (6 × 10⁻⁸ Pa) with a fracturer (Riber FR 100) and studied with a CMA analyser (Riber OPC 103). With our modification the fracturer was operated within the −150°C −+230°C temperature range. The fracture surfaces were tested with a scanning electron microscope (JEOL JSM 35). The evaluation of Auger spectra was based on the PHI (PALMBERG et al.). Handbook, however the backscattering correction of Jablonski was applied in some cases. The choice of adequate fracturing temperature proved to be very important. Low temperature fracture of this steel alloy is producing very rigid transgranular fracture. The effects of sample heat treatment and of fracturing temperature as well were studied in details. The Auger spectra of fracture surfaces are strongly affected by the heat treatment of the samples. The grain boundary fracture surface of a sample austenitized at 1100°C quenched and tempered at 600°C exhibited a strong enrichment of P, correlating with the enrichment of Cr, V and Mo. The transgranular fracture surface of the same sample but without tempering corresponded to the bulk composition. In some cases and spots on the fracture surfaces, giant S or P peaks were associated with secondary phases (inclusions) on the SEM pictures.     

External field induced tricritical phenomenon in the isotropicnematic phase transition of hard non-spherical particle systems

The effect of static external field is studied on the isotropic–nematic phase transition of a system of hard non-spherical particles (rods or platelets) with negative anisotropic polarizability (susceptabilities). On the basis of Onsager theory, the phase coexistence curve is calculated numerically without any approximation. It is found that a weakly ordered nematic phase (uniaxial planar) is in coexistence with a highly ordered biaxial nematic phase which ends at a tricritical point. In the limit of infinite field strength, the orientations of the particles are confined in a plane perpendicular to the field and continuous isotropic–nematic phase transition takes place.     

Bi-exponential diffusion signal decay in normal appearing white matter of multiple sclerosis

Purpose

Our aim was to characterize bi-exponential diffusion signal changes in normal appearing white matter of multiple sclerosis (MS) patients.

Methods

Diffusion parameters were measured using mono-exponential (0–1000 s/mm²) and bi-exponential (0–5000 s/mm²) approaches from 14 relapsing-remitting subtype of MS patients and 14 age- and sex-matched controls after acquiring diffusion-weighted images on a 3T MRI system. The results were analyzed using parametric or nonparametric tests and multiple linear regression models.

Results

Mono-exponential apparent diffusion coefficient (ADC) slightly increased in controls (P=.09), but decreased significantly in MS as a function of age, nonetheless an elevated ADC was observed with increasing lesion number in patients. Bi-exponential analyses showed that the increased ADC is the result of decreased relative volume fraction of slow diffusing component (f_s). However, the fast and slow diffusion components (ADC_f, ADC_s) did not change as a function of either age in controls or lesion number and age in MS patients.

Conclusions

These data demonstrated that the myelin content of the white matter affects diffusion in relapsing-remitting subtype of multiple sclerosis that is possibly a consequence of the shift between different water fractions.     

Noise Corrections to Stochastic Trace Formulas

We review studies of an evolution operator for a discrete Langevin equation with a strongly hyperbolic classical dynamics and a Gaussian noise. The leading eigenvalue of yields a physically measurable property of the dynamical system, the escape rate from the repeller. The spectrum of the evolution operator in the weak noise limit can be computed in several ways. A method using a local matrix representation of the operator allows to push the corrections to the escape rate up to order eight in the noise expansion parameter. These corrections then appear to form a divergent series. Actually, via a cumulant expansion, they relate to analogous divergent series for other quantities, the traces of the evolution operators ⁿ. Using an integral representation of the evolution operator , we then investigate the high order corrections to the latter traces. Their asymptotic behavior is found to be controlled by sub-dominant saddle points previously neglected in the perturbative expansion, and to be ultimately described by a kind of trace formula.     

Kondo effect and spin filtering in triangular artificial atoms

We studied, strongly correlated states in triangular artificial atoms. Symmetry-driven orbital degeneracy of the single particle states can give rise to an SU(4) Kondo state with entangled orbital and spin degrees of freedom, and a characteristic phase shift δ=π/4. Upon application of a Zeeman field, a purely orbital Kondo state is formed with somewhat smaller Kondo temperature and a fully polarized current through the device. The Kondo temperatures are in the measurable range. The triangular atom also provides a tool to systematically study the singlet-triplet transitions observed in recent experiments [Phys. Rev. Lett., 88 (2002) 126803, cond-mat/0208268 (2002)].     

A validated method for measurement of serum total,serum free,and salivary cortisol,using high-performance liquid chromatography coupled with high-resolutionESI-TOF mass spectrometry

Blood cortisol level is routinely analysed in laboratory medicine, but the immunoassays in widespread use have the disadvantage of cross-reactivity with some commonly used steroid drugs. Mass spectrometry has become a method of increasing importance for cortisol estimation. However, current methods do not offer the option of accurate mass identification. Our objective was to develop a mass spectrometry method to analyse salivary, serum total, and serum free cortisol via accurate mass identification. The analysis was performed on a Bruker micrOTOF high-resolution mass spectrometer. Sample preparation involved protein precipitation, serum ultrafiltration, and solid-phase extraction. Limit of quantification was 12.5 nmol L^?1 for total cortisol, 440 pmol L^?1 for serum ultrafiltrate, and 600 pmol L^?1 for saliva. Average intra-assay variation was 4.7 %, and inter-assay variation was 6.6 %. Mass accuracy was <2.5 ppm. Serum total cortisol levels were in the range 35.6–1088 nmol L^?1, and serum free cortisol levels were in the range 0.5–12.4 nmol L^?1. Salivary cortisol levels were in the range 0.7–10.4 nmol L^?1. Mass accuracy was equal to or below 2.5 ppm, resulting in a mass error less than 1 mDa and thus providing high specificity. We did not observe any interference with routinely used steroidal drugs. The method is capable of specific cortisol quantification in different matrices on the basis of accurate mass identification.