2. Analysen Materialien der Industrie, des Handels und der Landwirtschaft

Ohne Zusammenfassung     

Zur bestimmung von natrium- und lithiumbenzoat

Ohne Zusammenfassung     

Stable isotope-free quantitative shotgun proteomics combined with sample pattern recognition for rapid diagnostics

Mass spectrometry (MS) has become a powerful tool for the quantitative analysis of complex protein samples. A high-throughput strategy for the comparative analysis of multiple protein samples with high complexity becomes more and more important. Two strategies, spectral count and peak intensity, for label-free MS analysis of prefractionated complex mixtures have been described recently to be useful for quantitation. Here we compare both strategies for rapid and quantitative 1-D shotgun LC/MS/MS analyses of highly complex protein mixtures using silica-based monolithic columns. First, we validated linearity and sensitivity of these methods by spiking varying amounts of an internal standard protein in a complex plant protein extract. Secondly, quantitative data of proteins of Medicago truncatula nodules were visualized with independent components analysis using data either obtained from spectral count or peak integration performed with commercial software. Spectral count showed apparent advantages over peak integration because several peptides per protein are automatically averaged, the linear dynamic range of quantitation increases in complex matrices and the number of quantified proteins surpasses the number of proteins using peak integration. Thus, for the need of rapid comparative analysis of highly complex protein samples, spectral count enables sample pattern recognition and identification of biomarkers in nongel based proteomic studies.     

Supramolecular stabilization of hydroxylamine TEMPOH by complexation with an amphiphilic calixarene

In an ethanol/water mixture, the nitroxyl radical TEMPO abstracts a hydrogen atom from a phenolic OH group of the amphiphilic para-hexanoylcalix[4]arene, and the hydroxylamine TEMPOH formed yields a stable inclusion complex with another molecule of the calixarene.     

Two-dimensional wave patterns of spreading depolarization: Retracting, re-entrant, and stationary waves

We present spatio-temporal characteristics of spreading depolarizations (SD) in two experimental systems: retracting SD wave segments observed with intrinsic optical signals in chicken retina, and spontaneously occurring re-entrant SD waves that repeatedly spread across gyrencephalic feline cortex observed by laser speckle flowmetry. A mathematical framework of reaction-diffusion systems with augmented transmission capabilities is developed to explain the emergence and transitions between these patterns. Our prediction is that the observed patterns are reaction-diffusion patterns controlled and modulated by weak nonlocal coupling such as long-range, time-delayed, and global coupling. The described spatio-temporal characteristics of SD are of important clinical relevance under conditions of migraine and stroke. In stroke, the emergence of re-entrant SD waves is believed to worsen outcome. In migraine, retracting SD wave segments cause neurological symptoms and transitions to stationary SD wave patterns may cause persistent symptoms without evidence from noninvasive imaging of infarction.     

Quasilinear elliptic equations with subquadratic growth

In this paper we consider nonlinear boundary value problems whose simplest model is the following:

(0.1)     

Embedding a quantum rank three quadric in a quantum P3

We continue the classification, begun in [11], [14] and [12], of quadratic Artin-Schelter regular algebras of global dimension 4 which map onto a twisted homogeneous coordinate ring of a quadric hypersurfcice in P³. In this paper, we consider those cases where the quadric has rank 3. We also give sufficient conditions for the point scheme of any quadratic regular algebra of global dimension 4 to be the graph of an automorphism.     

Simultaneous Determination of 11 Elements in Fly Ash by Inductively Coupled Plasma Orthogonal Acceleration Time-of-Flight Mass Spectrometry After Closed-Vessel Microwave-Assisted Extraction with Ammonium Fluoride

A method for simultaneous multi-element analysis of fly ash samples by inductively coupled plasma orthogonal acceleration time-of-flight mass spectrometry (oaTOF-ICP-MS) after closed-vessel microwave extraction with ammonium fluoride was introduced here. Corrosive and/or toxic acids like HF, HCl or HClO₄, as well as HNO₃, which are commonly used during sample preparation of the fly ash samples, are avoided in this method. The spectral effects due to the formation of different Cl, Na, K, Ca, Mg-containing polyatomic species interfering with the determination of a number of elements like As, Se or Ni during the oaTOF-ICP-MS analysis are negligible. Under the optimum experimental extraction conditions evaluated using a fractional factorial design (10 mg of the sample extracted with 5 mL of 140 g/L NH₄F for 10 min at 200°C), analysis of the resulting supernatant with Rh as an internal standard enabled precise and accurate simultaneous determination of 11 elements (Li, Be, Ni, As, Se, Rb, Sb, Cs, W, Tl and U) at trace and ultratrace levels. The accuracy was assessed by analysing two certified reference materials, namely Fine Fly Ash CTA-FFA-1 and Constituent Elements in Coal Fly Ash Standard Reference Material® 1633b. The precision of the reported method was better than 10%.     

Preliminary investigation of a medium power argon radiofrequency capacitively coupled plasma as atomization cell in atomic fluorescence spectrometry of cadmium

The single ring electrode radiofrequency capacitively coupled plasma torch (SRTr.f.CCP) operated at 275W, 27.12 MHz and Ar flow rate below 0.7 lmin(-1) was investigated for the first time as atomization cell in atomic fluorescence spectrometry (AFS) using electrodeless discharge lamps (EDL) as primary radiation source and charged coupled devices as detector. The signal to background ratio (SBR) and limit of detection for Cd determination by EDL-SRTr.f.CCP-AFS were compared to those obtained in atomic emission spectrometry using the same plasma torch. The detection limit in fluorescence was 4.3 ngml(-1) Cd compared to 65 ngml(-1) and 40 ngml(-1) reported in r.f.CCP-atomic emission (AES) equipped with single or double ring electrode. The lower detection limit in EDL-SRTr.f.CCP-AFS is due to a much better SBR in fluorescence. The limit of detection was also compared to those in atomic fluorescence with inductively coupled plasma (0.4 ngml(-1)), microwave plasma torch (0.25 ngml(-1)) and air-acetylene flame (8 ngml(-1)). The influence of light-scattering through the plasma and the secondary reflection of the primary radiation on the wall of the quartz tube on the analytical performance are discussed. The non-spectral matrix effects of Ca, Mg and easily ionized elements are much lower in EDL-SRTr.f.CCP-AFS compared to SRTr.f.CCP-AES. The new technique was applied in the determination of Cd in contaminated soils, industrial hazardous waste (0.4-370 mgkg(-1)) and water (113 microgl(-1)) with repeatability of 4-8% and reproducibility in the range of 5-12%, similar to those in ICP-AES. The results were checked by the analysis of a soil and water CRM with a recovery degree of 97+/-9% and 98+/-4%, for a confidence limit of 95%. The present EDL-SRTr.f.CCP-AFS is a promising technique for Cd determination in environmental samples.