Studies on pre-hump and main fractions of cellulose-2,5-acetate in acetone

Technical cellulose-2.5-acetates (CA 2.5) were characterized regarding their carbohydrate composition in comparison to the raw material. The association of the CA 2.5 samples in acetone was studied by size exclusion chromatography (SEC) using various acetone grades and styrene divinylbenzene copolymer columns. In HPLC grade acetone with and without addition of 1% water up to three different pre-humps eluted in front of the main fraction of the polymer. The evaluation of the main peak by light scattering measurements resulted in high molar masses indicating that for these technical CA 2.5 samples even the main fraction is not dissolved without association. No pre-humps or association phenomena were observed after addition of 1 ppm LiBr to HPLC grade acetone or with p.a. grade acetone. In addition pre-hump enriched and pre-hump free fractions were isolated by fractionated precipitation. The carbohydrate composition of these fractions was determined and correlated with their association pattern in SEC investigations.     

Zur Berechnung Stekloffscher Eigenwerte

Zusammenfassung Es wird ein neues Verfahren zur numerischen Berechnung des ersten nichttrivialen Stekloffschen Eigenwertes beschrieben. Dieses Verfahren arbeitet nur mit oberen Schranken.

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We describe a new procedure for the numerical evaluation of the first nontrivial Stekloff eigenvalue. This procedure works only with upper bounds.

     

Development and characterisation of a new interface for coupling capillary LC with collision-cell ICP–MS and its application for phosphorylation profiling of tryptic protein digests

A comparison of different nebulisers for direct hyphenation of capillary and nano liquid chromatography (Cap-LC, Nano-LC) and quadrupole-based collision cell inductively coupled plasma mass spectrometry (CC-ICP–MS) for phosphorylation profiling of tryptic protein digests is described. Helium was used as cell gas and specially tuned instrumental conditions were used to achieve background minimisation at the mass of phosphorus, because of kinetic energy discrimination of the interfering polyatomic ions. The proposed set-up is based on a modified capillary electrophoresis interface and a home-made 4 mL spray chamber. It enables the use of gradient conditions with a highly concentrated organic mobile phase as often used in protein phosphorylation analysis, without the need to apply membrane desolvation for removal of the organic phase or further background minimisation. No significant signal suppression or other negative effects caused by the organic mobile phase occur, because of the low flow rates used in Cap-LC and the robust plasma conditions of the CC-ICP–MS instrument. A tryptic digest of beta-casein was investigated as model compound to demonstrate the applicability of the proposed set-up for phosphorylation profiling in protein analysis using quadrupole based collision-cell ICP–MS as phosphorus-specific detector. Detection limits for phosphorylated peptides down to the sub picomole level were obtained. As a complementary technique, electrospray ionisation tandem mass spectrometry (ESI–MS–MS) with data base searching was used for further characterisation of the phosphorylated peptides detected.     

Darstellung und Kristallstruktur des ersten polymeren Phosphorselenids catena-(P4Se4)x

Preparation and Crystal Structure of the First Polymeric Phosphorus Selenide catena-(P₄Se₄)_x Catena-(P₄Se₄)_x was prepared in crystalline form from the elements using iodine as a catalyst, and characterized by means of X-ray diffraction and IR spectroscopy. Single-crystal investigations (space group P2₁/c, a = 1 119.2(3), b = 728.2(2), c = 1 142.5(3) pm, β = 115.91(2)°, V = 837.5(7) · 10⁶ pm³) revealed parallel chains of P₄Se₃ hetero-norbornane units linked via Se atoms. Thus, being the first phosphorus selenide which does not contain discrete molecules, catena-(P₄Se₄)_x can be regarded as a polymeric form of α-P₄Se₄ or as a crystalline modification of vitrous phosphorus selenide.     

Simultaneous determination of alkylphenol ethoxylates and their biotransformation products by liquid chromatography/electrospray ionisation tandem mass spectrometry

Reversed-phase LC-MS/MS is used to determine major estrogenic alkylphenol ethoxylates (APEOs) and their biotransformation products. It allows the simultaneous analysis of eight APEOs, alkylphenoxy carboxylates (APECs) and alkylphenols (APs) in sewage treatment plant (STP) effluents in the same extract after solid-phase enrichment on polymeric Oasis HLB. As precursor ions, [APEO + NH4]+, [APEC - H]- and [AP - H]- were monitored. Instrumental limits of detection (LOD) were 2-600 pg, corresponding to sample concentrations of 0.04-12 ng l(-1), without correction for overall method recoveries. Matrix-induced signal suppression during electrospray ionisation (ESI) and extraction as well as overall method recoveries were assessed and the suitability of deuterated surrogates as internal standards was evaluated.     

The vitamin D3 pathway in human skin and its role for regulation of biological processes

The skin is the only tissue yet known in which the complete ultraviolet-B (UV-B)-induced pathway from 7-dehydrocholesterol to hormonally active calcitriol (1alpha,25-dihydroxyvitamin D(3)) occurs under physiological conditions. Epidermal synthesis of calcitriol could be of fundamental relevance because calcitriol regulates important cellular functions in keratinocytes and immunocompetent cells. Because of their antiproliferative and prodifferentiating effects, calcitriol and other vitamin D analogs are highly efficient in the treatment of psoriasis vulgaris. The known antipsoriatic effect of UV-B light could, at least in part, be mediated via UV-B-induced synthesis of calcitriol. In addition, mounting evidence indicates that cutaneous vitamin D(3) synthesis is of high importance for the prevention of a broad variety of diseases, including various malignancies. New but controversially discussed sun-protection guidelines were established for the prevention of internal cancers. A better understanding of the metabolism of vitamin D in the skin opens new perspectives for therapeutic applications of vitamin D analogs.