An online nano‐LC‐ESI‐FTICR‐MS method for comprehensive characterization of endogenous fragments from amyloid β and amyloid precursor protein in human and cat cerebrospinal fluid

Amyloid precursor protein (APP) is the precursor protein to amyloid β (Aβ), the main constituent of senile plaques in Alzheimer's disease (AD). Endogenous Aβ peptides reflect the APP processing, and greater knowledge of different APP degradation pathways is important to understand the mechanism underlying AD pathology. When one analyzes longer Aβ peptides by low‐energy collision‐induced dissociation tandem mass spectrometry (MS/MS), mainly long b‐fragments are observed, limiting the possibility to determine variations such as amino acid variants or post‐translational modifications (PTMs) within the N‐terminal half of the peptide. However, by using electron capture dissociation (ECD), we obtained a more comprehensive sequence coverage for several APP/Aβ peptide species, thus enabling a deeper characterization of possible variants and PTMs. Abnormal APP/Aβ processing has also been described in the lysosomal storage disease Niemann–Pick type C and the major large animal used for studying this disease is cat. By ECD MS/MS, a substitution of Asp7 → Glu in cat Aβ was identified. Further, sialylated core 1 like O‐glycans at Tyr10, recently discovered in human Aβ (a previously unknown glycosylation type), were identified also in cat cerebrospinal fluid (CSF). It is therefore likely that this unusual type of glycosylation is common for (at least) species belonging to the magnorder Boreoeutheria. We here describe a detailed characterization of endogenous APP/Aβ peptide species in CSF by using an online top‐down MS‐based method. Copyright © 2012 John Wiley & Sons, Ltd.     

Nonlinear dynamics of parts in engineering systems

By definition, chaotic vibrations arise from nonlinear deterministic physical systems or non-random differential or difference equations. In numerous engineering systems there exist nonlinearities which might affect the dynamic behaviour of the system. The objectives in this work are to summarise previous work on nonlinear dynamics of engineering parts and products and to investigate if research on how nonlinear parts can effect the total behaviour of the products have been performed. It is found that common nonlinear parts are machine elements such as gears, bearings, brakes and suspension systems. The most studied part in a product is of impact hammer type. The products are ordinary products, from sewing machines, drilling machines and printers to railway vehicles. In order to be able to design reliable products the methodology should be further developed to enable use by engineers. One can conclude that the effect of nonlinear parts on the total system behaviour is still a fairly uninvestigated area.     

Expanding the hydride chemistry: antiperovskites A3MO4H (A = Rb,Cs; M = Mo,W) introducing the transition oxometalate hydrides

The four compounds A₃MO₄H (A = Rb, Cs; M = Mo, W) are introduced as the first members of the new material class of the transition oxometalate hydrides. The compounds are accessible via a thermal synthesis route with carefully controlled conditions. Their crystal structures were solved by neutron diffraction of the deuterated analogues. Rb₃MoO₄D, Cs₃MoO₄D and Cs₃WO₄D crystallize in the antiperovskite-like K₃SO₄F-structure type, while Rb₃WO₄D adopts a different orthorhombic structure. ²H MAS NMR, Raman spectroscopy and elemental analysis prove the abundance of hydride ions next to oxometalate ions and experimental findings are supported by quantum chemical calculations. The tetragonal phases are direct and wide band gap semiconductors arising from hydride states, whereas Rb₃WO₄H shows a unique, peculiar valence band structure dominated by hydride states.

The synthesis, structures and electronic properties of the first four heteroanionic compounds containing both hydride and transition oxometalate ions are reported.     

Quantification of Polymer Fouling on Heat Transfer Surfaces During Synthesis

During the synthesis and processing of polymers, a significant amount of polymer may be deposited on the heat transfer surfaces. This deposit is unwanted and is usually named fouling. This study deals with the fouling behavior of a vinyl acetate/vinyl ester copolymer during emulsion polymerization and compares this to fouling of an already reacted vinyl acetate/ethylene copolymer dispersion. Besides the state of polymerization, also the influence of the wall temperature is investigated. The experiments are performed on cooled and heated surfaces. The deposition process is quantified by the mass‐based fouling resistance, the height of the fouling layer, and the surface coverage using a digital microscope. It is found that the state of polymerization and the temperature gradient between wall and bulk exert a strong influence on the fouling behavior, especially on the structure of the fouling layer.     

Studies towards the total synthesis of an epoxy isoprostane phospholipid,a potent activator of endothelial cells

We report studies toward the total synthesis of an epoxy isoprostane, namely the preparation of compound 9 which is an analogue of the elimination product 7 of the naturally occurring epoxy isoprostane 4 by a straightforward route using a three-component coupling, and have shown by several spectroscopic criteria that it closely resembles the natural material.     

New Aquapentachlorochromate(III) Compounds: K2[CrCl5(H2O)] and (NH4)2[CrCl5(H2O)]

Synthesis and crystal structures of two new compounds, K₂[CrCl₅(H₂O)] ( I ) and (NH₄)₂[CrCl₅(H₂O)] ( II ) are reported. Both compounds were prepared from chromium(VI) salts by two different methods and reaction pathways of these syntheses are suggested. The crystal structures of these two aquapentachlorochromates(III) have been determined from three dimensional X‐ray data collected at low temperature, 173 K. The two structures are isomorphous and their unit cell dimensions are quite similar. They are orthorhombic, space groups Pnma, with Z = 4. Both structures are composed of [CrCl₅(H₂O)]^2? units held together by the counterion framework. The coordination around the chromium ion deviates from a regular octahedron due to the shorter equatorial chromium‐oxygen bond.     

Molecular structure of decamethylgermanocene in the solid state

The low temperature X-ray structure analysis of decamethylgermanocene reveals two independent molecules in the unit cell, both of which have a bent sandwich structure with angles between the planes of the two C₅Me₅ rings of 31.26(0.09)° and 31.55(0.10)°, respectively. The perpendicular germanium to ring distances are 220 pm, corresponding to Ge-C bond lengths ranging from 240 to 266 pm.     

Reaction of H-Phosphonate Diesters with Trityl Halides

Abstract

A study on the reaction of H-phosphonate diesten with trityl halides under different reaction conditions has been performed. The reactions were evaluated using 31P NMR spectroscopy. For the study we selected simple H-phosphonate diesters, i.r. diphenyl H-phosphonate and diethyl H-phosphonate. Depending on the reaction conditions used the products obtained differed substantially. Formation of C-phosphonate 1 vs 2 depended primarily on the kind of trityl derivative used for the reaction.     

Methodology for determination of <Superscript>89</Superscript>Sr and <Superscript>90</Superscript>Sr in radiological emergency: II. Method development and evaluation

In this work a method for the determination of both ⁸⁹Sr and ⁹⁰Sr is presented. The method can potentially be used in radiological emergency and deliver results shortly after an incident. The method development was based on theoretical calculations of potential interferences from other fission products and how these could be discriminated when applying different chemical separation schemes. Validation was done on reactor coolant water containing short-lived fission products, and on a reference material. The results indicate that correct results of ⁸⁹Sr and ⁹⁰Sr can be obtained 4 and 9 days, respectively, after an incident.