Time-resolved GISAXS and cryo-microscopy characterization of block copolymer membrane formation

Time-resolved grazing-incidence small-angle X-ray scattering (GISAXS) and cryo-microscopy were used for the first time to understand the pore evolution by copolymer assembly, leading to the formation of isoporous membranes with exceptional porosity and regularity. The formation of copolymer micelle strings in solution (in DMF/DOX/THF and DMF/DOX) was confirmed by cryo field emission scanning electron microscopy (cryo-FESEM) with a distance of 72 nm between centers of micelles placed in different strings. SAXS measurement of block copolymer solutions in DMF/DOX indicated hexagonal assembly with micelle-to-micelle distance of 84–87 nm for 14–20 wt% copolymer solutions. GISAXS in-plane peaks were detected, revealing order close to hexagonal. The d-spacing corresponding to the first peak in this case was 100–130 nm (lattice constant 115–150 nm) for 17 wt% copolymer solutions evaporating up to 100 s. Time-resolved cryo-FESEM showed the formation of incipient pores on the film surface after 4 s copolymer solution casting with distances between void centers of 125 nm.     

Chromatographische Untersuchungen zur Polydispersität von Hydroxyethylstärke

Chromatographic Studies on the Polydispersity of Hydroxyethyl Starch. A representative sample of clinically used hydroxyethyl starch was separated by semipreparative HPSEC into narrow fractions in the range of approx. 3.000 to 800.000 D. The original sample and selected fractions were characterised by gaschromatographic methylation analysis according to their substitution degrees MS and DS, which were differentiated by the substitution positions at C2, C3 and C6 of the anhydroglucoses and their kind of glycosidic bonding α-1, α-1,4 or α-1,4,6, respectively. Furthermore, polydispersity in relations to the degree of branching was determined. Mark-Houwink and molecular weight distribution parameters determined by multi-detection HPSEC are reported. The presented data demonstrate a extensive homogeneity of the original sample. The clinical relevance is discussed.     

Cx43 Promotes Endothelial Cell Migration and Angiogenesis via the Tyrosine Phosphatase SHP-2

The gap junction protein connexin 43 (Cx43) is associated with increased cell migration and to related changes of the actin cytoskeleton, which is mediated via its C-terminal cytoplasmic tail and is independent of its channel function. Cx43 has been shown to possess an angiogenic potential, however, the role of Cx43 in endothelial cell migration has not yet been investigated. Here, we found that the knock-down of Cx43 by siRNA in human microvascular endothelial cells (HMEC) reduces migration, as assessed by a wound assay in vitro and impaired aortic vessel sprouting ex vivo. Immunoprecipitation of Cx43 revealed an interaction with the tyrosine phosphatase SHP-2, which enhanced its phosphatase activity, as observed in Cx43 expressing HeLa cells compared to cells treated with an empty vector. Interestingly, the expression of a dominant negative substrate trapping mutant SHP-2 (CS) in HMEC, via lentiviral transduction, also impaired endothelial migration to a similar extent as Cx43 siRNA compared to SHP-2 WT. Moreover, the reduction in endothelial migration upon Cx43 siRNA could not be rescued by the introduction of a constitutively active SHP-2 construct (EA). Our data demonstrate that Cx43 and SHP-2 mediate endothelial cell migration, revealing a novel interaction between Cx43 and SHP-2, which is essential for this process.     

Safety investigations of trinitrotoluene/water emulsions

In the disposal of explosives, preparation of the dismantled material is necessary before subjecting it to a breakdown process. Knowledge of the material properties and determination of safety-related parameters are major prerequirements when designing a disposal facility and increasing handling safety. When TNT is treated using emulsion processing, a desensitization of the TNT melt via the aqueous phase is obtained, in addition to increasing the surface area of the TNT phase. During the entire process of TNT treatment, the system is exposed to a wide range of different stresses as a result of the mechanical energy applied. This study presents the results of an investigation on the sensitivity of pure TNT melts and TNT/water emulsions at different concentrations on exposure to the applied impact or shock energies. It is found that the impact sensitivity of a TNT/water emulsion is lower by a factor of 4 when the TNT concentration has been reduced from 50 wt % to 30 wt %. On exposure to stress from a detonation shock wave, a desensitization of the system due to the aqueous phase is also found, so that the safety of the TNT treatment process can be increased by using a TNT/water emulsion when applying mechanical breakdown methods.     

Photoinitiierte Polymerisation mit Dialkoxythiocarbonyldisulfiden – eine Polymerisationsreaktion mit Primärradikalabbruch

Photoinitiated Polymerization with Dialkoxy Thiocarbonyl Disulfides – a Polymerization Reaction with Primary Radical Termination The photoinduced free radical polymerization of methyl methacrylate (MMA) and some other vinyl monomers using dialkoxy thiocarbonyl disulfides ( 1 – 4 ) as photoinitiators was studied. The photolysis of these initiators leads to cleavage of the S S bond, which was determined by spin trapping experiments with phenyl tert-butyl nitrone. No evidence was found for a further thermal decomposition of the primary alkoxy thiocarbonyl sulfide radicals (R·) at room temperature. In the absence of scavengers the primary radicals react back exclusively to the initial compounds, due to a strong cage effect. By means of UV spectroscopic measurements and in the presence of MMA the quantum yields of the initiator decomposition were detected to be 0.8. The polymerization of acrylic and methacrylic derivatives can be initiated by the R·, contrary to the situation with fumarates and maleates. The mechanism of MMA polymerization depends on the light intensity absorbed by the initiators. At high intensities the combination of primary and polymer radicals terminates the chain reaction. This follows from the measured monomer exponent of α = 2, the light intensity exponent of β = 0,2 and the number of thiocarbonyl end groups of 2 in the polymers isolated. Contrary to this, in the low intensity region the experimental data obey the ideal kinetic equation. Kinetic modelling gives evidence for an interaction of the monomer with the cage radicals.     

Performance evaluation principles for vector- and multiprocessor systems

Skilful computer system measurement, modelling and performance evaluation techniques are needed for supercomputer architectures. They allow to accurately determine characteristics performance values, to find potential hardware- and software-bottleneck; they also help to efficiently distribute and schedule user tasks. This paper is an extended version of a tutorial contribution at the IEEE CompEuro 87 and surveys fundamental performance issues and their solution for supercomputer architectures.     

Processing of Emulsions of Explosive Melts

In the context of the waste disposal of explosives, generally the suitability of the processing method is of importance. When processing explosives, the choice method of treatment, after having melted out the explosive, is to emulsify the aqueous solution of the melt for the purpose of disposing the emulsified explosives by subsequent emulsions the first aim is to produce a multiple phase system consisting of two components that are practically immiscible. For this purpose, emulsifying machines that work according to the rotational-stationary principle are used. Colloid millsm, for instance, employ the viscous tensions in the laminar flow field to disrupt the droplets. Gear-ring dispersing machines, on teh other hand, will cause a disruption oif the droplets by turbulent eddies. In this work the emulsifying equipment along with the mechanisms of drop deformation with subsequent disruption will be trated.     

Phytochemical composition and antioxidant capacity of various botanical parts of the fruits of Prunus × domestica L. from the Lorraine region of Europe

Mirabelle plums represent a famous fruit from the Lorraine region, however little is known about their phytochemical composition. The oil of the fruit contained predominantly oleic acid (59%) and linoleic acid (29%). The total content of phenolic antioxidants in the whole fruits was 5.338 g/kg with 456 mg/kg (9%), 701 mg/kg (13%) and 4159 mg/kg (78%) detected in the peels, flesh and pits respectively. The peels contained solely 3,4-dihydroxybenzoic acid (270 mg/kg) and rutin (186 mg/kg), the flesh exclusively echinoids (723 mg/kg), whereas the pits contained a rich variety of phenolic compounds (4.2 g/kg) dominated by amygdalin (3.8 g/kg), but with significant contributions from vanillin (102 mg/kg), guajacyl-glycerin-coniferyl aldehyde isomers (87 mg/kg), dehydro-diconiferyl aldehyde (52 mg/kg), and vanillin diglucoside (48 mg/kg). Of the major phenolic compounds tested across a range of in vitro assays, rutin was the superior antioxidant.