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.     

Stabilität von Ionenaustauschern gegen Salpetersäure und Bestrahlung. I. Nitrosierender Abbau der Iminodiessigsäuregruppen in Chelonaustauschern

The Stability of Ion Exchangers towards Nitric Acid and Radiation. I. Nitrosative Cleavage of the Iminodiacetic Acid Groups in Chelating Ion Exchangers The behaviour of the chelating ion exchangers Wofatit MC 50, Dowex A 1 and Chelex 100 with aminoacetic acid – and iminodiacetic acid-groups towards nitric acid in the range of the concentration 1…︁10,5 mol/l and at temperatures ⩽68°C was determined. It is found that the COOH capacity and the N content are rapidly reduced leading to the formation of CO₂ and N₂. If the exposure to HNO₃ continues there is again a rise in the COOH capacity. The i.r.- and mass spectra show that the iminodiacetic acid-groups are destroyed by nitrosative cleavage and CHO groups result, which are then oxidized to COOH groups. The mass spectrum shows that the aminoacetic acid-groups of the resin are nitrosated, which has also been confirmed by the use of nitric acid labelled with ¹⁵N.     

Azoperoxide. VI. Selektive Spaltungen von β-Azo-acylperoxiden

Azoperoxides. VI. Selective Decomposition of β-Azoacylperoxides The selective decomposition of the O O-Groups in the azoperoxides 1 and 2 is possible by reaction with dimethylaniline at 35°C. Rate constants were measured and the decomposition products were analyzed. Intermediates are azoalkyl radicals. The radical yield of the amine induced decomposition of 2 in ethylbenzene is 8.2% at 35°C. UV irradiation of the azoperoxides 1 and 2 at 20°C in ethylbenzene results in a quantitative and selective decomposition of the azo groups. Intermediates are C-radicals with intact peroxide groups. The reaction of 1 and 2 with triethylstannane yields reduction products of the O O-groups and the NN-groups, respectively.     

Monoclinic Zirconia Bodies by Thermoplastic Ceramic Extrusion

Two ultrafine, undoped ZrO₂ powders with median primary particle sizes of 9 and 25 nm were used to prepare ceramic suspensions for thermoplastic extrusion. The organic vehicle consisted of an industrial-grade poly(ethylene- co -vinyl acetate) (EVA) or polyethylene (PE-HD) and decanoic acid as a dispersing agent. The powder volume loadings achieved were 44% and 52% by volume for the two powders, respectively. The amount of dispersant needed was calculated from a new model based on available chemisorption sites on the powder surface. Mixing and extrusion were conducted using a conventional modular plastic processing unit. Green bodies were dewaxed up to 450°C in an inert atmosphere and sintered to full density in air at 1060° and 1100°C, respectively. Analysis of the ceramic phase content and the microstructure of the bodies is presented.     

Influence of Membrane Intrusion on Permeate‐Sided Pressure Drop During High‐Pressure Reverse Osmosis

By replacing thermal concentration processes, high‐pressure reverse osmosis has the potential to contribute to cost and energy savings regarding concepts for industrial water reuse. To provide a better understanding of the spiral‐wound element behavior during high‐pressure operation, this study focusses on the investigation of their performance by scrutinizing the crucial effect of the permeate‐sided pressure drop induced by membrane‐spacer interactions. The experiments show a considerable influence of membrane intrusion on the element performance with a strong dependence on the feed pressure.     

Selective Hydrolysis of Arabinogalactan into Arabinose and Galactose Over Heterogeneous Catalysts

Abstract  

The application of solid acid catalysts for the production of monomers from hemicelluloses can be one of the key steps in developing the concept of an integrated forest biorefinery. Arabinogalactans (AG) are hemicelluloses which can be extracted on an industrial scale from larch wood species and has a great potential as a sustainable feedstock for bio-based products. Hydrolysis of AG to monomers over acidic heterogeneous catalysts (Smopex-101 and Amberlyst 15) was successfully demonstrated for the first time to selectively produce arabinose as the primary product, followed by the release of galactose without further degradation of the monomers.     

Anticancer Potential of (Pentamethylcyclopentadienyl)chloridoiridium(III) Complexes Bearing κP and κP,κS‐Coordinated Ph2PCH2CH2CH2S(O)xPh (x=0–2) Ligands

Iridium(III) complexes of the type [Ir(η⁵‐C₅Me₅)Cl₂{Ph₂PCH₂CH₂CH₂S(O)_xPh‐κP}] (x=0–2; 1 – 3 ) and [Ir(η⁵‐C₅Me₅)Cl{Ph₂PCH₂CH₂CH₂S(O)_xPh‐κP,κS}][PF₆] (x=0–1; 4 and 5 ) with 3‐(diphenylphosphino)propyl phenyl sulfide, sulfoxide, and sulfone ligands Ph₂PCH₂CH₂CH₂S(O)_xPh were designed, synthesized, and characterized fully, including X‐ray diffraction analyses for complexes 3 and 4 . In vitro studies against human thyroid carcinoma (8505C), submandibular carcinoma (A253), breast adenocarcinoma (MCF‐7), colon adenocarcinoma (SW480), and melanoma (518A2) cell lines provided evidence for the high biological potential of the neutral and cationic iridium(III) complexes. Neutral iridium(III) complex 5 proved to be the most active, with IC₅₀ values up to about 0.1 μM , representing activities of up to one order of magnitude higher than cisplatin. Using 8505C cells, apoptosis was shown to be the main mechanism through which complex 5 exerts its tumoricidal action. The described iridium(III) complexes represent potential leads in the search for novel metal‐based anticancer agents.     

Characteristics of carcass composition,fat metabolism and meat quality of genetically different pigs

The aim of the study was to quantify the differences in meat and fat quality and lipid metabolism of pigs with either high or medium capacity for lipid accretion. A total of 58 castrated males of the breeds German Saddle Back (SB) and German Landrace (DL) were included in the experiment. Animals were housed individually and fed twice daily semi ad libitum. Saddle Back pigs indicated a lower lean meat content (41.4% vs 52.6%) and a higher fat percentage (40.9% vs 28.2%) in comparison to DL as a result of high lipid accumulation. The larger fat content of SB was related to an increased intramuscular fat concentration of longissimus muscle. A significant correlation between intramuscular fat content and fatty acid composition was estimated in both breeds. The relative concentration of saturated fatty acids was significantly increased in SB pigs. The percentage of polyunsaturated fatty acids (8.3%) in SB muscle fat was significantly lower than in DL muscle fat (10.7%). The de novo biosynthesis of fatty acids resulted in mostly saturated fatty acids and oleic acid. The higher activities of lipogenetic enzymes in backfat of SB proved a higher lipogenetic capacity. There were no significant differences in meat quality traits of longissimus muscle between the two breeds.     

Polyphenolrückgewinnung aus Olivenölabwasser durch Einsatz von Membrantechnologie

Olive mill wastewater (OMW) is obtained as byproduct of oil production in large quantities after the olive harvest, mainly in the Mediterranean region. One problem is the high load of organic matter, such as phytotoxic polyphenols, which causes significant environmental problems. However, due to their antioxidant properties the use of these polyphenols is also popular in several industry branches, e.g. production of plastics, cosmetics and drugs. A combined wastewater treatment permits besides water purification also recovery of the polyphenolic compounds for industrial use. One possibility is membrane technology. An overview of research studies concerning polyphenol recovery from OMW using membrane technologies is given.     

Phase separation of a hafnium alkoxide-modified polysilazane upon polymer-to-ceramic transformation—A case study

The polymer-to-ceramic transformation of a hafnium alkoxide-modified polysilazane was investigated via thermogravimetric analysis coupled with in situ mass spectrometry (TG/MS), nuclear magnetic resonance (MAS NMR) and transmission electron microscopy (TEM). The results indicate that the structural evolution of the polysilazane upon ceramization is strongly affected by the modification with hafnium alkoxide. Thus, the content of carbon in the ceramic backbone was relatively low, whereas a large amount of SiN₄ sites and a segregated carbon phase was present in the sample. Furthermore, this study revealed the formation of a SiHfCNO amorphous single phase ceramic via pyrolysis of the polymer at 700 °C, whereas at higher pyrolysis temperatures precipitation of hafnia was observed, leading to an amorphous hafnia/silicon carbonitride ceramic nanocomposite. The precipitation of hafnia was shown to not rely on decomposition processes, but to be a result of rearrangement reactions occurring within the ceramic material.