Selektivhydrierung von Fettstoffen mit metallorganischen Mischkatalysatoren nach Ziegler-Sloan-Lapporte I: Selektive Hydrierung von Linolsäuremethylester und Modelldienen mit isolierten Doppelbindungen

Selective Hydrogenation of Fats and Derivatives Using Ziegler-Type Organometallic Catalysts I: Selective Hydrogenation of Methyllinoleat and Other Dienic Compounds with Isolated Double Bonds Homogeneous catalysts of Ziegler-Sloan-Lapporte-type, containing nickel, cobalt or palladium, were used to hydrogenate methyllinoleate under very mild conditions selectively to monounsaturated products. The question, wether this selectivity is caused by the 1,4-position of the olefinic double bonds, led to hydrogenation experiments with non-conjugated α,ω-dienes of different chain length. A significant selectivity was only observed for the reduction of 1,4-pentadiene to pentene, dienes with greater distance between the double bonds than in linoleic acid were hydrogenated with less selectivity. To explain these facts, a kinetic model, including catalyst-substrate-complexes of different stabilities, is proposed.     

Microviscosity of togavirus membranes studied by fluorescence depolarization: influence of envelope proteins and the host cell

The microviscosities of the hydrophobic regions of the membranes of intact Semliki forest and Sindbis viruses grown on BHK-21 cells, of liposomes derived from the extracted viral lipids, and of protease-treated virions were measured by fluorescence depolorization using the fluorescence probe 1, 6-diphenyl-1,3,5-hexatriene. The intact virus membranes were found to have a higher microviscosity than did virus-derived liposomes, indicating the viral envelope proteins contribute to microviscosity. However, protease-treated virus, devoid of protruding spikes but with residual lipophilic peptide tails, was found to have a microviscosity more similar to that of the intact virus than to that of protein-free liposomes. Sindbis virus grown in BHK-21 cells at 37 C had a much higher microviscosity than did Sindbis virus grown on Aedes albopicuts cells at 22 C. Sindbis virus grwon in A. albopictus and BHK-21 cells also gave higher microviscosity values than did the intact host cells. These data indicate that both the virion proteins and the cellular lipids selected during viral growth and maturation contribute to the increased microviscosity of togavirus membranes.     

Extraction and properties of microcapsulated alpha-chymotrypsin

A method of microencapsulating of the proteolytic enzyme alpha-chymotrypsin into semi-permeable nylon membranes is worked out. The membrane is a polimer of 1,6-hexamethylenediamine and sebacoyl chloride. alpha-Chymotrypsin is enclosed into the capsule together with polyethyleneimine, capable of joining the walls of microcapsules and making the membrane more stable. The optimal concentrations of polyenthyleneimine and alpha-chymotrypsin are 5% and 1% correspondingly. The highest yield of microencapsulated enzyme was obtained for completely acetylated delta-chymotrypsin. The kinetic properties of microencapsulated alpha-chymotrypsin change very slightly as compared to those of the native one.     

Selektivhydrierung von Fettstoffen mit metallorganischen Mischkatalysatoren nach Ziegler-Sloan-Lapporte IV: Isomerenverteilung während der Hydrierung mehrfach ungesättigter Fettsäuremethylester

Selective Hydrogenation of Fats and Derivatives Using Ziegler-Type Organometallic Catalysts IV: Distribution of Isomers during Hydrogenation of Polyunsaturated Fatty Acid Methylesters Hydrogenation of methyl linoleate using a Ziegler-type catalyst, containing nickel stearate and triethyl aluminium, proceeds mainly without previous conjugation or trans-isomerization. Both olefinic double bonds are hydrogenated with equal probability. As long as the reaction mixture contains double unsaturated esters, these compounds are inhibiting hydrogenation and isomerization of single unsaturated esters. During hydrogenation of methyl linolenate there is only less selectivity to formation of methyl linoleate. Intermediate product is a mixture of single and double unsaturated fatty acid methylesters. In the latter compounds after consumption of triple unsaturated esters both double bonds are separated by two or more methylene groups. Polyenic compounds with 1,4-position of olefinic double bonds are preferably hydrogenated than polyenic compounds with greater distance between the double bonds.     

Verlustfreie Katalysatorrezirkulation durch ein neuartiges Verfahrensprinzip bei der Hydroformylierung höhermolekularer Olefine

Free-of-loss Catalyst Recycling in the Hydroformylation of Higher Molecular Olefins by a Novel Process Technology In this paper a novel homogenous-heterogeneous procedure for the hydroformylation reaction of higher molecular olefins is presented, at which the reaction itself is homogeneously catalyzed and only after the reaction the catalyst complex is heterogenized only for separation. This procedure is achieved by using the lithium salt of triphenylphosphine monosulfonic acid (Li-TPPMS) as complex ligand for the hydroformylation catalyst and methanol as solubilizer. Li-TPPMS and its complexes with metal carbonyls are highly soluble in water and methanol, but completely insoluble in almost all other organic solvents. After the reaction the methanol is distilled off. The catalyst system becomes insoluble and can be separated from the reaction product by filtration or by extraction with water. The aqueous catalyst solution is evaporated to dryness and the catalyst system dissolved in methanol for a new reaction.     

Self-assembled nano-phase particles for enhanced oxygen barrier coatings on polymeric materials

Aqueous-based inorganic–organic hybrid coating materials comprising self-assembled nanophase particles (SNAP) were investigated for their potential to confer high gas barrier performance to flexible polymeric substrates, particularly to improve suitability of the substrates as encapsulation materials for organic photovoltaic (OPV) devices. Potential benefits of this approach include versatility in barrier coating formulation to achieve specific barrier properties, and application of coatings in a reel-to-reel process under ambient conditions. The present study focused on enhancement of the oxygen barrier performance of polypropylene (PP) substrates by applying SNAP-based coatings with and without the addition of an oxygen scavenging additive. SNAP particles were characterised using ²⁹Si NMR and dynamic light scattering, and coatings were analysed using atomic force microscopy and X-ray photoelectron spectroscopy. SNAP particle preparation and coating formulation was optimised with respect to oxygen transmission rate (OTR) of the coating on PP, and mechanical properties of the coating solution. In the absence of oxygen scavenger, the lowest OTR attained for the SNAP-based coatings was 0.87 cm³ mil m⁻² day⁻¹ atm⁻¹. The OTR was further reduced to 0.22 cm³ mil m⁻² day⁻¹ atm⁻¹ on addition of 9,10-anthraquinone-2,6-dissulfonic acid (AQDS) into the coating as an oxygen scavenger. These results represent a decrease in OTR by 4 orders of magnitude compared with uncoated PP, and the oxygen barrier obtained by addition of AQDS surpasses the performance of many plastic materials considered to be high oxygen barriers in the food and pharmaceutical industries.