Plasma Lipid Peroxidation and Vitamin E Supplementation during High Intakes of Fish-Oil Fatty Acids

High intakes of fish oil concentrates (15g/day MaxEPA) resulted in increased TBARS in plasma after 2 weeks irrespective of the vitamin E intake and plasma content. After 4 weeks TBARS values returned to normal despite continued MaxEPA supplementation and different vitamin E levels. Fish oil supplements resulted in increased whole-blood aggregation and higher plasma glucose concentrations which did not occur when extra vitamin E was given. No significant differences in plasma cholesterol levels were observed.     

Lubrication Studies with Alumina-on-Alumina, Steel-on-Steel, and Steel-on-Alumina Bearing Systems

In metal bearing systems, good lubricants for boundary lubrication generally show chemical interaction with the bearing surface under the conditions of temperature and pressure generated in the sliding contact. In this study, tests in a four-ball wear tester have been used to compare lubricants under similar loadings using steel-on-steel, steel-on-alumina, and alumina-on-alumina bearing systems. In general, the alumina appears to be far less reactive with lubricants than steel. Alumina-on-alumina bearing systems do show a sensitivity to lubricant chemical composition with generally higher wear values than the other two bearing systems. Steel-on-alumina bearing systems generally show better wear characteristics than the all-alumina systems which indicates the improved chemical interactions between the steel and the lubricant. This study shows that the chemical reactivity of the lubricant with the bearing surface is important in the wear process.     

Identification of the state of palladium in various hydrogenation catalysts by XPS

Various commercial supported palladium hydrogenation catalysts were studied by XPS and treated at ambient pressure with hydrogen and air. Unused catalysts exhibit a significant fraction of divalent Pd (oxide) which is reduced by hydrogen treatment at room temperature. Exposure to air in systems with carbonate, alumina, silica or active carbon as support causes the formation of a solid solution of oxygen in Pd characterized by a Pd 3d chemical shift of ca. + 0.4 eV. The absolute binding energy of Pd depends strongly on the matrix, indicating a significant contribution of extra-atomic screening, which prevents a direct comparison of reference samples and supported catalysts. Using the oxidation of CO to CO₂ at 300 K as in situ chemical probe it was confirmed that Pd supported on carbonate, silica and alumina exists in the same metallic state which could be activated for the test reaction irrespective of the variation in XPS binding energies.     

Characterizing cerebral oxygen metabolism employing oxygen-17 MRI/MRS at high fields

This article provides a comprehensive overview of oxygen (¹⁷O) magnetic resonance spectroscopy and imaging, including the advantages and challenges offered by the different methods developed thus far. The physiological role and relevance of oxygen, and its participation in aerobic metabolism, are addressed to emphasize the importance of the investigations and the efforts related to these developments. Furthermore, a number of methods employed in the determination of the cerebral metabolic rate of oxygen in neural cells will be presented, focusing primarily on methodologies enabling absolute quantification.     

Structural characterization of octadecyl modified MCM-41 silica by NMR and FTIR

Mesoporous MCM-41 silica spheres were prepared via the pseudomorphic route, using commercial prontosil silica spheres. Surface modification offers a great opportunity to adjust both the pore structure and surface properties of MCM-41 type materials which results in materials of improved hydrothermal and mechanical stability to make them promising candidates for chromatographic applications. In the present context, the obtained MCM-41 silica spheres were surface modified with octadecyl (C₁₈) alkyl chains, by using direct grafting and surface polymerization methods, in order to vary the degree of surface hydrophobicity. The resulting materials were characterized before and after surface modification using various characterization techniques, with special emphasis on NMR and FTIR spectroscopies, for studying the attachment, mobility and the conformational order of the attached alkyl chains.     

Photokatalytische Bildung von Wasserstoff aus Thiolen in Gegenwart von Vitamin B12-Modellverbindungen mit Azid als photochemischem Opferliganden

Photocatalytic Hydrogen Formation from Thioles in the Presence of Vitamin-B₁₂ Model Complexes with Azide as Photochemical Sacrificial Ligand The photolysis of [N₃Co(chelat)B] complexes ( 1–3 ) (chelat = dimethylglyoxime, dmg; N,N′-o-phynylenebis(salicylidenimine), salphen; N,N′-ethylene-bis(salicylidenimine), salen; B = pyridine) leads by homolytic cleavage of the Co–N₃ bond to both coordinatively unsaturated cobalt(II) chelates [Co(chelat)B] and N₃ ligand radicals that undergo fast decay to dinitrogen. The photolysis of the cobalt (III) complexes 1–3 in the presence of thiophenole and other thioles proceeds catalytically and yields the corresponding disulphides and dihydrogen. The mechanism of this photocatalytic generation of dihydrogen is due to the catalytic activity of the coordinatively unsaturated cobalt(II) species formed photochemically. A photocatalytic cycle is proposed describing the generation of hydrogen. Possible photochemical and thermal steps of that cycle are discussed.     

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.     

Photochemische Untersuchungen von Vitamin B12-Modellverbindungen mit Azid bzw. Thiolat als Axialliganden – Precursorverbindungen für koordinativ ungesättigte Cobalt(II)-Komplexe

Photochemistry of Azido and Thiolato Vitamin-B₁₂ Model Complexes as Precursor Compounds for Coordinatively Unsaturated Cobalt(II) Complexes The photolysis of [LCo(chelat)B] complexes ( 1–3 ) (L = azide, N; thiolate, RS⁻; chelat = dimethylglyoxime, dmg; N,N′-o-phenylene-bis(salicylidenimine), salphen; N,N′-ethylene-bis(salicylidenimine), salen; B = pyridine, imidazole, triphenylphosphine) leads upon the homolytic cleavage of the Co L bond to both coordinatively unsaturated reactive cobalt(II) chelates [Co(chelat)B] and ligand radicals L^•. The efficiency of these photochemical redox reactions is described in relation to the structure of the cobalt(III) chelates, the wavelength of irradiation, the light-intensity as well as the solvents and substrates used during the photochemical experiments. Further, sensitization experiments using [Ru(bipy)₃]Cl₂ as sensitizer are described and the redox potentials of the investigated complexes are discussed.