A Study on the Feasibility of Measuring the Emissivity with the Laser-Flash Method

The laser-flash method is a fast, widely used and well established technique to measure the thermal diffusivity. Since its introduction in the 1960s, it was proposed to expand this technique to the measurement of heat capacity and emissivity. Currently, the measurement of spectral emissivity at high temperatures is connected with relatively large uncertainties, although the spectral emissivity is an essential parameter for applications, e.g., in the lamp industry and fusion research. In this work, a theoretical study is presented on the possibility of emissivity measurements using the laser-flash method. Two mathematical approaches are discussed which solve the problem, that a measured temperature rise—necessary to calculate the emissivity—itself depends on the emissivity. It is shown that both methods have a negligible arithmetic error, making them applicable to be used in future work.     

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.     

Partialsynthesen von Cardenoliden und Cardenolid-Analogen. XIII. Synthese substituierter 14,21-Epoxy-5β,14β-card-20(22)-enolide

Partial Syntheses of Cardenolides and Cardenolide Analogues. XIII. Synthesis of Substituted 14,21-Epoxy-5β,14β-card-20(22)-enolide The 12-substituted 14,21-epoxy-5β,14β-card-20(22)-enolides 3 and 5 were synthesized by oxidation of the appropriate 17β-(3-furyl) derivatives 2b and 2c , respectively, with chromic acid. 5 was converted to the conjugated Δ⁹⁽¹¹⁾-12-ketone 6 by dehydrogenation with selenium dioxide. The biological activities of the new compounds were investigated and are discussed.