Longitudinal nuclear relaxation measurements in hcp H2

Measurements of T₁ in the hep phase of H₂, over the temperature range 2°–12°K and the ortho concentration range between 0.5 and 0.97 are presented. At temperatures below 10°K, the thermally activated self-diffusion is negligible and the mechanism for nuclear relaxation is that attributed by Moryia and Motizuki and by Harris to intramolecular dipolar interaction, modulated by intennolecular electric quadrupole-quadrupole (EQQ) interaction. The gaussian approximation for the correlation function was used by these authors to predict T₁. From the comparison between experiment and theory, we determine the EQQ parameter Γ/k_B to be 0.67°K. Above 10°K the effect of diffusion influences T₁, and the experimental results for an 88 per cent ortho H₂ sample up to the melting point suggest that the relaxation mechanisms resulting from EQQ interaction and diffusion are not independent of one another.     

Synthesis of tumor-associated glycopeptide antigens for the development of tumor-selective vaccines

In contrast to normal cells, the glycoprotein profile on epithelial tumor cells is distinctly altered. Due to an incomplete formation of the glycan side-chains resulting from a premature sialylation, additional peptide epitopes become accessible to the immune system in mucin-type glycoproteins on tumor cells. These tumor-associated structure alterations constitute the basis for a selective immunological attack on cancer cells. For the construction of immunostimulating antigens, glycopeptide partial structures from the mucins MUC1 and MUC4 carrying the tumor-associated sialyl-T(N), alpha2,6-sialyl-T and alpha2,3-sialyl-T antigens have been synthesized. Employing different linkers such as the allylic HYCRON or the fluoride-sensitive PTMSEL anchor, the antigenic glycopeptide structures were constructed on the solid phase utilizing pre-assembled glycosyl amino acid building blocks prepared in solution by convergent chemical or chemoenzymatic strategies. The proliferation of cytotoxic T cells has been induced applying a construct composed of a sialyl-T(N) MUC1-glycopeptide conjugated with a tetanus toxin T cell peptide epitope.     

‘Face-to-Face’-Benzo-anellierte homologe Hypostrophene. Synthesen,Röntgenstrukturanalysen und PE-Spektren

‘Face-to-Face’ Benzo-anellated Homologous Hypostrophenes. Syntheses, X-Ray-Structure Analyses and PE Spectra ‘Face-to-face’ Benzo-anellated homologous hypostrophenes (series M ), of interest as substrates for [6 + 6]-photocycloaddition reactions, have been synthesized. From X-ray structural analyses of 13b and 13c shortest C? C distances of 2.80(2.76)/2.71 Å and interorbital angles (ω) of 129° (128°)/130° between the benzene rings have been determined. The PE spectra are discussed in the context of transannular π,π interactions.     

Die Kristallstruktur des Natriumorthogermanats,Na4GeO4

The crystal structure of the title compound has been determined from single crystal X-ray diffraction data and refined toR=0.125. The unit cell is triclinic, space group P, (No. 2),a=5.688(1),b=5.701(1),c=8.583(1) Å, =81.32(1), =71.50(1), =67.95(1)° andZ=2. The structure consists of isolated [GeO₄] tetrahedra linked together by four- and five-coordinate sodium atoms. Na₄GeO₄ is isostructural with Na₄CoO₄ (which has been described to be non-centrosymmetric and for which a centrosymmetric model is presented), K₄GeO₄, K₄SnO₄ and K₄PbO₄.

     

Spektroskopische Bestimmung der Doppelbindungslage in Phospholinen

Zusammenfassung Die Spin-Spin-Kopplungskonstanten der olefinischen Protonen mit dem ³¹P sowie die Feinstruktur der ¹H-NMR-Spektren sind charakteristisch für die Lage der Doppelbindung. Vielfach kann auch die Intensität der _C=C-Schwingung im IR zur Bestimmung der Doppelbindungslage benutzt werden. Massenspektren geben nur in Ausnahmefällen Hinweise, können jedoch zur exakten Bestimmung des Molekulargewichts dienen.

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Summary The spin-spin coupling constants of the olefinic protons with the phosphorus-31 as well as the fine structure of the nmr-spectra are characteristic for the position of the double bond. In the infrared, the intensity of the _C=C-frequency may often serve as indication of the position of the double bond. The applicability of mass spectra is limited to a small number of compounds. They may be used, however, for an accurate determination of the molecular weight.

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Die Ausführung der Untersuchungen erfolgte unter Mitarbeit von Herrn F. Dlugosch, Herrn H. Au und Fräulein R. Barth.

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Herrn Dr. C. A. Reilly, Shell-Development Company, Emeryville, USA, danken wir für die Überlassung getesteter Programmkartensätze zur Berechnung der NMR-Spektren.     

4-Aryldihydropyridines,a New Class of Highly Active Calcium Antagonists

The aryldihydropyridines first prepared by Hantzsch almost 100 years ago have recently been found to be highly effective calcium antagonists with suitable pharmacological profiles. An illustrative example is dimethyl-l,4-dihydro-2,6-dimethyl-4-(o-nitrophenyl)pyridine-3,5-dicarboxylate (Nifedipine) which is already employed therapeutically. This substance lowers the frequency of attack of angina pectoris and reduces blood pressure. The discovery of the therapeutic activity of this class of substances initiated renewed investigation of the Hantzsch condensation and the synthesis of numerous 4-aryldihydropyridines and related compounds. Qualitative and quantitative structure/activity relationships of these substances can be deduced from their biological data.     

Synthese und Konfigurationszuordnung von potentiell antimikrobiellen 5,6-Dihydroxyisobenzofuranonen

Summary Oxidation of isobenzofuranone1 yielded in a diastereoselective reaction epoxide2. Acidolysis of2 resulted in a mixture oftrans-glycols6 a (88%) and7 a (4%), which were separated by crystallization. The relative configuration of6 a and7 a at the chiral centers 3 a, 5, 6, and 7 a was determined by¹H-NMR-spectroscopy and X-ray analysis of O-acetylated and 7 a-methylated derivatives.

     

Chemoselective Removal of Protecting Groups from O-Glycosyl Amino Acid and Peptide (Methoxyethoxy)ethyl Esters Using Lipases and Papain

The selective C-terminal deprotection of O-glycopeptide (methoxyethoxy)ethyl esters is achieved under mild conditions (pH 6.6, 37 degrees C) by enzymatic hydrolysis using papain or lipase M from Mucor javanicus to give building blocks useful for chain-extending glycopeptide synthesis. On the other hand, the selective removal of acetyl protecting groups from the saccharide portion of glycopeptides is accomplished by alternative enzymatic hydrolysis with lipase WG from wheat germ to furnish model substrates for enzymatic glycosyl transfer reactions in order to extend the carbohydrate side chain of these conjugates.