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  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 113 (1980), S. 2891-2915 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Riburonic and Lyxuronic Purine Nucleoside Derivatives - Synthesis, Separation, and Structural Elucidation of the Various Linkage Isomers1)By direct, molten state condensation of riburonic (1) and lyxuronic acid derivatives (14) with silylated purine (2a), chloro- and amino-purines (2b-g), respectively, N-7 and N-9 purinyl nucleosides with both α- and β-configuration were obtained in mixtures of varying composition, depending, inter alia, on the structure of the carboxyl function; the linkage isomers were separated quantitatively by medium pressure chromatography on silica gel columns of high separation potential. To test the known criteria for structural assignment on the wide range of glycosidic isomers thus available, UV, 1H-NMR and 13C-NMR spectra were recorded under standardized conditions for all derivatives. Assignment of purine regiochemistry from UV data proved not reliable; it can be established, though, unequivocally from the 13C-NMR data of the aglycone. The configuration at the anomeric center of the sugar moiety, on the other hand, is readily determined from the furanoside 13C-shifts of the 2′,3′-O-isopropylidenated nucleosides.
    Notes: Durch Schmelzkondensation von Riburonsäure- (1) und Lyxuronsäure-Derivaten (14) mit silyliertem Purin (2a) bzw. silylierten Chlor- und Aminopurinen (2b-g) wurden - u. a. in Abhängigkeit von der Struktur der Carboxylfunktion - verschiedene Anteile an N-7- und N-9-verknüpften α- und β-konfigurierten Purinnucleosiden erhalten; die Verknüpfungsisomeren wurden durch Mitteldruckchromatographie an leistungsfähigen Trennsäulen quantitativ aufgetrennt. Um die bisherigen Kriterien für die Strukturzuordnung daran zu prüfen, wurden von allen Derivaten unter standardisierten Bedingungen UV-, 1H-NMR- und 13C-NMR-Spektren aufgenommen. Die Regiochemie am Purin war zwar nicht zuverlässig aus UV-Daten, jedoch eindeutig aus den 13C-NMR-Daten des Aglycons zu ermitteln; die Konfiguration am anomeren Zentrum des Zuckers andererseits ließ sich aus den Furanosid-13C-Verschiebungen der 2′,3′-O-isopropyliden-geschützten Nucleoside sicher bestimmen.
    Additional Material: 9 Tab.
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 115 (1982), S. 3427-3435 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: [4 + 2] Cycloadducts with Alternate Structure from 7,7-Difluoro- and 7,7-Dialkoxy-1,3,5-cycloheptatrienes and 4-Phenyl-1,2,4-triazoline-3,5-dioneWith 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD), 7,7-difluoro-, 7,7-dimethoxy-, 7,7-(trimethylenedioxy)- and 7,7-(ethylenedioxy)-1,3,5-cycloheptatriene (1c-f) form 1:1 cycloadducts of different structure. For the cycloadducts from 1d, e and cycloheptatriene itself, 13C and 1H NMR spectra establish a structure formally derived from the norcaradiene valence tautomer (2a, d, e) by [4 + 2] cycloaddition (NCD-type, 4). 1c, f and tropone, on the other hand, undergo [4 + 2] cycloaddition at C-1/C-4 of the cycloheptatriene skeleton, yielding adducts of the CHT-type 3.
    Notes: 4-Phenyl-1,2,4-triazolin-3,5-dion (PTAD) bildet mit 7,7-Difluor-, 7,7-Dimethoxy-, 7,7-(Trimethylendioxy)- und 7,7-(Ethylendioxy)-1,3,5-cycloheptatrien (1c-f) 1:1-Cycloaddukte unterschiedlicher Struktur. Nach 13C- und 1H-NMR-Spektren besitzen die Cycloaddukte aus 1d, e und dem unsubstituierten Cycloheptatrien eine Struktur, die sich vom Norcaradien-Valenztautomeren (2a, d, e) durch [4 + 2]-Cycloaddition ableiten läßt (NCD-Typ, 4). Bei 1c, f und beim Tropon dagegen erfolgt [4 + 2]-Cycloaddition an C-1/C-4 des Cycloheptatrien-Skeletts: es entstehen Addukte vom CHT-Typ 3.
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  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Rapid Communications 16 (1995), S. 435-447 
    ISSN: 1022-1336
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A cross-linked polysiloxane carrying non-ionic amphiphilic side-groups attached with their hydrophobic end to the polymer backbone is synthesized. The amphiphilic groups are selectively deuterated at the α-position of the hydrophobic alkyl chains. The phase behavior with water is studied by deuterium nuclear magnetic resonance spectroscopy. A lamellar phase (La) is observed on the low-water-concentration side of the liquid-crystalline regime. The domains of the La-phase can be aligned macroscopically by uniaxial compression of the sample.
    Additional Material: 4 Ill.
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  • 14
    ISSN: 0173-0835
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: The recent introduction of the PhastSystem, an automatic electrophoresis and staining system with precast gradient-gels, allows rapid and reproducible analysis of proteinuria in patients suffering from renal injury. A routine method for sodium dodecyl sulfate-polyacrylamide gradient gel electrophoresis (SDS-PAGE) and silver staining of unconcentrated urine specimens in the PhastSystem is described and compared to our conventional “macro”-method with self-cast SDS-polyacrylamide gradient gels. The method described for the PhastSystem using 0.3 μL sample volumes and an 8-25% polyacrylamide gradient gel leads to highly reproducible results within 1.5 h. Before electrophoresis urine specimens were neither concentrated nor dialyzed. Samples with a protein concentration exceeding 5 mg/mL had to be diluted 1:5 (v/v). Analysis and documentation of PhastGels appeared as easy as with our conventional SDS-PAGE. Protein bands could reliably be identified by Western blotting. Urine and serum proteins, separated in PhastGels, were electrophoretically transferred to nitrocellulose and detected with specific antibodies against human albumin, transferrin, alpha-1-antitrypsin and IgG. Comparison of several standard kits for molecular weight determination revealed considerable differences concerning the quality of protein separation patterns. Availability of precast gels and automatization of SDS-PAGE and staining allows easy standarization of urine SDS-PAGE among clinical routine laboratories.
    Additional Material: 5 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 95 (1962), S. 1307-1310 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Unter extremen Bedingungen wird Thia-cyclohexan von elementarem Schwefel ausschließlich zum Thia-thio-α-pyron (III) dehydriert und oxydiert, das dem isoelektronischen Grund-Trithion sehr ähnlich ist. Das isomere Thia-thio-γ-pyron (V) fällt nicht an. Die Struktur von III wird gesichert.
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  • 16
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The fragmentation of 2,7-octanedione, induced by chemical ionization with methane as a reagent gas (CI (CH4)), is shown to be extensively governed by the interaction of the two carbonyl groups. Tandem mass spectrometry reveals that a sequential loss of H2O and C2H4O from the [M + H]+ ion competes with sequential loss of H2O and C6H10, and that both processes occur via the same [MH - H2O]+ intermediate. This intermediate is likely to be formed via intramolecular gas-phase aldol condensation and subsequent dehydration. The resulting C(1) protonated 1-acetyl-2-methylcyclopentene structure readily accounts for the observed further decomposition to CH3C≡O+ and 1-methylcyclopentene (C6H10) or, alternatively, to [C6H9]+ (e. g. 1-methylcyclopentenylium) ions and acetaldehyde (C2H4O). Support for this mechanistic rationale is derived from deuterium isotope labelling and low-energy collision-induced dissociation (CID) of the [MH - H2O]+ ion. The common intermediate shows a CID behaviour indistinguishable by these techniques from that of reference ions, which are produced by gas-phase protonation of the authentic cyclic aldol or by gas-phase addition of an acetyl cation to 1-methylcyclopentene in a CI (CH3COOCH3) experiment.
    Additional Material: 7 Ill.
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  • 17
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
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  • 18
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Peptide Science 4 (1998), S. 289-293 
    ISSN: 1075-2617
    Keywords: Bradykinin antagonist ; dimer ; diaminodicarboxylic acid ; bridge residue ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Enhancement of a ligand's interaction with a receptor through presenting the ligand in multimeric form is a topic of general interest. Thus dimerization of single-chain bradykinin antagonist peptides has previously been shown to be beneficial in terms of potency and duration of action. While crosslinking polypeptides at terminal positions using suitable dicarboxylic acids and diamines is comparatively straightforward synthetically, internal dimerizations are usually achieved through oxidation or double S-alkylations of cysteine residues, resulting in metabolically unfavourable disulphide and thioether cross-links. Using suitably modified standard solid-phase peptide synthesis protocols, dimeric bradykinin antagonist peptides [H-(d-Arg)-Arg-Pro-Hyp-Gly-Phe]2-X-[(d-Phe)-Leu-Arg-OH]2 were synthesized where X corresponds to a l,l-2,7-diaminosuberic or l,l-2,9-diaminosebacic acid residue, respectively. The biological activity of these peptides was comparable to that of conventional dimeric bradykinin antagonists cross-linked through cystine or bis(succinimido)alkyl bridges. © 1998 European Peptide Society and John Wiley & Sons, Ltd.
    Additional Material: 2 Ill.
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  • 19
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary columns, glass ; Enantioselectivity test procedure ; Cyclodextrin/amide phase comparison ; Enantiomer separation ; Chiral resolution (cR) ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A test mixture is proposed which allows assessment of the enantioselective separation potential of chiral amide phase capillary columns. This CHIRAL-Test I includes a range of chromatographically problematical substrates, covering the temperature range from 100-200°C. One test component, the N-pivaloyl leucine methyl ester enatiomers, may be used exemplarily to calculate chiral resolution (chirale Auflösung, cR). Unlike separation factors α, cR values take account of peak shape as well as of relative retention time of both enantiomers, and thus are a measure of affective chromatographic separation. In combination with the Grob test, the CHIRAL-Test may be used for characterizing the chromatographical properties of columns coated with chiral amide phases.
    Additional Material: 2 Ill.
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  • 20
    ISSN: 0044-2313
    Keywords: Alkali uranium halides, A2UX5 (A = K, Rb; X = Cl, Br, I) ; preparation ; crystal structure ; magnetic susceptibility ; UV-Vis spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese, Kristallstruktur, Magnetismus und Absorptionsspektren von Halogeniden des Typs A2UX5 (A = K, Rb; X = Cl, Br, I)Die ternären Uran(III)-halogenide A2UX5 (A = K, Rb; X = Cl, Br, I) wurden aus den binären Komponenten AX und UX3 in verschweißten Tantalampullen gewonnen. Nach Guinier-Aufnahmen (Raumtemperatur) kristallisieren sie sämtlich im K2PrCl5/Y2HfS5-Typ. Einkristall-Strukturverfeinerungen wurden für K2UI5 und Rb2UCl5 unternommen. Magnetische Suszeptibilitätsmessungen erfolgten mit einem SQUID-Magnetometer von Raumtemperatur bis zur Temperatur des flüssigen Heliums: Eindimensionale (innerhalb einer Kette) und dreidimensionale antiferromagnetische Ordnung wird bei tiefen Temperaturen, abhängig vom Abstand U3+—U3+, beobachtet. Absorptionsspektren wurden zwischen 4000 und 28000 cm-1 aufgenommen. Sie zeigen die für U3+ charakteristischen Übergänge und, abhängig vom Halogenid, sehr starke f - d Übergänge oberhalb 14000 bzw. 15000 cm-1.
    Notes: The ternary uranium(III) halides A2UX5 (A = K, Rb; X = Cl, Br, I) have been prepared from the binary components AX and UX3 in sealed tantalum containers. According to their Guinier X-ray powder patterns, they all crystallize with the K2PrCl5/Y2HfS5 type of structure. Lattice constants for ambient temperature are reported. Single-crystal structure refinemens were undertaken for K2UI5 and Rb2UCl5. Magnetic susceptibility data were recorded with a SQUID magnetometer from liquid helium to room temperature. One-dimensional (intrachain) and three-dimensional antiferromagnetic ordering occur at low temperatures dependent upon the U3+—U3+ distance. Absorption spectra were recorded between 4 000 and 28 000 cm-1. They show f - f transitions typical for U3+ and, depending on the halide, very strong f - d transitions above 14 000 to 15 000 cm-1, respectively.
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