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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1997 (1997), S. 1303-1313 
    ISSN: 0947-3440
    Keywords: S-Glycosylation, base-promoted, acid-catalyzed ; S-Glycosides ; Anomeric S-alkylation ; Glycosyltrichloroacetimidates ; Lewis X analogues ; Oligosaccharides, thio- ; Carbohydrates ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of thio-linked Lewis X and sialyl Lewis X-derived epitopes 3-5 has been achieved using a small number of building blocks. The key building-block was 1-O-silyl-protected 4-S-acetyl-2,6-di-O-benzoyl-3-S-(2,3,4-tri-O-acetyl-α-L-fucopyranosyl)-3,4-dithio-β-D-glucopyranose (15), which was obtained from the fucosyl donor 6 together with 3-thiogalactose 7 as the acceptor. Their acid-catalyzed S-glycosylation afforded the thio-linked disaccharide 8 which was subsequently converted to the 4a-O-unprotected derivative 12. Conversion to the 4a-triflate followed by treatment with KSAc in tetrahydrofuran led, under inversion of configuration, to 15 in good overall yield. Selective removal of the S-acetyl group followed by base-promoted S-glycosylation with acetobromogalactose gave the acyl-protected Lewis X analogue 25. Acetobromogalactose gave the acyl-protected Lewis X analogue 25. Transformation into trichloroacetimidate 27, followed by acid-catalyzed S-glycosylation of heptylthiol and complete deacylation afforded target molecule 3. Similarly, acid-catalyzed reaction of donor 27 and the 3b,4b-O-unprotected lactose derivative 31 as acceptor led to pentasaccharide 32, complete deacylation of which afforded target molecule 4. Transformation of 15 into the donor trichloroacetimidate 34, followed by acid-catalyzed S-glycosylation of heptylthiol afforded thioglycoside 35. Selective removal of the S-acetyl group and subsequent base-promoted S-glycosylation with the known donor 37 furnished the thio-linked tetrasaccharide 38. Cleavage of all the O-acyl groups and hydrolysis of the methyl ester moiety afforded the sialyl Lewis X analogue 5.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1995 (1995), S. 2113-2121 
    ISSN: 0947-3440
    Keywords: C-Saccharides ; C-Glycosides ; C-Lactosamine ; 1-Lithiogalactal ; Vinyllithium ; Branched sugars ; Glucosamine, C-formyl ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4-C-Formyl-2-azidoglucopyranoside 12a, required for N-acetyl-C-lactosamine synthesis as electrophile, was obtained from thexyldimethylsilyl 2-azido-2-deoxy-glucopyranoside 3 via readily available 4-O-unprotected 6a and then 4-C-methylene derivative 8a in overall seven steps. Alternatively, regioselective silylation of 3 with tert-butyldimethylsilyl chloride gave 4-O-unprotected 6b which was transformed by a similar reaction sequence into 12a. In order to circumvent a Wittig reaction, 6a was transformed into triflate 13 the reaction of which with 4-C-cyano derivative 14 followed by reduction with DIBAH and base-catalyzed isomerization also afforded 12a. Reaction of 12a with 1-C-lithiated 2-phenylsul-finyl-D-galactal 15 as nucleophile furnished C-disaccharide intermediates 16a and 16b as diastereoisomers. Ensuing removal of the phenylsulfinyl group with Raney nickel and diastereospecific 2b-hydrogen and 3b-hydroxy transfer afforded β(1→4)-connected N-acetyl-C-lactosamines 19a and 19b; their structures were deduced from derivatives 20a, b and 21a, b on the basis of 1H-NMR data. Hydrogenolytic O-debenzylation of 19b afforded hydroxymethylene-bridged N-acetyl-C-lactosamine 2b′.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1997 (1997), S. 865-872 
    ISSN: 0947-3440
    Keywords: Glycosylations, sulfur ; Glycosyl trichloroacetimidates ; Protecting groups, acyl, selective removal of ; Oligosaccharides ; S-Glycosides ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of sulfur-linked GM3 epitope 2 is based on acid-catalyzed and base-promoted S-glycosylation processes. As a precursor, 2-O-benzoyl-3-thiogalactoside 10 was required, and was obtained from 4,6-O-benzylidene-galactoside 3 in six high-yielding steps. Base-promoted S-glycosylation of 10 with neuraminic acid functionalized β-halogenose 11 in the presence of NaH as base and Kryptofix 21 as coactivator afforded α(2-3)-thio-linked disaccharide 13, which was readily converted to α-halogenose 20. Heptyl 1-thioglycoside 22 was obtained from O-galactosyl trichloroacetimidate 21 and heptylthiol via acid-catalyzed S-glycosylation. 22 was transformed into 2,3,6-tri-O-acylgalactoside 26 which, via the 4-O-triflate and treatment with potassium thioacetate, followed by selective removal of the S-acetyl group, furnished the 2,3,6-tri-O-acyl-4-thioglucoside 28. Base-promoted S-glycosylation of 28 with halogenose 20 led to fully acylated target molecule 29, which was quantitatively converted into 2.
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  • 4
    ISSN: 0947-6539
    Keywords: computer simulations ; conformations ; Lewis glycolipids ; molecular dynamics ; thioglycosides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several monomeric and dimeric Lewis glycolipids have been investigated by NMR spectroscopy, and structural aspects were modelled by computer. From the pseudo-C2-symmetric tetrasaccharide unit that forms the recognition domain of the Lewis Y and Lewis b antigens, a totally C2-symmetric tetrasaccharide was designed that contains the structural element common to all Lewis antigens. Finally, a model for the presentation of dimeric Lewis antigens at membrane surfaces was derived. The overall shapes of the dimeric Lewis oligosaccharides are defined by the connectivity of the sugar residues within rigid tri- and tetrasaccharide building blocks.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 98 (1981), S. 97-112 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The stress-strain behaviour of sol/gel-polymers of 2-chloro-butadiene was investigated. The modulus of the raw polymers increases linearly while the gel component increases. Einstein's equation which deals with the viscosity of colloidal suspensions is applicable to the sol/gel-systems in investigation. There exist no strong interactions between the gel particles and the sol matrix which are characteristic for active fillers, so that the gel particles are able to move freely in the shear gradient of a processing machine without remarkable deformation. During vulcanization of the sol/gel-rubbers in investigation, the gel particles are only insufficiently covulcanized with the sol matrix. When the gel fraction of the rubber increases, and when the amount of vulcanizing agents in the sol phase increases, the homogenization of tension in the vulcanizate is increasingly disturbed. Tensile strength and ultimate elongation of the vulcanizate are impaired on account of the disadvantageous network structure which takes rise from the overcure and from the insufficient connexion between the gel particles and the sol phase.
    Notes: Es wurde das Zug-Dehnungs-Verhalten von Sol/Gel-Polymeren aus 2-Chlorbutadien untersucht. Der E-Modul der Rohpolymeren steigt linear mit deren Gelanteil. Für die untersuchten Sol/Gel-Systeme gilt die Einsteinsche Beziehung über die Viskositätserhöhung kolloidaler Suspensionen. Zwischen Gelpartikeln und Solmatrix bestehen keine starken, aktive Füllstoffe kennzeichnende Wechselwirkungen, so daß die Gelpartikel im Schergradienten einer Verarbeitungsmaschine (z. B. Extruder) als quasistarre Kugeln abzugleiten vermögen und keine wesentliche Deformation erfahren. Bei der Vulkanisation der untersuchten Sol/Gel-Kautschuke werden die Gelpartikel nur unzureichend mit einer Solmatrix verknüpft. Die Spannungshomogenisierung im Vulkanisat wird zunehmend behindert, wenn der Gelanteil des Kautschuks zunimmt und wenn die Vernetzerkonzentration in der Solphase zunimmt. Durch die ungüstige Netwerkstruktur, die durch Übervernetzung und durch unzureichende Verknüpfung der Gelteilchen mit der Solphase entsteht, werden Zugfestigkeit und Bruchdehnung des Vulkanisats vermindert.
    Additional Material: 13 Ill.
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  • 6
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Selective hydrogenation of the double bonds in nitrile rubber (NBR) yields polymers, which in principle could be obtained by the terpolymerisation of ethene, 1-butene and acrylonitrile. The chemical and physical differences of the starting materials and the hydrogenated products can be explained by the specific properties of 1,4-linked butadiene sequences and the therefrom resulting ethene sequences. In contrast to butadiene segments the ethene sequences are chemically more resistant and are able to cristallize. This is shown by thermal and dynamic-mechanical measurements as well as by the tensile strengths of the raw rubber and of carbon black filled vulcanizates.
    Notes: Durch selektive Hydrierung der Doppelbindungen von Nitrilkautschuk (NBR) erhält man Produkte, die formal aus Ethen, 1-Buten und Acrylnitril aufgebaut sind. Chemische und physikalische Unterschiede zwischen dem Ausgangs- und Endprodukt werden durch die spezifischen Eigenschaften von 1,4-verknüpften Butadien- und den daraus abgeleiteten Ethensequenzen erklärt. Im Gegensatz zu Butadiensequenzen sind Ethensequenzen chemisch beständiger und können kristallisieren. Dies wird durch thermische und mechanisch-dynamische Untersuchungen sowie die Bestimmung der Zugfestigkeit am Rohkautschuk und am rußgefüllten Vulkanisat gezeigt.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die van der Waals Zustandsgleichung für reale Netzwerke wird mit Erfolg auf verschiedene Gummisysteme angewendet. Eine neue Methode der Charakterisierung von Netzwerken wird vorgestellt. Konsequenzen werden diskutiert.
    Notes: The utility of the van der Waals equation of state for real networks is demonstrated by its application to various rubbers. A new method of characterization of networks as well as a discussion of its consequences are presented.
    Additional Material: 7 Ill.
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  • 8
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sulfur crosslinking systems are well established for curing of rubbers containing olefinic bonds and are well optimized for various processing and end product requirements. This is achieved by the clever selection of accelerator or their combinations or varying sulfur to accelerator ratio. This ratio defines primarily the structure and density of the sulfur crosslinks. Semi efficient crosslinking systems allow in NR as in SBR best compromise of properties with respect to processing, static and dynamic behaviour and ageing. In NR the structure of the crosslinks contrary to SBR has a larger influence on dynamic crack propagation. Polysulfidic crosslinks are preferred for higher tensile strength, tear and fatigue resistance.Great challenges for accelerated sulfur crosslinking exist to meet new ecological and toxicological requirements such as avoidance of nitrosamines in rubber industry. The present work shows that there is a potential for new developments in the classical sulfur vulcanization to satisfy the present needs and meet the future challenges.
    Additional Material: 13 Ill.
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  • 9
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The photocrosslinking efficiency of a series of commercial photoinitiators and multicomponent photosensitive systems on uncrosslinked acrylic matrices has been estimated. Copolymers used for this study are tricyclo[5.2.1.02,6]dec-4-en-8-yl acrylate/ethyl acrylate copolymers of variable composition (100/0, 40/60, 20/80, 0/100) synthesized in solution by a free-radical process. The irradiations were carried out at large wavelengths (λ ≥ 310 nm). Systems of benzophenone/benzoyl peroxide led to really fast crosslinking kinetics for 10 min of irradiation.
    Notes: L'efficacité de photoréticulation de toute une série de photoamorceurs commerciaux et de systèmes photosensibles multicomposants a été évaluée sur des matrices acryliques non réticulées. Les polymères utilisés pour cette étude sont des homopolymères et des copolymères d'acrylate de dicyclopentadiène/acrylate d'éthyle de composition variable (100/0, 40/60, 20/80, 0/100) synthétisés en solution par voie radicalaire. Les irradiations ont été effectuées à des grandes longueurs d'ondes (λ ≥ 310 nm). Les systèmes benzophénone/peroxyde de benzoyle ont permis d'obtenir des cinétiques de réticulation très rapides pour des temps d'irradation de 10 min.
    Additional Material: 12 Tab.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 191 (1990), S. 169-184 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(vinyllactams) form a class of non-ionic water-soluble polymers from which only poly-(1-vinyl-2-pyrrolidone) (PVP) is well known and has been investigated extensively. The homologues poly(1-vinyl-2-piperidone) (1, poly[1-(2-oxo-1-piperidyl)ethylene]) and poly(N-vinylcaprolactam) (2, poly[1-(2-oxoperhydroazepin-1-yl)ethylene]) which are still soluble in water at room temperature have not yet been studied in aqueous solution. In this work the synthesis of these two polymers by radical polymerization in solution and the investigation of the dilute aqueous solution properties of these polymers by static and dynamic light scattering measurements are presented. Special attention is paid to the influence of the increasing hydrophobicity of these polymers on coil dimensions and structures in aqueous solution.
    Additional Material: 6 Ill.
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