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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 204 (1993), S. 51-61 
    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: Dielektrizitätskonstante (ε′) nd dielektrischer Verlust (ε″) von drei Carboxymethylcellulose-Proben mit verschiedenem Substitutions- und Polymerisationsgrad wurden im Frequenzbereich 0,1 - 10000kHz bei Temperaturen zwischen 10 und 60oC gemessen. Im Gegensatz zu nativer Baumwollecellulose, die zwei Relaxztionsprozesse (β und γ) zeigt, wurde nur jeweils ein Relaxationsprozeß zwischen 0,1 und 1kHz gefundern. Die dielektrischen Eigenschaften hängen dabei nicht nur vo Substritutionsgrad, sondern auch vom gewichtsmittleren Polymerisationsgrad und der Homogenität der Substitution ab.
    Notes: The dielectric constant, ε′, and dielectric loss, ε″, were determined for three solid carboxymethyl cellulose samples having different levels of substitution and different degrees of polymerization over a frequency range of 0.1 - 10 000 kHz at temperatures from 10-60°C. In contrast to the two relaxation processes, γ and β, previously observed in native cotton cellulose, only one relaxation process within a frequency range of 0.1 - 1 kHz was identified. It was found that the dielectric properties do not only depend on the degree of substitution, but also on the weight-average degree of polymerization and uniformity of distribution.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 204 (1993), S. 63-71 
    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: Es wird ein neues Kapillar-Rheometer beschrieben, bei dem der Druck, mit dem die Meßflüssigkeit durch die Kapillaren gepreßt wird, durch eine hydraulische Vorrichtung erzeugt wird. Das Gerät ist voll zautomatisiert und wird durch einen PC gesteuert. Verschiedene Meß-Moden können vorgewählt und dann automatisch ausgeführt werden. Einige vorläufige Ergebnisse an Newtonschen Flüssigkeiten und an Polymerlösungen zeigen das Funktionieren des neuen Rheometers.
    Notes: A new capillary rheometer design is described, in which a hydraulic device is used to produce the pressure driving the sample fluid through capillaries. The device is fully automated and controlled by a PC unit. Various measuring modes can be preselected and are automatically executed. Some preliminary results with New tonian fluids and with polymer solutions show the functioning of the new rheometer.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 204 (1993), S. 73-83 
    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: Naphthochinonderivate wurden als Elektronen- und Protonenüberträger in Polymermembranen für Redoxreaktionen eingesetzt. Eine solche, Vitamin K1 enthaltende Membran, läßt den Oxidations-Reduktions-Prozeß zwischen zwei wäßrigen Lösungen von Eisen(III) cyanid bzw. Natriumdithionit nur ziemlich langsam ablaufen. Ein effektiverer Überträger war Vitamin K3; die Reaktion verlief zunächst rasch, jedoch beiweideerholten Anwendungen immer langsamer, da ein Teil dieses, in senier reduzierten Form wasserlöslichen Überträgers während der Reaktion aus der Membran herausgelöst wurde. 2-Alkyloxy-1,4-naphthochinone wie z.B. das Hexyloxyderivat erwiesen sich als wirksame, die Reaktion unterstützende Elektronen- und Protonenüberträger, und in diesen Fällen führten wiederholte Anwendungen nicht zu Verzögerungen.
    Notes: A redox reaction was mediated by polymeric membranes which contain naphthoquinone derivatives as electron and proton carriers. When such a membrane containing vitamin K1 was placed between two aqueous solutions of potassium ferricyanide and sodium dithionite, the oxidation-reduction of them took place, but the reaction was rather slow. Although vitamin K3 was a more effective carrier and the reaction proceeded fast, the reaction rate decreased in the repeated runs. Since the reduced form of this carrier is slightly soluble in water, a part of the carrier got dissolved in the aqueous phase from the membrane during the reaction. 2-Alkyloxy-1,4-naphthoquinones such as 2-hexyloxy-1,4-naphthoquinone effectively transported electrons and protons through the polymeric membranes, promoting the membrane-mediated reaction; in these cases no retardation was observed in the repeated runs.
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  • 4
    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 peroxide-initiated copolymerisation of an unsaturated polyester with zinc acrylate, diallyl phthalate prepolymer and a solid vinyl ester resin was investigated. The curing was followed by means of gelation curves and differential scanning calorimetry. The studies showed that zinc acrylate has the highest reactivity.
    Notes: Die Peroxid-initiierte Copolymerisation eines ungesättigten Polyesters mnit Zinkacrylat, Diallylphthalat-Prepolymer und einem Vinylesterharz wurde untersucht. Der Härtungsverlauf wurde anhand der Gelierungskurven und mitels Differentialkalorimetrie verfolgt. Die Prüfungen zeigten, daß Zinkacrylat die größte Reaktivität hat.
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  • 5
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 204 (1993), S. 91-100 
    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 Kinetik der isothermen Kristallisation des anionisch hergestellten Copolyamids PA 8/12 aus ω-Octanlactam (OL) und ω-Laurinlactam (12-Dodecanlactam) (LL) wurde nach der Avrami-Gleichung über den gesamten Zusammensetzungsbereich mittels DSC untersucht. Die Kristallisationsparameter Halbwertszeit (t1/2), Avrami-Index (n), Geschwindigkeitskonstante (k) und Kristallinitätsgrad wurden für verschiedene Kristallisationstemperaturen bestimmt. Eine Beziehung dieser Parameter zur Copolyamidzusammensetzung sowie zu Kristallisations- und Unterkühlungstemperaturen wurde untersucht und die Ergebnisse diskutiert. Desweiteren wurden die Werte de hier behandelten mit denen der in der Literaturgeschriebenen Homopolymeren verglichen.
    Notes: The isothermal crystallization kinetics of the anionic copolyamides of ω-octanelactam (OL) with ω-laurolactam (LL) (nylon-8/nylon-12), covering a wide composition range (0/100 - 100/0 OL/LL, mol/mol), was established according to the Avrami equation by the use of differential scanning calorimetry. The crystallization parameters half-time crystallization (t1/2), Avrami index (n), rate constant (k), and reduced crystallinity were determined for various crystallization temperatures. These parameter values are correlated to the composition of the copolyamides, the crystallization and supercooling temperature, and the results are discussed.Differences in kinetic parameter values between the homopolymers of this paper and those for the hydrolytic nylon-8 and nylon-12 reported in literature were observed and discussed.
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  • 6
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 204 (1993), S. 111-118 
    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: Abhängig von den Fällbedingungen tritt Poly(p-phenylen-1,3,4-oxadiazole) in zwei Modifikationen auf. Dies kann sowohl durch FTIR-Spektroskopie als auch mit Röntgenweitwinkelstreuung nachgewiesen werden. In beiden Fällen zeigt jede Modifikation charakteristische Peaks. Bei der Verarbeitung zu Fäden oder Filmen aus Lösungen in konzentrierter Schwefeläure durch Fällen in Wasser wird die im thermodynamischen Ungleichgweicht stehende β-Modifikation erhalten. Unter speziellen Bedingungen ist es möglich, die dreidimensional geordnete Gleichgewichtsstruktur direkt herzustellen. Verarbeitungsprodukte aus dieser α-Modifikation weisen merklich höhere Festigkeiten auf.
    Notes: Depending on the coagulation conditions, poly(p-phenylene-1,3,4-oxadiazole) in the solid state forms two modifications, as can be evidenced by FTIR spectroscopy and by wide-angle X-ray scattering curves (WAXS). In both cases each modification is detectable by characteristic peaks. Processing of fibers or films from solutions in concentrated sulfuric acid by coagulation in water results in the formation of a thermodynamically non-equilibrium form, defined as β-modification. Under special conditions it is possible to obtain the three-dimensionally ordered equilibrium α-structure that leads to processing products with markedly higher tenacities.
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  • 7
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 204 (1993), S. 101-110 
    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: By a new technique for the addition of monomers it is possible to increase the reproducibility of the synthesis of poly(1,4-phenylene-1,3,4-oxadiazoles) by one order of magnitude in relation to the known method, measured by the standard deviation of the relative viscosity of polymer solutions in concentrated sulfuric acid. This method leads to polymers with very high molecular weights under markedly milder reaction conditions and in shorter reaction times than by the classic method.The influence of the most important reaction parameters on the reaction rate and equilibrium of the polycondensation was investigated. An [η]/Mw-relation was established based on light-scattering and viscometric investigations of polymer solutions in concentrated sulfuric acid.
    Notes: Die Reproduzierbarkeit der Synthese von Poly(p-phenylen-1,3,4-oxadiazolen) in Oleum Kann durch eine veränderte Monomerzugabetechnik, gemessen an der Standardabweichung der relativen Lösungsviskosität, um eine Größenordunung verbessert werden. Die Polykondensation verläft unter deutlich milderen Bedingungen in kürzeren Reaktionszeiten zu Polymeren mit höheren Molmassen als nach der bekannten Methode.Der Einfluß verschiedener Parameter auf die Reaktionsgeschwindigkeit und das Polykondensationsgleichgewicht wurde eingehend untersucht. Auf der Basis streulicht photometrischer und viskosimetrischer Messungen an Polymerlösungen in konzentrierter Schwefelsäure wurde eine [η]/Mw-Bezeihung ermittelt.
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  • 8
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 204 (1993), S. 127-137 
    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: Water-borne paints have received greater attention. Existing concepts related to suitable binders are polymethacrylate dispersions crosslinkable by autoxidation. Essential synthesis steps of such dispersions and characteristic properties also of adequate coatings are described.Oil fatty acid structure units are enriched in the shell-region of the dispersed particles and the rest of nearly 30% is localized in the water phase as substituent of a water-soluble copolymer.
    Notes: Wäßrige Anstrichsysteme setzen sich in zunehmendem Maße durch. Als eine Entwicklungsvariante für diesbezüglich geeignete Bindemittel kommen autoxidativ vernet zende Polymethacfrylatdispersionen in Betracht. Es werden wesentliche Schritte der Synthese derartiger Dispersionen un dcharakteristische Eigenschaften auchvon Beschichtungen vorgestellt.Die Ölfettsäurestruktureinheiten sind im Schalenbereich der disperigierten Teilchen angereichert, und sie befinden sich außerden zu etwa 30% in der wäßrigen Phase als Substituenten eines löslichen Copolymeren.
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  • 9
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 204 (1993), S. 153-159 
    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: Ein hochvernetztes duroplastisches Epoxidharz wurde durch “reactive blending” in Gegenwart von Bisphenol A-Polycarbonat (PC) modifiziert. FTIR-Untersuchungen zeigten, daß der Umsatz nach dem Härtungs- und Nachhärtungsprozeß durch den PC-Anteil im Blend erniedrigt wird. Darüber hinaus wurde beobachtet, daß Bruch festigkeit des Blendsystems mit wachsendem PC-Gehalt merklich steigt. Für die Phasentrennung der Unterschußkomponente während der Vernetzung wurden keine Beweise gefunden.
    Notes: A highly crosslinked thermosetting epoxy resin was modified by a reactive blending process carried out in the presence of bisphenol-A polycarbonate (PC). FTIR spectroscopy investigations demonstrated that the presence of PC in the blend decreases the reactants conversion after the curing and postcuring processes. Moreover, it was found that the fracture toughness of this blend system increases markedly by increasing the PC content in the blend. No evidence of phase separation of the minor component during the crosslinking reaction steps was observed.
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  • 10
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 204 (1993), S. 119-125 
    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 antibakterielle Wirkung von Homopolymeren von Cetyldimethyl(4-vinylbenzyl)ammoniumchlorid (VB16), Lauryldimethyl(4-vinylbenzyl) ammoniumchlorid (VB12) und TRimethyl(4-vinylbenzyl)ammoniumchlorid (VB1) und deren Copolymeren mit Acrylnitril wurde untersucht. Alle Homo- und Copolymeren wirkten bei den getesteten Bakterienarten-B. subtilis, S. aureus, E. coli und P. aeruginosa - keimtötend. Besondrs stake Effekte zeigten sich bei gram-positiven B.-subtilis- und S.-aureus-Kulturen. Die keimtötende Wirkung nahim in der Reihe VB16 〉 VB12 ≫ VB1 ab.
    Notes: Homopolymers of cetyldimethyl(4-vinylbenzyl)ammonium chloride (VB16), lauryl-dimethyl(4-vinylbenzyl)ammonium chloride (VB12), and trimethyl (4-vinylbenzyl)ammonium chloride (VB1), and copolymers of these compounds with acrylonitrile were examined for antibacterial activity using B. subtilis, S. aureus, E. coli, and P. aeruginosa. All homopolymers and copolymers showed germicidal action to the bacterias, especially strong action to gram-positive B. subtilis and S. aureus. The strength of the germicidal action of the quaternary ammonium branches was in the order: VB16 〉 VB12 ≫ VB1.
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  • 11
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 204 (1993), S. 161-175 
    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 permeability of gases in films and membranes of thermoplastic starch (TPS) was investigated. The permeability- and diffusion coefficients were measured with the time-lag method on films on TPS with different plasticizer contents and at different temperatures. The experimentally determined low permeabilities were comparable to those of synthetic polymers available on the market. TPS shows at low water activities permeabilities similar to good gasbarrier materials. With increasing water content - as it is already shown for other hydrophilic polymers - the gasbarrier property of TPS gets lost. Together with earlier works on the structure and the thermodynamical behaviour of the starch, the molecular parameters and their influence on the permeability were discussed.
    Notes: Als Alternative zu den heutigen Massenkunststoffen wurde die Möglichkeit eines Einsatzes von thermoplastischer Stärke (TPS) als Barrierewerkstoff in Filmen und Membranen untersucht. Die Permeations- und Diffusionskoeffizienten wurden mitels der Induktionszeit-Methode an Filmen aus TPS in Abhängigkeit von Temperatur und Weichmachergehalt ermitelt. Die expermentell gefundence gute Gasbarriereeigen schaft der Stärke gegenüber Sauerstoff und Stickstoff wurde durch vergleichende Messungen an Handelsprodukten ergänzt. Die TPS zeigt bei nieedrigen Wassergehalten denhandelsüblichen Barrierepolymeren vergleichbare Gaspermeationsraten. Mit steigen dem Wassergehalt verliert sie- wie die meisten hydrophilen Polymere - ihre Gasbarrierewirkung.Gemeinsam mit früheren Arbeiten über die Struktur und die Eigenschaften von thermoplastischer Stärke wurden die molekularen Parameter und ihr Einfluß auf die Gasdurchlässigkeit diskutiert.
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  • 12
    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: Durch Phasengrenzflächenpolykondensation von 4,4'-Bis(mercaptomethyl)biphenyl mit ausgewählten aliphatischen und isomeren Phthalsäuredichloriden wurden neue Polythioester erhalten.Um die optimalen Bedingungen der Phasengrenzflächenploykondensation zu bestimmen, wurde der Einfluß folgender Faktoren auf die reduzierte Viskosität and die Ausbeute der Polythioester ermittelt: Art der organischen Phase, Konzentration der Reagenzien. Verhältnis der wässeigen zur organischen Phase, Art und Konzentration des HCI-Akzeptors, Reaktionstemperatur und -zeit. Die Polykondensation von Dithiol mit Adipinisäuredichlorid und Isophthalsäuredichlorid wurde als Modellsystem genauer untersucht. Die Polythioesterstrukturen wurden mittels Elementaranalyse, IR-Spektroskopie und Röntgenstrukturanalyse bestätigt. Aus der thermogravimetrischen Analyse wurde die Zersetzungstemperatur, der Gewichtsverlust bei dieser Temperatur und das Maximum der Zersetzungsgeschwindigkeit erhalten. Es wurden weiterhin einige physikalisch-chemische, mechanische und dielektrische Eigenschaften ermittelt. Aufgrund der schlechten Löslichkeit der Polythioester konnten die mittleren Molekulargewichte nicht bestimmt werden.
    Notes: New polythioesters were synthesized by interfacial polycondensation of 4,4'-bis(mercaptomethyl)biphenyl with selected aliphatic and isomeric phthaloyl dichlorides.To determine optimum polycondensation conditions, the influence of the following factors on reduced viscosity and yield were studied: type of organic phase, concentration of reagents, aqueous/organic phase ratio, type and concentration of hydrogen chloride acceptor, rate of acid chloride addition, reaction temperature and reaction time.A thorough examination was carried out only for the polycondensation of dithiol with adipoyl and isophthaloyl dichlorides chosen as a model system. The structures of polythioesters were confirmed by elemental analysis, X-ray analysis and infrared spectroscopy. The temperature of initial decomposition, the percentage of its mass loss, and temperature of the fastest decomposition process from curves of differential and thermogravimetric analysis were determined. Some physicochemical, mechanical and electrical properties were determined. The molecular weights were not measured because of the low solubility of the obtained polythioesters.
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  • 13
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    Angewandte Makromolekulare Chemie 204 (1993), S. 177-189 
    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: Investigations on chemical coupling of heterogeneous polystyrene-polybutadiene blends were carried out using an organic sulfonylazide. The coupling process was realized in the melt mixing process on a laboratory melt kneader. The efficiency of the coupling agent was evaluated by IR-spectroscopical, microscopical, and dynamic-mechanical analysis and by mechanical properties of the blends. The graft copolymers forming in the melt cause an increase of the stress-strain properties and the impact strength of the blends.
    Notes: Es wurden Untersuchungen zur chemischen Kopplung heterogener Polystyrol-Polybutadien-Blends bei Einsatz eines organischen Sulfonylazids während des Schmelzemischens im Laborinnenmischer angestellt. Die Wirksamkeit des Kopplungsagens wurde anhand infrarotspektroskopischer, mikroskopischer und dynamisch-mechanischer Analysen sowie anhand des merchanischen Eigenschaftsbildes der Belends beurteilt. Die sich in der Schmelze bildenden Pfropfcopolymeren führen zu einer Erhöhung der Phasenwechselwirkungen un dami zu einer Verbesserung der Festigkeits- und Zähigkeits-eigenschaften der Blends.
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  • 14
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    Angewandte Makromolekulare Chemie 205 (1993), S. 19-30 
    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: Interpenetrating polymer networks (IPN) were obtained by the simultaneous crosslinking of unsaturated polyester resins and Bisphenol A dicyanate. The copolymerization of the unsaturated polyester with styrene occurred according to the radical mechanism, whereas Bisphenol A dicyanate underwent a cyclotrimerization, thus forming a polytriazine (polycyanurate) network. The IPNs are characterized by elevated glass transition temperature and increased mechanical strength in comparison with corresponding unsaturated polyester resin without Bisphenol A dicyanate.
    Notes: Interpenetrierende Polymernetzwerke (IPN) wurden durch die gleichzeitige Vernetzung ungesättigter Polyesterharze und Dian-Dicyanat erhalten. Die Copolymerisation von ungesättigtem Polyester mit Styrol erfolgte nach dem radikalischen Mechanismus, während das Dian-Dicyanat cyclotrimerisierte, wodurch sich ein Polytriazin(Polycyanurant)- Netzwerk bildete. Die IPN zeichnen sich durch erhöhte Glastemperatur und mechanische Festigkeit im Vergleich zum entsprechenden ungesättigten Polyesterharz ohne Dian-Dicyanat-Zusatz aus.
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  • 15
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    Angewandte Makromolekulare Chemie 205 (1993), S. 1-17 
    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: Simultaneous TG/DTA analysis has been used for determination of surface coating of CaCO3-filler with stearic acid (STS) or isopropyl triisostearoyl titanate (titanate). The method has been used for several model samples as well as for commercial fillers with surface coating concentrations of 0-2.7% for stearic acid and 0-4.0% for titanate. A reliable agreement of surface coating concentration of STS determined by simultaneous TG/DTA analysis and C-analysis was achieved if the temperature range of decomposition of the surface-modifying agent was taken into account. This was found for stearic acid between 180 and 450°C (〉1% STS at 500°C) and for titanate between 120 and 450°C (〉 1% titanate at 500°C) from the slopes of the TG- and DTA curves. The mass loss in the range of decomposition is equal to the concentration of surface coating in the case of STS. For titanate-modified fillers an amount of 10% of the mass loss must be added. For determination of surface coating of CaCO3-fillers having higher contents of humidity (〉 0.2%) it is necessary to know this amount, otherwise the STS determination has to be performed by oxidation heat.
    Notes: Zur Bestimmung des Modifikatorgehaltes von Stearinsäure(STS)-bzw. Isopropyltriisostearyltitanat(Titanat)-modifizierten CaCO3-Füllstoffen wurde die simultane TG/DTA-Analyse genutzt. die Methode wurde für Modellproben sowie für verschiedene kommerzielle Füllstoffe mit einem Konzentrationsbereich von 0 - 2,7% STS bzw. 0 - 4% Titanat angewendet. Eine ausreichende Übereinstimmung der Modifikatorkonzentrationen für STS, bestimmt durch simultane TG/DTA-Analyse sowie eine C-Analyse, wird erreicht, wenn der Zersetzungsbereich des Modifikators berücksichtigt wird. Dieser liegt für Stearinsäurezwischen180°C und 450°C (bei STS 〉 1% bei 500°C) und für Isopropyltriisostearyltitanat zwischen 120 und 450°C (Titanat 〉 1% bei 500°C) und wird aus dem Anstieg der TG-bzw. DTA-Kurve erhalten. Der diesem Zersetzungsbereich zuzuordnende Masseverlust entspricht bei STS-modifizierten Füllstoffen dem Stearinsäuregehalt. Bei Titanat-modifizierten CaCo3-Füllstoffen ist ein Betrag von 10% des Masseverlustes hinzuzufügen. Für die Modifikatorgehaltsbestimmung von CaCo3-Füllstoffen, die einen höheren Feuchtigkeitsgehalt (〈 0,2%) aufweisen, ist die Kenntnis dieser Größe notwendig, anderenfalls ist die STS-Bestimmung über die Oxidationswärme zu realisieren.
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  • 16
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    Angewandte Makromolekulare Chemie 204 (1993), S. 191-191 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 17
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    Angewandte Makromolekulare Chemie 205 (1993), S. 31-45 
    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 Entfernung von Methylorgane (MO) aus Wasser oder einer Pufferlösung (pH7) durch Adsorption and Reaktionsprodukten von Poly(gylcidylmethacrylat) (PGMA) mit Tetraethylenpentamin oder mit einem Polyethylenimin mit einem Molekulargewicht von 600 (PE1600) wurde untersucht. Das Adsorptionsverhalten läßt sich besser mit der Freundlich-Gleichung als mit der Klotz-Gleichung beschreiben. Adsorptionsgeschwindigkeit und adsorbierte Menge waren in Wasser größer als in der Pufferlösung, in der durch Salzbildung die Adsorption vermindert wird. Die adsorbierte Menge hängt nicht immer von der Menge der an PGMA gebundenen PE1600-Gruppen ab.
    Notes: A study was made of the removal of methyl orange (MO) solutes in water and in a pH 7 buffer solution by the reaction products of insoluble poly(glycidyl methacrylate) (PGMA) with tetraethylenepentamine (TEP) or polyethylenimine (PEI) having molecular weight of about 600 (PEI600). An examination was made of the adaptability of the Freundlich adsorption formula and the Klotz equation to removal behaviour of these polymers, which was noted to conform better to the Klotz equation than to the Freundlich adsorption formula. The removal rate and the amount removed were greater in water than in a pH 7 buffer solution, and decreased due to coexisting salts. The amount removed does not always depend on the amount of PEI600 groups bound to PGMA.
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  • 18
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    Angewandte Makromolekulare Chemie 205 (1993), S. 59-74 
    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: Das Zug-Dehnungs-Verhalten von verschiedenen Blends aus Poly(ethylen-co-vinylacetat) (EVA, 28 wt.-% VA-Anteil) und Polyethylen (LDPE) wurde bei unterschiedlichen Dehnungsgeschwindigkeiten und Temperaturen untersucht. Die Zug-Dehungs-Kurven solcher semikristalliner Polymerblends bestehen aus drei Teilen - elastischer oder Hookescher Bereich, Bereich des Aneinanderabgleitens der Ketten sowie Dehnungshärtungsbereich. Eine Verminderung der Dehnungsgeschwindigkeit bewirkt eine Vergrößerung des Dehnungshärtungsbereiches. Die Erhöhung der Meßtemperatur beeinflußt der Dehnungshärtung bei erhöhten Temperaturen vom Kristallschmelzpunkt der Hauptkomponente des Blends abhängt. Röntgen- und DSC-Untersuchun-gen zeigen, daß die Dehnungshärtung von einer Veränderung der Kristallistruktur in LDPE und LDPE-reichen Blends ausgeht, während sie in EVA und EVA-reichen Blends auf eine induzierte Kristallisation in der amorphen Phase zurückzuführen ist.
    Notes: Stress-strain behaviour of different blends of poly(ethylene-co-vinyl acetate) (EVA) (28 wt.-% VA content) and low density polyethylene (LDPE) is studied under various strain rates and temperatures. It is found that stress-strain plots of such semicrystalline polymer blends consist of three parts, namely, elastic or Hookeian region, region of chain slippage and region of strain hardening. Decrease in strain rate has an increasing effect on the strain hardening region. Increase in measurement temperature adversely affects the whole stress-strain plot. It is apparent from the study that at an elevated temperature the process of strain hardening is dependent on the crystalline melting point of the major component in the blend. The X-ray and DSC studies reveal that the process of strain hardening is mainly due to a change in internal order of crystallites in LDPE and LDPE-rich blends, whereas in EVA and EVA-rich blends it is due to induced crystallization in the amorphous phase.
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  • 19
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    Angewandte Makromolekulare Chemie 205 (1993), S. 47-58 
    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: Methylmethacrylat (MMA) mit einem Prepolymergehalt von 6-8% wurde mit unterschiedlichen Anteilen (1-20%) 2-Ethylhexylmethacrylat (EMMA), n-Hexylmethacrylat (HMA), 2-Ethylhexylacrylat (EHA) oder n-Hexylacrylat (HA) copolymerisiert. Aus den erhaltenen Copolymeren wurden Folien hergestellt, an denen der Einfluß der Copolymerstruktur auf Lichtdurchlässigkeit, Dichte und mechanische Eigenschaften ermittelt wurde. zugsfestigkeit and Speichermodul nahmen mit zunehmendem Comonomergehalt ab. Die Dehnung stieg im Fall von MMA/EHA- und MMA/HA-Copolymerfolien mit 15 und 20 Gew.-% Comonomeranteil merklich an. Mittels DMTA wurde die Erweichungstemperatur der Copolymeren bestimmt. Die HDT und die Erweichungstemperatur nahmen unter Biegebelastung mit steigendem Comonomergehalt de Copolymeren ab.
    Notes: The paper describes the fabrication of cast acrylic sheets by copolymerizing a prepolymer syrup of methyl methacrylate (MMA) with varying amounts (1-20 wt.-%) of 2-ethylhexyl methacrylate (EHMA), n-hexyl methacrylate (HMA), 2-ethylhexyl acrylate (EHA) and n-hexyl acrylate (HA). The effect of structure of copolymer on light transmittance, density and mechanical properties was evaluated. Tensile strength and storage modulus decreased with increasing comonomer content. Strain increased significantly in the case of MMA/EHA and MMA/HA copolymer sheets having 15 and 20 wt.-% of comonomer. Softening temperature of copolymer samples was determined using dynamic mechanical thermal analysis. Heat deflection temperature under flexural load and softening temperature decreased with increasing comonomer content in copolymer.
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  • 20
    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: Poly[(N-(4-hydroxyphenyl)maleimid)-alt-(p-trimethylsilyl-a-methylstryol)] (a-PHTMMS) und einige N-(4-hydroxyphenyl)maleimid-alt-p-trimethylisilyl-a-methylstyrol-enthaltende Copolymere wurden synthetisiert, um mit Diazonaphtochinonsulfonat neue Resists für den nahen UV-Bereich (DNS) zu entwickeln.Durch die kettenversteifende Wirkung der Maleimid-Gruppe wurde eine hohe thermische Stabilität mit einer Glasübergangstemperatur von 240°C und einer Zersetzungstemperatur von 425°C erreicht. Daraus hergestellte lithographische Biler widerstanden noch bei 250°C thermischer Verformung. Die hergestellten siliciumhaltigen Resists wurden auch als oberste Schicht in zweischichtigen Materialien für die Anwendung in der Mikrolithographie untersucht.
    Notes: Poly[(N-(4-hydroxyphenyl)maleimide)-alt-(p-trimethylsilyl-α-methylstyrene)] (α-PHTMMS) and several N-(4-hydroxyphenyl)maleimide -alt-p-α-methylstyrene related copolymers were synthesized for novel positive near-UV resists containing diazonaphthoquinone sulfonate (DNS). The chain-stiffening effect of the maleimide group was responsible for high thermal resistance. Thus, a high glass transition temperature of 240°C and thermal decomposition temperature of 425°C were obtained. Lithographic positive images were obtained which resisted thermal deformation at 250°C. The prepared silicon-containing resists were also used as the top imaging layer of a bilayer resist for microlithographic application.
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  • 21
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    Angewandte Makromolekulare Chemie 205 (1993), S. 91-95 
    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 Polymerisation von Styrol in Anwesenheit von Fluoreszenzfarbstoffen, Derivaten des Benzanthrons, wurde untersucht. Die Abhängigkeit der Polymerisationsgeschwindigkeit des Styrols vom Charakter des Farbstoffs wurde ermittelt. Spektrophotometrisch wurde festgestellt, daß 70-80% des Farbstoffs in das Polymere eingebaut werden, ohne daß dies zu einer bedeutenden Veränderung des Molekulargewichts und der Molekulargewichtsverteilung führt.
    Notes: The polymerization of styrene in the presence of some fluorescent dyes, benzanthrone derivatives, has been investigated. The dependence of the polymerization rate of styrene on the character of the dye was determined. It was found spectrophotometrically that 70 - 80% of the dye reacted in the polymerization, thus the coloured fluorescent polymers were obtained. They are resistant to wet treatment and decolouration by solvent. The incorporation of the dye into the polymer chain does not significantly affect the molecular weight and polydispersity of the coloured polymers.
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  • 22
    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: Im vorliegenden Beitrag wird über die Veränderungen der dynamischen Moduli und der thermiscen Übergänge von Polyvinylidenfluorid in kompatiblen Blends mit Polymethylmethacrylat und in nicht kompatiblen Blends mit Polystyrol berichtet. Die Wirkung des Sepioliths auf die Kompatibilität dieser Blends wurde untersucht.
    Notes: This paper reports on a study of dynamic moduli and thermal transitions of poly(vinylidene fluoride) in compatible blends with poly(methylmethacrylate) and in non-compatible blends with polystyrene. The effects of sepiolite on the compatibility of these blends have been studied.
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  • 23
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    Angewandte Makromolekulare Chemie 205 (1993), S. 107-115 
    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 Strahlungsvulkanisation von Naturgummilatex (NRL) mit n-Butylacrylat führt bei daraus hergestellten Filmen zu höheren Zugfestigkeiten. Die Alterungseigenschaften von strahlungsvulkanisiertem Naturgummi (RVNRL) wurden in Gegenwart unterschiedlicher Antioxidantien untersucht. Um für die Filme aus RVNRL geeignete Antioxidantien zu finden, wurde die Gelfraktion mit Xylol in Gegenwart von 1-Gew.-% Antioxidans unter einem Luftstrom extrahiert. Antioxidantien, die während der Extraktion einer durch oxidativen Abbau bedingten Verringerung des Gelanteils entgegenwirken, sind für die Alterungssuntersuchungen mit RVNRL geeignet. Es zeigte sich, daß Tris(nonylphenyl)phosphit (Nonflex TNP) und 2,5-Di-tert-amylhydrochinon (Antage DAH) unter 12 getesteten Antioxidantien am effektivsten waren.
    Notes: Radiation-vulcanization of natural rubber latex (NRL) with n-butyl acrylate gives a higher tensile strength for films obtained after casting. The ageing properties of radiation-vulcanized natural rubber in the presence of various antioxidants have been investigated. In order to find out suitable antioxidants for radiation-vulcanized natural rubber latex (RVNRL) films, extraction of the gel fraction was carried out in xylene with 1 wt.-% antioxidant and air bubbling. Antioxidants which give less reduction in gel fraction due to oxidative degradation during extraction are effective for ageing tests of RVNRL films. It was found that tris(nonylated phenyl) phosphite (Nonflex TNP) and 2,5-di-tert-amylhydroquinone (Antage DAH), among 12 different antioxidants tested, were the most effective antioxidants for RVNRL films.
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  • 24
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    Angewandte Makromolekulare Chemie 205 (1993), S. 131-139 
    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: Stearinsäure bzw. Dibutylphthalat wurden als Adhäsionsverbesserer zu mit Calciumcarbonat gefüllten ternären Blends, bestehend aus einem Polyethylen/Poly(strol-co-divinylbenzol)-Interpolymeren und Polypropylen, zugegeben. Daraus wurden nach einem bereits beschriebenen Verfahren poröse Ionenaustauschermembranen (PIEM) hergestelt. Die Adhäsionsverbesserer führen dabei zu einer beträchtlichen Erhöhung des Porendurchmessers, da die Diffusion von Chlorsulfonsäure zu den Calciumcarbonatkörnern und damit die Bildung großer Mengen Kohlendioxid erleichtert wird. Andere PIEM-Eigenschaften werden nicht sigifikant beeinflußt.
    Notes: The previously described preparation of porous ion-exchange membranes (PIEM's) from the ternary blends of polyethylene interpolymer with poly(styrene-co-divinylbenzene) and polypropylene and calcium carbonate filler has been supplemented with the use of stearic acid and dibutyl phthalate as adhesion promoters. It was noted that both promoters govern the huge increase of pore diameter without any significant disturbances in the other PIEM's properties. The facilitating effect of chlorosulfonic acid diffusion toward calcium carbonate grains and large amounts of carbon dioxide volatilization was concluded. This is the basic point of pore creation to be discussed in this paper.
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  • 25
    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: Makroporöse Membranen aus Terpolymeren von 2,3-Epoxypropylmethacrylat, N-Vinyl-2-pyrrolidon und Ethylendimethacrylat, wurden durch radikalische Suspensionscopolymerisation hergestellt und danach mit Ammoniak modifiziert. Charakteristische Eigenschaften der Membranen wei Porosität, spezifische Oberfläche, Porengröße, Wasserdurchlässigkeit und mechanische Eigenschaften wurden bestimmt. Ein niedriger Gehalt an N-Vinyl-2-pyrrolidon verbessert die mechanischen Eigenschaften der Membranen. Der Mechanismus der Bildung der makroporösen Struktur und der Heterogenitäten wird diskutiert.
    Notes: Macroporous membranes based on terpolymers of 2,3-epoxypropylmethacrylate, N-vinyl-2-pyrrolidone, and ethylenedimethacrylate were prepared by radical suspension copolymerization and subsequently modified with ammonia. The membranes were characterized by their porosity, specific surface area, pore size, water permeability and mechanical properties. The low content of N-vinyl-2-pyrrolidone improves the mechanical properties of the membranes. The mechanism of formation of the macroporous structure and heterogeneities is discussed.
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  • 26
    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 aim of the studies was to characterize the ultrafiltration properties of a variety of photochemically modified membranes, made by a new approach starting with two types of PAN-UF membranes and using nine aromatic azides bearing different more or less hydrophilic or hydrophobic substituents. The influence of the surface functionalization (hydrophilization, introduction of charges/hydrophobization) realized by this means onto the water permeability, the dextrane selectivity, and the permeabilities during and after UF, resp., after simple contact with solutions of ovalbumine and lysozyme was the major subject. Modified membranes made using the aryl azides with hydrophilic groups, 4-azidobenzoic acid, Ib, (4-azidophenyl)trimethylammonium iodide, If, sodium (4-azido)-benzene sulfonate, Id, showed enhanced water fluxes and reduced dextrane retention. All the other azides caused reduced water permeability, enhanced dextrane selectivity, and significant flux reductions as a consequence of contact with ovalbumin solutions (pH = 5.0). The strongest effects were achieved with the two expecially hydrophobic compounds, 2-naphthyl azide, Ih, and 2-naphthoyl azide, IX. On the other hand, a pronounced positive effect of photo-modification on the protein fouling behaviour became evident in the UF of lysozyme (0.05%, pH = 10.5). Using the membranes modified with Id a much higher filtrate flux (Jv = 48.1 l/m2h) was observed as compared with the original PAN membrane (Jv = 13.1 I/m2h). The perspectives and the limitations of the developed modification strategy are discussed.
    Notes: Nach einem neuartigen Verfahren mit Hilfe von neun, mit verschieden hydrophilen bzw. hydrophoben Substituenten synthetisierten aromatischen Aziden unterschiedlich photochemisch modifizierten Polyacrylnitril-Ultrafiltrations-Membranen wurden in UF-Versuchen charakterisiert. Dabei sollte der Einfluß der so erzielten Oberflächenfunktionalisierungen (Hydrophilierung, Einführung von Ladungen oder Hydrophobierung) auf das Trennverhalten (Wasserdurchläassigkeit und Selektivitäat für Dextrane, Permeabilität während und nach der UF bzw. nach einfachem Kontakt mit Ovalbuminund mit Lysozym-Lösungen) studiert werden. Die Modifizierung mit den Arylaziden, die hydrophile Gruppen enthalten (4-Azidobenzoäure, Ib, (4-Azidophenyl)-tri-methylammoniumiodid, If, Natrium-4-azidobenzolsuflfonat, Id), führt zu einer erhöhten Durchlässigkeit der Membranen für Wasser und Dextrane. Alle anderen Azide, darunter besonders stark die deutlich hydrophoben 2-Naphthoylazid, Ih, und 2-Naphthoylazid, IX, verringern die Wasserpermeabilität, erhöhen das Rückhaltevermögen für Dextrane und verstärken die Effekte der Wechselwirkungen mit Ovalbumin (pH = 5,0). Das wird in Flußreduzierungen verglichen mit der unmodifizierten PAN-UF-Membran sichtbar. Ein positiver Effekt der Photomodifizierung wird besonders deutlich bei der UF von Lyasozym (0,05%, pH = 10,5) mit der mit Id modifizierten Membran (Jv = 48,1 l/m2h) im Vergleich zur Ausgangs-Membran (Jv = 13,1 1/m2h). Die Perspektiven und die Grenzen des Modifizierungsverfahrens werden abschließend diskutiert.
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  • 27
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    Angewandte Makromolekulare Chemie 210 (1993), S. 197-205 
    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: For solving specific problems of separation, high demands on membrane materials will be made in relation to thermal stability and resistance in a wide pH-range and against organic solvents. Membranes from poly(p-phenylen-1,3,4-oxadiazole) are prepared by different methods and their separation properties in ultrafiltration are investigated.
    Notes: Poly(p-phenylen-1,3,4-oxadiazol) (POD) ist aufgrund seiner thermischen Stabilität, pH- und Lösungsmittelbeständigkeit ein interessanter Werkstoff zur Herstellung von Membranen. Die Herstellung von POD-Membranen und deren Trenneigenschaften im Prozeß der Ultrafiltration werden untersucht.
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  • 28
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    Angewandte Makromolekulare Chemie 211 (1993), S. 79-87 
    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: Ein Poly(sulfidsulfon) wurde durch aktivierte nucleophile Substitution der Nitrogruppen von Bis(4-nitrophenyl)sulfon mit wasserfreiem Natriumsulfid bei 200 C in N-Methyl-2-pyrrolidon (NMP) hergestellt. Das Polymere löst sich in NMP, Dimethylformamid (DMF), Dimethylsulfoxid und anderen hochpolaren Lösungsmitteln. Das Molekulargewicht des Polymeren mit einer inhärenten Viskosität von 15 ml/g bei 30°C in DMF wurde mittels 1H-NMR-Spektroskopie zu Mn = 2500 bestimmt. Die Glastemperatur liegt bei ca. 73°C; der Veraschungsrückstand bei 600°C in Luft beträgt 36%, der Sauerstoffindex (LOI) ca. 37.
    Notes: A poly(sulfide sulfone) was synthesized by activated nucleophilic displacement reaction between bis(4-nitrophenyl)sulfone and anhydrous sodium sulfide at 200°C in N-methyl-2-pyrrolidone (NMP). The polymer is soluble in NMP, dimethylformamide, dimethylsulfoxide and other highly polar solvents. The molecular weight of the polymer (M̄n = 2.500) having an inherent viscosity of 15 mL/g at 30°C in DMF was determined by 1H-NMR spectroscopy. The polymer has a glass transition at approx. 73°C and char residue of 36% at 600°C in air. The limiting oxygen index of the polymer is ∼37.
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  • 29
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    Angewandte Makromolekulare Chemie 211 (1993), S. 35-51 
    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: Es wurden Untersuchungen durchgeführt, um ein auf experimentellen Ergebnissen basierendes mathematisches Modell zu entwickeln, welches die Durchmischung und andere Polymerisationsparameter mit der Partikelgröße von PVC korreliert und die Grenzen der Rührgeschwindigkeit in einem definierten Rührersystem festlegt.Dazu wurde eine Computer-Regressionsanalyse von etwa 30 in Reaktoren von 10L bis 27 m3 Volomen durchgeführten Vinylchlorid-Polymerisationen berechnet. Die Partikelgröße (d50) hängt dabei ab von den Polymerisationsparametern Rührerdurchmesser (D), Rührergeschwindigkeit (N), Durchmesser des Reaktorbehälters (T), Flüssigkeitsstand (H1) und Volumen des Reaktorbehälters (V) (NWe = Weber-Zahl): d50 = 4346.8 (N)-0.905 (D)-0.901 (T)-0.514 (H1)-0.131d50/D = 273292.1 NWe-0.51 undNmin = 3049.1 D-1.1 (T/D)-0.113In diesen Gleichungen sind nur die Werte 3049, 1, -0,113, 4346, 8 und 273 292, 1 abhängig von der Zusammensetzung des Polymerisationsgemisches. Wird dieses geändert, müssen diese Variablen anhand von einer oder zweier Polymerisationen im Pilotmaßstab ermittelt werden, um die Beziehungen an die neue Zusammensetzung anzupassen und so eine Übertragung auf einen größeren Reaktor zu ermöglichen.
    Notes: Studies were carried out to develop a mathematical model based on experimental results to correlate agitation and other polymerization parameters with the particle size of PVC and to specify the limits of agitation speed within the defined agitation system. Computer regression analysis of about 30 vinyl chloride polymerizations in reactors with 10 L to 27 m3 tank volume are carried out. The particle size of PVC (d50) is correlated to various polymerization parameters such as impeller diameter (D), impeller speed (N), reactor tank diameter (T), liquid height (H1) and tank volume (V) (NWe = Weber number): d50 = 4346.8 (N)-0.905 (D)-0.901 (T)-0.514 (H1)-0.131d50/D = 273292.1 NWe-0.51Nmin = 3049.1 D-1.1 (T/D)-0.113In these equations only the values 3049.1, -0.113, 4346.8 and 273 292.1 depend on the recipe. When the recipe is changed these variables must be determined by one or two bench-scale polymerizations to adjust the correlations to the new recipe conditions so that they can be also used for scale-up purposes with the new recipe.
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  • 30
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    Angewandte Makromolekulare Chemie 211 (1993), S. 61-77 
    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: 4-Phenyl-4-(2,3-expoxypropyl)benzoate (I) can be cured to thermoset networks with a different degree of order by using isomeric aminophenyl aminobenzoates II to V as curing agents. The formation of intermediates during the curing reaction was studied by means of model compounds. From the reaction of the monoamino-substituted phenylbenzoates VI to IX the reactivities for the primary and the secondary aminoprotons towards epoxide was determined. The kinetic data were used for a stepwise simulation of the curing reaction. Arguments were found that in case of diamines with 4-aminobenzoate structure well ordered intermediates are formed, which crosslink in an early stage of the reaction.
    Notes: Die Härtung von 4-Phenyl-4-(2,3-epoxypropoxy)benzoat (I) mit den isomeren Aminophenylaminobenzoaten II bis V führt zu unterschiedlich geordneten Epoxidnetzwerken. Die Bildung verschiedener Intemediate während der Härtungsreaktion wurde anhand von Modellverbindungen studiert. Aus der Reaktion der monoamino-substituierten Phenylbenzoate VI bis IX mit Epoxid wurden die Reaktionskostanten für die Addition an das primäre und das sekundäre Wasserstoffatom der Aminogruppen bestimmt. Die kinetischen Daten lassen sich für eine schrittweise Simulation des Härtungsverlaufs verwenden. Es wurden Argumente dafür gefunden, daß sich bei Verwendung der Amine mit 4-Aminobenzoat-Strukturen gut geordnete, schnell vernetzende Intermediate bilden.
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  • 31
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    Angewandte Makromolekulare Chemie 211 (1993), S. 89-101 
    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 diskontinuierliche Polymerisation von Butadien in Hexan bei 45°C mit einem in-situ-aktivierten Ziegler-Katalysator aus Neodymversatat, Ethylaluminiumsesquichlorid und Triisobutylauminium wurde untersucht. Die Polymerisationsgeschwindigkeit wurde durch Dichtemessungen verfolgt. Zur Beschreibung der Polymerisationskinetik bei verschiedenen Katalysatorzusammensetzungen wurde ein mathematisches Modell entwickelt. Bei einem molaren Aluminium/Neodym-Verhältnis über 40 kann mittels Gelpermeationschromatographie eine bimodale Molmassenverteilung beobachtet werden, was zu der Annahme führt, daß im Polymerisationssystem mehr als eine aktive Spezies anwesend ist.
    Notes: The batch polymerization of butadiene in hexane with an in-situ-activated Ziegler-Catalyst containing neodymium versatate, ethylaluminium sesquichloride and triisobutylaluminium was studied at 45°C. The rate of polymerization was determined by online density measurements. A mathematical model has been developed which is able to describe the kinetics of polymerization at different catalyst ratios. At molar ratios of aluminium/neodymium above 40 a bimodal molar mass distribution can be observed by gel permeation chromatography which leads to the assumption of more than one active species being present in the polymerization system.
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  • 32
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 206 (1993), S. 1-9 
    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: Die Fähigkeit von zwei Polymeren zur Adsorption von Escherichia coli (E. coli) in sterilisierter physiologischer Kochsalzlösung wurde untersucht. Als Polymere wurden die Reaktionsprodukte von unlöslichen Poly(glycidylmethacrylat)-Kügelchen (PGMA) mit Tetraethylenpentamin (TEP) bzw. Polyethylenimin mit einem Molekulargewicht von 60 (PEI600) verwendet. Die Zahl der vermehrungsfähigen Zellen nahm in Gegenwart dieser Polymeren ab. Elektronenmikroskopisch konnte nachgewiesen werden, daß diese Abnahme durch Adsorption der Bakterien auf der Polymeroberfläche verursacht wird. Die Koeffizienten (D) der Abnahme der vermehrungsfähigen Zellen (E. coli) betragen 53 und 62 ml g-1 h-1 für PGMA-TEP bzw. PGMA-PEI600. Sie werden mit den Koeffizienten bereits untersuchter Polymerer verglichen.
    Notes: A study was made of the removal of Escherichia coli (E. coli) from water by systems based on insoluble poly(glycidyl methacrylate)-g-tetraethylenepentamine and -g-polyethylenimine, i.e., the reaction products of insoluble poly(glycidyl methacrylate) (PGMA) beads with tetraethylenepentamine (TEP) or polyethylenimine having molecular weights of about 600 (PEI600). The polymers (PGMA-TEP and PGMA-PEI600) were brought into contact with E. coli in sterilized physiological saline. These polymers made the viable cell numbers decrease in this medium. It was confirmed by observation of polymer surfaces with a scanning electron microscope that this decrease was caused by adsorption of the bacterial cells onto these polymers. The decrease coefficients of viable cell numbers (D) for E. coli by these polymers were 53 ml g-1 h-1 for PGMA-TEP and 62 ml g-1h-1 for PGMA-PEI600, being compared with D by other polymers studied previously.
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  • 33
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 206 (1993), S. 11-20 
    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 Dehydrochlorierungsgeschwindigkeit von PVC in Gegenwart von Gummisamenöl (RSO), epoxydiertem Gummisamenöl (ERSO) sowie Metallseifen der daraus hergestellten Fettsäuren wurde unter Stickstoff gemessen. Die Anfangsgeschwindigkeiten der Dehydrochlorierung und die Zeit bis zu einem Abbauumsatz von 1% zeigen einen stabilisierenden Effekt der RSO-Derivate mit der Reihenfolge ERSO-Metalseifen 〈 RSO-Metalliseifen 〈 ERSO 〈 RSO.
    Notes: Dehydrochlorination rates of PVC in nitrogen atmosphere were determined in the presence of rubber seed oil (RSO), epoxidized rubber seed oil (ERSO), barium soap of rubber seed oil fatty acids and barium soap of epoxidized fatty acid of rubber seed oil. The initial rates of dehydrochlorination and the time required for the degradation to attain 1% conversion showed that the rubber seed oil derivatives exert a stabilizing effect on the degradation of PVC. The order of the stabilizing effect was found to be metal soaps of ERSO 〈 metal soaps of RSO 〈 ERSO 〈 RSO.
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  • 34
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 206 (1993), S. 21-38 
    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: To improve materials performance like the temperature of deformation under flexural load of thermoplastic polyurethanes (TPU) blending with thermoplastics is sensible. A good compatibilization and phase adhesion of thermodynamical incompatible blend-components can be achieved by the use of the right coupling agents. In the case of blends with TPU and PA6 diisocyanate is given into the melt during the extrusion. Through the chemical reactions effects of compatibilization are achieved in the cases of blends with polyesterpolyurethanes and PA6 produced by extrusion and injection moulding and by reactions in solution, too. These could be perceived as consequence of MDI-initiated reactions within the phase boundary layer. The possible reactions with the PA6-phase will be discussed by the use of a model-system made in solution. No effects of compatibilization by MDI could be proved in the polyetherpolyurethan/PA6-system. The chemical characterization of the blends was realized by GPC and FTIR whereas the properties of the morphology are proved with the help of DSC, DMA and transmission electron microscopy (TEM).
    Notes: Zur Verbesserung der Werkstoffeigenschaften von thermoplastischen Polyurethanen (TPU), wie etwa der Wärmeformbeständigkeit, ist es sinnvoll, ein Blending mit Thermoplasten vorzunehmen. Eine gute Phasenverträglichkeit und Phasenhaftung bei thermodynamisch unverträglichen Blendkomponenten kann durch geeignete reaktive Koppler erreicht werden. Bei den Blends aus TPU and PA6 wird Diisocyanat während der Extrusion in der Schmelze eingebracht. Durch die ablaufenden chemischen Reaktionen werden bei extrudierten und verspritzten Blends und bei aus der Lösung erzeugten Systemen aus Polyesterpolyurethan und PA6 verträglichkeitsverbessernde Wirkungen erreicht. Diese wurden als Folge von mit 4,4′-Diphenylmethandiisocyanat (MDI) initiierten Reaktionen in der Grenzschicht erkannt, wobei die möglichen Reaktionen mit der PA6-Phase anhand eines Modellsystems aus der Lösung diskutiert werden. Bei Blends aus Polyetherpolyurethan und PA6 wurde keine Verträglichkeitsvermittlung durch MDI nachgewiesen. Die chemische Charakterisierung der Blends erfolgte durch GPC und FTIR, während die morphologischen Eigenschaften mittels DSC, DMA und Elektronenmikroskopie dokumentiert wurden.
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  • 35
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 206 (1993), S. 39-52 
    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 Reaktion von 4,9-Dioxa-1,12-dodecandiamin (DDDD) mit dem Diglycidylether von Bisphenol A (DGEBA) wurde mittels isothermer und dynamischer Differentialkalorimetrie untersucht. Die Enthalpie der Reaktion einer Epoxygruppe mit einem Amin-Wasserstoff wurde zu 112 ± 5 kJ/mol bestimmt.Die Gültigkeit eines kinetischen Modells wurde bestätigt. Es beinhaltet zwei konkurrierende Mechanismen: zum einen die Katalyse durch Hydroxy-Gruppen, die entweder an die Epoxykette gebunden sind oder während der Reaktion gebildet werden (Aktivierungsenergie 77 ± 5 kJ/mol), zum anderen eine nicht katalysierte Reaktion mit einer höheren Aktivierungsenergie (103 ± 3 kJ/mol).Eine Gelierung beeinflußt die Kinetik der isothermen Härtung nicht. Aus den Gelzeiten wurde die Bruttoaktivierungsenergie ermittelt (62 ± 2 kJ/mol).
    Notes: The reaction between the diglycidylether of bisphenol A (DGEBA) and 4,9-dioxa-1,12-dodecanediamine (DDDD) has been studied by means of isothermal and dynamic differential scanning calorimetry. The enthalpy of the reaction of an epoxy group with an amino-hydrogen has been determined to be 112 ± 5 kJ/mol. A kinetic model has been validated. It involves two competitive mechanisms: one is catalysed by the hydroxy groups initially present on the epoxy chain or generated during the reaction (activation energy 77 ± 5 kJ/mol), the other is not catalysed with a higher activation energy (103 ± 3 kJ/mol).For each isothermal curing, the kinetics are not modified by gelation. Evaluated from the gel times, the overall activation energy of the reaction is equal to 62 ± 2 kJ/mol.
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  • 36
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 206 (1993), S. 63-68 
    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: Durch Grenzflächen-Polykondensation von N,N′-bis(4-hydroxyphenyl)pyromellitsäurediimid mit Dichloriden verschiedener Phosphoramide wurden flammhemmende Polymere erhalten. Diese wurden mittels IR- und 1H-NMR-Spektroskopie und Elementaranalyse charakterisiert. Thermische Stabilität und Entflammbarkeit wurden thermogravimetrisch bzw. durch Bestimmung des Sauerstoff-Indexes untersucht.
    Notes: Flame-retardant poly(pyromellitic imide aryl phosphoramide-ester)s were synthesized by interfacial polycondensation of N,N′-bis(p-hydroxyphenyl)pyromellitic diimide with aryl phosphoramidic dichlorides. The polymers were characterized by IR and 1H-NMR spectroscopy. The molecular composition was confirmed by elemental analysis. The thermal stability and flammability of the polymers were studied by thermogravimetry and limiting oxygen index, respectively.
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  • 37
    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: Der Einfluß von Zusammensetzung und chemischer Struktur auf die thermischen Eigenschaften von Polyimiden aus handelsüblichen Allyl-„Nadimid“-Harzen und Phosphor enthaltenden “Nadimid”-Harzen wurde untersucht. Thermogravimetrische Messungen unter Stickstoff an Harzen, die 1 h bei 300 gehärtet wurden, ergaben eine Erhöhung der thermischen Stabilität.
    Notes: The effect of composition and chemical structure of addition polyimides on thermal characteristics was investigated using commercially available allyl nadic-imide resins and phosphorus-containing nadimide resins. Thermogravimetric analysis, in N2 atmosphere, of resins cured at 300°C for 1 h revealed improvement of thermal stability.
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  • 38
    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: Polyethylenglykol-Makromonomere mit Methacryloyl-Endgruppen wurden in Gegenwart von 2,2′-Azo(N,N′-dimethylenisobutyramidin) in einem Ethanol/Wasser-Gemisch (4:1, v/v) bei verschiedenen Temperaturen mit Styrol copolymerisiert. Die Gesamtaktivierungsenergie dieser Dispersionscopolymerisation beträgt 48 kJ/mol.
    Notes: Copolymerization of poly(ethylene glycol) macromonomers with terminal meth-acryloyl groups with styrene was carried out in the presence of 2,2′-azobis(N,N′-dimethyleneisobutyramidine) in ethanol/water mixture (4:1, v/v) at various temperatures. The overall activation energy for the dispersion copolymerization was obtained as 48 kJ/mol.
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  • 39
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    Angewandte Makromolekulare Chemie 212 (1993), S. 147-155 
    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: Magnetische Zellulosepartikel wurden aus Viskose und Eisenpulver mit einer den thermischen Sol-Gel-Übergang nutzenden Suspensionsmethode hergestellt. Die so erhaltenen Teilchen konnen mit einem von außen angelegten, rotierenden Magnetfeld eines üblichen Permanentmagneten durchmischt werden. Die Abtrennung der Partikel von der Reaktionssuspension sollte in einer dünnen Schicht des Materials durch ein starkes Magnetfeld erfolgen. Magnetische Zellulosepartikel, die mit einer SmCoFe-Legierung anstelle des Ferrits hergestellt wurden, besitzen bessere magnetische Eigenschaften.
    Notes: Mangetic bead cellulose was prepared from viscose and ferrite powder by employing the suspension procedure using the thermal sol-gel transition. The particles thus obtained can be stirred if acted upon by an external rotary magnetic field of a common permanent magnet. Isolation of the particles from reaction suspensions should proceed in a thin layer using a strong magnetic field. Magnetic bead cellulose prepared from supermagnetic powder of the SmCoFe alloy shows a better behaviour in the magnetic field than ferrite materials.
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  • 40
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    Angewandte Makromolekulare Chemie 212 (1993), S. 103-119 
    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: Unterschiedliche Methoden zur Messung der thermo-oxidativen Stabilität von Polypropylen wurden verglichen. Die Induktionszeiten des oxidativen Abbaus wurden mittels Differentialkalorimetrie (DSC) zwischen 160 und 240°C bis zu 10000 min gemessen. Die gleichen Proben wurden bei 130 bis 160°C 13000 h einer Alterung im Heizofen ausgesetzt.Unterschiedlich stabilisierte Proben ergaben bei dynamischen DSC-Messungen unterschiedliche Ergebnisse. Die Übereinstimmung zwischen dynamischen und statischen Experimenten waren bei kleinen Heizraten am besten.Die Arrhenius-Diagramme der isothermen DSC-Messungen unterscheiden sich von denen der Alterungsversuche; die erhaltenen Geraden schneiden sich entweder in der Nähe der Polypropylen-Schmelzpunkte oder verschieben sich bei den durch Temperung gealterten Proben zu längeren Zeiten. Die scheinbaren Aktivierungsenergien aus den Ofen-Temperungsmessungen sind sehr vie1 niedriger als die aus den DSC-Messungen berechneten und liegen bei allen Proben in einem einheitlichen Bereich, während bei den DSC-Experimenten ein Einfluß des Stabilisators zu erkennen ist.Die thermische Stabilität von Polypropylen wird auch von Antistatika und Farbpigmenten beeinflufßt. Besonders Rot-Pigment wirkt als Stabilisator für Polypropylen, was aus den Ofen-Alterungsversuchen hervorgeht; es verliert diesen Effekt aber bei höheren Temperaturen.
    Notes: The correlation between different methods of measuring thermo-oxidative stability of polypropylene has been studied. The oxidation induction times were measured using differential scanning calorimetry (DSC) in the temperature range from 160°C to 240°C up to 10000 min. The same samples were oven-aged in the temperature range from 130°C to 160°C up to 13000 h.The dynamic experiments performed by DSC show different results for differently stabilized samples. At slow heating rates the results of the dynamic experiments corresponded best to the results of the isothermal experiments.The straight-line Arrhenius plots of the isothermal DSC measurements do not correlate with the straight-line Arrhenius plots of the oven-aging tests. The Arrhenius plots obtained by these two methods either intersect close to the melting temperature of polypropylene or show jumps towards longer times when switching from DSC to oven-aging. It was found that the apparent activation energies obtained from the oven-aging tests are much lower than these obtained by DSC measurements. Almost the same activation energies were obtained for all the samples in oven-aging, while for the differently stabilized samples the activation energies from DSC measurements showed different results.Antistatic additives and colour pigments influence the thermal stability of polypropylene. Especially red pigment acts like a stabilizer for polypropylene, which is noticed at oven-aging testing, but at higher temperatures it loses this stabilizing effect.
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  • 41
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    Angewandte Makromolekulare Chemie 212 (1993), S. 201-202 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 42
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    Angewandte Makromolekulare Chemie 207 (1993), S. 31-41 
    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: Aktiviertes Aluminiumoxid wurde mit den Produkten der Reaktionen von chlormethyliertem Polystyrol mit Diethylamin, von Poly(styro1-co-chlormethylstyrol) mit Diethanolamin und von Poly(styro1-co-glycidylmethacrylat) mit Diethanolamin belegt und zur Adsorption von Escherichia-coli-Bakterien aus Wasser eingesetzt. 100 mg belegtes Trägermaterial wurden mit einer E.-coli-Suspension (20 ml, 107-8 Zellen/ml) gerührt, wobei die Zahl der lebensfähigen Zellen durch Adsorption abnahm; das Adsorptionsgleichgewicht wurde nach etwa 2 h erreicht. Der Abnahme-Koeffizient D (entspricht der Adsorptionsgeschwindigkeitskonstante) wurde aus der Abnahme der Zahl der lebensfähigen Zellen nach 2 h Adsorption gemessen.
    Notes: Reaction products of soluble chloromethylated polystyrene with diethylamine, poly(styrene-co-chloromethylstyrene) with diethanolamine, and poly(styrene-co-glycidyl methacrylate) with diethanolamine were prepared and supported on activated alumina granules. A study was made of removal of Escherichia coli cells from water by these supported alumina granules. When these granules (0.100 g) were stirred in a viable cell suspension (107-8 cells/ml, 20 ml), the viable cell number decreased by the adsorption of the cells to the granules. The adsorption attained approximately to the equilibrium (saturated adsorption) after about 2 h from the start of the adsorption. The decrease coefficient (D, which corresponds to the adsorption rate constant) was determined from the decrease in the viable cell number in the adsorption for about 2 h from the start.
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  • 43
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    Angewandte Makromolekulare Chemie 207 (1993), S. 43-52 
    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 radikalische Polymerisation von Bisphenol-S enthaltenden Mono- und Dimethacrylsaureestern (BPS-M und BPS-DM) wurde bezüglich Polymerisationsgeschwindigkeit, Läsungsmitteleinfluß, Copolymerisation und Kinetik der Photovernetzung untersucht. Es zeigte sich, daß das Lösungsmittel die Polymerisationsgeschwindigkeit signifikant beeinflußt; polare Lösungsmittel wie DMSO und Acetonitril verlangsamen die Polymerisationsgeschwindigkeit. Die Copolymerisation von BPS-M (M1) mit MMA (M1) wurde in Aceton bei 60°C untersucht. Die Copolymerisationsparameter wurden nach der Fineman-Ross-Methode zu r1 = 3,72 ± 0,0l und r2 = 0,80 ± 0,0l berechnet. Die hohe Reaktivität von BPS-M in diesem Copolymerisationssystem kann vermutlich dem „Matrix-Effekt“ zugeschrieben werden. Funktionelle Polymere mit Methacrylat- Seitengruppen wurden erfolgreich modifiziert und durch Bestrahlung in Gegenwart von Benzoinisopropylether photovernetzt. Die Kinetik der Photovernetzung ist zweiter Ordnung.
    Notes: Radical polymerizations of mono- and di-methacrylic esters containing bisphenol-S (BPS-M and BPS-DM) were studied in terms of polymerization rate, solvent effect, copolymerization and kinetic measurements of photocrosslinking. The solvents were found to affect significantly the polymerization rate. Polar solvents such as DMSO and acetonitrile were found to slow down the polymerization rate. Copolymerization of BPS-M(M1) with MMA(M2) was studied in acetone at 60°C. The monomer reactivity ratios were calculated to be r1 = 3.72 ± 0.01 and r2 = 0.80 ± 0.01 by the Fineman-Ross method. The high reactivity of BPS-M observed in this copolymerization system may be due to the “matrix effect”. Functional polymers containing methacrylate side-groups were successfully modified and photocrosslinked by irradiation in the presence of benzoin isopropyl ether. The photocrosslinking process is found to be of second order kinetics.
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  • 44
    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 Reaktion von Chlorsilanen (Me3SiCl, R2SiCl2, SiCl4; R=Me, Ph) mit MgCl2 · 6 H2O wurde bezüglich der Entfernung des Kristallwassers untersucht. Die Dehydratisierungsgeschwindigkeit hängt von der Art des Chlorsilans ab. Bei der Reaktion mit Dichlordiphenylsilan entsteht in hoher Ausbeute ungelöstes, wasserfreies Magnesiumchlorid, das als Trägermaterial für die Herstellung eines Titan-Katalysators verwendet wurde. Dieser zeigt mit Et3Al und Ph2Si(OMe), als Cokatalysatoren eine hohe Aktivität für die Propylenpolymerisation.
    Notes: Reaction of chlorosilanes (Me3SiCl, R2SiCl2, SiCl4; R=Me, Ph) with MgCl2 · 6 H2O were investigated for the efficiency of removal of water. The nature of chlorosilane is found to govern the rate of dehydration. The treatment of hydrated magnesium chloride with dichlorodiphenylsilane gives unsolvated anhydrous magnesium chloride in high yields. Anhydrous MgCl2 is used as support for the preparation of titanium catalyst. The catalyst in conjunction with Et3Al and Ph2Si(OMe)2 as cocatalyst system shows high activity for propylene polymerization.
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  • 45
    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: Es wird die Synthese verschiedener, mindestens bifunktioneller Azoverbindungen und deren Einbau in eine Polymerhauptkette mittels Grenzflächenpolykondensation beschrieben. Die thermischen und photochemischen Eigenschaften von Modellverbindungen sowie der Polymeren wurden durch UV-Spektroskopie und DSC-Messungen untersucht. Mit Hilfe von Viskositätsmessungen wurde der Kettenabbau eines Azopolymeren nachgewiesen.
    Notes: The synthesis of new, unsymmetrically functionalized azo compounds and their incorporation into polymers is described. Their photochemical decomposition and thermal stability was studied by UV spectroscopy and differential scanning calorimetry (DSC), respectively. Chemical degradation was followed by viscosity measurements.
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  • 46
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    Angewandte Makromolekulare Chemie 207 (1993), S. 173-186 
    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: Durch Phasengrenzflächenpolykondensation von 4,4′-Dimercaptobiphenyl mit ausgewählten aliphatischen und isomeren Phthalsäuredichloriden wurden neue Polythioester erhalten. Um die optimalen Bedingungen der Phasengrenzflachenpolykondensation zu bestimmen, wurde der Einfluß folgender Faktoren auf die reduzierte Viskosität und Ausbeute der Polythioester ermittelt: Art der organischen Phase, Konzentration der Reagenzien, Verhältnis der wässrigen zur organischen Phase, Art und Konzentration des HC1-Akzeptors, Reaktionstemperatur und -zeit. Die Polykondensation von Dithiol mit Isophthalsäuredichlorid wurde als Modellsystem speziell untersucht. Die Polythioesterstrukturen wurden mittels Elementaranalyse, IR-Spektroskopie und Riöntgenspektroskopie bestimmt. Aus der thermogravimetrischen Analyse wurden die Anfangszersetzungstemperatur, die Gewichtsabnahme bei dieser Temperatur und das Maximum der Zersetzungsgeschwindigkeit erhalten. Es wurden weiterhin einige physikalisch-chemische, mechanische und dielektrische Eigenschaften ermittelt. Aufgrund der geringen Löjslichkeit der Polythioester konnten die mittleren Molekulargewichte nicht bestimmt werden.
    Notes: New polythioesters were obtained by interfacial polycondensation of 4,4′-dimercaptobiphenyl with selected aliphatic and isomeric phthaloyl dichlorides.To determine the optimum polycondensation conditions, the influence of the following factors on reduced viscosity and yield were studied: type of organic phase, concentration of hydrogen chloride acceptor, type of catalyst, reaction temperature and rate of acid dichloride addition.A thorough examination was carried out only for the polycondensation of dithiol with isophthaloyl dichloride chosen as a model system. The structures of polythioesters were determined by elemental analysis, X-ray and infrared spectra. The temperature of initial decomposition, the percentage of its mass loss, and temperature of the fastest decomposition process were determined from curves of differential and thermogravimetric analysis.Some physicochemical, mechanical and electrical properties were determined. The molecular weights were not measured because of the low solubility of the obtained polythioesters.
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  • 47
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    Angewandte Makromolekulare Chemie 207 (1993), S. 215-216 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 48
    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 negativ geladene Oberfläche von feindispersen anorganischen Materialien wie Kieselgur, Perlit, Kaolin oder Glas kann durch die Adsorption von kationischen Polyelektrolyten umgeladen werden. Bei hohen Mengen an adsorbiertem Polykation besitzen die Oberflächen der unterschiedlichen Materialien dann gleiche elektrokinetische Eigenschaften. An den derart modifizierten Grenzflächen können anionische Farbstoffe adsorbiert werden. Bei Zugabe eines Polyanions, resultierend in der Bildung eines Polyelektrolytkomplexes, kann die Zahl der kationischen Zentren in der Grenzfläche und damit die Adsorptionskapazität für den Farbstoff erhöht werden. Die experimentellen Resultate deuten darauf hin, daß das Zetapotential bestimmt wird durch die außeren Bereiche der PEC-Schicht, wahrend die Farbstoffadsorption auch durch die inneren Regionen der Oberfläche mitbestimmt wird. Unmittelbar nach der Modifizierung mit Poly(diallyldimethylammoniumchlorid) und Poly(maeinsäure-co-α-methylstyrol) besitzen die modifizierten Materialien bei einem hohen Überschuß des Poly-anions ein negatives Zetapotential, aber ein positives nach der Abtrennung der überstehenden Lösung. Dieses Verhalten steht in Übereinstimmung mit der Bildung eines nichtstochiometrischen PEC mit Polykation im Überschuß und einer reversiblen Wechselwirkung mit überschüssigem Polyanion in der Lüsung. Die Ergebnisse deuten an, daß die Oberflache als fest-analoger Polyelektrolyt in Konkurrenz zu dem Polyanion an der Reaktion beteiligt ist.
    Notes: The surface charge of inorganic finely dispersed materials like diatom earth, perlite, glass or clay may be changed from negative to positive by the adsorption of cationic polyelectrolytes. Different materials exhibit equivalent electrokinetic surface properties with high amounts of the polycation adsorbed. Interfaces modified this way are able to adsorb anionic dye stuffs. Their adsorption capability for the dye stuff may be enhanced by addition of polyanions due to the formation of a nonstoichiometric polyelectrolyte complex (PEC) and therefore an increased number of cationic centres in the interface. Experimental results indicate that the zeta potential is correlated to the outer PEC layer whereby dye stuff adsorption measurements are sensitive for the more inner surface regions, too. Immediately after modification, materials modified with poly(diallyldimethylammonium chloride) and poly(maleic acid-co-α-methylstyrene) have negative zeta potentials at high excess of added polyanion and a positive one after separation of the solid. This behaviour is attributed to the formation of a nonstoichiometric PEC with polycation in excess and reversible interaction with polyanion in the surrounding solution. Experimental results indicate that the surface may act as “solid-like” polyelectrolyte in competition to the polyanion.
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  • 49
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    Angewandte Makromolekulare Chemie 207 (1993), S. 195-202 
    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 dielektrischen Relaxationsprozesse in Sulfobetain-Polyurethanionomeren mit Polyethersegmenten (Co2+ -komplexierte und H,S-behandelte Formen) wurden mit der TSDC-Methode untersucht und mit denen nichtionischer Polyurethane und verwandter Verbindungen verglichen. Vier mit c, βs, β′ und βh bezeichnete Relaxationsprozesse wurden in Polyurethanionomeren im Temperaturbereich von 110 bis 370 K beobachtet und mit möglichen molekularen Bewegungsprozessen korreliert. Die Einflüsse des Gehalts an Hartsegmenten, der Komplexierung sowie der H2S-Behandlung auf die Relaxationsprozesse wurden unter Berücksichtigung der strukturellen Modifikationen der harten und der weichen Mikrophasen erklärt.
    Notes: Dielectric relaxation processes in sulfobetaine polyurethane ionomers based on polyether, were studied comparatively to nonionic polyurethane and related compounds with Co2+ (complexed and H2S-treated forms) by using thermally stimulated depolarization currents (TSDC).Four relaxation processes denoted as γ, βs, β′ and βh in polyurethane ionomers over the 110-370 K range were observed. Molecular origin of these processes was suggested. The effects of the hard segments content, complexation and H2S treatment on the relaxation processes were explained in terms of the structural modifications of the hard and soft microphases.
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  • 50
    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 Komplexierung von Co(II), Ni(II), Cu(II), Zn(II) und Hg(II) in Amin-funktionalisierten, mit N-(Acrylamidomethyl)acrylamid (NNMBA) vernetzten Polyacrylamiden wurde untersucht. Die Metallionenaufnahme hängt vom Vernetzungsgrad ab und nimmt in der Reihenfolge Hg(II) ≫ Cu(II) 〉 Zn(II) 〉 Ni(II) 〉 Co(II) ab. Die Kinetik der Komplexierung ist erster Ordnung. Die Metallkomplexe wurden mittels IR- und EPR-Spektroskopie charakterisiert. Die Harze können ohne Kapazitätsverlust nach Dekomplexierung mehrmals verwendet werden; die desorbierten Harze komplexieren bevorzugt das vorher gebundene Metallion. Das Quellvermögen der komplexierten ist geringer als das der nichtkomplexierten Harze und hängt vom Vernetzungsgrad ab.
    Notes: The complexation of amino functions supported on poly(acrylamides) with 2-20 mol-% of N-(acrylamidomethyl)acrylamide (NNMBA) crosslinks towards Co(II), Ni(II), Cu(II), Zn(II), and Hg(II) ions was investigated. The metal ion uptake was found to be dependent on the extent of the NNMBA crosslinking. The observed trend in complexation is Hg(II) ≫ Cu(II) 〉 Zn(II) 〉 Ni(II) 〉 Co(II). The kinetics of complexation was found to be of first order. The derived metal complexes were characterised by IR and EPR. The complexed resins can be recycled several times without capacity loss. The metal-desorbed resins showed specificity to the metal ion which was initially present. The extent of swelling of the complexed resins is lower than that of the uncomplexed resins and it varies with the extent of crosslinking.
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  • 51
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    Angewandte Makromolekulare Chemie 208 (1993), S. 17-23 
    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 elektrische Leitung von mit verschiedenen Übergangsmetallen (Fe, Co, Cu, Cr) dotiertem Polycarbonat (PC) wurde im Temperaturbereich von 293 bis 493 K untersucht. Die Leitfähigkeit von PC mit FeCl, war siebenmal höher als jene der anderen Proben. Die effektive Potentialschwelle Φ wurde zu 0,2 eV berechnet. Weiterhin wurde die Dielektrizitätskonstante bei verschiedenen Temperaturen untersucht.
    Notes: The electrical conduction of polycarbonate (PC) doped with different transition metals was studied in the temperature range of 293-493 K. The conductivity of PC doped with FeCl3 is 7 orders higher in comparison with the other samples. The effective potential barrier (Φ) for pure PC was calculated (0.2 eV). Also, the dielectric constant at different temperatures was studied.
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  • 52
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    Angewandte Makromolekulare Chemie 208 (1993), S. 25-38 
    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 Wirkung von Lichtstabilisatoren im ersten Stadium der Alterung von Polyethylen niedriger Dichte (LDPE) wurde mit elektrischen Methoden untersucht. Drei verschiedene UV-Stabilisatoren wurden verwendet: ein Phosphit-Derivat (3,9-Bis[(2,4-di-tert-butyl)phenoxy]-2,4,8,l0-tetraoxa-3,9-diphosphaspiro[5.5]undecane), ein Benzophenon-Derivat (2-Hydroxy-4-octyloxybenzophenon) und ein Chelat [2,2′-Thiobis(4-tert-octylphenolato)(n-butylamino)nickel(II)]. Diese Stabilisatoren, speziell das Chelat, verbesserten die UV-Stabilität von LDPE für elektrische Anwendungen.
    Notes: The efficiency of light stabilizers is investigated by electric methods in the initial stage of photooxidative ageing of low density polyethylene (LDPE). Three types of UV light stabilizers are tried to improve the UV stability of LDPE: a phosphite type (3,9-bis-[(2,4-di-tert-butyl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane) a benzophenone type [2-hydroxy-4-octyloxy-benzophenone] and a stabilizer based on chelate salt [2,2′-thiobis(4-tert-octyl phenolato) (n-butylamine) nickel (II)]. LDPE is very susceptible to ultraviolet light. UV light stabilizers improve the stability of low density polyethylene for electrical applications, especially the UV stabilizer based on chelate salt.
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  • 53
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    Angewandte Makromolekulare Chemie 208 (1993), S. 39-46 
    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: Ein Poly(vinylalkohol)-Film (PVA) wurde nach Erhitzen in siedendem Wasser gequollen und durch Bestrahlen mit Elektronen vernetzt. Das so erhaltene PVA-Hydrogel weist eine höhere Elastizität und bessere mechanische Eigenschaften auf, obwohl es noch quellbar ist. Das Volumen des vernetzten Hydrogels reagiert sehr empfindlich auf einen Wechsel des Quellungsmittels und eine Temperaturänderung. Nach Kontraktion durch Eintauchen in Aceton nimmt die Zugfestigkeit zu. Durch wiederholtes Erhitzen des Hydrogels in siedendem Wasser und anschließendes Abkühlen wurden Kontraktions-Quellungs-Zyklen durchlaufen. Bei Temperaturen oberhalb 40°C nimmt das Quellungsverhältnis stark ab.
    Notes: Responsive poly(vinyl alcohol) PVA hydrogels obtained by electron irradiation after heating of a water-swollen film show higher elasticity and tougher properties even after boiling in water, although some swelling did occur. The volume of the hydrogel after boiling was very sensitive to solvent (acetone) and temperature. The crosslinked hydrogels show higher tensile strength after rapid contraction by immersion in acetone. The crosslinked PVA was boiled and cooled to induce contraction and swelling cycles. The swelling ratio of hydrogel decreased remarkably at temperatures higher than 40°C.
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  • 54
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    Angewandte Makromolekulare Chemie 208 (1993), S. 65-77 
    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 Umsetzung von 2,2′,6,6′-Tetrabrombisphenol A (TBBPA) mit Phosgen in einer mit Trialkylamin katalysierten Grenzflächenpolykondensation liefert nur Polymere mit niedrigem Molekulargewicht. Die geringe Reaktivität von TBBPA wird auf dessen sterisch anspruchsvolle Struktur und den elektronenziehenden Charakter der o-Bromsubstituenten zurückgeführt. Aus der Bildung von Carbamaten bei der Reaktion einer Modellverbindung (2,4,6-Tribromophenylchlorformat, TBPC) mit Trialkylaminen geht hervor, daß durch Zerfall des Katalysator-TBPC-Komplexes die Polymerisation abgebrochen wird. Das Carbamat wird durch Zersetzung des Acylammoniumsalzes gebildet, wobei eine nucleophile Substitution durch das Chloridion an dem an das positiv geladene Stickstoffatom gebundenen Kohlenstoffatom stattfindet.
    Notes: 2,2′,6,6′-Tetrabromobisphenol-A (TBBPA), a sterically hindered bisphenol, is known to give only low-molecular-weight polymers using the interfacial phosgenation process. The low reactivity is attributed to the bulkiness and electron-withdrawing character of bromine substituents at the ortho positions. From the formation of carbamate products in model compound (2,4,6-tribromophenyl chloroformate, TBPC) reactions with trialkylamines, the trialkylamine catalyst was found to act as a terminator by the degradation of the chloroformate-trialkylamine complex. The generation of carbamate occurs through the decomposition of the acyl ammonium salt proceeding via nucleophilic displacement by Cl- at the carbon attached to the positive nitrogen center. The relative catalytic abilities of trialkylamines and pyridine derivatives were determined in the homogeneous (dichloromethane) and interfacial (dichloromethane/water) systems. From the results of model reactions with TBPC and sodium tribromophenolate, 4-dimethylaminopyridine (DMAP) was found to be the best catalyst.
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  • 55
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    Angewandte Makromolekulare Chemie 208 (1993), S. 47-64 
    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 thermische Alterung von extrudierten Proben von mit Elektronenstrahlen vernetztem linearem Polyethylen wurde im Temperaturbereich von 110-170°C untersucht. Kurz- und langfristige Veränderungen der mechanischen (Dehnungs-)Eigenschaften wurden beobachtet; die entsprechenden Alterungsmechanismen werden auf der Basis ergänzender Sol-Gel-, Dichte-, FTIR- sowie gravimetrischer Messungen und Zugversuche an Mikrotomschnitten diskutiert.Zwei Mechanismen führen zu kurzfristigen Eigenschaftsänderungen: eine Nachvernetzung und eine Änderung der Kristallstruktur (bei Proben oberhalb ihrer Schmelztemperatur). Im vorliegenden Fall wurden die Polymeren im festen Zustand vernetzt, so daß die Änderung der Kristallstruktur zu einer erkennbaren Abnahme der Streckspannung (ca. 5 MPa) führte.Die langfristigen Veränderungen treten nach dem Ende der Oxidationsinduktionsperiode auf. Sie können als Übergang vom zähen in den spröden Zustand interpretiert werden, der durch Strukturänderungen sowohl auf molekularer (durch Kettenspaltung) als auch makroskopischer Ebene (durch diffusionskontrollierte Kinetik der Oxidation verursachte Kern-Schale-Struktur) hervorgerufen wird. Durch IR- und DSC-Analysen wurde festgestellt, daß wahrnehmbare Änderungen in der Dehnung erst kurz vor dem Ende der Induktionsperiode auftreten.
    Notes: The thermal aging of extruded samples of electron beam-crosslinked linear polyethylene has been studied in the 110-170°C temperature range. Short and long term changes of mechanical (tensile) properties were observed, and the corresponding mechanisms are discussed on the basis of complementary sol-gel and gravimetric measurements on whole samples, and density, FTIR and tensile testing on microtome sections.Two mechanisms are involved in short term changes: a post-crosslinking and a change of the crystalline morphology (for samples exposed above the melting point). The latter effect is especially important in the case under study where the polymer was crosslinked in the solid state and leads to a noticeable decrease (∼5 MPa) of the yield stress.The long term changes take place after the end of the induction period of oxidation. They can be interpreted in terms of ductile-brittle transition induced by structural changes occurring on the macromolecular level (chain scission) as well as macroscopically (core-shell structure resulting of the diffusion control of oxidation kinetics). It appears that noticeable changes of ultimate elongation occur just before the end of the induction period as detected by IR or DSC method.
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  • 56
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    Angewandte Makromolekulare Chemie 209 (1993), S. 95-109 
    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: Poly(epichlorhydrin) wurde durch nukleophile Substitution mit aliphatischen Kaliumcarboxylaten mit endstandigen Doppelbindungen (10-Undecenoat, 4-Pentenoat und 3-Butenoat) modifiziert. Die Reaktionsbedingungen wurden variiert, um ihren Einfluß auf den erreichten Substitutionsgrad zu untersuchen. Die hergestellten Polyether wurden mittels Elementaranalyse, spektroskopischen und thermischen Methoden sowie Viskositäts- und osmometrischen Messungen charakterisiert. Es wurde sowohl eine geringe Vernetzung als auch die bereits bekannte Hauptkettenspaltung beobachtet. Während der Substitutionsreaktion isomerisierte das Vinylacetat zum Crotonsäureester.
    Notes: Poly(epichlorohydrin) was modified by nucleophilic substitution with some aliphatic potassium carboxylates containing terminal double bonds (10-undecenoate, 4-pentenoate and 3-butenoate). In order to monitor the degree of substitution achieved, different reaction conditions were tested. The polyethers obtained were characterized by spectroscopic techniques, elemental analysis, thermal methods, viscosity determinations and osmometric measurements. A slight crosslinking and the reported main chain cleavage were both detected. Finally, it must be pointed out that, during the substitution reaction with the vinylacetate, isomerization to crotonic ester took place.
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  • 57
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    Angewandte Makromolekulare Chemie 210 (1993), S. 21-32 
    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: Polypropylen wurde mittels Gasentladung unter niedrigem Druck behandelt. Die Oberflaäachenmodifizierung wurde durch ESCA-Analysen, Messungen der Benetzbarkeit und Adhäasionsunterschungen in Abhäangigkeit von der Behandlungszeit und der Art des verwendeten Gases (Luft oder Argon) charakterisiert. Die Ergebnisse von “advancing”- und “receding” -Kontaktwinkelmessungen mit Wasser (sehr polar) und Diiodmethan (unpoler) in einem automatischen dynamischen Tensiometer ziegen eine Zunahme der Benetzbarkeit nach der Oberfläachenbehandlung. Dier wird auf die entstehung hochenergetisch polarer Stellen auf der Oberfläache zuräuckgefäuhrt. Die ESCA-Analyse belegt, daß die modifizierte Oberfläahe aud niedermolekularem Material besteht; sie ist in Methanol läolich.Die Adhäsion von Aluminium an der Polypropylen-Oberfläche wird bereits durch eine wenige Sekunden dauernde Gasentladungsbehandlung verbessert. Sie hängt von der polaren Komponente der Oberflächenenergie des Polymeren ab.
    Notes: Low-pressure discharge treatments were applied to the surface of polypropylene. ESCA analyses, wettability measurements and adhesion tests were carried out to characterize surface modifications as a function of treatment time and nature of gas (air or argon). Advancing and receding contact angles were measured with an automatic dynamical tensiometer. The liquids used were water (very polar liquid) and methylene iodide (apolar liquid). The results show an increase in wettability by the surface treatment. This is due to the creation of high-energy polar sites. ESCA analysis also shows that the modified surface layer is soluble in methanol and is made up of low-molecular-weight material.Adhesion of polypropylene/aluminium is also increased by the low pressure discharge treatment from the few first seconds of the treatment. This adhesion increase is a function of the polar component of the polymer surface energy.
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  • 58
    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: Blends aus Poly-ε-caprolacton (PCL) und Polymethylmethacrylat (PMMA) wurden durch Polymerisation von Methylmethacrylat in Gegenwart von PCL hergestellt. Die thermeischen, morphologischen, dynamisch-mechanischen und mechanischen Eigenschaften der Blends wurden ermittelt. Zum Vergleich wurden Blends durch mechanisches Mischen von PCL-und PMMA-Homopolymerschmelzen hergestellt und charakterisiert. Die nach beidenMethoden hergestellten Blends unterscheiden sich wesentlich in der phasenstrukturund den mechanischen eigenschafte, was wahrscheinlich auf die bildung von gepfropften Anteilen bei der erstgenannten Methode zuräuckgefäuhrt werden kann.
    Notes: Blends of poly-ε-caprolactone (PCL) and poly(methylmethacrylate) (PMMA) were prepared by a reactive method and characterized by thermal, morphological, dynamic mechanical and mechanical analyses. For comparison, “mechanical” blends, obtained by melt-mixing of preformed polymers, have been prepared and characterized. The two series of blends are different in phase structure and in mechanical tensile properties, probably due to the formation of grafted species during reactive blending.
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  • 59
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    Angewandte Makromolekulare Chemie 210 (1993), S. 33-46 
    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: Der Einfluß der Oberfläachenbehandlung von Säagemehl auf die physikalisch mechanischen Eigenschaften von mit Säagemehl gefäulltem Polypropylen wurde untersucht. Wäahrend mit Elastomerem beschichtetes Säagemehl die Festigkeit der Compostie veschlechtert, fäuhrt diein-situ-Addition von Oberfläachenmodifikatoren (mit Maleinsäaureanhydrid oder N-(3-Maleimidophenyl) maleimid modifiziertes Polypropylen) wäahrend des Knetens des Polypropylens mit unbehandeltem odermit Elastomerem vorbehandeltem Säagemehl zu einer Verbesserung der mechanischen Eigenschaften bei nurgeringer Beeinträachtigung der Schlagzäahigkeit. Die chemische Natur des Oberfläachenmodifikators ist dabei von besonderer Bedeutung, d.h. mit Maleinsäaurenhydrid modifiziertes Polypropylen erwies sich als der effektivste der untersuchten Modifikatoren. Halogenierte Elastomere und mit einem Phenolharz modifiziertes Polypropylen verbessern das Brandverhalten der Composite. Außerdem häangen die Eigenschaften von der Größe der Holzfasern ab. Die morphologische Untersuchung von Bruchfläachen der Composite zeigte, daß die Grenzfläachenadhäasion durch das mit Maleinsäaureanhydrid modifizierte Polypropylen verbessert wird.
    Notes: The effect of surface treatment of saw dust on the physico-mechanical properties of saw dust-filled polypropylene composites was studied. Whereas the elastomer-pretreated saw dust decreases the strength of composites, in-situ addition of interface modifiers, such as maleated polypropylene, m-phenylene bismaleimideSystematic name: N-(3-maleimidophenyl)maleimide.-modified polypropylene, during kneading of polypropylene with untreated or elastomer-pretreated saw dust improved the mechanical properties with a marginal sacrifice of impact strength. The chemical nature of interphase modifiers played an important role on the mechanical properties of the composites, e.g., maleated polypropylene was most effective among the modifiers used in this study. Halogenated elastomers and phenolic modified polypropylene improved the flame resistant properties of the composites. More over, properties varied with the particle size of wood fiber. The morphological study of the fracture surfaces of composites revealed that interfacial adhesion is improved by adding maleated polypropylene.
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  • 60
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    Biopolymers 21 (1982), S. 17-24 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Computer simulation shows that the time required to attain near sedimentation equilbrium is dramatically reduced by a two-step initial loading in which a macromolecular solution at low or zero concentration is layered above one at a higher concentration. To achieve the minimum time requires a good estimate of the molecular weight, but at least a 50% reduction in time can be achieved if the molecular weight of the macromolecule is known only within a factor of 2. Numerical solutions to the differential equation of the ultracentrifuge are calculated using the finite element method. An efficient Gaussian elimination algorithm can be used to minimize calculation time and computer storage requirements.
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  • 61
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    Biopolymers 21 (1982), S. 79-88 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The aldehydes present in acid-soluble type I collagen react with pyrenebutyrylhydrazine to form various types of complexes under different reaction conditions. These complexes exhibit one or more of three different pyrene fluorescence bands: monomer, excimer, and aggregate fluorescence. Collagen, whose aldehydes have been reduced with NaBH4, does not react with this fluorescent hydrazine, confirming that the hydrazine reacts specifically with aldehyde groups to form hydrazones. The absence of a reaction with pepsin-treated collagen also shows that the fluorescent labels are primarily in the nonhelical terminal telopeptides. Upon dialysis, the pyrene label bound to a saturated aldehyde in an α-chain is lost; whereas that bound to an unsaturated aldehyde remains on the protein. The pyrene monomer fluorescence in the β-chain of old collagen is stronger than that of young collagen. The formation of the pyrene excimer fluorescence implies the proximity of two pyrene molecules, probably attached to two adjacent aldehydes. Upon changing from acidic to neutral pH, both excimer and aggregate fluorescence bands disappear within a few seconds, revealing a very rapid alteration at the telopeptides.
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  • 62
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    Biopolymers 21 (1982), S. 147-157 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We describe conditions which lead to complete helix formation of poly(I) in the presence of NH4+. Binding of NH4+ is shown to be specific in the presence of Li+, which does not by itself support helix formation under these conditions. The NH4+-poly(I) complex is characterized by uv, CD, and ir spectroscopy. The CD spectrum is strikingly different from those of the Na+ or K+ complexes, the first extremum being changed from negative for the metal ions to positive for NH4+. A stereospecific model is proposed for the NH4+-poly(I) helix in which the N of NH4+ is located on the axis of the four-stranded helix, midway between planar tetramers formed by the bases. The model is consistent with the tetrahedral symmetry of NH4+, the requirement for four acceptable hydrogen bonds, the observed stability of the helix, and the accepted geometry of the backbone.
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    Biopolymers 21 (1982), S. 159-167 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It has recently been proven that the counterion condensate around an isolated line charge in an electrolyte, as characterized by nonlinear Poisson-Boltzmann theory, is an encapsulating δ-function. Here the identical result is shown to hold in the framework of the polyelectrolyte theory of Fuoss, Katchalsky, and Lifson. The proof fully exploits analytic solutions to the differential equation which are not available for the nonlinear, cylindrical Poisson-Boltzmann equation.
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  • 64
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    Biopolymers 21 (1982), S. 203-218 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The extent and modes of binding of the divalent metal ions Mn2+ and Co2+ to DNA and the effects of salt on the binding have been studied by measurements of the effects of these paramagnetic metal ions on the longitudinal and transverse relaxation rates of the protons of the solvent water molecules, a technique that is sensitive to overall binding. The number of water molecules coordinated to the DNA-bound Mn2+ and Co2+ is found to be between five and six, and the electron spin relaxation times and the electron-nuclear hyperfine constants associated with Mn2+ and Co2+ are little or not affected by the binding. These observations indicate little disturbance of the hydration sphere of Mn2+ and Co2+ upon binding to DNA. An average 2-3-fold reduction in the exchange rate of the water of hydration of the bound metal ions and an order-of-magnitude increase in their rotational correlation time are attributed to hydrogen-bond formation with the DNA. The binding constants of Mn2+ to DNA, at metal concentrations approaching zero, are found to be inversely proportional to the second power of the salt concentration, in agreement with the predictions of Manning's polyelectrolyte theory. A remarkable quantitative agreement with the polyelectrolyte theory is also obtained for the anticooperativity in the binding of Mn2+ to DNA, although the experimental results can be well accounted for by another simple electrostatic model. The various modes of binding of divalent metal ions to DNA are discussed.
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  • 65
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    Biopolymers 21 (1982), S. 265-275 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dc electrical conductivity of films of the polyelectrolyte complexes of glycol chitosan (GlChi) with the sodium salts of dextran sulfate (DS), carboxymethyl cellulose (CMC), polygalacturonic acid (GalUA)n, and alginic acid (AlgA) was measured at temperatures above and below room temperature. The maximum field strength in the thinnest film used amounted to 3 × 104 V/cm. A plot of normalized current against the reciprocal of the absolute temperature revealed two regions with different slopes, and activation energies in these two regions have been obtained for all the complexes. The activation energies in the high-temperature region vary from 0.85 to 1.18 eV and in the low-temperature region from 0 to 0.22 eV. Reasons are given to show that the conductivity is probably ionic. Near room temperature, the current-voltage relation is almost linear in the GlChi-DS complex, while in the other three complexes the current varies as a power n of the voltage with the value of n ranging from 1.7 to 2.5. A rise in temperatures causes an increase in the slope of the log I vs log V plot in GlChi-DS and GlChi-CMC complexes. The nonlinear current-voltage relation is ascribed to a space-charge-limited conductivity.
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  • 66
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    Biopolymers 21 (1982), S. 301-319 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Five different glucomannan samples were recrystallized from dilute solution. Depending on the experimental conditions, the crystals obtained could be identified as corresponding to the mannan I (anhydrous precipitate of more or less regular lozenge-shaped crystals) or mannan II (hydrated gel-forming pseudo-fibrillar precipitate). High-molecular-weight material, low temperature of crystallization, or a polar crystallization medium favored the mannan II polymorph, whereas a low-molecular weight, a high temperature of crystallization, and a crystallization medium of low polarity yielded the mannan I polymorph. Since the base-plane unit-cell dimensions are fairly constant with respect to variation of glucose, it is likely that isomorphous replacement of mannose by glucose occurs in glucomannan crystallization; the data also indicate that perfection of the glucomannan crystals was reduced in specimens having a high glucose:mannose ratio. The oriented crystallization of glucomannan on cellulose microfibrils was also studied under conditions where the mannan I polymorph was obtained. This gave shish-kebab structures that were characterized.
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  • 67
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The primary hydration process of native biopolymers is analyzed in a brief review of the literature, pertaining to various aspects of biopolymer-water systems. Based on this analysis, a hydration model is proposed that implies that the solution conformation of native biopolymers is stable at and above a critical degree of hydration (hp′ = 0.06-0.1 g H2O/g polymer). This water content corresponds to the fraction of strongly bound water, and amounts to ∼20% of the primary hydration sphere. In order to test this model, detailed sorption-desorption scanning experiments were performed on a globular protein (α-chymotrypsin). The results obtained are consistent with the proposed hydration model. They show that under certain experimental conditions, sorption isotherms can be obtained that do not exhibit hysteresis. These data represent equilibrium conditions and are thus accessible to thermodynamic treatment. Valid thermodynamic functions, pertinent to the interaction of water with biopolymers in their solution state, can be obtained from these sorption experiments.
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    Biopolymers 21 (1982), S. 451-458 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The light scattering of bovine serum albumin (BSA) has been measured at protein concentration up to 90 g/L and at pH values between 4.4 and 7.6. The dependence of scattering on both protein concentration and pH may be quantitatively accounted for by a simple extension of the hard-sphere model for protein solutions [Ross, P. D. & Minton, A. P. (1977) J. Mol. Biol. 112, 437-452] allowing for electrostatic repulsions between molecules. According to the extended model, the radius of the effective hard spherical particle representing BSA varies with the net electrical charge of the BSA molecule in a manner which may be calculated from electrostatic theory.
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  • 69
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    Biopolymers 21 (1982), S. 475-497 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A complete analysis of all possible conformations with correct hydrogen bonds of the collagen II type was performed on the basis of developed simultaneous equations. Using a unimodal search (by varying Ψ3), the energetically favorable structure was obtained. No other energetically satisfactory structural solutions are possible. The next aim was to obtain a precise model of the molecule. The program used includes a subroutine for continual deformation of the pyrrolidine rings. The set of parameters determining the structure consists of 14 independent variables (8 dihedral and 6 bond angles). As starting points for the energy optimization, conformations produced by scanning and some structures from previous work were used. The final structures (practically the same for both polymers) have helix parameters h = 0.285 nm and t = 52°, which are in excellent agreement with the 7/2 symmetry of diffraction data. The conformations of the pyrrolidine rings are of the B type, i.e., C2-Cβ-exo-Cγ-endo. For both polypeptides, the conformations of imino acids in position 3 of the triplet are the same; in position 2, however, they are slightly different. The difference in diffraction patterns for the 7/2 and 10/3 helices is discussed.
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    Biopolymers 21 (1982), S. 547-563 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The CD spectrum of the enzyme adenylate kinase has been investigated. Theoretical calculations, based on the x-ray crystal structure, have been carried out by means of an origin independent matrix formalism. The entire molecule was included in the calculations in the sense that essentially all electronic transitions that occur at wavelengths longer than 185 nm were included in the basis set. A linear dielectric function was utilized to evaluate the intertransition coupling potentials. The results of the theoretical calculations were in reasonable agreement with experimental CD spectra of the molecule.
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    Biopolymers 21 (1982), S. 633-652 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mode of action of many antitumor agents entails the inhibition of nucleic acid synthesis. Because many of the drugs can intercalate, it is assumed that intercalation is an important step in the mechanism of biological activity. As intercalants contain a planar chromophore as an ingredient essential for intercalation, chromophores that should fit into DNA are desired. This is the main theme of this investigation. Binding to DNA of fundamental moieties, protonated pyridine, aniline, phenol, quinone, and 4H-thiopyran-4-one, is studied to determine their optimum placement in DNA. The optimum orientations for each moiety are superimposed to form polyaromatic systems that can intercalate in a manner in which functional groups on these chromophores are oriented as in the moieties themselves. Ideal intercalants proposed contain three and four fused ring system, have protonated ring nitrogen atoms located to maximize the electrostatic interactions with DNA, hydroxy and amino groups that can hydrogen bond to the OII and O5′ phosphate backbone atoms, and carbonyl and sulfur groups in the central position of the ring system to provide variations in the chromophore and to interact with the relatively positive region in the intercalation site. The optimum orientation occurs when the chromophore and the base pairs overlap to the maximum extent. The ideal intercalants are fundamentally of the type:
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    Biopolymers 21 (1982), S. 665-677 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: DNA reassociation kinetics using the phenol emulsion reassociation technique (PERT) [Kohne, D. E., Levison, S. A. & Byers, M. J. (1977) Biochemistry 16, 5329-5341] has been investigated at high DNA concentrations using an endonuclease S1 assay of reaction progress. Apparent second-order rate constants fall on two intersecting straight lines when presented as a function of DNA concentrations on a log-log plot. In the low DNA concentration range, the rate constants drop about 10-fold when concentration increases 1000-fold. In the high DNA concentration range, the rate constants drop more than 10-fold when concentration increases 10-fold. The slopes of these lines are the same in different solvents and at different temperatures. The intersection between the lines occurs when the available catalytic surface is saturated. At high DNA concentrations, high-complexity heterologous denatured DNA apparently competes 2-4 times better for the surface than homologous DNA because it does not participate in a reassociation reaction. Native and partially native DNA molecules cannot compete with single-stranded DNA for a saturated surface. At high DNA concentrations, reactions using PERT become dependent on the single-strand DNA length. Increasing length lowers reassociation rates.
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  • 73
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 21 (1982), S. 859-872 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Classical potential functions (CPF) calculations on 3′-mononucleotides, the building blocks of nucleic acids, predict a correlation between the sugar ring pucker and the torsion angle Φ′ around the C3′—O3′ bond. In ribonucleotides, the value of Φ′ depends on the sugar pucker, viz. the C2′-endo sugar pucker is associated with Φ′ = 210° and 270°, while the C3′-endo sugar pucker favors only Φ′ = 210°. On the other hand, in deoxyribonucleotides, both sugar puckers show a preference for Φ′ = 180°. These theoretical predictions are fully corroborated by the results obtained from x-ray and nmr studies on mono-, di-, and polynucleotides.
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    Topics: Chemistry and Pharmacology
    Notes: The effect of several surfactants on the secondary structure of bovine β-lactoglobulin B was determined from the circular dichroism spectra. The spectra were measured at several concentrations of surfactant ranging from 1 mg/mL to the critical micelle concentration. The surfactants studied were sodium dodecyl, decyl, and octyl sulfate, sodium dodecyl sarcosinate, dodecyltrimethylammonium bromide. The data were analyzed using the method of Chen et al. [Biochemistry (1974) 13, 3350-3359] to determine the percentage of α-helix, β-sheet, and unordered form at each surfactant concentration. In every case, an increase in structured form and a 20-25% decrease in the amount of unordered form was noted when the surfactant concentration reached the critical micelle concentration. However, the relative amounts of the two structured forms present depend on the surfactant used. The profile of the secondary structure of the protein also varied from surfactant to surfactant as the protein was titrated, probably reflecting the delicate balance between ionic and nonionic forces that governs the secondary structure of β-lactoglobulin and most other globular proteins in aqueous solution.
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    Topics: Chemistry and Pharmacology
    Notes: Amino acids are known to differ in their individual preferences for each of the four positions of the β-turn conformation formed by tetrapeptide segments. Proline and glycine show relatively high preferences for positions 2 and 3, respectively, of the β-turn. Using tripeptides of the type N-acetyl-Pro-Gly-X-OH, where X = Gly, Ala, Leu, Ile, and Phe, we have sought to study the influence of the 4th residue X on the stability of the β-turn conformation in these tripeptides. Our nmr and CD results show that the β-turn stability is quite significantly governed by the nature of the amino acid residue at this position in the following order: Leu 〉 Ala 〉 Ile, Gly 〉 Phe.
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    Biopolymers 21 (1982), S. 1153-1166 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermodynamic studies of the binding of adamantanecarboxylate to cyclodextrins have been made as a function of temperature and added organic cosolvent (methanol) using flow microcalorimetry. The negative heat capacity change associated with the adamantanecar-boxylate/β-cyclodextrin interaction and the fact that the interaction is weakened by the addition of methanol implicate the binding process as being a hydrophobically driven one. The negative enthalpy change (ΔH0 = -5.5 kcal/mol) and near-zero entropy change (ΔS0 = 1.5 cal/mol deg) are quite different from the values normally expected for a hydrophobic bond, indicating that other bonding forces are important in addition to the hydrophobic effect. The relative contribution of the hydrophobic effect and other bonding forces (most likely van der Waals forces) to the overall binding was judged from an analysis of the dependence of the thermodynamics of the association process on the surface tension of the water-methanol mixtures following a model for “solvophobic” bonding described by Sinanoglu [Molecular Associations in Biology (1968) Academic Press, New York, pp. 427-445]. From this analysis, adamantane-carboxylate/cyclodextrin complex formation is found to be driven to the extent of -1.9 kcal/mol by the hydrophobic effect. Furthermore, the hydrophobic driving force is found to be characterized by a positive ΔS0 of 10 cal/mol deg. The remaining free energy of binding (and the ΔH0 of binding of ∼-6 kcal/mol) is then due to the intrinsic (surface-tension-independent) van der Waals interaction between the ligand and cyclodextrin cavity.
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    Biopolymers 21 (1982) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 79
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Pivaloyl-L-Pro-Aib-N-methylamide has been shown to possess one intramolecular hydrogen bond in (CD3)2SO solution, by 1H-nmr methods, suggesting the existence of β-turns, with Pro-Aib as the corner residues. Theoretical conformational analysis suggests that Type II β-turn conformations are about 2 kcal mol-1 more stable than Type III structures. A crystallographic study has established the Type II β-turn in the solid state. The molecule crystallizes in the space group P21 with a = 5.865 Å, b = 11.421 Å, c = 12.966 Å, β = 97.55°, and Z = 2. The structure has been refined to a final R value of 0.061. The Type II β-turn conformation is stabilized by an intramolecular 4 → 1 hydrogen bond between the methylamide NH and the pivaloyl CO group. The conformational angles are φPro = -57.8°, ψPro = 139.3°, φAib = 61.4°, and ψAib = 25.1°. The Type II β-turn conformation for Pro-Aib in this peptide is compared with the Type III structures observed for the same segment in larger peptides.
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    Biopolymers 21 (1982), S. 1333-1363 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The folding-unfolding process of reduced bovine pancreatic trypsin inhibitor was investigated with an idealized model employing approximate free energies. The protein is regarded to consist of only Cα and Cβ atoms. The backbone dihedral angles are the only conformational variables and are permitted to take discrete values at every 10°. Intraresidue energies consist of two terms: an empirical part taken from the observed frequency distributions of (φ,ψ) and an additional favorable energy assigned to the native conformation of each residue. Interresidue interactions are simplified by assuming that there is an attractive energy operative only between residue pairs in close contact in the native structure. A total of 230,000 molecular conformations, with no atomic overlaps, ranging from the native state to the denatured state, are randomly generated by changing the sampling bias. Each conformation is classified according to its conformational energy, F; a conformational entropy, S(F) is estimated for each value of F from the number of samples. The dependence of S(F) on energy reveals that the folding-unfolding transition for this idealized model is an “all-or-none” type; this is attributable to the specific long-range interactions. Interresidue contact probabilities, averaged over samples representing various stages of folding, serve to characterize folding intermediates. Most probable equilibrium pathways for the folding-unfolding transition are constructed by connecting conformationally similar intermediates. The specific details obtained for bovine pancreatic trypsin inhibitor are as follows: (1) Folding begins with the appearance of nativelike medium-range contacts at a β-turn and at the α-helix. (2) These grow to include the native pair of interacting β-strands. This state includes intact regular secondary conformations, as well as the interstrand sheet contacts, and corresponds to an activated state with the highest free energy on the pathway. (3) Additional native long-range contacts are completely formed either toward the amino terminus or toward the carboxyl terminus. (4) In a final step, the missing contacts appear. Although these folding pathways for this model are not consistent with experimental reports, it does indicate multiple folding pathways. The method is general and can be applied to any set of calculated conformational energies and furthermore permits investigation of gross folding features.
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Peptide NH chemical shifts and their temperature dependences have been monitored as a function of concentration for the decapeptide, Boc-Aib-Pro-Val-Aib-Val-Ala-Aib-Ala-Aib-Aib-OMe in CDCl3 (0.001-0.06M) and (CD3)2SO (0.001-0.03M). The chemical shifts and temperature coefficients for all nine NH groups show no significant concentration dependence in (CD3)2SO. Seven NH groups yield low values of temperature coefficients over the entire range, while one yields an intermediate value. In CDCl3, the Aib(1) NH group shows a large concentration dependence of both chemical shift and temperature coefficient, in contrast to the other eight NH groups. The data suggest that in (CD3)2SO, the peptide adopts a 310 helical conformation and is monomeric over the entire concentration range. In CDCl3, the 310 helical peptide associates at a concentration of 0.01M, with the Aib(1) NH involved in an intermolecular hydrogen bond. Association does not disrupt the intramolecular hydrogen-bonding pattern in the decapeptide.
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    Biopolymers 21 (1982), S. 1469-1472 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Biopolymers 21 (1982), S. 1479-1487 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A formalism for extracting the conformations of a proline ring based on the bistable jump model of R. E. London [(1978) J. Am. Chem. Soc. 100, 2678-2685] from 13C spin-lattice relaxation times (T1) is given. The method is such that the relaxation data are only partially used to generate the conformations; these conformations are constrained to satisfy the rest of the relaxation data and to yield acceptable ring geometry. An alternate equation for T1 of 13C nuclei to that of London is given. The formalism is illustrated through an example.
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    Biopolymers 21 (1982), S. 1521-1534 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have used broadline proton magnetic resonance to study molecular motion in cellulose, a sodium pectate solution, a calcium pectate gel, and isolated bean cell walls. All samples were prepared in D2O to minimize the contribution of water to the observed signals. For each sample, a free induction decay was obtained, and the second moment, spin-lattice relaxation, and dipolar relaxation were measured. Our results show that the large majority of protons in cellulose are immobile. Rigid and mobile domains were also observed in the pectate samples. We have shown that gelation induces large-scale changes in the free induction decay, the second moment, and the relaxation behavior of the pectate. As with the other samples, rigid and more mobile domains were found in bean cell walls. The fraction in the rigid domains is much larger than the fraction of cellulose in the sample, suggesting that the noncellulosic wall components are also organized into rigid and mobile domains.
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    Topics: Chemistry and Pharmacology
    Notes: Conformational energy computations were carried out on collagenlike triple-stranded conformations of several poly(tripeptide)s with the general structure CH3CO—(Gly—X—Y)3—NHCH3. The sequences considered had various amino acid residues in position X or Y of the central tripeptide, with either Pro or Ala as a neighbor, i.e., Gly-X-Pro, Gly-X-Ala, Gly-Pro-Y, and Gly-Ala-Y. Minimum-energy conformations were computed for the side chains, and their distributions were compared for the four sequences. The residues used were Abu (= α-aminobutyric acid), Leu, Phe, Ser, Asp, Asn, Val, Ile, and Thr. The conformational energy of a —Ch2—CH3 side chain in Abu was mapped as a function of the dihedral angle χ1. Intrastrand interactions with neighboring residues do not affect the conformations of a side chain in position Y, and they have a minor effect on it in the X-Ala sequence, but they strongly restrict the conformational freedom of the side chain in the X-Pro sequence. Conversely, interstrand interactions do not affect side chains in position X, but they strongly restrict the conformational freedom of a side chain in position Y if there is a nearby Pro residue in a neighboring strand. Hydrogen bonds with the backbone can be formed in some conformations of long polar side chains, such as Asp, Asn, or Gln. All amino acid residues can be accommodated in collagen. Because of the interactions mentioned above, steric and energetic constraints can be correlated with observed preferences of certain amino acids for positions X or Y in collagen. Hence, these preferences may be explained, in part, in terms of differences in the conformational freedom of the side chains in the triple-stranded structure.
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    Biopolymers 21 (1982), S. 1657-1666 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ionization constants of the tyrosyl groups of chymotrypsinogen and of nitrated-chymotrypsinogen (two tyrosyl residues nitrated) have been determined by difference spectrophotometry. In chymotrypsinogen, two of the four tyrosyl groups ionize without any time dependence. Above pH greater than ca. 12.5, time-dependent spectral changes are seen for 0.7 group equivalent. The data can be fitted to the values of pK′1 9.75 ± 0.07, pK′2 11.55 ± 0.05, pK′3 13.30 ± 0.05. In nitrated-chymotrypsinogen, the two nitrated tyrosyl residues have pK′1 6.44 and pK′2 8.30. For both proteins, these pK′ values are in agreement with those evaluated from potentiometric titration and calorimetric data using computer-assisted curve-fitting analysis.
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    Biopolymers 21 (1982), S. 2195-2203 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformation of several samples of poly(α,β-L-Asp) with a molar fraction of β-bonds ranging from 0.1 to 0.55 was investigated by means of ir and CD spectroscopy and potentiometric titration and compared with the results obtained previously with poly(α-L-Asp). All samples investigated underwent a conformational change induced by changes in their degree of ionization: unpronounced ir absorption of amide V at 650 cm-1 was shifted to 620 cm-1 and substantially increased on deionization; CD spectra changed with the degree of ionization, passing through an isosbestic point; and the pattern of the titration curves was more complex than that of a simple polyelectrolyte. The conformation developing with the decreasing degree of ionization may be considered to be α-helix, as deduced according to the analogous behavior of other polypeptides. The extent of the conformational change in the individual samples depends on the molar fraction of β-bonds: the higher it is, the lower is the helix-forming ability of the sample.
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    Biopolymers 21 (1982), S. 2225-2239 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The use of 1H-nmr spectroscopy is demonstrated to be a useful analytical method to characterize the structure of synthetic peptides attached to soluble, macromolecular polyoxyethylene (POE) supports in the liquid-phase method (LPM) of peptide synthesis. We report an extensive 360-MHz 1H-nmr study of POE-bound homo-oligo-L-methionine peptides. A combination of high field and selective saturation or Redfield pulse methods allows resolution of individual backbone NH and α-CH resonances of dilute peptides in the presence of strong resonances from macromolecular POE and/or protonated solvents. The nmr spectra for the POE-bound peptides in CDCl3 are qualitatively similar to those of the low-molecular-weight Boc-L-Metn-OMe peptide esters. This corroborates other observations that POE has little effect on peptide stucture. The backbone α-CH region of peptides is overlapped by signals from the terminal oxyethylene group of POE, but the peptide side-chain and low-field backbone NH resonances are well resolved. In trifluoroethanol the Boc-(L-Met)n-NH-POE heptamer and octamer adopt the right-handed α-helical structure, and the present nmr studies provide evidence for two strong intramolecular hydrogen bonds to stabilize the helices. In water, the N-deblocked derivatives, (L-Met)n-NH-POE oligomers adopt β-sheet structure and manifest well-resolved nonequivalent NH resonances with 6-7 Hz 3JNH-CH coupling constants.
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    Biopolymers 21 (1982), S. 2241-2252 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The concerted model of Monod, Wyman, and Changeux is generalized so that all effects of interactions for an enzyme operating at a nonequilibrium stationary state are considered. In contrast to the original model, which is based on an analogy to equilibrium ligand binding, the generalization may show both “positive” and “negative cooperativity” in both catalytic binding and conformational processes. Furthermore, in contrast to any equilibrium binding model, the Hill coefficients may be greater than the number of sites n. For catalysis, the maximum value is 2n, and for conformational changes, n + 1. These points are illustrated by two cases that yield simpler analytic expressions. The first obtains when catalysis occurs on a much faster time scale than the conformational changes, and the second, when this situation is reversed.
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    Biopolymers 21 (1982), S. 2315-2316 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 91
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    Biopolymers 21 (1982), S. 1473-1477 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Biopolymers 21 (1982) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 93
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    Biopolymers 21 (1982), S. 1503-1520 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By combining gel permeation chromatography (GPC) and light-scattering spectroscopy, including photon correlation and angular distribution of absolute scattered intensity, we were able to characterize immunologically active Haemophilus influenzae type b polysaccharide (HIB Ps) bovine serum albumin (BSA) conjugates in terms of equivalent hydrodynamic radius rh ∼ (6.2 ± 0.6) × 102 Å, apparent radius of gyration rg ∼ (5.4 ± 0.3) × 102 Å, apparent molecular weight Mw ∼ (3.5 ± 0.4) × 106 g/mol, and a second virial coefficient A2 ∼ (1.9 ± 0.3) × 10-4 cm3 mol/g2. We could study the effects of each of the processes in the conjugate formation according to the following procedure: BSA (dialysis, modification, fractionation) + HIB Ps → HIB Ps/BSA conjugate (conjugate formation, fractionation). Narrow distributions of HIB Ps BSA conjugate formation can be achieved using fractionated BSA.
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  • 94
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    Biopolymers 21 (1982), S. 1569-1586 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have measured the ir absorption of 5′CMP, 5′IMP, and poly(I)·poly(C) from ∼25 to ∼500 cm-1. From a comparison of the data with the previously measured absorption of the corresponding nucleosides and bases we can identify several “lines” associated with the deformation of the ribose ring. Out-of-plane deformation of the bases contributes strongly to vibrations near 200 cm-1. The same ribose vibrations observed in the nucleotides are found in poly(I)·poly(C). They sharpen with increasing water absorption. A study of the spectra of poly(I)·poly(C) as a function of the adsorbed water indicates that water does not contribute in a purely additive fashion to the polynucleotide spectrum but depends on the conformation of the helix. However, the only spectral feature that shifts drastically with conformation is near 45 cm-1. Measurements at cryogenic temperatures indicate some sharpening of the spectrum of poly(I)·poly(C). Instead, no sharpening is observed in the spectrum of the nucleotides. Shear degradation of poly(I)·poly(C) produces significant spectral changes in the 200-cm-1 region and sharpening of the features assigned to the low-frequency ribose-ring vibrations.
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  • 95
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    Biopolymers 21 (1982), S. 1735-1747 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of the oxygen replacement reaction of carbon monoxide-saturated hemoglobin (HbA0) was carried out using spectroscopic, calorimetric, and pH titration methods. Under fully saturated conditions the replacement reaction can be defined by a single partition constant over all ratios of bound oxygen to carbon monoxide. This indicates that under saturating conditions Haldane's first law for the ligand binding of gas mixtures holds for any CO/O2 ratio. It further shows that there is no appreciable difference in relative CO-O2 affinity between the α- and β-chains. The same partition coefficient was found to hold for different pH, buffer, and allosteric effector conditions. The lack of any pH dependence of the partition coefficient was confirmed by the absence of proton changes for the replacement reaction. The temperature dependence of the partition coefficient and calorimetric results yield a value for the enthalpy of the reaction of -3.65 ± 0.29 kcal/mol/heme.
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    Biopolymers 21 (1982), S. 1763-1780 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We demonstrate that the isotropic absorption and linear dichroism in an unknown flow field can be used to determine base tilt in polynucleotides if three transitions are measured and the directions of the corresponding dipoles are known. The method is applied here to reach conclusions about the base tilt in poly(rA), poly(rA)+·poly(rA), and poly(rC). The respective values are: 28° tilt about the axis + 50° toward C8 from the C1′ → N9, and 25° tilt about the axis + 118° toward C5 from C1′ → N1. The results for poly(rA)+·poly(rA) are consistent with the accepted model. Spectra were measured for poly(rC)+·poly(rC), but definite conclusions must await reliable directions for transition dipoles. The dipole direction for the 218-nm transition in rC is found to be +13° or +43° toward C5 from C1′ → N1. The CD spectra to about 168 nm are presented and discussed.
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    Biopolymers 21 (1982), S. 1811-1832 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Measurements of stress relaxation in uniaxial extension and associated time-dependent birefringence have been made on bovine fibrin film, prepared by gentle compaction of coarse fibrin clots, containing 13-22% fibrin plasticized with either aqueous buffer or glycerol. Both unligated and ligated (i.e., with α-α and γ-γ ligation by fibrinoligase, factor XIIIa) films were studied. Both types showed two stages of stress relaxation, with time scales of approximately 10 and 103-104 s, respectively, with a plateau region between. In the plateau, the nominal (engineering) stress for ligated glycerol-plasticized film is proportional to In λ, where λ is the stretch ratio, up to λ ≅ 2, and it decreases with increasing temperature. For unligated glycerol-plasticized film, the stresses are smaller by a factor of one-half to one-third. For ligated film, the second stage of relaxation is relatively slight, and recovery after release of stress is often nearly complete. For unligated film, the second stage involves a substantial drop in stress, and after recovery there is a significant permanent set. A second relaxation for ligated film reproduces the first, but for unligated film it reproduces the first only if the initial relaxation is terminated before the second stage; otherwise, the second relaxation shows a weaker structure. The behavior of water-plasticized film is similar to that of glycerol-plasticized except that the second stage of relaxation occurs at shorter times. During the first stage of stress relaxation, up to about 100 s, the birefringence and the stress-optical coefficient increase; during the plateau zone of stress relaxation, the birefringence of ligated films is approximately constant and is proportional to 2λ2/(λ2 + 1) - 1, where λ is the stretch ratio. This dependence is predicted by a two-dimensional model in which rodlike elements in the plane of the film are oriented with independent alignment. During the final stage of stress relaxation, the birefringence of ligated films decreases slightly; that of unligated films decreases substantially, but less rapidly than the stress, corresponding to a further increase in the stress-optical coefficient. With additional information from small-angle x-ray scattering reported in an accompanying paper, the first stage of relaxation is attributed to partial release of bending forces in the fibers by orientation, accompanied by increased birefringence. The second stage is attributed, for ligated films, to an internal transition in the fibrin units accompanied by elongation of some of the fibers; and in the unligated films, to a combination of the latter transition with slippage of protofibrils lengthwise within the fiber bundles that causes some loss of orientation, which diminishes the birefringence.
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    Biopolymers 21 (1982), S. 1899-1908 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A microscope capable of measuring the CD of intact single eukaryotic cells, DNA microcrystals, and other microscopic structures has been constructed and tested. It can measure the CD spectra in the 200- and 800-nm wavelength range and consists of a modification to a standard Cary 60 CD machine in combination with a Zeiss uv microspectrometer. Preliminary CD spectra of red blood cells and lymphocytes are presented.
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    Biopolymers 21 (1982), S. 1909-1926 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The distribution of fibers in agarose gels has been studied by electron-microscopic examination of replicas formed from freeze-fracture surfaces. For gels set in water, the results obtained support the model proposed for the gel structure by Arnott et al. (1974) of a random array of long, straight, connected fibers, with each fiber having a diameter equivalent to that of an aggregate of approximately 10-30 agarose helixes, depending on the initial agarose concentration. The density of these fibers, their water content, and the total length of fibers per unit volume have been derived from the measured distribution of intersections per unit area of freeze-fracture surfaces. For gels set in the presence of salt, the distribution of fibers becomes distinctly non-Poissonian, leading to larger interfiber spaces and a gel of greater effective pore size. The larger pore size of gels set in the presence of salt also has been revealed by electrophoretic measurements in which the relative migration rates of plasmid DNA molecules of varying conformations have been determined.
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    Biopolymers 21 (1982), S. 1933-1943 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Energy embedding has been shown recently to be a useful extension of the distance geometry approach to conformational calculations in the case of very small molecules and simple energy functions. This paper tests the ability of energy embedding to locate low energy conformations satisfying both weak and strong geometric constraints when the molecule is the small protein, bovine pancreatic trypsin inhibitor, and the energy function is the complicated Oobatake-Crippen residue-residue potential. Using the potential function alone, the algorithm reaches a structure with energy lower than that of the native conformation, but with little resemblance to it. Aided by numerous geometric constraints, such as preformed secondary structure segments, the algorithm again finds a local minimum with energy better than that of the native, and with only 3.3 Å rms deviation from it. This is significantly closer to the native value than can be obtained using standard distance geometry and the geometric constraints alone. Thus, energy embedding using the Oobatake-Crippen potential function is a significant help in finding native conformations of proteins. However, additional trials on a hairpin bend fragment of trypsin inhibitor demonstrate the potential's shortcomings in encouraging proper secondary structure.
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