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  • Chemistry  (19,136)
  • 1995-1999
  • 1990-1994  (10,531)
  • 1980-1984  (6,410)
  • 1925-1929  (2,195)
  • 1993  (10,531)
  • 1980  (6,410)
  • 1929  (2,195)
Collection
Years
  • 1995-1999
  • 1990-1994  (10,531)
  • 1980-1984  (6,410)
  • 1925-1929  (2,195)
Year
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular evolution 15 (1980), S. 79-101 
    ISSN: 1432-1432
    Keywords: Molecules ; Interstellar ; Chemistry ; Isotopes ; Solar system
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The study of interstellar molecules broadly includes two areas of interest. One area uses the unique ability of molecules to act as probes of the physical conditions in the cold, dense, visually opaque component of the interstellar medium. The physical properties of this and other components of the interstellar medium are summarized. The other area deals with the chemistry of interstellar molecules, recent aspects of which are emphasized in this review. Gas-phase chemistry, shock chemistry, and grain surface chemistry are discussed in the context of recent observations. No present observations suggest that surface reactions are relevant, but neither can they be ruled out. Ion-molecule reactions are clearly operative, at least for the simpler species. Chemical isotope fractionation is reviewed, andd it is concluded that the complexities of the chemistry allow no cosmological conclusions to be drawn from observations of deuterium in interstellar molecules, while the presence of13C in interstellar molecules permits an estimate of the12C/13C ratio which is consistent with the current concepts of the nucleosynthesis history of the Galaxy. Possible connections between interstellar molecules and the early molecular history of the solar system are discussed.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Pure and applied geophysics 118 (1980), S. 128-151 
    ISSN: 1420-9136
    Keywords: Galactic cosmic rays ; Solar proton events ; Particle precipitation ; Chemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract An assessment is made of the relative contribution of certain classes of energetic particle precipitation to the chemical composition of the middle atmosphere with emphasis placed on the production of odd nitrogen and odd hydrogen species and their subsequent role in the catalytic removal of ozone. Galactic cosmic radiation is an important source of odd nitrogen in the lower stratosphere but since the peak energy deposition occurs below the region where catalytic removal of O3 is most effective, it is questionable whether this mechanism is important in the overall terrestrial ozone budget. The precipitation of energetic solar protons can periodically produce dramatic enhancement in upper stratospheric NO. The long residence time of NO in this region of the atmosphere, where catalytic interaction with O3 is also most effective, mandates that this mechanism be included in future modelling of the global distribution of O3. Throughout the mesosphere the precipitation of energetic electrons from the outer radiation belt (60°≲Λ≲70°) can sporadically act as a major local source of odd hydrogen and odd nitrogen leading to observable O3 depletion. Future satellite studies should be directed at simultaneously measuring the precipitation flux and the concomitant atmosphere modification, and these results should be employed to develop more sophisticated models of this important coupling.
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  • 3
    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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  • 4
    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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  • 5
    Electronic Resource
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    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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  • 6
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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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  • 7
    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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  • 8
    Electronic Resource
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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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  • 9
    Electronic Resource
    Electronic Resource
    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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  • 10
    Electronic Resource
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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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  • 11
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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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  • 12
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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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  • 13
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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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  • 14
    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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  • 15
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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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  • 16
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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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  • 17
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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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  • 18
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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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  • 19
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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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  • 20
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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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  • 21
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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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  • 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: 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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  • 23
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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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  • 24
    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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  • 25
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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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  • 26
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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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  • 27
    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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  • 28
    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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    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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    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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    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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    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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  • 33
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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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  • 34
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    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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  • 35
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    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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  • 36
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    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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  • 37
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    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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  • 38
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    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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  • 39
    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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  • 40
    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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  • 41
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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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  • 42
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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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  • 43
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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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  • 44
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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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  • 45
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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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  • 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: 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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  • 47
    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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  • 48
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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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  • 49
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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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  • 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 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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  • 51
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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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  • 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 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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  • 53
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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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  • 54
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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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  • 55
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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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  • 56
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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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  • 57
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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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  • 58
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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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  • 59
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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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  • 60
    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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  • 61
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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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  • 62
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    Biopolymers 19 (1980), S. 823-831 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of the DNA-binding oligopeptide distamycin A on the B to A transition of DNA in ethanol/water solutions has been studied by means of CD. (The overbars indicate that it does not matter which particular form of the corresponding families is considered.) The results show that increasing the concentration of distamycin A reverses the A conformation (in 82% ethanol) to the B conformation due to its strong binding and stabilization of the latter. In accordance with previous data for pure aqueous solutions, a site size of 3.5 base pairs is obtained from the studies in water/ethanolic solutions. From the data on the B to A transition in the presence of distamycin A, we estimated the length of the cooperativity ν0 = 10 base pairs.The results demonstrate that the oligopeptide systems of distamycin, as well as those of netropsin, are effective stabilizers of the DNA B-conformation.
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  • 63
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tetrapeptides with proline in position 2, asparagine or leucine in position 3, and glycine in positions 1 and 4, with end groups free or blocked on the N-terminal side, were studied in their various ionic states in 2H2O and in Me2SO-d6 by 1H- and 13C-nmr. In order to clarify or refine some details, successive substitutions of the residues in these peptides with amino acids enriched to 85% in 13C, or to 85% 13C plus 97% 2H were carried out. The 1H and 13C chemical shifts as well as the 1H-1H, 13C-13C, and 13C-1H coupling constants and the signal intensities show strong similarity of behavior between the tetrapeptides of asparagine and leucine. The main conformational characteristics are (1) the almost total stabilization of the trans conformer in the type I β-turn structure when the peptide is in the zwitterion state dissolved in Me2SO. This is deduced from the 3JC3αH-N3H and the 3JC2′-H3α coupling constants, which both furnish a dihedral angle of φ3 = -90°, and from the positive value of the temperature coefficient of the glycine-4 amide protons, which suggests a type 4 → 1 hydrogen bond; (2) the evolution of cis and trans isomer fractions which change with the ionic state of the peptides in Me2SO, whereas they remain constant in aqueous solution; and (3) the conformation of the pyrrolidine ring as it follows the variations in cis:trans isomer populations together with the side-chain rotamer fractions of the residue in position 3. In the β-turn conformation the isomer cis is less abundant and the pyrrolidine ring is more flexible; this explains the perfect accommodation of the proline residue in position 2 of a bend. The interdependence of these phenomena where interactive forces play a predominant role underlines the importance of cooperative effects in the molecule. The results also suggest that the cis isomer of proline can adapt itself just as well as the trans isomer to position 2 of a type I β-turn.
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  • 64
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An algorithm is presented for the Monte Carlo simulation of the decay of fluorescence polarization from segmentally flexible molecules. Based on the random walk model of Brownian motion, the treatment explicitly follows the stochastic changes in the diffusion coefficients as the molecule bends. It includes the effects of a linear restoring force opposing the bending and the effects of hydrodynamic coupling between the translational, rotational, and bending motions. One application is presented: the simulation of anisotropy decay curves for hinged rods. A variety of decay curves are obtained, including single- and multiexponential behavior, and the following conclusions are reached: (1) increasing the flexibility is usually, but not always, accompanied by a more rapid rate of depolarization; (2) reducing the size of the fluorescent subunit will usually, but not always, increase the rate of depolarization; and (3) the complex interplay between the effects of molecular shape, relative sizes of the subunits, restoring force, and orientation of the transition dipoles renders it unlikely that any simple method can be used to interpret anisotrophy data without simulation. In particular, it is not possible to determine the extent of bending by fitting the data with the two-exponential approximation used by some investigators in the past.
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  • 65
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    Biopolymers 19 (1980), S. 977-990 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C-nmr spectra of red seaweed galactans, belonging to the agar and carrageenan groups or having the “intermediate” type of structure, were interpreted on the basis of 13C-nmr spectra of model compounds. Signal assignments have been made for most of the known extreme structures of such galactans. 13C-nmr spectroscopy was shown to be a rapid and convenient method of structural analysis, which permits one to determine the type of galactan structure, the absolute configurations of its constituents (galactose and 3,6-anhydrogalactose), and the positions of the sulfate and O-methyl groups in a polysaccharide molecule.
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  • 66
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dielectric response of human umbilical cord hyaluronic acid in various environments has been studied at microwave frquencies using a resonant microwave cavity as a probe. Both the real and imaginary parts of complex dielectric constant and the loss tangent for hyaluronate solutions are obtained by utilizing equations for perturbation of a resonant cavity. Dielectric changes at room temperature have been observed in aqueous solutions of hyaluronic acid as a function of concentration ranging from 0 to 350 mg/ml. The data indicate the existence of ordered phases in hyaluronate solutions at selective concentrations, that is, exhibiting lyotropic-type transitions. Hyaluronate solutions at 1.5 and 3 mg/ml concentrations have been studied at various pH in the range of 6-8 and at constant ionic strength 0.1. A temperature-dependent transition in hyaluronate solution of 120 mg/ml concentration has been observed at physiological temperature. It is shown that this temperature-dependent behavior can be related to the orientational polarizability term in the Debye theory of polar molecules in liquids.
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  • 67
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    Biopolymers 19 (1980), S. 945-964 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In 1974, Zimm described a theory which predicts that the sedimentation coefficient of high-molecular-weight DNA will decrease as the rotor speed of measurement increases. In 1979, this theory was revised, and the new formula predicts speed-dependence effects that are substantially smaller than the predictions of the original version. This report describes the results of subjecting both the original and the revised versions of the theory to quantitative tests using a well-defined sucrose-gradient system and a DNA of known molecular weight (T4c DNA). T4c bacteriophage is a mutant, whose DNA contains the unmodified base cytosine, instead of the glucosylated hydroxymethylcytosine characteristic of the T-even bacteriophages, and has a molecular weight of 115 ± 3 × 106. The DNA of the wild-type phage (T4D+) was also used in some experiments.In addition to the quantitative tests, the experiments test for an effect first observed by Rubenstein and Leighton, which showed that the sedimentation coefficient measured for T2 DNA depended on the composition of the centrifuge tube used for the measurement (tube composition effect). It can be inferred from this observation that an interaction occurs between particle and tube wall during sedimentation, and this leads to a reduction in sedimentation velocity independent of the reduction in S described by Zimm's theory.The results show that in the range of 25,000-50,000 rpm, the original but theoretically incorrect form of the theory quite accurately describes the sedimentation behavior of both T4c and T4D+ DNA, although T4D+ was a special case in some respects. The revised (corrected) form of the theory predicts much less of a speed-dependence effect than that actually observed. The discrepancy between corrected theory and observation suggests that other factors (perhaps arising from the use of the swinging bucket rotor geometry) are causing the additional observed reduction in S20,w. However, the experiments show that the tube composition effect does not seem to be one of these.
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  • 68
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The fixation of cis (NH3)2Cl2Pt(II) to poly(I)·poly(C) leads to the formation of two complexed species. One involves coordination to a single base (accounting for about 70% of the total platinum bound over the rb range 0.07-0.25) and the other to two bases which are not adjacent to each other but may be on the same strand and separated by a loop. Reaction of the platinum compound with poly(I) gives in addition to the above two species a minor one (about 15%, independent of rb over the range 0.05-0.30) in which the platinum is bound to two adjacent bases. The availability of such coordination reduces the dominance of the 1:1 species, which, however, remains the major one (ca. 55%).
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  • 69
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    Biopolymers 19 (1980), S. 1329-1344 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complex of CH3Hg(II) with the accessible cysteines of glyceraldehyde-3-phosphate dehydrogenase (GAPD, EC 1.2.1.12) from rabbit muscle has been studied by phosphorescence and optically detected magnetic resonance (ODMR) spectroscopy. The wavelength dependence of the phosphorescence decay kinetics has also been measured. Comparison of CH3Hg(II)-GAPD with GAPD by these methods shows that a specific optically resolved tryptophan site of GAPD is perturbed by the interaction with a nearby mercury atom. The perturbation on the luminescence and ODMR properties is typical of an external heavy-atom effect. Based on the x-ray diffraction structure of the lobster enzyme, it is proposed that the heavy-atom effect results from the interaction of tryptophan-310 with CH3Hg(II) bound to cysteine-281 in the rabbit muscle enzyme.
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  • 70
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    Biopolymers 19 (1980), S. 1415-1434 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The energy of interaction of a spermine molecule with the A- and B-forms of DNA has been calculated, assuming that the molecule of spermine is fixed in the narrow groove of the DNA helix with the formation of hydrogen bonds between the amino groups of spermine and the phosphate groups of DNA. The atom-atom potentials method was used. Optimal structures for the A-DNA-spermine and B-DNA-spermine complexes are suggested. It is shown that, in agreement with the experimental data, the interaction of the spermine molecule with the A-DNA is energetically more favorable than that with the B-DNA. Two main factors are responsible for this: (1) the distance between neighboring phosphates of the chain in A-DNA (which is about 1 Å less than that in B-DNA) corresponds better to the distance between the amino groups of the propyl part of spermine; and (2) the orientation of phosphate groups in A-DNA inside the groove is preferable for complex formation with spermine to the outside groove arrangement of the phosphates in B-DNA. These conclusions are further confirmed by the calculations for DNA-propane diamine complexes.
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  • 71
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The crystal structure of a synthetic analog of valinomycin, cyclo[-(D-Ile-Lac-Ile-D-Hyi)3-] (C60H102N6O18), has been determined by x-ray diffraction procedures. The crystals are orthorhombic, space group P212121, with cell parameters a = 11.516, b = 15.705, c = 39.310 Å, and Z = 4. The atomic coordinates for the C, N, O atoms were refined in the anisotropic thermal motion approximation and for the H atoms in the isotropic approximation. Values of standard (R) and weighted (Rw) reliability factors after refinement are 0.073 and 0.056, respectively. The structure is completely asymmetric. The cyclic molecular backbone is stabilized by six intramolecular hydrogen bonds N—H…O=C, five bonds being of the 4→1 type and one being of the 5→1 type. The side chains are located on the molecular periphery. The conformational state of isoleucinomycin in the crystal is intermediate between the corresponding crystalline states of valinomycin and meso-valinomycin. The observed conformation suggests that complexation could proceed via entry of the ion at the face possessing the L-Lac residues, the less crowded face.
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  • 72
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    Biopolymers 19 (1980), S. 1555-1566 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Possible conformations of lacto-N-tetraose, lacto-N-neotetraose, related disaccharides, and other milk oligosaccharides have been studied by an energy-minimization procedure using empirical potential functions. Lacto-N-tetraose favors a “curved” conformation, while lacto-N-neotetraose favors an approximately “straight” conformation. These two conformations differ mainly in the position of the terminal galactose residue with respect to the rest of the molecule. This difference explains the greater strength of lacto-N-neotetraose compared with lacto-N-tetraose in its ability to inhibit the cross-reaction of blood group P1 fractions with Type XIV pneumococcal antipolysaccharide. Although the favored conformation of lacto-N-tetraose (inactive) agrees with the model proposed by the earlier workers, that for lacto-N-neotetraose (active) differs. The favored conformations for the disaccharides galactose-β(1-4)-N-acetylglucosamine, galactose-β(1-3)-N-acetylglucosamine, and lactose are similar in overall shape, differing only in the nature and orientation of the side groups. This explains their nearly equal inhibitory activity. These theoretical models also explain the increased activity of lacto-N-fucopentaose I over that of lacto-N-tetraose and the relative activities of the substituted lactoses. The present studies suggest that it is the overall shape of the molecule which is important for activity, rather than the terminal β(1-4)-linked galactose residue alone.
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    Biopolymers 19 (1980), S. 1571-1585 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C spin-lattice relaxation times of poly(L-lysine) have been obtained at 67.9 MHz in aqueous solution and in a mixed solvent (40% methanol/60% water). A concomitant determination of the conformation by CD permits the correlation of conformation and rotational diffusion of the polymer. The dependence on pH of the spin-lattice relaxation times of the 13Cα and the side-chain carbon resonances reflects the diffusional motion in the random-coil conformation, in the helix-coil transition, and in the conformation of the α-helix. In the mixed solvent the reorientational correlation time of the Cα-Hα vector increases from τ = 0.37 nsec (random coil) to τ = 12.0 nsec (α-helix). In aqueous solution the correlation time of this vector increases from τ = 0.33 nsec (random coil) to τ ≫ 11 nsec. The reorientation rates of the side-chain methylene groups in the two solvents are markedly different. The reorientation of all methylene groups is reduced in the mixed solvent.
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  • 74
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solid-state conformation of copolymers of β-benzyl-L-aspartate [L-Asp(OBzl)] with L-leucine (L-Leu), L-alanine (L-Ala), L-valine (L-Val), γ-benzyl-L-glutamate [L-Glu(OBzl)], or ∊-carbobenzoxy-L-lysine (Cbz-L-Lys) has been studied by ir spectroscopy and circular dichroism (CD). The ir spectra in the region of the amide I and II bands and in the region of 700-250 cm-1 have been determined. The results from the ir studies are in good agreement with data obtained by CD experiments. Incorporation of the amino acid residues mentioned above into poly[L-Asp(OBzl)] induces a change from the left-handed into the right-handed α-helix. This conformational change for the poly[L-Asp(OBzl)] copolymers was observed in the following composition ranges: L-Leu, 0-15 mol %; L-Ala, 0-32 mol %; L-Val, 0-8 mol %; L-Glu(OBzl), 3-10 mol %; and Cbz-L-Lys, 0-9 mol %.
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    Biopolymers 19 (1980), S. 1667-1673 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dry purified ligamentum nuchae elastin has been investigated for physical aging. The samples were quenched from a temperature (197°C) close to the softening point to a number of measuring temperatures ranging from -20 to +180°C. At each temperature, the small-strain torsional creep properties were determined at a number of elapsed intervals after the quench. Aging effects were found over the whole temperature range, and the creep and aging behavior of elastin turned out to be very similar to that of synthetic polymers.
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  • 76
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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 19 (1980), S. 1705-1713 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Covalently closed circular DNA can exist in different configurations known as circular, toroidal, and interwound. Changes among these forms can be made in several ways, including the insertion of dye molecules between adjacent base pairs, which tends to untwist the double-helical structure. The aim of this paper is to discuss these configurations, and the changes among them, in the context of classical elastomechanics. The concepts of twisting, linkage and writhing are explained. Simple experiments on a twisted linear-elastic rod are described, and it is shown that although the circular and interwound forms may be modeled in this way, the toroidal form does not occur, being mechanically unstable. Theoretical energy calculations by Levitt on bent and twisted DNA show that DNA exhibits a particular kind of nonlinear elasticity in which there is an unusual coupling between bending and twisting. The aim of the paper is to show qualitatively that this special kind of elasticity can stabilize the toroidal form of closed circular DNA.
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  • 78
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    Biopolymers 19 (1980), S. 1357-1374 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Light-scattering, viscosity, and sedimentation experiments on aqueous solutions of k-carrageenan show that this sulfated polygalactose is an expanded flexible random coil. This expansion is due to long-range interactions that are predominantly electrostatic. Extrapolation of viscosity data to infinite ionic strength provided values for the intrinsic viscosity which were subjected to the Stockmayer-Fixman analysis, giving a value for the Mark-Houwink coefficient under theta-conditions, Kθ, of 0.27. The characteristic ratio, C∞, under these conditions is 7.8, and the conformation factor σ is 2. In a solution of 0.118 ionic strength, where a Mark-Houwink exponent aη of 0.86 is found, the radii of gyration calculated from viscosity data are lower than those found from the angular dependence of scattered light. On the other hand, the radius of gyration found from the sedimentation rate agrees well with the light-scattering radius. The relations between molecular parameters are corrected for the poly-dispersity of the sample.
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    Biopolymers 19 (1980), S. 1407-1414 
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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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  • 80
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    Biopolymers 19 (1980) 
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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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  • 81
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    Biopolymers 19 (1980), S. 1475-1489 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An approximate analytic expression for the translational friction coefficient of a toroid modeled as a continuous shell of frictional elements is derived using the Kirkwood approximation. The accuracy of this expression was determined by comparing the friction coefficients predicted by it to those predicted by extrapolated shell-model calculations using the modified Oseen tensor. To show that these calculations do indeed yield the correct friction coefficients, actual translational friction coefficients were determined by observing settling rates of macroscopic model rings or toroids in a high-viscosity silicone fluid. Our conclusion is that the approximate expression yields friction coefficients that are about 1.5-3% low for finite rings. For thin rings, a comparison is also made with the exact result of Yamakawa and Yamaki [J. Chem. Phys. 57, 1572 (1972); 58, 2049 (1973)] for the translational friction of plane polygonal rings. This comparison shows that the approximate expression yields results which are low by 2-3% unless the rings are extremely thin, in which case the error is larger. In the limit of an infinitely thin ring the approximate expression reduces to the Kirkwood result [J. Polym. Sci. 12, 1 (1954)], which is low by 8.3%. We discuss briefly how this work may be useful in determining the structure of DNA compacted by various solvent-electrolyte systems and polyamines.
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    Biopolymers 19 (1980), S. 1451-1474 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Internal Brownian motions of clean φ29 and λ-DNAs have been studied using photon-correlation techniques at both visible (λ0 = 632.8 nm) and uv (λ0 = 363.8 nm) wavelengths. The present dynamic light scattering data, which extend to K2 = 19 × 1010 cm-2, can in every case be satisfactorily simulated by a Rouse-Zimm model polymer with an appropriate choice of the three model parameters. The effects of pH, salt concentration, single-strand breaks, and molecular weight on those model parameters have also been investigated. Intact clean DNAs exhibit surprisingly little variation with pH from 7.85 to 10.25, with salt concentration from 0.01 NaCl to 5.4M NH4Cl, or with molecular weight or GC content. The single-strand breaks have no effect at pH 9.46, but produce dramatic changes in the model parameters at pH 10.0 and 10.25, indicating the introduction of titratable joints at those pHs. The failure of either single-strand breaks or a large change in GC content to alter the model parameters in the neutral pH range is a strong indication that local denaturation is not required for those flexions and torsions that dominate the relaxation of fluctuations in the scattered light. The Langevin relaxation time for the slowest internal mode of a particular Rouse-Zimm model derived from the dynamic light scattering data is compared with pertinent literature data extrapolated to the same molecular weight. The present algorithm for determining model parameters from the light-scattering Dapp vs K2 curve actually yields a Langevin time in fairly good agreement with the literature value. For unknown reasons the light-scattering D0 values generally exceed those obtained from the molecular weight and sedimentation coefficient by about 20%.
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    Biopolymers 19 (1980), S. 1507-1515 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Raman spectra of polyribouridylic acid excited in the uv region, from 363 to 290 nm, are reported. The conformational changes of the polymer from random coil to ordered structure with stacked bases at high and low temperature, respectively, are reflected by important changes in the Raman line intensities; this Raman hypochromism is itself a function of the excitation wavelength - its profile has been determined and shows negative values in the region of 290 nm (near resonance), i.e., hypochromism becomes hyperchromism. Thus the knowledge of the hypochromism excitation profile is important in following order-disorder transition of a polymer using resonance Raman spectroscopy. Theoretical attempts are proposed for explanation, involving not only the relative variations of the molar extinction coefficient on the order-disorder transition of the polymer, but also the damping factors of the vibronic levels. The theoretical curve is found to fit adequately the experimental data over the excitation range, using only the frequency of the O-O transition of uracil and a vibronic linewidth of 2200 cm-1.
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    Biopolymers 19 (1980), S. 2177-2190 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preferential interaction of sodium poly(α-L-glutamate) and poly(α-L-glutamic acid) with the solvent components in water/2-chloroethanol mixtures has been determined using density-increment measurements. The degree of preferential interaction was deduced from the density increments at constant molality of 2-chloroethanol and at constant chemical potential of 2-chloroethanol. Sodium poly(α-L-glutamate) and poly(α-L-glutamic acid) are both preferentially hydrated in the whole range of solvent composition. A dehydration process occurs during the 2-chloroethanol-induced coil-to-helix transition of sodium poly(α-L-glutamate). This dehydration process was attributed to the release of some moles of water from the neighborhood of the peptide bond during the nucleation of the helix. After the conformational transition, sodium poly(α-L-glutamate) is solvated by one 2-chloroethanol molecule. The location of water and 2-chloroethanol molecules in the different parts of the residue (more polar and less polar portions) is also discussed.
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    Biopolymers 19 (1980), S. 2223-2245 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complex formation between tryptamine and mononucleotides and dinucleoside phosphates containing adenine and/or cytosine has been studied at five pD's ranging from 1.1 to 7.4 by proton magnetic resonance spectroscopy. Chemical shifts of base ring protons and the ribose anomeric proton in the nucleotides and indole ring protons in tryptamine were monitored and their changes with pD and intermolecular interactions interpreted qualitatively. Stacked complexes were found to exist at all pD's in the range studied. Complex geometries differ depending on pD. An electrostatic interaction between the tryptamine amino group and the nucleotide phosphate group contributes to complex formation above pD 4 but is not strong enough to shift the dinucleoside phosphate equilibrium towards the unstacked conformer.
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Empirical conformational energy calculations have been carried out for N-methyl derivatives of alanine and phenylalanine dipeptide models and N-methyl-substituted active analogs of three biologically active peptides, namely thyrotropin-releasing hormone (TRH), enkephalin (ENK), and luteinizing hormone-releasing hormone (LHRH). The isoenergetic contour maps and the local dipeptide minima obtained, when the peptide bond (ω) preceding the N-methylated residue is in the trans configuration show that (1) N-methylation constricts the conformational freedom of both the ith and (i + 1)th residues; (2), the lowest energy position for both residues occurs around φ = -135° ± 5° and ψ = 75° ± 5°, and (3) the αL conformational state is the second lowest energy state for the (i + 1)th residue, whereas for the ith residue the C5 (extended) conformation is second lowest in energy. When the peptide bond (ωi) is in the cis configuration the ith residue is energetically forbidden in the range φ = 0° to 180° and ψ = -180° to +180°. Conformations of low energy for ωi = 0° are found to be similar to those obtained for the trans peptide bond. In all the model systems (irrespective of cis or trans), the αR conformational state is energetically very high. Significant deviations from planarity are found for the peptide bond when the amide hydrogen is replaced by a methyl group. Two low-energy conformers are found for [(N-Me)His2]TRH. These conformers differ only in the φ and ψ values at the (N-Me)His2 residue. Among the different low-energy conformers found for each of the ENK analogs [D-Ala2,(N-Me)Phe4, Met5]ENK amide and [D-Ala2,(N-Me)Met5]ENK amide, one low-energy conformer was found to be common for both analogs with respect to the side-chain orientations. The stability of the low-energy structures is discussed in the light of the activity of other analogs. Two low-energy conformers were found for [(N-Me)Leu7]LHRH. These conformations differ in the types of bend around the positions 6 and 7 of LHRH. One bend type is eliminated when the active analog [D-Ala6,(M-Me)Leu7]LHRH is considered.
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  • 87
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Based on steric and electrostatic considerations, the prerequisites for binding to DNA via the intercalation mechanism are proposed. Steric contour energy curves are presented to demonstrate the region inaccessible to an intercalant. They are calculated with a 6-n (n = 14) potential. This method is a soft potential analog of an excluded-volume approach. Electrostatic contours on the steric surface illustrate the relatively positive and negative regions of the binding site. The principal intercalation sites, predicted to fit into B-DNA via a tetramer-duplex unit, and the unconstrained dimer-duplex units, obtained in crystal structures, are examined. These contours illustrate the requirements of size, conformation, and net atomic charges necessary for intercalation and optimum binding. Based on the limited space available for intercalation by the presence of the backbone and the maximum base-pair separation of 8.25 Å, an Essential Metabolite Exclusion Hypothesis is presented.
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  • 88
    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 near-uv CD spectrum of lysozyme was carried out in the presence and absence of the inhibitor tri-N-acetylglucosamine, and theoretical chiroptical calculations based on the tetragonal crystal structure of the enzyme and the enzyme-inhibitor complex were performed. The results of these calculations indicate that the near-uv CD spectrum of lysozyme can be adequately explained in terms of negative rotatory strengths arising from the tryptophan 1La (293-300 nm) and the disulfide n-σ* bands (250 rm), and positive rotatory strength contributions from the tryptophan 1Lb bands (291 nm) and the tyrosine 1Lb bands (275 nm). Contributions to the rotatory strength of each band were approximated in terms of specific interactions between chromophores. It was found that the rotatory strength of most of the near-uv transitions arises primarily from coupling interactions involving other side-chain chromophores and amide groups which are in close proximity. Changes which are observed in the lysozyme CD spectrum on binding of tri-N-acetylglucosamine may be explained in terms of changes in the rotatory strength which result from interactions of the 1La transitions of the active-site tryptophans with the acetamide groups of the inhibitor. The reasonable agreement which is found between the experimental and calculated rotatory strengths implies that the crystal conformation of lysozyme must resemble the solution conformation.
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  • 89
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of the following oligo- and co-oligopeptides by the liquid-phase method is described: (L-Met)15 (I), [L-Glu(OBzl)]20 (II), (L-Val)8-Gly (IV), (L-Ile)8-Gly (V), (L-Ile)4-Gly-(L-Ile)4 (VI), (L-Ile)4-Pro-(L-Ile)4 (VII), (L-Met)5-L-Pro-(L-Met)5 (VIII), [L-Glu(OBzl)]7-L-Pro-[L-Glu(OBzl)]7 (IX). The oligomers are covalently bound to bifunctional polyethylene glycol (PEG) and monofunctional PEG-M of Mr 5 × 103-2 × 104. Analytical controls were carried out after each step of synthesis in order to ensure quantitative coupling yields. All products could be obtained in high purity as indicated by amino acid analysis, thin-layer chromatography and chiroptical methods. The solubility of the oligomers was strongly enhanced by the presence of the C-terminal PEG group, enabling conformational investigations in a variety of solvents. A significant relationship between conformation and physicochemical properties of the oligopeptides was observed. Oligomers with tendencies to adopt α-helical (I, II) or unordered structures (VI-IX) showed no pronounced change in solubility or coupling kinetics during chain elongation, whereas the onset of a β-structure (IV, V) was paralleled by a drastic decrease in solubility and reactivity of the terminal amino groups. Most notably, the insertion of a proline or glycine in the middle of a β-forming peptide chain (VI, VII) resulted in a considerable increase in solubility compared to the corresponding homo-oligomers. The impact of the conformational properties of a peptide chain on strategic considerations of peptide synthesis in solution is delineated.
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  • 90
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational analysis of the CD spectrum is reported for the synthetic and membrane-modifying nonadecapeptide analog of alamethicin N-t-Boc-(Aib-L-Ala)5-Gly-Ala-Aib-Pro-Ala-Aib-Aib-Glu(OBzl)- Gln-OMe. The CD data are evaluated according to three different methods and are discussed with respect to those obtained from natural alamethicin and suitable models such as N-t-Boc-(Aib-L-Ala)7-OPOE, fragments of the synthetic nonadecapeptide, and the hexadecapeptide N-t-Boc-(Aib-L-Ala)5-Pro-Ala-Aib-Aib-Glu(OBzl)-Gln-OMe. The synthetic nonadecapeptide with the longer helical region exhibits membrane activities comparable to those of alamethicin, whereas the hexadecapeptide with the shorter helix is inactive.
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  • 91
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 19 (1980) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 92
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 19 (1980), S. 231-240 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper deals with the light scattering from particles rotating in a flow with a transverse velocity gradient. It is theoretically substantiated and experimentally proved that the scattered light spectrum contains reliable information of the particle configuration and dimensions. The proposed technique may prove also very promising for the analysis of particle polydispersion.
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  • 93
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of poly(ε-L-lysine) is described. This is a poly(ε-amino acid) in which the ε-amino group of lysine is condensed with the α-carboxyl group to produce a chain backbone that is a variant of the usual one seen in proteins and the side chain is the α-amino group. Conformational studies of poly(ε-L-lysine) and its t-butyloxycarbonyl derivative suggest the likelihood of a chain order that is formally similar to the antiparallel pleated-sheet conformation of proteins.
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  • 94
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have studied the kinetics of oscillatory tensile forces in collagen membranes. These forces were generated by sinusoidal electric fields applied across the membrane. Both the magnitude and phase of the measured force changed with frequency over a three-decade range. The membrane-separated electrolyte baths had different ionic strength but identical non-isoelectric pH. Changes in intramembrane ionic strength due to the electric field were calculated over the same frequency range via an electrodiffusion model that was generalized to include convection and electrokinetic coupling. A comparison of the experimental and theoretical phases and amplitudes versus frequency suggests that electrodiffusion is the dominant rate-limiting process in this electromechanochemical transduction. These results are relevant to electrostatic interactions in connective tissues and to membrane-based filtration devices in which membrane permeability may be actively varied and controlled by an applied electric field.
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  • 95
    Electronic Resource
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    New York : Wiley-Blackwell
    Biopolymers 19 (1980), S. 263-272 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Integral enthalpies of solution of several dipeptides and tripeptides in water at low concentrations have been determined at 25 and 35°C. These data have been used to derive the changes in heat capacity on dissolution at infinite dilution ΔCp0 at 30°C. Limiting partial molal heat capacities ΔCp20 have been determined by combining ΔCp0 with Cp2 (heat capacity of pure solid peptides). Using the data on ω-amino acids and these peptides, the partial molal heat capacity of a peptide group —CONH— was semiquantitatively estimated.
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  • 96
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    New York : Wiley-Blackwell
    Biopolymers 19 (1980), S. 273-284 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Integral enthalpies of solution at low concentrations of several amino acids and peptides in 2 and 6M urea solutions have been determined at 25 and 35°C. These data have been used to derive the enthalpies of transfer (at 25 and 35°C) and heat capacities of transfer (at 30°C) of these amino acids and peptides from water to aqueous urea solutions. Furthermore, the enthalpies of transfer and heat capacities of transfer per CH2 group and per peptide group —CONH— have also been estimated. These results show that while the enthalpies and heat capacities of transfer per CH2 group are positive and negative, respectively, the reverse is true for —CONH— group. The implications of these results in the mechanism of the denaturation of proteins by urea are discussed.
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  • 97
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The CD spectra of cUpUp, cCpCp, and cGpGp derived from DCC-catalyzed polymerization of the relevant protected ribonucleoside 3′-phosphates are described. Similar studies on Up, U 〉 p, and cUp, as well as cUpUpUp and cUpUpUpUp, are presented. The spectral properties of the cyclic oligomers are compared with those of the corresponding linear oligomers with terminal 3′-phosphates so as to demonstrate that disruption of normal right-handed base stacking is considerable in these RNA loops.
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  • 98
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 19 (1980), S. 297-309 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of 1,2-anhydro-3,4,6-tri-O-benzyl-β-D-mannopyranose proceeds in the presence of Lewis acids, cationic coordination catalysts, and strong bases. Debenzylation of the products yields oligomeric saccharides or low polymers. Polymerization in toluene by means of potassium alkoxide complexed with crown ethers leads to essentially stereoregular (1 → 2)-α-D-mannopyranan. The original derivatives have been characterized by optical rotation, viscosity, molecular weight, gel permeation chromatography, and spectrometry. The free polysaccharides have been characterized by optical rotation, molecular weight, and 1H- and 13C-nmr spectrometry and compared to yeast mannan hydrolysate oligomers.
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  • 99
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular mechanics calculations have been used to determine the preferred physical association sites of the known alkylating agent dimethyl aziridinium ion (Az+) and a CH3+ prototype test probe with B-form, tetrameric DNA sequences. Electrostatic interactions are most important in determining these preferential physical association sites. In turn, the intermolecular energy minima depend on the charge distribution assigned to the DNA sequence. However, for three reported DNA charge distributions, only two distinct sets of energy minima were obtained for the CH3+-like ion interacting with (G-C)4, (A-T)4, and [(G-C)·(A-T)]2 deoxyribonucleic acids. These minima correspond to physical association geometries in which the CH3+-like ion is near known alkylation sites. The results of the Az+ … [(G-C)·(A-T)]2 interaction are virtually identical to those found for the CH3+-like ion. Aqueous solvation energetics have little effect on the physical association of Az+ with [(G-C)·(A-T)]2.
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  • 100
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 19 (1980), S. 325-340 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of molecular orbital calculations, using MINDO/3 and CNDO/2L methods, have been used to characterize the chemical reaction of protonated aziridine with DNA nucleophilic base sites. The N-7 atom of guanine is found to be the preferred alkylation site only when the O-6 atom of guanine is involved in base-pair hydrogen bonding. Otherwise O-6 is the predicted major site of alkylation. This indirectly suggests that protonated aziridine alkylation processes involve base-paired DNA structures, since N-7 guanine is the observed major site of alkylation. Alkylation of N-3 adenine is predicted to be more favorable than chemical attack of the N-7 adenine position. Both of these sites, however, are predicted to be less reactive than N-7 of guanine. These chemical reactivity studies resolve alkylation specifically not achieved in the DNA-alkylator physical association calculations reported in the preceding paper.
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