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  • Polymer and Materials Science  (3,277)
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  • 1995-1999  (6,779)
  • 1990-1994
  • 1950-1954
  • 1997  (6,779)
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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 244 (1997), S. 43-66 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The market development of bisphenol-A-polycarbonate has shown higher growth than any other engineering thermoplastic. The reasons can be found in the permanent improvement of the cost/performance-relationship and in the technical use of the variability of the basic structure. Incorporation of specific monomer units leads to tailor-made properties for a wide range of applications, as for example medical devices, electronic parts and glazing.This process has not yet slowed down, rather it is accelerated by new results from research and development. The improvement of flaw behavior and pit replication for new grades of materials for the next generation of compact discs, new grades that can be sterilized by γ-radiation without degradation and the microstructuring by low-energy laser systems are examples for the ongoing expansion of polycarbonate applications. Surface modification by hardcoatings with nanosized particles will allow to enter the fast growing market of glazing.
    Additional Material: 27 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 244 (1997), S. 67-92 
    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: Polyamide, Polyester und Polyoxymethylen sind mit einem weltweiten Verbrauch von derzeit 2,4 Mio t pro Jahr wichtige technische Kunststoffe. Sie werden aufgrund ihrer besonderen Eigenschaftsprofile überwiegend im Fahrzeugbau und in der Elektroindustrie für hochbelastete Funktionsbauteile eingesetzt. Der vorliegende Beitrag behandelt Polymerisationswege, Eigenschaften und ausgewählte neue Entwicklungen dieser Polymerklassen.Teilaromatische Polyamide stoßen durch ihre Dimensionsstabilität und thermische Belastbarkeit in Anwendungen vor, die bisher Duromeren oder Metallen vorbehalten waren. Glasfaserverstärkte Polyamide mit besonders hoher Dauerwärmebeständigkeit übemehmen wichtige Funktionen im Motorbereich von Fahrzeugen. Polyamid-Blends sind als Karosseriewerkstoffe ein Schlüssel zu leichten Autos mit niedrigem Treibstoffverbrauch. Halogenfrei flammgeschützte Polyamide erhöhen Sicherheit und Umweltverträglichkeit in brandgefährdeten Anwendungsbereichen.Polybutylenterephthalat als technisch wichtigster Polyester eröffnet in Mischung mit amorphen Polymeren neue Perspektiven durch geringerenVerzug und bessere Oberfläche bei glasfaserverstärkten Teilen. Polybutylennaphthalat erweitert den Anwendungsbereich zu höheren Temperaturen. Von Polybutylenterephthalat abgeleitete Copolyester sind biologisch abbaubar und daher vielversprechend für kompostierbare Folien.Polyoxymethylen-Copolymere haben ihre Stärke in der günstigen Kombination aus Steifigkeit, Dimensionsstabilität, Gleit/Reibe-Verhalten und Beständigkeit gegen heißes Wasser und Kraftstoff.Aufgrund ihres hohen und noch weiter steigerungsfähigen Leistungsvermögens werden Polyamide, Polyester und Polyoxymethylen das in den letzten Jahren gezeigte Wachstum in Zukunft weiter ausbauen können.
    Notes: Polyamide, polyester and polyoxymethylene having presently a worldwide sales volume of 2,4 million tons a year are important engineering thermoplastics. Based on their special property profiles they are mainly used in the automotive and electronic industry for high performance functional parts. This contribution presents polymerisation processes, properties, and selected new developments for these polymer classes.Semiaromatic polyamides due to their dimensional stability and thermal resistance lend themselves to applications which were so far reserved for thermosets or metals. Glass fiber reinforce polyamides designed to have the highest possible heat ageing resistance can take important functions under the hood. A polyamide blend used as a material for exterior body parts is key to light weight cars with strongly reduced fuel consumption. Halogene free flame retardant polyamide increases fire safety and environmental safety in flame sensitive applications.Polybutyleneterephthalate as the technically most important polyester offers new perspectives in blends with amorphous polymers leading to lower distortion and better surface quality in glass fiber reinforced parts. Polybutylenenaphthalate is widening the range of application of polyesters towards higher temperatures. Copolyesters derived from polybutyleneterephthalate are biologically degradable and are therefore promising materials for fermentable foils.Polyoxymethylene copolymers show an outstanding combination of stiffness, dimensional stability, friction and wear as well as resistance against hot water and fuel.As a result of their excellent properties and the existing potential for further improvements polyamide, polyester and polyoxymethylene will continue to grow above average in the future.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 244 (1997), S. 121-133 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The world-wide production of polyurethanes has exceeded 6 mio. metric tons in 1994. Compared with the produced amounts of large-scale thermoplastics such as PE, PVC, PP and PS, polyurethanes keep the 5th place.Polyurethanes (PUR) are segmented polymers, which can be synthesized from preformed building blocks in a modular unit construction system. The chemical modules and the various possibilities of combination will be discussed here.Tailor-made polyurethane materials can be divided into two main-fields of application: foams and compact PUR.The main constituents of polyurethane materials are diisocyanates and polyols. These key- chemicals are well characterised with respect to their technological, economical and ecological properties. Taking into account the availability, the masses of production and the experiences that have been collected with the PUR main constituents, these PUR precursors seem to be very mature already.In contrast to this, the PUR-materials made from these building blocks still offer numerous novel problem-solutions, resulting from the variability of the diisocyanate-poly-addition reaction: PUR materials are most commonly segmented into several phases. The formation of hard- and softsegments can be easily demonstrated by looking at thermoplastic polyurethanes (TPU). A deeper understanding of this phase separation and the molecular organisation within these materials promises to realize prospectic polymeric architectures with new and improved properties. PUR materials will still be able to offer new answers to future requirements in balancing economical and ecological needs. By looking at the life-cycles of soft and hard-foams, polyurethane-coatings and thermoplastic PUR-elastomers, this contribution will adress the question: “Is PUR-chemsitry still a challenging field?”
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 245 (1997), S. 23-35 
    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 Zugabe von 10-20 Gew.-% Kaliumnitrat (KN03) zu Polyamid 6 (PA 6) vermindert die Brennbarkeit des Polymeren. Das thermische Verhalten der KN03/PA 6-Mischung wurde mittels Thermogravimetrie, Differentialkalorimetrie und Analyse der fluchtigen Anteile untersucht. Feste Zersetzungsprodukte der Mischung wurden mittels Infrarotspektroskopie, Rontgendiffraktometrie und Elektronenresonanzspek-'troskopie analysiert. Es wurde gefunden, daß KNO3 dem Flielßen und Tropfen der Schmelze vorbeugt und die Karbonisierung auf der Oberflache des Polymeren fordert. Das verringert die Brandgefahr und verbessert die Feuerbestandigkeit. Andererseits geht KNO3 mit PA 6 in der kondensierten Phase eine exotherme Reaktion ein und setzt Sauerstoff frei, der wiederum die Brennbarkeit von PA 6 begiinstigt. Der Mechanismus der chemischen Wechselwirkung van KNO3 mit PA 6 wird diskutiert.
    Notes: The addition of 10-20 wt.-% of potassium nitrate (KNO3) to polyamide 6 (PA 6) improves the fire retardance of the polymer. The thermal decomposition behaviour of the PA 6/KN03-mixture was studied using thermogravimetry, differential scanning calorimetry and thermal volatilisation analysis. Solid products of the thermal decomposition of the mixture were analysed by infrared spectroscopy, X-ray diffraction and electron paramagnetic resonance. It was found that KNO, prevents flowing and dripping of the melt and promotes charring on the surface of the polymer which decreases its fire hazard and improves its fire retardance. On the other hand, KNO3 exothermally reacts with PA 6 in the condensed phase and supplies oxygen to the gas phase which increases the combustibility of PA 6. The mechanism of the chemical interaction of KN03 with PA 6 is discussed.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 245 (1997), S. 49-62 
    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 einer Beimischung von Tricalciumphosphat (TCP), Hydroxyethylmethacrylat (HEMA) und Ethylenglycoldimethacrylat (EGDMA) auf die Eigenschaften eines chirurgischen Knochenzements wurde untersucht. Die in Zugversuchen entstandenen Bruchflächen wurden mittels Rasterelektronenmikroskopie charakterisiert. Der Einfluß der Additive auf den Temperaturanstieg während der Polymerisation wurde geprüft. Zug-, Biege- und Druckfestigkeit des ausgehärteten Zements nahmen mit zunehmendem TCP-Gehalt ab, der Elastizitätsmodul stieg dagegen an. Die Zugfestigkeit nahm mit steigendem HEMA-Gehalt geringfügig zu und blieb oberhalb 15 Gew.-% HEMA konstant. Zug-, Biege- und Druckfestigkeit zeigten bei einem EGDMA-Gehalt von 2 Gew.-% (in HEMA) ein Maximum. HEMA und EGDMA beschleunigten die Polymerisation, wogegen TCP retardierend wirkte.
    Notes: The effects of the addition of tricalcium phosphate (TCP), hydroxyethyl methacrylate (HEMA), and ethylene glycol dimethacrylate (EGDMA) on the properties of standard surgical Simplex-P radiopaque bone cement have been investigated. The fracture surface after tensile test was studied by scanning electron microscopy. The influence of these components on the temperature rise during polymerization was investigated. It was found that the tensile strength, the bending strength, and the compressive strength decreased with increasing TCP content, whereas the inverse was observed for the Young's modulus. The tensile strength slightly increased with increasing HEMA content and then it levelled off when the HEMA content was higher than 15 wt.-%. It seemed that there were maximum tensile, bending and compressive strengths when 2 wt.-% EGDMA (in HEMA) was added. Polymerization occurred more rapidly when HEMA and EGDMA were added, whereas the inverse result was found with TCP.
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  • 6
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 245 (1997), S. 89-104 
    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: Polyurethanelastomere wurden in Gegenwart von zwei Dihydroxynaphthalin(DHN)-Verbindungen und deren bromierter Derivate als Kettenverlängerer hergestellt. Als Polyole wurden Polycaprolactondiol und Polytetramethylenglykol und als Diisocyanat-Komponenten Diphenylmethandiisocyanat (MDI) und Dicyclohexylmethan-4,4′-diisocyanat (HMDI) eingesetzt. Der Einfluß der Struktur der Kettenverlängerer auf die physikalischen und thermischen Eigenschaften der Polyurethane wurde untersucht. Wegen der besseren Phasenmischungswirkung der 1,5-DHN-Segmente haben die damit hergestellten Polyurethane höhere Glasübergangstemperaturen und bessere dynamische Eigenschaften als die Polyurethane auf 2,7-DHN-Basis. Der Einbau von bromierten DHN-Einheiten erschwert die Entflammbarkeit. Durch das große freie Volumen der Bromatome wird jedoch die Rotation der DHN-Einheiten eingeschränkt, was zu Polyurethanen mit verringerten Phasenmischungs- und Kristallisationsgraden führt. Die bromhaltigen Polyurethane zeigen zudem eine Verschlechterung der mechanischen und physikalischen Eigenschaften und eine erhöhte Löslichkeit.
    Notes: Polyurethane elastomers were synthesized based on polyols such as poly(caprolactonediol) and poly(tetramethylene glycol), diisocyanates such as diphenylmethane-4,4′-diisocyanate (MDI) and dicyclohexylmethane-4,4′-diisocyanate (HMDI), and two dihydroxynaphthalenes (DHNs) and their brominated derivatives used as chain extenders. The effects of the chemical structures of the chain extenders on the physical and thermal properties of the polyurethanes were investigated. Because of the higher degree of phase mixing of the 1,5-DHN unit, the 1,5-DHN-based polyurethanes have higher Tg values and higher dynamic properties than 2,7-DHN-based polyurethanes. Introduction of bromine atoms increased the flame retardance. However, the large free volume of bromine atoms restricted the rotation of DHNs, thus, directly decreasing the degree of phase-mixing and crystallinity of the polyurethanes. Introducing bromine atoms also decreased the mechanical and dynamic properties and increased the solubility of the polyurethanes.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 245 (1997), S. 139-147 
    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: Aus Poly(oxytetramethylen), 4,4′-Bibenzyldiisocyanat, N-Methyldiethanolamin als Kettenverlängerer und Acrylsäure/Polyacrylsäure als Quaternisierungsagens wurden Poly(etherurethan)-Kationomere hergestellt. In aus diesen Kationomeren hergestellten Filmen wurde Pyrrol (15 Gew.-%) in Gegenwart von CuCl2 polymerisiert. Die Filme wurden mittels dynamisch-mechanischer Analyse, Thermogravimetrie und Differentialthermoanalyse charakterisiert. Die elektrische Leitfähigkeit beträgt für den Film ohne Polypyrrol 7.5 · 10-12 Ω-1 cm-1 und mit Polypyrrol 4.5 · 10-6 Ω-1 cm-1.
    Notes: Poly(ether urethane) cationomers based on poly(oxytetramethylene), 4,4′-bibenzyldiisocyanate, N-methyldiethanolamine as chain extender, and acrylic acid/poly(acrylic acid) as quaternization agent were synthesized. Pyrrole (15 wt.%%) was polymerized in films of the ionomer containing CuCl2. The films were characterized by dynamic mechanical analysis, thermogravimetry and differential scanning calorimetry. The electric conductivity of the film without polypyrrole is 7.5 · 10-12 Ω-1 cm-1, while incorporation of polypyrrole increases the conductivity to 4.5 · 10-6 Ω-1 cm-1.
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  • 8
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 245 (1997), S. 155-164 
    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: Wachsartige Monomere und Vernetzer wurden aus kommerziellen Wachsen durch Veresterung mit 2-Hydroxyethylmethacrylat, Glycerindimethacrylat oder Glycidylmethacrylat oder durch Funktionalisierung mit 2-Isocyanatoethylmethacrylat synthetisiert. Die erhaltenen opaken Methacrylate mit Schmelzpunkten zwischen 45 und 80°C wurden in Substanz bzw. Toluollösung in Gegenwart von Radikalinitiatoren polymerisiert. Die Polymeren zeichnen sich durch eine breite Molmassenverteilung aus. Im Gegensatz zur Substanzpolymerisation ist der Doppelbindungsumsatz nach der Lösungspolymerisation nahezu vollständig. Aufgrund der hohen Molmasse der Monomeren ist der beobachtete Polymerisationsschrumpf sehr gering. Polymerisate mit Vernetzermonomeren zeigen eine verbesserte mechanische Stabilität.
    Notes: Waxy monomers and crosslinkers, respectively, were synthesized from commercially available waxes by esterification with 2-hydroxyethyl methacrylate, glycerol dimethacrylate, or glycidyl methacrylate or by functionalization with 2-isocyanatoethyl methacrylate. The resulting opaque methacrylates with melting points between 45 and 80°C were polymerized in bulk and in toluene solution in presence of free radical initiators. The obtained polymers were characterized by a broad molecular weight distribution. Opposite to the bulk polymerization, the double bond conversion in solution polymerization is nearly quantitative. The observed volume shrinkage during polymerization is very low due to the high molecular weight of the monomers. Polymerizates containing crosslinking comonomers exhibit improved mechanical stability.
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  • 9
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 245 (1997), S. 165-181 
    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 stabilized free-radical precipitation polymerization of the cationic monomer N-(2-methacryloyloxyethyl)-N,N-dimethylbenzylammonium chloride (MADAMBQ) in aqueous solutions of sodium chloride was studied by reaction calorimetry. Poly(ethylene oxide) was used as stabilizer. The rate of polymerization reaches its maximum immediately after initiation and remains nearly constant up to 50 % conversion followed by a decrease that could be described by a first order kinetics. The particles formed are approximately 1 to 30 μm in diameter and are stable over a period of several months.A model based on the theory of homogeneous particle nucleation is suggested to describe the kinetic course of polymerization, taking into account the rate of polymerization in both phases. With the assumption that the concentration of monomer in the phases is determined by a Nernst distribution law, the kinetics of the early stage of polymerization can be modelled reasonably well.The solution polymerization and the unstabilized precipitation polymerization of MADAMBQ was also studied.
    Notes: Die Kinetik der stabilisierten Fällungspolymerisation des kationischen Monomeren N-(2-Methacryloyloxyethyl)-N,N-dimethylbenzylammoniumchlorid (MADAMBQ) in wäßrigen Natriumchlorid-Lösungen wurde mittels Reaktionskalorimetrie untersucht. Polyethylenoxid höherer Molmasse wurde als Stabilisator eingesetzt. Die Reaktionsgeschwindigkeit ist über einen größeren Umsatzbereich nahezu konstant und fällt anschließend mit dem Umsatz annähernd linear ab. Die Teilchengrößenverteilung der gebildeten Dispersion ist bimodal mit Teilchen von etwa 1 bis 30 μm Durchmesser.Zur Beschreibung des Geschwindigkeitsverlaufs der Fällungspolymerisation wird ein Modell vorgeschlagen, das die Polymerisation in der Wasser- sowie in der Polymerphase berücksichtigt. Die Teilchenbildung soll durch homogene Nukleierung erfolgen. Es wird angenommen, daß die Konzentration des Monomeren in den Phasen durch ein Nernstsches Verteilungsgleichgewicht bestimmt wird. Zu Vergleichszwecken wurde auch die Polymerisation von MADAMBQ in Lösung und als nicht stabilisierte Fällungspolymerisation durchgeführt.
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  • 10
    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: Cellulosepulver, hergestellt durch Nitrierung von Eichen-Furfural-Lignocellulose, wurde mit Acrylamid radikalisch gepfropft. Die Pfropfreaktion wurde sowohl in Gegenwart eines äußeren Magnetfeldes (0,15-0,35 T) als auch ohne Magnetfeld durchgeführt. Der Einfluß von Monomerkonzentration, Initiatorkonzentration, Polymerisationszeit und temperatur sowie der magnetischen Feldstärke auf den Polymerisationsverlauf wurde untersucht. Es wurde festgestellt, daß der Pfropfumsatz mit zunehmender Feldstärke signifikant ansteigt.
    Notes: Cellulose powder obtained from oak furfural lignocellulose by nitration reaction was grafted with acrylamide using a radical initiation. The grafting reactions were carried out and compared both in presence and in absence of a continuous external magnetic field with the intensity extended between 0.15-0.35 T. The effect of monomer and initiator concentration, time and temperature of reaction and magnetic field intensity onto the grafting process were examined. It was observed that the presence of a magnetic field leads to a significant increase of the graft conversion.
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  • 11
    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(L-milchsäure) ist ein biokompatibler, semikristalliner, thermoplastischer Polyester mit ungünstigen mechanischen Eigenschaften. Daher wurde in einem “reactive blending”-Prozeß ein Acrylkautschuk, n-Butylacrylat, mittels einer Suspensionspolymerisation in Wasser auf in einem organischen Lösungsmittel gelöste Poly(L-milchsäure) gepfropft. Die gebildeten Copolymeren konnten isoliert und durch NMR-Spektroskopie und DSC-Messungen charakterisiert werden. Die Untersuchung der mechanischen Eigenschaften ergab keine befriedigenden Ergebnisse, weil die Kautschukphase wahrscheinlich aus viskosen linearen Makromolekülen besteht und daher keine elastischen Eigenschaften besitzt. In weiteren Arbeiten soll der Syntheseweg so modifiziert werden, daß durch den Einbau von Diacrylaten eine zumindest partielle Vernetzung der Kautschukphase erreicht wird.
    Notes: Poly(L-lactic acid) is a biocompatible polyester, semicrystalline, thermoplastic, with low versatility in mechanical properties. To overcome this problem, a reactive blending procedure was performed by grafting an acrylic rubber, n-butyl acrylate, via water suspension polymerization onto poly(L-lactic acid) dissolved in an organic solvent. It was possible to isolate the copolymeric phase formed from the two polymers and characterize it by using NMR and DSC techniques. Mechanical tests on blends gave no satisfactory response, probably because the rubbery phase is composed essentially of viscous linear macromolecules, not able to perform elastic properties. Work is in progress to modify the synthetic pathway to incorporate diacrylates in order to realize a rubbery phase at least partially cross-linked.
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  • 12
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Zur Entwicklung von neuen Styrol-Butadien-Kautschuken (SBRs) für Reifenanwendungen sind mehrere Arten von Zinn-Polymer-Bindungen (Styryl-, Butadienyl-, Isoprenyl- and α-Methylstyryl-Zinn) sowohl in linearen als auch in verzweigten Ketten untersucht worden. Die dynamisch-mechanischen Eigenschaften von Vulkanisaten mit Ruß wurden analysiert, um eine Beziehung zwischen den Strukturparametern der Polymeren und den Materialeigenschaften herzustellen. Der Polymer-Füll-stoff-Wechselwirkungsparameter, der durch das Verhältnis von mechanischen und dynamischen Termen definiert ist, wurde zur Charakterisierung der Verbindungen herangezogen. Der Einbau von verschiedenen Zinn-Polymer-Bindungen in lineare und in verzweigte SBR-Ketten bewirkte eine Verbesserung der Hystereseeigenschaf-ten der Vulkanisate und eine Veranderung des Wechselwirkungsparameters.
    Notes: Following the development of new SBRs for tyre applications, several kinds of tin-polymer bonds (styryl-, butadienyl-, isoprenyl- and α-methylstyryltin) have been studied, in both branched and linear chains.Dynamic-mechanical properties of the carbon black vulcanizates have been analyzed to establish a relationship between structural parameters of polymers and compound properties. The filler-polymer interaction parameter, defined by a ratio of mechanical and dynamic terms, has been used for the evaluation of the compounds. The introduction of different types of tin-polymer bonds, in branched and linear chains of the SBRs, implies an improvement in the hysteresis properties of the vulcanizates as well as a modification of the interaction parameter.
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  • 13
    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: Copoly (amid-ether) rnit zwei unteschiedlichen Aminfunktionalitäten wurden als antistatische Modifikatoren für Polyethylenterephthalatfasern (PET) eingesetzt. Die tertiären Aminogruppen schmelzegesponnener Copolymerfilamente wurden rnit drei Alkylierungsmitteln umgesetzt, wobei ein Sulfobetain, ein Carbobetain bzw. Ammoniumionen gebildet wurden. Dadurch wurde der scheinbare spezifische Widerstand der Filamente auf größfienordnungsmäßfiig 106 bis 108 Ω/cm verringert. Da sich die quaternisierten Copolymeren beim Blend-Spinnen rnit PET zersetzen, wurden Blendfasern von PET mit einem Copolymeren nach dem Schmelzespinnen einer Quaternisierung oder Vernetzung rnit Alkylierungsmitteln bzw. Epoxyvernetzern unterzogen, was die antistatischen Eigenschaften der Fasern im Vergleich rnit der unbehandelten Faser verbesserte. Insbesondere die mit Epoxiden vernetzten Fasern wiesen antistatische Eigenschaften auf, wie sie mit dieser Modifizierungsmethode bislang nicht erreicht wurden. Die antistatischen Eigenschaften blieben nach dem Fkben erhalten, da sowohl die hydrophilen als auch die ionischen Gruppen auf der Faseroberflache immobilisiert waren. Da Quaternisierung bzw. Vernetzung in einem Arbeitsgang rnit dem Verspinnen und Verstrecken der Fasern innerhalb einer kurzen Reaktionszeit erfolgen, sollte diese “spin-finishing„ genannte Methode konventio- nellen Verfahren bezuglich Kosten und Produktivitat uberlegen sein.
    Notes: Copoly(amide-ethers) containing two types of tertiary amine units were made as antistatic modifiers for poly(ethylene terephthalate) (PET) fibers. The filaments of the copolymers were melt-spun and reacted with three alkylating agents in order to quaternize the tertiary amine into a sulfo-betaine, a carbobetaine, and an ammonium ion. The apparent electric resistivity of the filaments was greatly reduced by this reaction, being in the range of 106 to 108 Ω/cm. However, because these quaternized copolymers incurred decomposition during blend spinning with PET, a blend PET fiber containing one type of copoly(amide-ether) was melt-spun and subjected to quaternization of the amino groups as well as to surface crosslinking with various alkylating and epoxy agents. The quaternized blend fibers obtained showed improved antistatic properties compared with the original blend fiber. Particularly, the fibers crosslinked with epoxy compounds were found to have the best antistatic properties that had ever been attained with this type of modification. The antistatic properties were retained even after dyeing, because both hydrophilic and ionic groups had been effectively immobilized on the surface. Since this quaternization and crosslinking could be conducted on-line with spinning and drawing within a short reaction time, this modification technique is called “spin-finishing method”, which should be superior to the conventional methods in terms of cost performance and productivity.
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  • 14
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    Angewandte Makromolekulare Chemie 249 (1997), 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: Filme aus Polyethylen niedriger Dichte (LDPE) wurden mit rauchender Salpetersäure behandelt. Die Oberflächeneigenschaften sowie die Bildung polarer Gruppen wie auf der geätzten Filmoberfläche wurden mit SEM-, IR- und XPS-Methoden analysiert. Die mechanische Festigkeit eines aus dem geätzten LDPE-Film und einem Epoxidharz hergestellten Laminats sowie die Bedruckbarkeit der geätzten Oberflächen wurden untersucht und mit einer unbehandelten Probe verglichen. Die Oberflächenrauhigkeit und die Gegenwart polarer Gruppen erhöhen die mechanische Festigkeit des Laminats aus dem geätzten Film durch mechanische Verankerung und chemischer Wechselwirkungen. Die Oberfläche des behandelten LDPE-Films ist besser bedruckbar als die des unbehandelten Films.
    Notes: Low-density polyethylene (LDPE) films were treated with fuming nitric acid (FNA). The surface characteristics and also the insertion of polar groups like on the etched LDPE film surface were measured by SEM, IR and XPS analyses, respectively. The mechanical performance of a laminate of the etched film with epoxy resin and also the printability of the etched film surface were tested and compared with the unetched sample. The surface roughening and the presence of polar groups enhance the mechanical strength of the laminate of FNA-treated film due to mechanical interlocking and chemical interaction. The printability of the treated film surface is also superior to that of the untreated LDPE film surface.
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  • 15
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    Angewandte Makromolekulare Chemie 249 (1997), S. 11-32 
    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: This paper reports on polymer membranes characterized by a surface layer of hydroxyalkyl derivatives of cellulose. Water compatible polymers like hydroxyalkyl derivatives of cellulose are preferably those exhibiting good chemical stability and desired membrane characteristics. Normally, water-compatible polymers used in the coating solutions must be rendered water-insoluble after coating. By adapting crosslinking conditions on separation problems, the membranes are useful for many processes in the fields of biotechnology, food and chemical industry.The membranes presented here possess the advantage of being highly resistant to chemical and biological degradation and, hence, have long lifetimes under many process conditions.
    Notes: Es wird die Entwicklung hydrophiler Polymermembranen diskutiert, die nach Beschichtung mit Celluloseethern und anschließender Vernetzung auf den asymmetrischen Trägermembranen interessante Permeations- und Trenneigenschaften bei hervorragenden chemischen Stabilitäten, vor allem beim Membrantrennverfahren der Nanofiltration, aufzeigen. Weiterhin werden Aussagen zu den Gastrenneigenschaften der Celluloseetherkompositmembranen getroffen.Erläutert werden die Permeations- und Trenndaten der Kompositmembranen in Korrelation zur Vernetzung der Celluloseether anhand verschiedener Einflußgrößen, was qualitative und gegebenenfalls quantitative Aussagen zum Vernetzungsmechanismus der Celluloseetherderivate erlaubt. Dabei stehen die Vernetzungstemperatur, der Einfluß der katalysierenden Wasserstoffionen und bedingt die Vernetzungszeit im Vordergrund. Abgerundet werden die Arbeiten durch Ermittlungen rheologischer Daten, die in Zusammenhang zu den Vernetzungsreaktionen und damit zu membranspezifischen Größen stehen.Infolge der hervorragenden chemischen Stabilität der Celluloseether werden Einsatzmöglichkeiten der Kompositmembranen zur Nanofiltration niedermolekularer Verbindungen aus organisch hochbelasteten Systemen beschrieben.
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  • 16
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    Angewandte Makromolekulare Chemie 251 (1997), S. 13-21 
    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: Polysulfide wurden mit hoher Ausbeute durch Hochtemperatur-Lösungspolykondensation von 4,4′-Dimercaptobiphenyl mit ausgewählten aliphatischen und aromatisch-aliphatischen Dihalogenkohlenwasserstoffen hergestellt. Um die optimalen Polykondensationsbedingungen zu bestimmen, wurde der Einfluß folgender Faktoren auf die reduzierte Viskosität und die Ausbeute der Polysulfide ermittelt: Art des organischen Lösungsmittels, Art des Halogenwasserstoff-Akzeptors, Konzentration der organischen Reagenzien, Reaktionstemperatur und -zeit. Die Polykondensation des Dithiols mit Bis(4-chlormethylphenyl)methan wurde als Modellsystem eingehender untersucht. Die Polysulfidstrukturen wurden mittels Elementaranalyse, IR-Spektroskopie und Röntgenstrukturanalyse bestätigt. Aus der thermogravimetrischen Analyse wurden die Zersetzungstemperatur, der Gewichtsverlust bei dieser Temperatur und das Maximum der Zersetzungsgeschwindigkeit erhalten. Weiterhin wurden einige physikalisch-chemische, mechanische und dielektrische Eigenschaften ermittelt. Die beste thermische und chemische Bestandigkeit zeigt das aus dem Dithiol und 4,4′-Bis(chlormethyl)biphenyl hergestellte Polysulfid, was auf dessen vorwiegend aromatische Struktur zuriickgefuhrt werden kann.
    Notes: Polysulfides were synthesized with high yield by high-temperature solution polycondensation of 4,4′-biphenyldithiol with selected aliphatic and aromatic-aliphatic hydrocarbon dihalides. To determine the optimum polycondensation conditions, the influence of the following factors on reduced viscosity and yield was studied: type of organic solvent, type of hydrogen halide acceptor, concentration of reagents, reaction temperature, and reaction time. A thorough examination was carried out only for the polycondensation of dithiol with bis(4-chloromethylphenyl)methane chosen as model system. The structures of the polysulfides were confirmed by elemental analysis, X-ray analysis, and infrared spectroscopy. The temperature of initial decomposition, the percentage of mass loss, and the temperature of the fastest decomposition, process were determined from curves of differential thermal and thermogravimetric analysis. Some physicochemical, mechanical and electrical properties were determined. The highest thermal and chemical resistance has been found for the polysulfide obtained from 4,4′-biphenyldithiol and 4,4′-bis(chloromethyl)biphenyl, probably because of the predominantly aromatic structure.
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  • 17
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    Angewandte Makromolekulare Chemie 251 (1997), S. 61-72 
    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: Drie organisch-anorganische Hybridmaterialien wurden nach dem Sol-Gel-Verfahren durch kovalenten Einbau von Poly(styrol-co-methylmethacrylat)(Poly(St-co-MMA))-, Polymethylmethacrylat(PMMA)- und Polystyrol(PS)-Struktureinheiten in ein SiO2-Netzwerk hergestellt und als Füllstoffe (bis zu 60 Gew.-%) in Dentalharzen verwendet. Der Einfluß der Füllstoffe auf einige mechanische Eigenschaften der Harze wurde untersucht. Die Härte der gefüllten Dentalharze nahm mit steigendem Füllstoffgehalt zu, wogegen die Biegefestigkeit abnahm. Die Druckfestigkeit der gefüllten Harze war besser als die des ungefüllten Harzes, nahm jedoch mit steigendem Füllstoffgehalt ab.
    Notes: By incorporating poly(methyl methacrylate) (PMMA), polystyrene (PS), and poly(styrene-co-methyl methacrylate) (poly(St-co-MMA)) structure units covalently into the SiO2 glass network via a sol-gel approach, three organic-inorganic hybrid materials (PMMA-SiO2, PS - SiO2, and poly(St-co-MMA) - SiO2) have been prepared. The three hybrid sol-gel materials were used as filler (up to 60 wt.-%) for dental composite resins. The effect of the three filler materials on several mechanical properties of the dental composite resins was investigated. The hardness of the filled dental composites increased with increasing filler content, whereas the bending strength decreased. The compressive strength of the composites was improved, compared with the unfilled resin, but decreased with inreasing filler content.
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  • 18
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    Angewandte Makromolekulare Chemie 251 (1997), S. 107-116 
    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 Adsorption von Benzol, Toluol und p-Xylol (BTX) aus wäßrigen Lösungen mittels hochvernetzter kationischer Stärke mit tertiären Amingruppen wurde untersucht. Der endotherme Adsorptionsvorgang ist vom Anfangs-pH-Wert und der Anfangskonzentration abhängig und kann mit einer Langmuir-Isotherme beschrieben werden.Die Adsorptionswärme (Δ) bei pH 4 beträgt für Benzol, Toluol und Xylol 29,45 kJ mol-1, 34,41 kJ mol-1 bzw. 35,58 kJ mol-1, bei pH 10 30,17 kJ mol-1, 35.56 kJ mol-1 bzw. 39,39 kJ mol-1. Die adsorbierte Menge nimmt in der Reihenfolge Benzol 〉 Toluol 〉 Xylol ab.
    Notes: The removal of benzene, toluene and p-xylene (BTX) compounds from aqueous solutions with highly crosslinked cationic starch containing tertiary amine groups was investigated. The adsorption process has found to be initial pH- and initial concentration-dependent, endothermic, and follows the Langmuir isothermal adsorption.The heats of adsorption (ΔH) at initial pH = 4 of benzene, toluene and p-xylene compounds are 29.45 kJ mol-1, 34.41 kJ mol-1, and 35.58 kJ mol-1, respectively, those at initial pH = 10 are 30.17 kJ mol-1, 35.56 kJ mol-1, and 39.39 kJ mol-1, respectively. The order of the amount of adsorbed BTX compounds on the adsorbent is benzene 〉 toluene 〉 p-xylene.
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  • 19
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    Angewandte Makromolekulare Chemie 251 (1997), S. 157-170 
    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: Bi-Sr-Ca-Cu-Komplexverbindungen von Polymethacrylsäure (PMAA) und Kresolnovolaken, die als Precursoren für Hochtemperatursupraleiter (HTSL) eingesetzt werden, sowie deren Cu-Komplexsalze wurden ESR-spektroskopisch und thermogravimetrisch untersucht. In den PMAA-Proben wurden drei verschiedene Cu2+-Spezies nachgewiesen: i) Cu2+-Paare, ii) isolierte Cu2+-Ionen und iii) Cu2+-Cluster. Bei niedrigem Cu-Gehalt der Proben bilden die Cu2+-Paar-Bindungen den Hauptanteil, bei hohem Cu-Gehalt überwiegen die Clusterbindungen. In den Novolakproben wurden nur isolierte Cu2+-Ionen und Cu2+-Cluster nachgewiesen. Die Einführung der Cu-Ionen erniedrigt die thermische Stabilität der Polymeren, der thermische Abbau erfolgt stufenweise. In den PMAA-Proben wird die erste Abbaustufe bei ≈ 220°C durch die Cu2+-Paar-Komplexe verursacht.
    Notes: Bi-Sr-Ca-Cu complexes of poly(methacrylic acid) (PMAA) and cresol novolac, which are precursors for high-temperature superconductors (HTSC) and Cu complexes of those polymers were investigated by ESR spectroscopy and thermogravimetry. In the PMAA samples three different kinds of Cu2+ species were detected: i) Cu2+ pairs, ii) isolated Cu2+ ions and iii) Cu2+ clusters. While Cu2+ pairs are the main species at low Cu concentrations, clusters become dominant at high Cu contents. In the novolac samples Cu2+ was only detected in isolated sites and clusters. The introduction of Cu ions lowered the thermal stability of the polymers and led to a stepwise decomposition. In the PMAA samples the first decomposition step at ≈ 220°C is caused by the Cu2+ pair complexes.
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  • 20
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    Angewandte Makromolekulare Chemie 251 (1997), S. 193-205 
    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: Neodymchlorid-2-ethylhexanolate mit der allgemeinen Formel NdCl3 · nL wurden durch eine Liganden-Austauschreaktion zwischen Neodymchloridisopropanolat (I) und 2-Ethylhexanol (EH) hergestellt. Die Hexanolate NdCl3 · 1,5 EH (II) und NdCl3 · 2,5 EH (III) wurden durch Elementaranalyse und Gravimetrie charakterisiert. Die katalytische Aktivität der Hexanolate bei der Homopolymerisation von 1,3-Butadien in Gegenwart von Triethylaluminium wurde untersucht. Die Verbindung III zeigte eine höhere Aktivität als die Verbindung II. Höhere Katalysator- und Cokatalysatorkonzentrationen sowie eine höhere Temperatur steigerten den Umsatz, wogegen die Viskosität der Produkte abnahm. Mit zunehmender Reaktionszeit erhöhten sich sowohl der Umsatz als auch die Viskosität. Die cis-1,4-Konformation wurde durch die Variation von Temperatur und Cokatalysatorkonzentration beeinflußt. Der gesamte Anteil der cis-1,4-Stuktur lag jedoch in allen Fällen über 99%, während die Produkte nur einen sehr geringen Vinyl-Anteil von 〈1% enthielten. Die Zugabe einer elektronenspendenden Verbindung verringerte den cis- 1,4-Gehalt aber auf 87%.
    Notes: Neodymium chloride 2-ethylhexanolates of the general formula NdCl3 · nL were prepared by ligand exchange reaction between neodymium chloride ispropanolate (I) and 2-ethylhexanol (EH). These hexanolates, NdCl3 · 1.5 EH (II) and NdCl3 · 2.5 EH (III), were characterized by elemental analysis and gravimetry. The catalytic activity of these hexanolates in combination with triethyl aluminium in the homopolymerization of 1,3-butadiene was studied, and the activity was found to be higher with III than II. The conversions increased with increasing the catalyst and co-catalyst concentrations and the temperature, whereas the intrinsic viscosity decreased. The conversions and the intrinsic viscosity decreased. The conversions and the intrinsic viscosity increased with reaction time. The cis-1,4 structure was influenced by variation in temperature and co-catalyst concentration, however, the total cis-1,4 structure was always more than 99% with very low vinyl content (〉1%). Addition of an external electron donor decreased the cis-1,4 content to 87%.
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  • 21
    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: MgCl2-Träger für einen Ethylenpolymerisationskatalysator wurden mit Hilfe der Rekristallationsmethode hergestellt, wobei Methanol als Lösungsmittel diente. Der Einfluß verschiedener Lösungsmethoden des rekristallisierten MgCl2-Alkohol-Adduktes auf die morphologischen Charakteristika der Katalysatoren wurde untersucht. Die Lösungsmethode beeinflußt die Eigenschaften der Katalysatoren beträchtlich. Die dargestellten Katalysatoren wiesen unterschiedliche Ti/Mg-Verhältnisse auf, sowohl was die Oberfläche als auch die gesamten Katalysator-Partikel betrifft. Betrachtet man die Ti-Verteilung und Aktivitätsprofile, dann erweisen sich nicht nur die Polymerisationsbedingungen, sondern auch die Ti-Verteilung auf dem Katalysator als wichtige Faktoren, welche die Dichte der Polymeren beeinflussen.
    Notes: The MgCl2 supports for an ethylene polymerization catalyst were prepared by the recrystallization method using methanol as a solvent. The effects of different desolvation methods of the recrystallized MgCl2-alcohol adduct on the morphological characteristics of the catalysts were examined. The desolvation method greatly affects the characteristics of the catalyst. The prepared catalysts had different Ti/Mg ratios with respect to both surface content and entire catalyst particles. Considering Ti distribution and activity profiles, not only the polymerization conditions but also the Ti distribution on the catalyst appear to be an important factor which affects the bulk density of the polymers.
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  • 22
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    Angewandte Makromolekulare Chemie 253 (1997), S. 89-97 
    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: Aromatische Poly(etherketon)e mit Ferrocen-Einheiten in der Hauptkette wurden durch direkte Polykondensation von 1,1′-Ferrocendicarbonsäure mit Diphenylether oder 1,4-Diphenoxybenzol hergestellt. Als Katalysatoren wurden Trifluormethansulfonsäure, Methansulfonsäure/P2O5 (Eatons Reagens) oder Trifluormethansulfonsäure/P2O5 verwendet. Polykondensationen bei Raumtemperatur für 24 h ergaben Poly(arylenetherketon)e mit Grenzviskositäten bis zu 40 mL g-1. Die Monoacylierung von Diphenylether mit Ferrocencarbonsäure wurde im Hinblick auf die Effektivität von Eatons Reagens als Katalysator und Lösungsmittel eingehender untersucht.
    Notes: Aromatic poly(ether ketone)s with ferrocene units in the main chain were prepared by direct polycondensation of 1,1′-ferrocenedicarboxylic acid with diphenyl ether or 1,4-diphenoxybenzene using various catalysts such as trifluoromethanesulfonic acid (triflic acid), a combination of methanesulfonic acid/P2O5 (Eaton's reagent) or a combination of triflic acid/P2O5. Polycondensations at room temperature for 24 h gave poly(arylene ether ketone)s with inherent viscosities up to 40 mL g-1. Monoacylation of diphenyl ether with ferrocenecarboxylic acid was studied in detail in order to show the efficiency of polymer formation employing Eaton's reagent as catalyst and solvent.
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  • 23
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    Angewandte Makromolekulare Chemie 251 (1997), S. 73-80 
    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 mechanischen und strukturellen Eigenschaften von Blends aus Phenolphthalein-Polyethersulfon und ultrahochmolekularem Polyethylen (UHMWPE) wurden anhand von Zug- und Biegeversuchen, Raster- und Transmissionselektronenmikroskopie untersucht. Die Zugabe einer geringen Menge UHMWPE (2 Gew.-%) führt zu einer Verstärkung der PES-C-Matrix. Höhere UHMWPE-Konzentrationen verschlechtern die mechanischen Eigenschaften. Die Strukturuntersuchungen zeigen, daß die Blends im gesamten Zusammensetzungsbereich mehrphasig sind. Bei geringen UHMWPE-Konzentrationen ist die UHMWPE-Phase gleichmäßig verteilt und entlang der Fließrichtung orientiert, was mit der starken Grenzflächenadhäsion zur Verbesserung des mechanischen Verhaltens beiträgt. Mit steigender UHMWPE-Konzentration nimmt die Domänengröß der UHMWPE-Phase zu.
    Notes: Mechanical and structural properties of blends of phenolphthalein poly(ether sulfone) (PES-C) with ultra-high molecular weight polyethylene (UHMWPE) were investigated using tensile and bending testing, scanning electron microscopy and transition electron microscopy. The incorporation of minor amounts of UHMWPE (2 wt.-%) into PES-C has a reinforcement effect. With higher concentrations of UHMWPE, the mechanical properties decrease gradually. Structural studies demonstrated that the blends are multiphasic in the whole composition range. The minor UHMWPE, dispersed uniformly and oriented along the flow direction, as well as the strong interfacial adhesion contribute to the increase of the mechanical performance of the blends. The domain size of the UHMWPE phase was found to increase with the increase of its concentration.
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  • 24
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    Angewandte Makromolekulare Chemie 251 (1997), S. 117-130 
    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 Redoxcopolymeres, ein makroporöses Poly(Styrol-co-Divinylbenzol) (S/DVB)-Harz mit N-Bromsulfonamidgruppen, wurde angewandt, um Cyanide aus wäßrigen Lösungen zu entfernen. Dieses Harz enthält aktives Brom in den funktionellen Gruppen (1.86 mmol g-1, 3.72 meq g-1) und weist Oxidationseigenschaften auf. Es wurde sowohl in statischen als auch in dynamischen Systemen für die Oxidation von Cyanidionen zu nichttoxischen Verbindungen angewandt. Die Reaktionen wurden in wäßrigen Lösungen mit 26-2600 mg L-1 CN- bei unterschiedlichen pH-Werten durchgeführt. Die Ergebnisse zeigten, daß dieses Harz die Cyanide leicht zu Cyanaten oxidiert, die ca. 1000 mal weniger toxisch sind. Bei Kontakt mit dem Harz fiel die Cyanidkonzentration in den Lösungen unter 0.05 mg L-1 CN-. Die —SO2NBrNa-Gruppen gingen dabei in —SO2NH2-Gruppen über. Diese konnten wiederum mit Natriumhypochlorit- und Natriumbromid-Lösungen reaktiviert werden. Es wurde auch eine Alternative zu der Cyanidionenoxidation mit N-Bromsulfonamid-Harz untersucht, indem ein analoges N-Chlorsulfonamid-Harz in Gengenwart von katalytischen Mengen von Bromiden angewandt wurde.
    Notes: A redox copolymer, macroporous poly(styrene-co-divinylbenzene) (S/DVB) resin having N-bromosulfonamide groups, was used for removal of cyanide ions from aqueous solutions. This resin contains active bromine in functional groups (1.86 mmol g-1, i. e. 3.72 meq g-1) and shows oxidative properties. It was employed in static and flow system for oxidation of cyanide ions to non-toxic compounds. The reactions were carried out in aqueous media containing 26-2600 mg L-1 CN- at different pH values. The data showed that the resin having active bromine easily oxidized cyanides, forming cyanates being 1000-times less toxic than cyanides. In contact with the resin the concentration of cyanides in tested solutions dropped below 0.05 mg L-1 CN-. During the oxidation processes the —SO2NBrNa groups transform to —SO2NH2 groups. They can be reactivated by use of sodium hypochlorite and bromide solutions. As an alternative to oxidation of cyanides by N-bromosulfonamide resin, the oxidation of these ions by N-chlorosulfonamide resin with addition of a small amount of bromides was examined.
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  • 25
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    Angewandte Makromolekulare Chemie 251 (1997), S. 207-208 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No Abstract
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  • 26
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    Angewandte Makromolekulare Chemie 252 (1997), S. 33-43 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Novel Polyester glycols with alkyl side groups were used for the improvement of thermal stability and hydrolytic stability of polyester urethane elastomers. The novel polyester glycols used are poly( β -methyl- δ -valerolactone)glycol (PMVL), poly(3-methyl pentamethylene adipate) glycol (PMPA), poly(nonamethylene-co-2-methyl octamcthylene carbonate) gycol (PNCO). A mixture of PNCO and poly(dimethyl siloxane)gycol (PNCO/PDMS) was also used. Polyurethane network elastomers were prepared from 4,4′-diphenylmethane diisocyanate (or 2,4-tolylene diisocyanate), and a mixture of 1,4-butane diol and trimethylol propane by a prepolymer method. Mechanical properties, Tg, thermal stability, and hydrolytic stability were measured. Morphology were also measured by means of polarizing microscopy, dynamic viscoelastometer, and ESR. The properties of novel polyurethane elastomers have good mechanical properties comparable to those of the general purpose polyester urethanes, and better thermal and hydrolytic stability than PTMG-based polyurethane. These polyurethane elastomers were exposed in out door during 2 year in Nagasaki, JAPAN. The novel polyurethane clastomers held alomost constant values for gel fraction, swelling ratio, relative modulus during 12 months, while poly(oxytetramethylene oxide)-based polyurethane as a control decreased the these values. Relationship of degradation behaviors with chemical structure and morphology were discussed.
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  • 27
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    Angewandte Makromolekulare Chemie 252 (1997), S. 139-151 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the chain oxidation of N-alkylamides with molecular oxygen, propagation is the ratedetermining step under conditions when the oxidation rate is independent of oxygen pressure. The oxidizability of lactams and lactam-based polyamides correlates with the energy of the formation of N-alkylamide radical by abstraction of hydrogen from the methylene group adjacent to nitrogen. While for lactams this energy depends on the number of carbons in the lactam ring, for N-alkylamides and polylactams such dependence is not observed.
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  • 28
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    Angewandte Makromolekulare Chemie 252 (1997), S. 179-193 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An X-band EPR-Imaging apparatus which allowed us to determine the distribution of nitroxyl radicals within solid samples of polymeric materials containing hindered amine stabilizers, is described. It is shown that EPR Imaging represents a powerful tool for investigating the growth and decay of nitroxyls formed in polymers irradiated under air for long periods. Since the variations of the radical concentration can be monitored both in time and in the space, this technique provides valuable information not easily attainable by means of other methods.
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  • 29
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    Angewandte Makromolekulare Chemie 252 (1997), S. 237-256 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A re-examination of the photo-oxidation mechanism of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) at both long and short irradiation wavelengths under accelerated conditions is reported. The formation rate of poly-2,6-dimethylphenoxy (PDMP) radicals, have been observed by esr spectroscopy, while benzylic-type radicals have been detected by spin trapping experiments using nitrosodurene under UV irradiation conditions. The changes of FTIR spectra obtained under accelerated photo-oxidative conditions show the formation of primary oxidation products such as aromatic aldehydes and quinones. The direct formation of radical cations and superoxide anions by a photo-induced electron-transfer reaction is suggested under our conditions. In addition, some results on the of photo-oxidation PPO/PS blends as a function of polystyrene tacticity are also reported. In the case of syndiotactic polystyrene the blend photostability shows some differences in comparison with the blend containing atactic polystyrene. This effect has been ascribed to the absence of excimers in syndiotactic polystyrene which are not revealed by fluorescence measurements. Finally, the chemical modification of PPO with bromine gave a bromomethylated PPO with different amounts of CH2 Br groups, which has been used for further substitution reactions with alkoxy sodium salts of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and 4-hydroxy-1,2,2,6,6-pentamethylpiperidine (PMPP). The accelerated photo-oxidation of a modified copolymer PPO-PMPP containing a 60% PMPP moieties as side groups and its blends with pure PPO has been followed by FTIR and esr spectroscopies. Some comparisons with a commercially available hindered amine light stabilizers (HALS) and a modified copolymer PPO-PMPP are also reported under the same photo-oxidative conditions.
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  • 30
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    Angewandte Makromolekulare Chemie 253 (1997), S. 27-49 
    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 innovative applications of plastics, which take advantage of special properties of polymeric materials, comprehensive understanding on strengthening and toughening mechanisms is required. The temperature-dependent mechanical behaviour of PMMA, PS and PC under dynamic loading conditions were investigated by means of an instrumented Charpy impact tester. The elastic-plastic fracture mechanics parameters, the energy-determined J-integral, and the deformation-determined crack opening displacement, δ, enable to do structure-related quantification of micromechanical processes. The J-integral values showed a maximum, resulting from an energy-dissipative process. The maximum values for PMMA occurred at 50°C and for PC at 40°C , which is related to the secondary(β) relaxation as evaluated from the frequency dependence of the mechanical loss factor. The 0-relaxation initiated shear deformation mechanisms, which led to a local increase of toughness. In polycarbonate, toughness is strongly increased due to a stress-induced shear flow process at temperatures higher than -25°C. Correlations between morphology and toughness can be derived with the help of optical investigations of stable crack propagation on fracture surfaces.
    Notes: Innovative Kunststoffanwendungen, die die speziellen Eigenschaften polymerer Werkstoffe gezielt ausnutzen, erfordern vertiefte Kenntnisse über festigkeits- und zähigkeitsbestimmende Mechanismen. Das sich in Abhängigkeit von der Temperatur ändernde Werkstoffverhalten von PMMA, PS und PC wurde bei dynamischer Beanspruchung mittels instrumentierter Kerbschlagbiegeprüfung bestimmt. Mit der verformungsbestimmten Rißöffnungsverschiebung δ und dem energiebestimmten J-Integral stehen Kenngrößen der Fließbruchmechanik zur Verfügung, die eine strukturbezogene Quantifizierung der temperaturabhängigen mikromechanischen Prozesse erlauben. Die J-Integralwerte zeigen für PMMA bei 50°C und für PC bei -60°C ein durch einen energiedissipativen Prozeß verursachtes Maximum. Dieses Maximum steht, wie sich aus der Interpretation der Frequenzabhängigkeit des mechanischen Verlustfaktors ergibt, mit der Neben(β)-Relaxation in Beziehung. Dabei initiiert die β-Relaxation Scherdeformationsmechanismen, die ihrerseits die lokale Zähigkeitserhöhung bewirken. Ab -25°C führt für PC ein spannungsinduzierter Scherfließprozeß zu einer erheblichen Zähigkeitssteigerung. Durch die Einbeziehung lichtmikroskopischer Untersuchungen des stabilen Rißfortschritts auf der Bruchfläche können Morphologie-Zähigkeits-Korrelationen abgeleitet werden.
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  • 31
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    Angewandte Makromolekulare Chemie 253 (1997), S. 71-88 
    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: Eine Reihe von Polyamidimid-Polyimid-Blockcopolymeren (PAI-PI-BCPs) wurde durch Polykondensation von PAI-Blöcken mit Amino-Endgruppen und PI-Blöcken mit Anhydrid-Endgruppen hergestellt. Zur Synthese der Blöcke mit Molekulargewichten im Bereich von ca. 2000 bis 15000 wurden nur technisch leicht zugängliche Monomere, wie Trimellitsäureanhydridchlorid, Benzophenontetracarbonsäuredianhydrid, 4,4′-Diaminodiphenylmethan, 2,4-Toluylendiamin und 4,4′-Diaminodiphenylsulfon eingesetzt. Dabei zeigte sich, daß durch den blockartigen Aufbau die Löslichkeit-und damit die Verarbeitbarkeit-im Vergleich zu den reinen, unlöslichen Polyimiden wesentlich verbessert werden konnte, bei nahezu gleichbleibender Thermostabilität. So wurden BCPs mit guten mechanischen Eigenschaften, Thermostabilitäten bis ca. 480°C (Thermogravimetrie, 5% Gewichtsverlust) und guten Löslichkeiten in Dimethylacetamid und anderen polaren aprotischen Lösungsmitteln erhalten.
    Notes: New poly(amide-imide)-poly(imide) block copolymers (PAI-PI-BCPs) were prepared by polycondensation of amino-terminated PAI-blocks with anhydride-terminated PI-blocks. For the syntheses of the blocks with molecular weights from 2000 to 15000 only commercially available monomers were used, e.g. trimellitic acid anhydride chloride, benzophenone tetracarboxylic acid dianhydride, 4,4′-diaminodiphenylmethane, 2,4-toluenediamine and 4,4′-diaminodiphenylsulfone. The BCPs were shown to have better solubility compared to the pure, insoluble PIs with only minor decrease of the thermostability. Thus, BCPs with good mechanical properties, thermostabilities up to 480°C (thermogravimetric analysis, 5% weight loss) and good solubility in dimethylacetamide and other polar aprotic solvents were obtained.
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    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: Eine Reihe von Polysiloxan/Poly(N-acetyliminoethylen)-(PSiO/PNAI)-Block- und -Pfropfcopolymeren wurde durch Polymerisation von 2-Methyl-2-oxazolin (MeOZO) mit funktionellen Polysiloxan-Prepolymeren als Initiatoren synthetisiert. Die Copolymeren wurden mit IR- und 1H NMR-Spektroskopie sowie Elementaranalyse, Differentialkalorimetrie und Thermogravimetrie charakterisiert. Der Einbau sowohl von hydrophoben als auch von hydrophilen Sequenzen verleiht den Polymeren amphiphile Eigenschaften. Ihre Eigenschaften in Lösung und als Feststoffe lassen die Produkte für Anwendungen als nichtionische Emulgatoren, Oberflächenmodifikatoren, Gele, usw. geeignet erscheinen.
    Notes: A series of polysiloxane/poly(N-acetyliminoethylene) (PSiO/PNAI) block and graft copolymers were synthesized by the initiation of 2-methyl-2-oxazoline (Me-OZO) polymerization with functional polysiloxane prepolymers. The copolymerization products were characterized by IR- and 1H NMR spectroscopy, elemental analysis, DSC and thermogravimetry. The insertion of both hydrophobic and hydrophilic sequences in the macromolecular structure induces a behavior characteristic of amphiphilic compounds. Their solution and solid state behavior evidenced peculiarities which make them able to act as nonionic emulsifiers, surface modifiers, gels, etc.
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  • 33
    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 Zustand von Wasser in Protonenaustausch-Membranen, hergestellt durch Pfropfen von Styrol auf Polyvinylidenfluorid-Filme (PVDF-g-PS) mittels Elektronenstrahlen und anschließendes Sulfonieren (PVDF-g-PSSA), wurde mittels Differentialkalorimetrie (DSC), Raman-Spektroskopie und Rontgen-Diffraktion (SAXS) ermittelt. Die Raman-Untersuchungen zeigten, daß einzelne Wassermolekule durch hydrophobe Wechselwirkungen an die Polymerketten gebunden sind. Die DSC-Untersuchungen zeigten, daß Wasser in den Membranen in drei verschiedenen Umgebungen vorliegt: nicht gefrierendes ionisch gebundenes Wasser, gefrierendes freies Wasser und gefrierendes gebundenes Wasser. Die Menge an nicht gefrierendem Wasser betragt unabhangig vom Pfropfungsgrad etwa 10 H2O/SO3H (mol/mol). Die Menge an gefrierendem Wasser ist stark vom Pfropfungsgrad abhangig. Oberhalb eines Pfropfungsgrades von 50% werden Werte von 40 H20/S03H (mol/mol) erreicht. Die Leitfahigkeit von nur nicht gefrierendes Wasser enthaltenden Membranen ist gering, d. h., das ionisch gebundene Wasser kann nicht allein die fur den Transport von Protonen und Wasser notwendigen Kanale bilden. Die SAXS Untersuchungen zeigten, daß Wasser/Sulfonsaure-Cluster in Membranen aus hydratisiertem PVDF-g-PSSA mit einem Bragg-Abstand von 25 Å gebildet werden. Diese Cluster formen die Kanale fur den Ionentransport und die Leitfähigkeit.
    Notes: The state of water in proton exchange membranes prepared by pre-irradiation (electron beam, 100 kGy) grafting of styrene onto poly(vinylidene fluoride) films (PVDF-g-PS), followed by sulfonation (PVDF-g-PSSA), has been studied with thermal analysis, Raman spectroscopy and small angle X-ray diffraction (SAXS). Raman spectra show that, in addition to free liquid water in the membranes, single water molecules are weakly bound to the polymer backbone. Thermal analysis shows that there are three types of water molecules in the membrane; non-freezable water associated with the ionic sites, freezable free water, and freezable bound water. The amount of non-freezable water is around 10 H2O/SO3H (mol/mol), and is independent of the degree of grafting (d.o.g.). The amount of freezable water is strongly dependent on the d.o.g. as long as the grafting has not penetrated the whole of the film, and reaches a value of around 40 H2O/SO3H (mol/mol) above a d.o.g. of 50%. The conductivity of membranes containing only the non-freezable water is low, i. e. the ionically bound water alone does not form the domains necessary for proton and water transport. SAXS measurements show that water/sulfonic acid clusters in hydrated PVDF-g-PSSA membranes with a Bragg distance of 25 Å are formed; these form the ion conducting channels in the membrane.
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  • 34
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    Angewandte Makromolekulare Chemie 253 (1997), S. 211-211 
    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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  • 35
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    Angewandte Makromolekulare Chemie 253 (1997), S. 201-210 
    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 Zug- und Biegemoduli von preßgeformten Polypropen-Probekörpern mit unterschiedlichen Oberflächenkristallinitäten wurden basierend auf der Annahme eines Schicht-Verbund-Modells untersucht. Es zeigte sich, daß die Spannungs-Dehnungs-Kurven der Zugversuche und die Werte der Biegeablenkung im wesentlichen von der Oberfächenkristallinität abhängen, jedoch erwiesen sich die Bruchspannungen als von der Oberflächenkristallinität unabhängig. Es wird angenommen, daß das beobachtete Zug- und Biegeverhalten der Proben auf der Grundlage eines Schicht-Verbund-Modells, bei dem eine massive, starre Platte zwischen zwei weichen Schichten eingebettet ist, charakterisiert werden kann.
    Notes: The tensile and flexural moduli of the compression-molded sheets of polypropene with different surface layer crystallinity were investigated based on a layered composite model. It was found that the tensile stress-strain curve and flexural deflection depended largely on the surface layer crystallinity, but the ultimate strain-at-break values were independent of the surface layer crystallinity. It is suggested that the tensile and flexural behavior can be characterized using a layered composite model in which a bulk plate was sandwiched between two surface layers.
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    Angewandte Makromolekulare Chemie 252 (1997), S. 45-54 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Addition of HALS-stabilisers, the cut-off wavelength of the light source, the temperature and the oxygen pressure have an influence on the UV-degradation mechanism of polyolefins. All these parameters influences the conversion of oxygen into polymeric carbonyls. The results are explained assuming that the initiation of the UV-degradation of pololefins is due to substrate-oxygen charge transfer complexes (CTCs).
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  • 37
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    Angewandte Makromolekulare Chemie 252 (1997), S. 69-88 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The applicability of fracture mechanics was studied on UV-exposed HDPE Charpy specimens. The failure distribution of the stress at failure measured in three-points bending tests showed a bifurcation in failure processes. At high stresses yielding occurs, resulting in large strain at failures. At lower stresses crack propagation causes low strain at failures. Due to the bifurcation in failure processes the ductile-brittle transition temperature of exposed specimens is hard to determine.Specimens notched after exposure showed a decrease in the critical stress intensity values. The effective notch depth of exposed specimens was found to be larger than the thickness of the oxidized layer measured by FT-IR and density measurements.
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  • 38
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    Angewandte Makromolekulare Chemie 252 (1997), S. 119-138 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the 2-hydroxyphenyl-1,3,5-triazines, the intramolecular hydrogen bond is stronger than in the corresponding 2-hydroxyphenylbenzotriazoles. Compounds with only one aryl group in the 2-hydroxyphenyl-1,3,5-triazine series show proton-transferred fluorescence with large Stokes shift and high quantum yield. No such fluorescence is observed, in contrast, for compunds with three aryi groups bearing no electrondonating groups on the aryl moieties. When the hydrogen atom of the intramolecular hydrogen bond is replaced by CH3, the respective derivative shows fluorescence with a normal Stokes shift.Various copolymers of MA-TIN 1 (2-[2-hydroxy-3-tert.-butyl-5-(O-[2-hydroxy-3-(2-methylpropenoyloxy)propyl]-2-carbonyloxyethyl)phenyl]benzotriazole), and MA-TZ 1 (2,4-Bis(2,4-dimethyl-phenyl)-6-[2-hydroxy-4-(2-hydroxy-3-[2-methylpropenoyloxy])propoxyphenyl]-1,3,5-triazine) with styrene, methyl methacrylate, and methacrylic acid have been synthesized by radical polymerization. The absorption spectra in the longwavelength UV region appear unchanged compared to those of the monomeric UV absorbers indicating that the stabilizer chromophores are conserved intact in the polymer. Both the monomeric and the polymeric stabilizers exhibit a strongly Stokesshifted, temperature-dependent, low-quantum-yield, proton-transferred fluorescence. This may be taken as evidence that the intramolecular hydrogen bond, which is essential for the photostability of this type of UV absorber, remains intact also in the copolymers. Activation energies of the radiationless deactivation process can be evaluated from the temperature dependence of this fluorescence. These energies lie between 4 and 5 kJ/mol for most of the benzotriazole and triazine stabilizers investigated.Fluorescence-decay measurements with crystalline MA-TIN 1 at different temperatures reveal a close correspondence of the temperature dependence between decay times and relative quantum yields. The radiationless process is thence concluded to originate from the proton-transferred level S1'. The decay time at room temperature is estimated at 70 ps, close to the value for crystalline TIN P (2-(2-hydroxy-5-methylphenyl)benzotriazole). The proton-transferred fluorescence of MA-TIN 1 exhibits a biexponential decay profile whereas solid TIN P, in contrast, displays only one single lifetime.
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  • 39
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    Biopolymers 41 (1997), S. 5-25 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Buckling transitions in superhelical DNA are sudden changes in shape that accompany a smooth variation in a key parameter, such as superhelical density. Here we explore the dependence of these transitions on the elastic constants for bending and twisting, A and C, important characteristics to DNA's bending and twisting persistence lengths. The large range we explore extends to other elastic materials with self-contact interactions, modeled here by a Debye-Hückel electrostatic potential.Our collective description of DNA shapes and energies over a wide range of ρ = A/C reveals a dramatic dependence of DNA shape and associated configurational transitions on ρ: transitions are sharp for large ρ but masked for small ρ. In particular, at small ρ, a nonplanar circular family emerges, in agreement with Jülicher's recent analytical predictions; a continuum of forms (and associated writhing numbers) is also observed.The relevance of these buckling transitions to DNA in solution is examined through studies of size dependence and thermal effects. Buckling transitions smooth considerably as size increases, and this can be explained in part by the lower curvature in larger plasmids. This trend suggests that buckling transitions should not be detectable for isolated (i.e., unbound) DNA plasmids of biological interest, except possibly for very large ρ. Buckling phenomena would nonetheless be relevant for small DNA loops, particularly for higher values of ρ, and might have a role in regulatory mechanisms: a small change in superhelical stress could lead to a large configurational change.Writhe distributions as a function of ρ, generated by Langevin dynamics simulations, reveal the importance of thermal fluctuations. Each distribution range (and multipeaked shape) can be interpreted by our buckling profiles. Significantly, the distributions for moderate to high superhelical densities are most sensitive to ρ, isolating different distribution patterns. If this effect could be captured experimentally for small plasmids by currently available imaging techniques, such results suggest a slightly different experimental procedure for estimating the torsional stiffness of supercoiled DNA than considered to date. © 1997 John Wiley & Sons, Inc.
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  • 40
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular mechanics and dynamics calculations were carried out on the disaccharides α-L-Rhap-(1 → 2)-α-L-Rhap-(1 → OMe) (1) and α-L-Rhap-(1 → 3)-α-L-Rhap-(1 OMe) (2), and the trisaccharide α-L-Rhap-(1 → 2)-α-L-Rhap-(1 → 3)-α-L-Rhap-(1 → OMe) (3). The semiflexible conformational behavior of these molecules was characterized by the occupation of a combination of different glycosidic linkage and side-chain conformational positions whose relative occupations were sensitive to dielectric screening. Molecular dynamics simulations of the trisaccharide 3 showed little difference between the linkage conformations in the trisaccharide and the component disaccharides 1 and 2.Experimental optical rotation data of 1 and 2 were obtained as a function of temperature in varying solvents. The molecular models were combined with the semiempirical theory of Stevens and Sathyanarayana to yield calculated optical rotations. Interpretation of the data of both 1 and 2 implied that a combination of conformations, both in glycosidic and side-chain positions, could explain the experimental data. Solvents effects were important in influencing the conformational mix and averaged optical rotation.Three-bond heteronuclear coupling constants 3JC, H were obtained for the glycosidic linkages of 1 and 2 in D2O and DMSO. Analysis of the coupling constants with a Karplus curve showed that small reductions in the glycosidic torsion angles of the conformations of the models used here of ca. 10°-15° in φ and 5°-10° in ψ were required to give better agreement with experiment; a combination of conformations for both 1 and 2 was consistent with the data. There was a negligible influence on the coupling constants of 1 on changing the solvent from D2O to DMSO. © 1997 John Wiley & Sons, Inc.
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  • 41
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    Biopolymers 41 (1997), S. 165-180 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For a minimalist model of protein folding, which we introduced recently, we investigate various methods to obtain folding sequences. A detailed study of random sequences shows that, for this model, such sequences usually do not fold to their ground states during simulations. Straightforward techniques for the construction of folding sequences, based solely on the target structure, fail. We describe in detail an optimization algorithm, based on genetic algorithms, for the “simulated breeding” of folding sequences in this model. We find that, for any target structure studied, there is not only a single folding sequence but a patch of sequences in sequence space that fold to this structure. In addition, we show that, much as in real proteins, nonhomologous sequences may fold to the same target structure. © 1997 John Wiley & Sons, Inc.
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    Biopolymers 41 (1997), S. 205-212 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The self-association of several N-urethanyl-L-amino acids (N-t-Boc-glycine, N-t-Boc-L-alanine, N-t-Boc-L-methionine, and N-t-Boc-O-Bz-L-tyrosine has been investigated in carbon tetrachloride by Fourier transform (FTIR) spectrometry. The fractions of nonbonded OH and NH groups have been determined from the intensities of the free OH and NH-stretching vibrations. The FTIR spectra have been examined in the carbonyl stretching regions by using Fourier self-deconvolution techniques. The results show that intermolecular hydrogen bonds are formed between the carboxylic acid group of one molecule and the urethane group of another molecule, suggesting that the leading factor for the self-association of N-t-Boc amino acids is the acidity of the OH groups. In N-t-Boc glycine, more heterodimers are formed than in the other amino acids. In N-t-Boc-O-Bz-L-tyrosine where the steric hindrance of the substituent implanted on the Cα atom is higher, the concentration of homodimers and heterodimers is lower than in N-t-Boc-L-alanine or N-t-Boc-L methionine. © 1997 John Wiley & Sons, Inc.
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    Biopolymers 41 (1997), S. 239-250 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A heteropolymer model of randomly self-interacting chains in two dimensions is studied with numerical simulations in order to elucidate the folding mechanism of protein. We find that the model occasionally shows folding propensity depending on the sequence of random numbers given to the chain. We study the thermodynamic and kinematic roles in the folding mechanism by grouping the local energy minima found in the simulations into clusters according to the similarity of their conformations. It is suggested that the local minima to which some heteropolymers show a folding tendency are always the lowest energy states of the energy spectrum within a cluster, though which cluster is selected depends on the sequence. For the eight random sequences we study, we find that the energy gap between the ground state and excited states is little correlated with folding or nonfolding. We rather find that folding propensities are correlated with the global structure of the average energy surface, implying a dominant kinetic role in the folding mechanism, although thermal factors cannot be ignored as the mechanism of choosing the ground state within a cluster of states connected by small deformations. We suggest that a hierarchical cluster structure plays an important role in selecting a unique folded state out of the huge number of local minima of heteropolymers. © 1997 John Wiley & Sons, Inc.
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  • 44
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The nucleocapsid protein NCp7, which is the major genomic RNA binding protein of human immunodeficiency virus type 1, plays an important role in several key steps of the viral life cycle. Many of the NCp7 activities, notably the nucleic acid annealing and the genomic RNA wrapping ones, are thought to be linked to a nonspecific binding of NCp7 to its nucleic acid targets. The mechanism of these activities is still debated but several clues are in favor of an intermediate aggregation of nucleic acids by NCp7. To check and characterize the nucleic acid aggregating properties of NCp7, we investigated the interaction of NCp7 with the model RNA homopolymer, polyA, by quasielastic light scattering and optical density measurements. The ordered growth of monodisperse large particles independently of the nucleic acid size and the almost complete covering of polyA by NCp7 strongly suggested an ordered aggregation mechanism. The aggregate kinetics of growth in the optimum protein concentration range (≥2 μM) were governed by a so-called Ostwald ripening mechanism limited by transfer of NCp7-covered polyA complexes from small to large aggregates. The aggregation process was strongly dependent on both Na+ and Mg2+ concentrations, the optimum concentrations being in the physiological range. Similar conclusions held true when polyA was replaced by 16S + 23S ribosomal RNA, suggesting that the NCp7 aggregating properties were only poorly dependent on the nucleic acid sequence and structure. Finally, as in the NCp7 annealing activities, the basic regions of NCp7, but not the zinc fingers, were found critical in nucleic acid aggregation. Taken together, our data indicate that NCp7 is a highly efficient nucleic acid aggregating agent and strengthen the hypothesis that aggregation may constitute a transient step in various NCp7 functions. © 1997 John Wiley & Sons, Inc.
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  • 45
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The nmr solution conformation of cyclotheonamide A (CtA) was determined in aqueous media. The data produced 15 distance and 10 torsional constraints which were used to generate conformations using restrained simulated annealing (SA) and distance geometry/simulated annealing (DG/SA) calculations. Two different calculation protocols were performed to ensure proper sampling of conformational space and even though the torsional restraints were input differently, both calculation methods yielded the same conformation of CtA. In the structure calculations, all solutions of the Karplus equation were sampled simultaneously using the restrained SA protocol and large ranges were used for the dihedral restraints in the DG/SA protocol because all solutions to the Karplus equation could not be sampled simultaneously. The solution conformation was also compared to the solid state x-ray conformations of CtA bound to thrombin and trypsin. The conformation of the residues important for active site binding (d-Phe, h-Arg, and Pro) are nearly identical in aqueous solution and solid state with largest differences at the a-Ala and v-Tyr residues. CtA appears to be preordered in structure and does not undergo a significant conformational change upon binding to the enzyme active site. © 1997 John Wiley & Sons, Inc.
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    Biopolymers 41 (1997), S. 381-389 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A Monte Carlo Protein Building method to construct the backbone and Cβ atomic coordinates from known Cα coordinates is reported. The method selects values of dihedral angles from ranges established from a statistical analysis of the relationship between dihedral angles of the backbone and Cα coordinates for a protein data base. The averaged coordinates from ten backbone models of a protein were used to define a mean structure that was refined by energy minimization using the AMBER force field (GB/SA). By the latter method the average atomic deviation and rmsd of the backbone and Cβ atoms for 24 proteins is between 0.14 and 0.32 Å (average 0.22 Å) and 0.22 and 0.61 Å (average 0.43 Å), respectively. A comparison with other methods is made. © 1997 John Wiley & Sons, Inc.
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  • 47
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    Biopolymers 41 (1997), S. 391-405 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A model of nine proteins including side-chain atoms have been built from the known Cα coordinates and amino acid sequences using a Monte Carlo Protein Building Annealing method. The Cartesian coordinates for the side-chain atoms were established with bond lengths and angles selected randomly from within previously determined ranges. A simulated annealing technique is used to generate some 300 structures with differing side-chain conformations. The atomic coordinates of the backbone atoms are fixed during the simulated annealing process. The coordinates of the side-chain atoms of 300 low energy conformations are averaged to obtain a mean structure that is minimized with the Cα atoms constrained to their position in the x-ray structure using the OPLS/AMBER force field with the GB/SA water model. The rms deviation of the main-chain atoms (without Cβ) compared with the corresponding crystal structures is in the range 0.20-0.64 Å. The rms deviation of the side-chain atoms is between 1.72 and 2.71 Å and for all atoms is between 1.19 and 1.99 Å. The method is insensitive to random errors in the Cα positions and the computational requirement is modest. © 1997 John Wiley & Sons, Inc.
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  • 48
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    Biopolymers 41 (1997), S. 443-450 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We analyze the electrostatic and hydrodynamic properties of a nuclease from the pathogenic gram-negative bacterium Serratia marcescens using finite-difference Poisson-Boltzmann methods for electrostatic calculations and a bead-model approach for diffusion coefficient calculations.Electrostatic properties are analyzed for the enzyme in monomeric and dimeric forms and also in the context of DNA binding by the nuclease. Our preliminary results show that binding of a double-stranded DNA dodecamer by nuclease causes an overall shift in the charge of the protein by approximately three units of elementary charge per monomer, resulting in a positively charged protein at physiologic pH. In these calculations, the free enzyme was found to have a negative (-1 e) charge per monomer at pH 7. The most dramatic shift in pKa involves His 89 whose pKa increases by three pH units upon DNA binding. This shift leads to a protonated residue at pH 7, in contrast to the unprotonated form in the free enzyme. DNA binding also leads to a decrease in the energetic distances between the most stable protonation states of the enzyme. Dimerization has no significant effect on the electrostatic properties of each of the monomers for both free enzyme and that bound to DNA.Results of hydrodynamic calculations are consistent with the dimeric form of the enzyme in solution. The computed translational diffusion coefficient for the dimer model of the enzyme is in very good agreement with measurements from light scattering experiments. Preliminary electrooptical calculations indicate that the dimer should possess a large dipole moment (approximately 600 Debye units) as well as substantial optical anisotropy (limiting reduced linear electric dichroism of about 0.3). Therefore, this system may serve as a good model for investigation of electric and hydrodynamic properties by relaxation electrooptical experiments. © 1997 John Wiley & Sons, Inc.
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  • 49
    ISSN: 0006-3525
    Keywords: biovector ; light scattering ; lipid ; microgel ; polysaccharide ; soft sphere ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure of a new supramolecular drug carrier (named Biovectors - BV) was studied using light scattering and scanning electronic microscopy techniques. This system consists of a polysaccharide core of chemically cross-linked maltodextrins to which phospholipids (and, in some cases, cholesterol) are added. Both polysaccharide cores and BV cross-linked with phosphate (negatively charged) and epichlorhydrin (no net charge) are spherical particles. The increase in the ionic strength of the medium increases the density of the charged polysaccharide cores. The lipid strongly interacts with neutral and negatively charged cores, decreasing both intra- and interparticle interactions. The results (mainly, ρ = Rg/Rh 〈 0.775 in some cases) suggest that BV are gel-like particles of variable density, referred to as microgels or soft spheres. Neutral polysaccharides have a strong tendency to self-aggregate. This self-aggregation of polysaccharide neutral cores is prevented by the addition of lipid or dimethylsulfoxide. © 1997 John Wiley & Sons, Inc. Biopoly 41: 511-520, 1997
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  • 50
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    Biopolymers 41 (1997), S. 533-544 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A dynamical model of interdomain “hinge bending” of T4 lysozyme in aqueous solution has been developed on the basis of molecular dynamics (MD) simulation. The MD model study provides a description of the conformational reorganization expected to occur for the protein in aqueous solution as compared to the crystalline environment. Three different 500 ps molecular dynamics simulations were calculated, each using a distinctly different crystal conformation of T4 lysozyme as the starting points of the MD simulations. Crystal structures of wild-type lysozyme and “open” and “closed” forms of M6I variant structures were analyzed in this study. Large-scale, molecular-conformational rearrangements were observed in all three simulations, and the largest structural change was found for the open form of the M6I allomorph. All three simulated proteins had closed relative to the wild-type crystal structure, and the closure of the “jaws” of the active site cleft occurred gradually over the time course of the trajectories. The time average MD structures, calculated over the final 50 ps of each trajectory, had all adapted to conformations more similar to each other than to their incipient crystal forms. Using a similar MD protocol on cytochrome P450BM-3 [M. D. Paulsen and R. L. Ornstein (1995) Proteins: Structure Function and Genetics, Vol. 27, pp. 237-243] we have found that the opposite type of motion relative to the starting crystal structure, that is, the open form of the crystal structure, had opened to a greater degree relative to the incipient crystal structure form. Therefore we do not believe that either result is merely a simulation artifact, but rather the protein dynamics are due to protein relaxation in the absence of crystal packing forces in the simulated solution environments. © 1997 John Wiley & Sons, Inc. Biopoly 41: 533-544, 1997
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  • 51
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Antibodies induced against intact foot-and-mouth disease Virus (FMDV) particles bind to the retro-inverso analogue of fragment 141-159 of the viral coat protein VP1 of FMDV, variant A, equally well as to the parent peptide. A conformational investigation of this retro-inverso peptide was carried out by nmr spectroscopy and restrained molecular modeling in order to identify the structural basis for the antigenic mimicry between these retro-inverso and parent peptides. In 100% trifluoroethanol a well-defined left-handed α-helical region exists from residue 150 to residue 159, which is consistently present in all conformational families obtained from restrained modelling. A less-defined left-handed helical region is present in the tract 144-148, which is also consistent for all structures. Conformational flexibility exists about Gly149, which leads to two types of structures, either bent or linear. In the bent structures, a three-residue inverse tight turn is found, which can be classified as an inverse γ-turn centered at Gly149. The overall structural features of the retro-inverso peptide are shown to be similar to those of the parent L-peptide. The two molecules, however, are roughly mirror images because they share inherently chiral secondary structure elements. By comparing these conformational conclusions with the x-ray structure of the Fab complex of a corresponding VP1 antigenic fragment, a rationale is proposed to account for the topological requirements of specific recognition that are implied by the equivalent antigenic activity of the natural and retro-inverso compounds. © 1997 John Wiley & Sons, Inc. Biopoly 41: 569-590, 1997.
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  • 52
    ISSN: 0006-3525
    Keywords: Leu-enkephalin ; [13C, 15N]-backbone-labeled ; reverse micelles ; conformation ; CD ; FTIR ; nmr ; distance geometry ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Enkephalin represents one of the bioactive peptide molecules most extensively investigated both in solution and in the crystal state. Depending upon the environment chosen for such studies, three main conformational states were identified for this flexible, linear pentapeptide - i.e., an extended conformation, a single-bend, and a double-bend structure. Since CD and Fourier transform ir (FTIR) spectra of Leu-enkephalin solubilized in negatively charged reverse micelles of bis (2-ethylhexyl)sulfosuccinate sodium salt/isooctane/water were supportive of a restricted conformational space of the aromatic side chains and of a bended type fold, we have analyzed by nmr the conformational preferences of Leu-enkephalin in reverse micelles using a synthetic [13C, 15N]-backbone-labeled sample. The overall conformation derived from nuclear Overhauser effect spectroscopy (NOESY) and 15N-filtered rotating frame NOESY (ROESY) spectra and by distance geometry calculations is a double-bend fold of the backbone that is comparable to one of the known x-ray structures. Thereby the tyrosine side chain is inserted into the hydrophobic core of the reverse micelles in a restrained conformational space as well evidenced by NOEs between the aromatic ring protons and the surfactant. The proximity of the aromatic rings of tyrosine and phenylalanine indicate a preferred structure consistent with the postulated conformation of the opioid peptide in the δ-receptor-bound state. These results confirm the interesting and promising properties of reverse micelles as membrane mimetica. © 1997 John Wiley & Sons, Inc. Biopoly 41: 591-606, 1997
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  • 53
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    Biopolymers 41 (1997), S. 673-702 
    ISSN: 0006-3525
    Keywords: protein folding ; coupling effect ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A 1-4 and 2-3 residue-correlation model is proposed to predict the β-turns in proteins. The average rate of correct prediction for the 455 β-turn tetrapeptides and 4018 non-β-turn tetrapeptides in the training data base is 80.1%, and that for the 223 β-turn tetrapeptides and 12562 non-β-turn tetrapeptides in the testing data base is 80.9%. Compared with the rates of correct prediction based on the residue-independent model reported previously, the quality of prediction is significantly improved by the new model, implying that the correlation effect between the 1st and the 4th residues and that between the 2nd and 3rd residues along a tetrapeptide are important for forming a β-turn in a protein during the process of its folding. © 1997 John Wiley & Sons, Inc. Biopoly 41: 673-702, 1997
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  • 54
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    Biopolymers 41 (1997), S. 721-729 
    ISSN: 0006-3525
    Keywords: Poly(β-L-aspartate)s ; helical conformations ; quantum mechanical calculations ; cooperative energy effects ; helix stability ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational preferences of the monomeric units of a series of poly(α-alkyl-β-L-aspartate)s were examined by quantum mechanical calculations. α-Alkyl-β-aspartamyl m-oligopeptides with a number of residues m ranging from 1 to 7 and arranged in the conformations experimentally observed for their corresponding polymers were computed. Both their total relative energies and their cooperative energy differences were compared as a function of the length of the oligopeptide and the nature of the alkyl side group. Results revealed that the 13/4 helical arrangement is the most stable structure for the isolated polymer chain for any side group, although a 17/4 helix becomes favored in the case of methyl and ethyl groups due to the packing effects. On the other hand, the stability of the 4/1 helix appears to be the preferred conformation for side groups with a branched constitution. © 1997 John Wiley & Sons, Inc. Biopoly 41: 721-729, 1997
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  • 55
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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  • 56
    ISSN: 0006-3525
    Keywords: gastrin ; lipo-gastrin derivatives ; cholecystokinin-B/gastrin receptor ; molecular modeling ; ligand binding sites ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Double-tailed lipo-tetragastrin derivatives of increasing fatty acid chain length were used to identify the minimum size of the fatty acid moieties (≥C10) that restricts the access to the CCK-B/gastrin (CCK: cholecystokinin) receptor via a membrane-bound pathway. Then dimyristoyl-mercaptoglycerol/maleoyl-gastrin adducts of increasing peptide chain length were synthesized to define the minimal peptide size required for receptor binding affinities comparable to those of underivatized gastrin peptides despite anchorage of the lipid tails in the membrane bilayer. The experimental results indicated that most of the little-gastrin sequence, i.e., 2-17, is needed for optimal interaction of the molecule with the binding cleft of the receptor. From these data experimentally based restraints could be derived for docking of lipo-gastrin onto a CCK-B/gastrin receptor model applying molecular dynamics simulations and energy minimizations. In the receptor-bound state some of the secondary structure elements of gastrin as determined by nmr analysis of gastrin-peptides in low dielectric constant media are retained. The N-terminal gastrin portion interacts in a more or less extended conformation with the receptor surface, and upon a sharp kink at the Ala-Tyr dipeptide portion the C-terminal pentapeptide amide part inserts deeply into the helix bundle. Besides Arg-57 on top of helix 1 of the receptor, for which no potential interaction with the ligand could be detected, the other amino acid residues identified by mutagenesis studies as involved in gastrin recognition were found to interact with the C-terminal portion of gastrin. Even taking into account the strong limitations of such a model system, it represents an interesting tool for rationalizing the experimental results of the extensive structure-function studies performed previously on gastrin and to delineate more precisely the putative ligand binding site on the extracellular face of the receptor. © 1997 John Wiley & Sons, Inc. Biopoly 41: 799-817, 1997
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  • 57
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    Biopolymers 42 (1997), S. 49-60 
    ISSN: 0006-3525
    Keywords: micellar catalysis ; cis/trans isomerization ; peptidyl-prolyl cis/trans isomerase ; proline ; FKBP12 ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Under physiological conditions, peptidyl-prolyl cis/trans isomerases catalyze powerfully the cis/trans isomerization of the -Xaa-Pro- bond (Xaa: natural amino acids) in oligopeptides and proteins (PPIases; EC 5.2.1.8). However, incorporation of proline containing tetrapeptide-4-nitroanilides in micelles and phospholipid vesicles also leads to increased rates of this unimolecular conformational interconversion. The isomerization rate was dependent on the detergent and vesicle concentration, respectively. The observed rate constants fit the pseudophase model of micellar catalysis allowing the calculation of micellar turnover numbers (kcismic) and dissociation constants (KCmic). Comparing kcismic values to the rate constants of the uncatalyzed cis to trans isomerization, an acceleration factor of about 20-fold was obtained for Suc-Ala-Phe-Pro-Phe-4-nitroanilide (Suc: succinyl) bound to zwitterionic SB12 (N-dodecyl-N,N-dimethylammonium-3-propanesulfonate) micelles. In addition, a marked increase in the population of the trans conformer relative to cis was noted for all investigated combinations of peptides and detergents. In a series of tetrapeptides, Suc-Ala-Xaa-Pro-Phe-4-nitroanilide kcismic/KCmic as well as kcismic values are linearly correlated with the high performance liquid chromatography capacity factor R′ describing the hydrophobicity of the amino acid Xaa. The same correlation can describe quantitatively the dependency of kcar/Km on substrate hydrophobicity for the FKBP12-catalyzed isomerization. Despite the great differences in catalytic power, these results confirm the suspicion that micelles and FKBP12 may share a common component in the catalytic mechanism of peptidyl-prolyl bond isomerization. © 1997 John Wiley & Sons, Inc. Biopoly 42: 49-60, 1997
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  • 58
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    Biopolymers 42 (1997), S. 89-100 
    ISSN: 0006-3525
    Keywords: tapping mode atomic force microscopy ; scleroglucan networks ; denaturation-renaturation ; fractal dimension ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tapping mode Atomic Force Microscopy (TmAFM) has been used to study the fungal polysaccharide scleroglucan deposited from aqueous solution and dimethyl sulfoxide (DMSO) onto a mica surface. The solutions from which the microscope samples were produced were prepared by first dissolving the solid scleroglucan in 0.1M NaOH, then neutralizing the solution with HCl, followed by dilution to the required concentration in either water or DMSO. It was found that from the aqueous solution described above, scleroglucan forms networks. Based on a comparison of the denatured-renatured and aqueous solution samples, network formation is due to the imperfect registration between the chains forming the triple helices. The relatively large stiffness of the scleroglucan triple helix is also assumed to contribute to the formation of the extended networks. The triple helix diameter was measured to be 0.92 ± 0.27 nm, which is in the same range as that obtained by other researchers using similar techniques. Denatured scleroglucan, deposited from DMSO onto mica, forms a web-like layer on top of which there are sphere-like structures. These morphologies are believed to be due to triple helix denaturation yielding highly flexible single chains in DMSO, which results in coiling and web-like dense packing of scleroglucan upon deposition onto mica. Most interestingly after addition of water to the samples deposited from DMSO, some of the chains can be renatured into short, stiff rod-like structures which are similar to the structures observed by other researchers. The imaging data for aqueous solution deposition can be analyzed by plotting maximum end-to-end distance versus the perimeter of the networks deposited onto mica. This yields a Flory-like exponent of 0.67, which is almost similar in value to that obtained by other researchers for linear structures of scleroglucan but less than that expected for a polymer chain following a self-avoiding walk (v = 0.75) model on a two-dimensional surface. The fractal dimension that can be used to characterize the networks was determined graphically to be 1.22 ± 0.06. © 1997 John Wiley & Sons, Inc. Biopoly 42: 89-100, 1997
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  • 59
    ISSN: 0006-3525
    Keywords: triple helix stabilization ; intercalation ; DNA ligands ; benzo[4,3-b]indole ; polynucleotides ; linear dichroism ; CD ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The binding modes of three benzopyrido [4,3-b]indole derivatives (and one benzo[-f]pyrido [4-3b] quinoxaline derivative) with respect to double helical poly(dA) · poly(dT) and poly[d(A-T)]2 and triple-helical poly(dA) · 2poly(dT) have been investigated using linear dichroism (LD) and CD: (I) 3-methoxy-11-amino-BePI where BePI = (7H-8-methyl-benzo[e]pyrido [4,3-b]indole), (II) 3-methoxy-11-[(3′-amino) propylamino]-BePI, (III) 3-methoxy-7-[(3′-diethylamino)propylamino] BgPI where BgPI = (benzo[g]pyrido[4,3-b]indole), and (IV) 3-methoxy-11-[(3′-amino)propylamino] B f P Q where B f P Q = {benzo[-f]pyrido[4-3b]quinoxaline}. The magnitudes of the reduced LD of the electronic transitions of the polynucleotide bases and of the bound ligands are generally very similar, suggesting an orientation of the plane of the ligands' fused-ring systems preferentially perpendicular to the helix axis. The LD results suggest that all of the ligands are intercalated for all three polynucleotides. The induced CD spectrum of the BePI chromophore in the (II-BePI)-poly[d(A-T)]2 complex is almost a mirror image of that for the (I-BePI)-poly(dA) · poly(dT) and (I-BePI)-poly(dA) · 2poly(dT) complexes, suggesting an antisymmetric orientation of the BePI moiety upon intercalation in poly[d(A-T)]2 compared to the other polynucleotides. The induced CD of I-BePI bound to poly(dA) · 2poly(dT) suggests a geometry that is intermediate between that of its other two complexes. The concluded intercalative binding as well as the conformational variations between the different BePI complexes are of interest in relation to the fact that BePI derivatives are triplex stabilizers. © 1997 John Wiley & Sons, Inc. Biopoly 42: 101-111, 1997
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  • 60
    ISSN: 0006-3525
    Keywords: molecular modeling ; c-erbB2 receptor ; dimerization ; coiled-coil structure ; wild transmembrane helices ; oncogenic transmembrane helices ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dimerization models of c-erbB2 transmembrane domains (Leu651-Ile675) are studied by molecular mechanics and molecular dynamics simulations. Both wild and Glu mutated transmembrane helices exhibit the same relative orientation for favorable associations and dimerize preferentially in left-handed coiled-coil structures. The mutation point 659 belongs to the interfacing residues, and in the transforming domain, symmetric hydrogen bonds between Glu carboxylic groups stabilize the dimeric structure. The same helix packing found for the wild dimers, except side-chain - side-chain hydrogen bonds, suggests that the transmembrane domains dimerize according to similar process. Structural and energetical characterization of the models are presented. © 1997 John Wiley & Sons, Inc. Biopoly 42: 157-168, 1997
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  • 61
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    Biopolymers 42 (1997), S. 183-189 
    ISSN: 0006-3525
    Keywords: electrophoresis ; retardation ; native proteins ; semidilute polymer solution ; scaling theory ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The retardation of proteins in the Mt range of 15-500 kDa in capillary electrophoresis conducted in semidilute solutions of the polymer polyethylene glycol (Mt range 0.2-8.0 × 106), was measured. The purpose was to test the predictions of the scaling theory with regard to the relation of retardation to (a) the Mt of the polymer, (b) the concentration of the polymer, and (c) the radius of the protein particles. These predictions derive from a mechanism that relates retardation to the screening length of the polymer solution, viewed as the average distance between the entanglement points of polymer chains.For the molecular weight range from 60 to 500 kDa of (near) spherical proteins, the retardation was found to be related to polymer concentration c asμ/μo = exp(-Ac0.69)where μ/μ0 is the retardation expressed as the ratio between the mobility in polymer solution and that in free solution. The value of the exponent of 0.69 is in close agreement with the value of 0.75 predicted by the scaling theory. Parameter A was found (a) to scale as the 0.04th power of Mt (polymer), approximating the predicted value of 0; and (b) to be proportional to particle radius as predicted. All measured values of retardation were independent of electric field strength in the range of 37-370 V/cm. Thus, experimental findings are consistent with the mechanism relating electrophoretic retardation to the screening length of the polymer network in the specified molecular weight range of proteins.Under the same conditions, log(μ/μ0) of proteins with Mt's less than 60 kDa (a) scales as the -0.06th power of Mt (polymer), and (b) is proportional to polymer concentration, suggesting a retardation mechanism that is not related to the screening length. © 1997 John Wiley & Sons, Inc. Biopoly 42: 183-189, 1997
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  • 62
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    Biopolymers 42 (1997), S. 191-202 
    ISSN: 0006-3525
    Keywords: molecular volume ; van der Waals radius ; molecular orbital calculation ; accessible surface area ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular volumes for hydrocarbons, amino acids, peptides, and 14 globular proteins were calculated by techniques using van der Waals radii and by semiempirical molecular orbital methods. The resulting values were compared to experimentally determined volumes. The values obtained by methods employing van der Waals radii were found to be up to three times smaller than the experimentally determined values in the case of proteins, 25% smaller than the experimental values for peptides, and up to 50% greater than experimental values for simple hydrocarbons. For the semiempirical calculations, neither the type nor precision of the calculation altered the percentage of the electron density required to reproduce the experimentally observed volumes for any of the different types of molecules tested. For molecules en vacuo, the amount of electron density included was approximately 98.5% of the total calculated value. For solvated molecules, the percentage was closer to 99.5%. From the results of our studies, we conclude that semiempirical techniques are more reliable, less arbitrary, and hence are more accurate for the determination of molecular volumes. The methods by which we employ semiempirical techniques for determination of molecular volume will be described in detail. © 1997 John Wiley & Sons, Inc. Biopoly 42: 191-202, 1997
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  • 63
    ISSN: 0006-3525
    Keywords: fourier transform ir spectroscopy ; protein conformations ; cytochrome C ; Langmuir-Blodgett film ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A qualitative and quantitative analysis of the conformation of Langmuir-Blodgett (LB) dried films of cytochrome C on silicon wafers was performed by Fourier transform ir (FTIR) spectroscopy. A deconvolution procedure was applied to the amide I band analysis, in order to determine the percentage of the different secondary structures. Qualitative analysis was performed by examining difference spectra.Films obtained by spreading protein solutions at pH 7.4 and 1, dried at 25 and 100°C, on silicon wafers were also examined in order to detect spectral components associated with denatured protein domains, and to compare them with cytochrome C LB films.FTIR spectroscopy showed that the following important changes characterise LB film spectra: (a) the α-helix component is higher (its percentage is 57 and 54%) than the one estimated in dried film obtained by spreading the solutions at pH 7.4 on a silicon substrate (43%), (b) there is an increase in the intensity of bands attributed to protonated carboxy group bands, involved and not involved in the formation of hydrogen bonds, and a decrease in those attributed to deprotonated carboxy groups, (c) the intensity of several bands attributed to aromatic amino acids and aliphatic chains increases, and (d) bands due to O(SINGLEBOND)H stretching vibrations of crystallization water are present.These conformational changes could be induced by protein-protein interaction caused by the close packing of molecules that occurs during LB film formation; it cannot be excluded that they may be accompanied by partial changes in the tertiary structure of the protein. A preferential orientation of protein molecules in LB films is also a possibility. © 1997 John Wiley & Sons, Inc. Biopoly 42: 227-237, 1997
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  • 64
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    Biopolymers 41 (1997), S. 407-418 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Zinc fingers, 30-residue peptides anchored on Zn(II) coordinated to pairs of cysteines and histidines, recognize DNA triplets and, as tandem modules, effect sequence read out. The focus of zinc finger-DNA interaction studies thus far has been to probe the nature of the binding of the 12-residue recognition element of the finger with DNA code bases. To understand the possible role of the Zn(II) ligand and to assess its own DNA interaction profile, [(CH)2Zn] (C: cysteine; H: histidine; Figure 1) was constructed from bis-t Boc-cystinyl-di-His-OMe via thiol-disulfide exchange, Zn(II) complexation, and deprotection. [(CH)2Zn] binds with polyd- (G·C)·polyd(G·C) with association constants - 1.8 × 107 M-1 (specific DNA-phosphate) and 3.3 × 103 M-1 (nonspecific DNA-phosphate); perturbs its B-DNA profile; and enhances the Tm from 62.5 to 70.15°C in a concentration-independent manner, with an ideal reversal profile on cooling, not observed in the DNA alone; releases polyd(G·C)·polyd(G·C)-bound ethidium bromide; enhances the fluorescence of polyd(G·C)·polyd(G·C)-bound ethidium bromide at low concentrations; and quenches it at higher ranges. [(CH)2Zn] also binds to d(ACGCTGGGCGT), the sequence associated with Zif-268, 3-finger binding site. Such interactions were not seen in parallel studies with (a) polyd(A·T)·polyd(A·T) and [(CH)2Zn] and (b) {[C′H2] (C′: cystine; H: histidine; the direct metal-free precursor of [(CH)2Zn]}, ionic zinc nitrate, and covalent zinc acetyl acetonate Zn(AcAc)2, with poly[d(G·C)·polyd(G·C)].The results are rationalized on the basis of two types of association between [(CH)2Zn] and polyd(G·C)·polyd(G·C), a nonspecific recognition of the sugar phosphate backbone, by an imidazole of [(CH)2Zn] and a specific one involving the amino group of [(CH)2Zn] and the guanine base of DNA. Control experiments show that the latter greatly promotes DNA recognition. The possibility for such specific interactions with relatively small structures of the type [(CH)2Zn] would be of use in the design of DNA recognition elements and also provide an explanation for the experimentally found variation in the placement of the zinc finger docking unit around the major groove of DNA. © 1997 John Wiley & Sons, Inc.
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthetic peptides of different size, reproducing the proteolytic processing site of proocytocin, were studied by CD under several experimental conditions in order to ascertain the ability of different solvents to stabilize secondary structural motifs, such as α-helix tracts and β-turns. A combination of deconvolution methods and empirical calculations subtracting the contributions due to unordered structures from the spectra suggests that in solution (a) mainly two distinct families of ordered conformers containing structurally different β-turns are present, (b) the relative stability of the different conformers depends from the nature of the solvent, and (c) in the case of the larger peptides, a population containing an α-helical conformation is also present. From the biological point of view the presence of at least two families of ordered conformers could be in line with current theories assuming that the catalytic effect of the receptor microenvironment may be determinant in shifting the equilibrium toward the active conformation. © 1997 John Wiley & Sons, Inc. Biopoly 41: 461-479, 1997
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  • 66
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    Biopolymers 41 (1997), S. 521-532 
    ISSN: 0006-3525
    Keywords: recombinant DNA ; pH responsive hydrophobic microdomains ; dn31 gene ; gel filtration chromatography ; CD ; fluorescence probe analysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Recombinant DNA technology has been employed to produce a polypeptide capable of forming pH responsive hydrophobic microdomains. The design of this peptide is based upon an idealized conceptual model in which electrostatic, hydrophobic, and hydration forces are responsible for the association of amphipathic α-helical elements. Reduction in solution pH is responsible for reducing electrostatic repulsions between similarly charged residues, promoting the hydrophobic collapse of helical elements. A polymerizable synthetic element (dn31) has been synthesized and inserted into an appropriate expression vector. A clone containing a single copy of the dn31 gene (designated dn31x1) was isolated and the corresponding gene product DN3Lx1 isolated. The physical properties of DN3Lx1 were examined in solution by gel filtration chromatography, CD, and fluorescence probe analysis. It was determined that DN3Lx1 self-associates in solution with the degree of aggregation dependent on pH and ionic strength. An initial objective of this work was to examine domain organization in higher molecular weight species containing ten or more repetitive sequences. However, attempts to express multiple repeats of DN3Lxn from concatemers were unsuccessful. © 1997 John Wiley & Sons, Inc. Biopoly 41: 521-532, 1997.
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  • 67
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    Biopolymers 42 (1997), S. 19-35 
    ISSN: 0006-3525
    Keywords: conformation ; ganglioside GA1 ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to investigate the significance of preferred conformations of the saccharide for the steric orientation and recognition of glycosphingolipids at the membrane surface, the conformational free energy calculations were carried out on the asialo-GM1 [GA1; β-D-Gal(1 → 3) β-D-GalNAc(1 → 4) β-D-Gal(1 → 4) β-D-Glc-O-ceramide] using a new program CONCARB (CONformational study program for CARBohydrate) in the unhydrated and hydrated states. The overall backbone conformation of GA1 appears nearly to be extended with a little bent at the glycosidic II-III linkage, in which two pyranose rings of Gal(IV)-GalNAc-(III) moiety orient approximately perpendicular to those of Gal(II)-Glc(I) moiety. This is consistent with the structures deduced from high-sensitivity differential scanning calorimetry experiments and the nmr study on GA1. The calculated glycosidic torsion angles of the lowest free energy conformation of GA1 in the hydrated state are in accord with the structures of relevant oligosaccharides deduced from nmr experiments and hard sphere exoanomeric calculations. A comparison of the values of glycosidic torsion angles φ and π of GA1 and its constituent oligosaccharides indicates that the overall backbone conformation of each oligosaccharide is retained when the oligosaccharide chain becomes longer. This implies that the short-range interactions between the nearest-neighbored saccharides are of significant importance in stabilizing the overall backbone conformation of GA1 in both the unhydrated and hydrated states. The different orientation and hydrogen bonds of hydroxymethyl and hydroxyl groups from one oligosaccharide to another suggest that the medium- and long-range interactions are also of consequence. Hydration seems to affect significantly the conformation of these groups, but not to perturb remarkably the overall backbone conformation of GA1. © 1997 John Wiley & Sons, Inc. Biopoly 42: 19-35, 1997
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    Biopolymers 44 (1997), S. 201-215 
    ISSN: 0006-3525
    Keywords: DNA ; thermodynamics ; calorimetry ; drugs ; intercalators ; groove binders ; free energy ; solvent-accessible surface area ; polyelectrolyte effect ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Understanding the thermodynamics of drug binding to DNA is of both practical and fundamental interest. The practical interest lies in the contribution that thermodynamics can make to the rational design process for the development of new DNA targeted drugs. Thermodynamics offer key insights into the molecular forces that drive complex formation that cannot be obtained by structural or computational studies alone. The fundamental interest in these interactions lies in what they can reveal about the general problems of parsing and predicting ligand binding free energies. For these problems, drug-DNA interactions offer several distinct advantages, among them being that the structures of many drug-DNA complexes are known at high resolution and that such structures reveal that in many cases the drug acts as a rigid body, with little conformational change upon binding. Complete thermodynamic profiles (ΔG, ΔH, ΔS, ΔCp) for numerous drug-DNA interactions have been obtained, with the help of high-sensitivity microcalorimetry. The purpose of this article is to offer a perspective on the interpretation of these thermodynamics parameters, and in particular how they might be correlated with known structural features. Obligatory conformational changes in the DNA to accommodate intercalators and the loss of translational and rotational freedom upon complex formation both present unfavorable free energy barriers for binding. Such barriers must be overcome by favorable free energy contributions from the hydrophobic transfer of ligand from solution into the binding site, polyelectrolyte contributions from coupled ion release, and molecular interactions (hydrogen and ionic bonds, van der Waals interactions) that form within the binding site. Theoretical and semiempirical tools that allow estimates of these contributions to be made will be discussed, and their use in dissecting experimental data illustrated. This process, even at the current level of approximation, can shed considerable light on the drug-DNA binding process. © 1998 John Wiley & Sons, Inc. Biopoly 44: 201-215, 1997
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    Biopolymers 44 (1997), S. 321-321 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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  • 70
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    Biopolymers 43 (1997), S. 419-431 
    ISSN: 0006-3525
    Keywords: bombolitins ; conformation ; amphipathic helices ; lytic peptides ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bombolitins are five structurally related heptadecapeptides originally isolated from the venom of a bumblebee, acting at membrane level and able to enhance the activity of Phospholipase A2. The biological activity of this class of natural peptides seems to be related to the their ability to form amphiphilic helical structures in the presence of phospholipid aggregates or related membrane model systems. We have carried out systematic investigations on a series of bombolitins and their synthetic analogs in order to establish the conditions in which amphipathic helices are formed and to elucidate the details of the interaction with phospholipids and related model systems. We have shown that bombolitins and their analogs interact with phospholipid aggregates and detergent micelles forming amphiphilic helices. By means of the Langmuir film balance technique, coupled with fluorescence microscopy, we have shown that bombolitins perturbe the structure of phospholipid monolayers, forming phase separated peptide domains. In aqueous solution, in the absence of detergent or phospholipids, bombolitins form oligomeric aggregates with consequent conformational transition from a random coil to an α-helical structure. In the aggregate structure, evidence was obtained that helices are oriented in an antiparallel fashion. In this article we summarize the most recent results of conformational studies by CD, NMR and computer simulations on a series of bombolitins and retro-, all-D- and all-D-retro-analogs. © 1998 John Wiley & Sons, Inc. Biopoly 43: 419-431, 1997
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    Biopolymers 44 (1997), S. 105-121 
    ISSN: 0006-3525
    Keywords: crystal structures ; minor groove drugs ; oligonucleotides ; sequence recognition ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This review surveys the crystal structures between minor groove drugs and oligonucleotides, of which over thirty have now been determined. The various factors that are involved in the observed A/T sequence selectivity of these drugs are examined in structural terms. The roles of, in particular, hydrogen-bond recognition and sequence-dependent groove width, are assessed, and as a consequence the minor groove drugs have been classified into two categories, dependent on the relative roles played by these two factors in sequence recognition. Implications for the recognition of non-A/T sequences are discussed. © 1997 John Wiley & Sons, Inc. Biopoly 44: 105-121, 1997
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    Biopolymers 44 (1997), S. 423-433 
    ISSN: 0006-3525
    Keywords: DNA recognition ; nucleosome recognition ; deformation ; DNA-binding protein ; conformational fluctuations ; protein-DNA complexes ; histone octamer ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The affinity of a DNA sequence for the histone octamer in a core nucleosome depends on the intrinsic flexibility of the DNA. This parameter can be affected both by the sequence-dependent conformational preferences of individual base steps and by the nature and location of the exocyclic groups of the DNA bases. By adopting highly preferred conformations particular types of base step can influence the rotational positioning of the DNA on the surface of the histone octamer. The asymmetry of the next higher order of chromatin structure is determined in part by the asymmetric binding of the globular domain of histone H5 to the core nucleosome. © 1998 John Wiley & Sons, Inc. Biopoly 44: 423-433 1997
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    Biopolymers 44 (1997), S. 361-403 
    ISSN: 0006-3525
    Keywords: helix bending ; protein/DNA recognition ; B-DNA ; FREEHELIX ; roll ; tilt ; kink ; curvature ; writhe ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Normal vectors perpendicular to individual base pairs are a powerful tool for studying the bending behavior of B-DNA, both in the form of normal vector plots and in matrices that list angles between vectors for all possible base pair combinations. A new analysis program, FREEHELIX, has been written for this purpose, and applied to 86 examples of sequence-specific protein/DNA complexes whose coordinates are on deposit in the Nucleic Acid Data Base. Bends in this sample of 86 structures almost invariably follow from roll angles between adjacent base pairs; tilt makes no net contribution. Roll in a direction compressing the broad major groove is much more common than that which compresses the minor groove. Three distinct types of B-DNA bending are observed, each with a different molecular origin: (1) Localized kinking is produced by large roll at single steps or at two steps separated by one turn of helix. (2) Smooth, planar curvature is produced by positive and negative roll angles spaced a half-turn apart, with random side-to-side zigzag roll at intermediate points, rather than a tilt contribution that might have been expected theoretically. (3) Three-dimensional writhe results from significant roll angles at a continuous series of steps. Writhe need not change the overall direction of helix axis, if it is continued indefinitely or for an integral number of helical turns. A-DNA itself can be formally considered as possessing uniform, continuous writhe that yields no net helix bending. Smooth curvature is the most intricate deformation of the three, and is least common. Writhe is the simplest deformation and is most common; indeed, a low level of continuous writhe is the normal condition of an otherwise unbent B-DNA helix of general sequence. With one exception, every example of major kinking in this sample of 86 structures involves a pyrimidine-purine step: C-A/T-G, T-A, or C-G. Purine-purine steps, especially A-A, show the least tendency toward roll deformations. © 1998 John Wiley & Sons, Inc. Biopoly 44: 361-403, 1997
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    Biopolymers 41 (1997), S. 1-4 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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    Biopolymers 41 (1997), S. 37-50 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The torsion angle motions, generated from molecular dynamics (MD) simulations, of the two aliphatic chains of 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC) in its lipid monolayer were evaluated by comparing these motions to those of an equivalent isolated (free) n-alkane chain, and the same n-alkane chain in its crystal lattice. The time-dependent autocorrelation and (1,2)-, (1,3)-, (1,4)-, and (1,5)-cross-correlation functions were constructed to analyze the torsion angle motions. It was found that the torsion angle motions of the DMPC lipid monolayer aliphatic chains are intermediate to those of the free n-alkane chain and the same n-alkane chain in its crystal lattice, particularly for short correlation times. The torsion angle motions of the aliphatic chains of DMPC are also found to be essentially independent of the charge state on the head group. The linear aliphatic chains of a DMPC lipid monolayer behave most like the isolated n-alkane chains with respect to torsion angle flexibility, even though the pairs of aliphatic chains of each DMPC are part of an ordered monolayer assembly. The aliphatic chains of the DMPC molecules in their monolayer exhibit at least two types of wave motions. One of the wave motions is the same in form, though somewhat more diffuse, as a traveling wave found in n-alkane crystals. The other wave motion involves major torsion angle transitions, and has some characteristics of the soliton properties observed in n-alkane crystals near their respective melt transition temperatures. © 1997 John Wiley & Sons, Inc.
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    Biopolymers 41 (1997), S. 61-72 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We developed an efficient Monte Carlo Simulated Annealing (MCSA) program for modeling protein loops with high speed. The total conformational energy in each step of MCSA simulation consists of two parts: the nonbonded atomic interaction represented by a simple soft-sphere potential and the harmonic distance constraint to ensure the smooth connection of the loop segment to the rest of the protein structure. The soft-sphere potential was a simplified potential that has been successfully used by the authors in modeling the carbohydrate part of glycoprotein systems [H. Zhang, Y. Yang, L. Lai, and Y. Tang (1996), Carbohydrate Research, Vol. 284, pp. 25-34]. It only considers the purely repulsive steric interactions to avoid artificial attractive forces between atoms in the absence of solvent molecules. The N-terminal of the loop segment was connected to the bulk protein part, and two dummy main-chain atoms N and Cα immediately following the C-terminal of the loop segment were constrained to their real positions in the protein structure, which not only assures the correct geometry of loop-protein connection but also is more rigorous than the previous work. To improve the speed, two strategies, the local region method and grid-mapping method, were devised to accelerate the computation of environmental interaction that is responsible for the major part of the computing consumption. The grid-mapping method can reduce computational time dramatically. Conformations with rational steric packing and smooth connection to the rest of the protein structure were generated by the MCSA program, and then were refined by the empirical force field CHARMm [B. R. Brook, R. E. Braccoleri, B. D. Olafson, D. J. States, S. Swaminathan, and M. Karplus (1983), Journal of Computational Chemistry, Vol. 4, pp. 187-217]. Bovine pancreatic trypsin inhibitor (BPTI) was used as an example to test the ability of loop modeling of the method, and five loops in BPTI were calculated. Conformations close to the crystal structure were generated for all of them. With the criteria of CHARMm energy, near-native conformations can be selected, for example, the backbone rms deviation 0.93 A from the crystal structure was gotten for the longest 9-residue loop. © 1997 John Wiley & Sons, Inc.
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    Angewandte Makromolekulare Chemie 245 (1997), S. 105-112 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Saure- und Alkalibestandigkeit einiger heterozyklischer Poly(amidimid)e wurde mit der von strukturahnlichen Polyimiden und Poly(amidimid)en ohne heterozyklische Gruppen verglichen. Alle untersuchten Polymeren erwiesen sich in saurem Medium als sehr stabil. Der Einbau zusatzlicher Heterozyklen wie 1,3,4- Oxadiazol oder Phenylchinoxalin in die Polymerkette eines Poly(amidimid)s fiihrte zu einer erheblichen Verbesserung der Alkalistabilitat. Polyamide mit Imid-Ringen in der Seitenkette sind bestandiger gegen Hydrolyse als Polyamide mit Imid-Grup-pen in der Hauptkette.
    Notes: The stability of some heterocyclic poly(amide imide)s in acidic and alkaline medium was compared to the structurally related polyimide and poly(amide imide)s without other heterocyclic groups. All the polymers have high stability in acidic medium. The introduction of additional heterocycles such as 1,3,4-0xadiazole or phenylquinoxaline into the macromolecular chain of a poly(amide imide) increases substantially the resistance to alkaline medium. Polyamides containing imide rings only in the side chain are more stable to hydrolysis than related polyamide having imide units in the main chain.
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    Angewandte Makromolekulare Chemie 245 (1997), S. 125-137 
    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: Ein trifunktionelles Hochleistungs-Epoxidharz auf Basis des Triglycidylethers von Tris(4-hydroxyphenyl)methane (TETM) wurde durch Kondensation von 4-Hydroxybenzaldehyd mit Phenol and anschließender Epoxidierung mit Epichlorhydrin hergestellt. Zur Strukturaufklärung wurde das Produkt mittels IR- und NMR-Spektroskopie sowie Masenspektrometrie untersucht. Durch Modifizierung mit einem aminoterminierten Poly(dimethylsiloxan) wurde die Eigenspannung des mit einem Phenolnovolak vernetzten TETM für die Anwendung als Verkapselung elektronischer Bauteile herabgesetzt. Durch das in der TETM-Matrix frei verteilte Silikonelastomere konnte die Spannung des vernetzten Epoxidharzes deutlich reduziert werden, indem der thermische Ausdehnungskoeffizient und der Elastizitätsmodul des Materials verringert wurden, während die Glasübergangstemperatur kaum abnahm.
    Notes: A high-performance trifunctional epoxy resin based on the triglycidyl ether of tris (4-hydroxyphenyl)-methane (TETM) was synthesized by the condensation of 4-hydroxybenzaldehyde with phenol followed by epoxidation with epichlorohydrin. The structure of TETM was confirmed by mass spectra, infrared and nuclear magnetic resonance spectroscopy. Amino-terminated poly(dimethylsiloxane)s were used to reduce the stress of the trifunctional epoxy resin cured with phenolic novolac resin for electronic encapsulation application. The dispersed silicone rubbers effectively reduce the stress of cured epoxy resins by reducing the coefficient of thermal expansion and flexural modulus while the glass transition temperature was hardly depressed.
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    Angewandte Makromolekulare Chemie 245 (1997), S. 149-154 
    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 kationische Polymerisation von Cyclohexenoxid wurde durch Reduktion eines Allylsulfoniumsalzes in Gegenwart von Ascorbyl-6-hexadecanoat und Kupfer(II)-benzoat ausgelöst. Für die Initiation wird eine Redoxreaktion diskutiert, in der die Kupferverbindung als Elektronenüberträger dient.
    Notes: The cationic polymerization of cyclohexene oxide was initiated by reduction of allyl sulfonium salt in the presence of ascorbyl-6 hexadecanoate and copper (II) benzoate. A redox reaction in which the copper compound serving as an electron carrier for the initiation step was proposed.
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    Angewandte Makromolekulare Chemie 245 (1997), S. 193-202 
    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: Neuartige Membranmaterialien für die Auftrennung von Benzol/Cyclohexan-Gemischen wurden durch die Pfropfung von Nylon 6 mit Oligooxyethylenen wie Diethylenglykol, Poly(ethylenglykol) 200 (PEG200) und Polyethylenglykol 400 (PEG400) synthetisiert. Membranen aus derartig modifiziertem Nylon 6 zeigten eine Permselektivität gegenüber Benzol, wobei einige der Membranen ausschließlich für Benzol permeabel waren.
    Notes: Novel membrane materials for pervaporation separation of benzene/cyclohexane mixtures were prepared by the introduction of oligo(oxyethylene)s, such as diethylene glycol, poly(ethylene glycol) 200 (PEG200) and poly(ethylene glycol) 400 (PEG400) onto Nylon 6. The polymeric membranes from modified Nylon 6 thus prepared showed permselectivity toward benzene. Some membranes exclusively permeated benzene from benzene/cyclohexane mixture.
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    Angewandte Makromolekulare Chemie 245 (1997), S. 211-212 
    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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    Angewandte Makromolekulare Chemie 246 (1997), S. 11-22 
    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: Durch Diels-Alder Reaktion von aus Kolophonium gewonnenen Säuren mit Diallylmaleat wurde ein ungesättigtes Produkt erhalten, welches sowohl als Monomeres als auch als Vernetzer für Allylpolymere verwendet werden kann. Das Monomere und daraus hergestellte Polymere wurden mit üblichen chemischen und physikalischen Methoden charakterisiert. Die Polymeren haben eine lineare Struktur, möglicherweise einhergehend mit intramolekularer Zyklisierung bei niedrigen Molekulargewichten, oder eine dreidimensionale Struktur bei hohen Umsätzen. Sie sind einigermaßen thermostabil.
    Notes: An unsaturated adduct has been synthesized by the Diels-Alder reaction between resin acids and diallyl maleate. The obtained polymerizable product can be used both as monomer in the formation of allyl polymers and crosslinking agent. The monomer and its polymers were investigated by usual physical and chemical methods. The synthesized polymers present a linear structure, possibly associated with intramolecular cyclization at low molecular weights, or a three-dimensional structure at high conversions. They are fairly thermostable substances with carboxylic groups in the polymer chain.
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    Angewandte Makromolekulare Chemie 246 (1997), S. 65-69 
    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: 2-Hydroxyethylmethacrylat wurde mit Ethylenglycol-dimethacrylate in Gegenwart von Hydrocortison als Modellsubstanz mit Gamma-Strahlen copolymerisiert, wobei ein “molecular imprinted polymer” (MIP) erhalten wurde. Das Hydrocortison wurde mit Chloroform extrahiert und anschließend aus Methanol wieder absorbiert. Nach 30 Tagen Lagerung in einer Methanol/Wasser-Mischung (3:1 v/v) waren noch 96% des Hydrocortisons in der Matrix eingelagert. Im Vergleich zu Hydrocortison wird Testosteron nur in geringer Menge absorbiert.
    Notes: Copolymerization by gamma irradiation of 2-hydroxyethyl methacrylate with ethylene glycol dimethacrylate in the presence of hydrocortisone as model drug gave a molecular imprinted polymer (MIP). The hydrocortisone was removed from the matrix with chloroform and incorporated again from methanol solution. Release data show that 96% of the incorporated drug is retained after 30 days storage in a methanol/water (3 : 1 v/v) mixture. In comparison with hydrocortisone, only a small quantity of testosterone is absorbed by the matrix.
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  • 84
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    Angewandte Makromolekulare Chemie 246 (1997), S. 97-107 
    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 gezeigt, daß es sowohl durch Oxidation, z.B. mittels Essigsäure/Wasserstoffperoxid oder Chromschwefelsäure, als auch durch Plasmabehandlung möglich ist, auf Poly(p-phenylensulfid) (PPS)-Oberflächen polare Gruppen einzuführen. Die änderungen and den PPS-Oberflächen wurden mit FTIR-Spektroskopie, Röntgen-Photoelektronenspektroskopie und Kontaktwinkelmessungen verifiziert. Die verbesserte Adhäsion der behandelten Oberflächen wurde mit Hilfe von Zug-Scher-Messungen nach dem Verkleben mit Acrylatklebstoffen quantitativ erfaßt. Die Untersuchung der Oberflächen mittels AFM (Atomic Force Microscopy) zeigt, daß die verbesserte Adhäsion auch durch eine größere Oberflächenrauhigkeit als Folge der Oberflächenbehandlung erreicht wird. Dieser Effekt ist besonders deutlich bei Proben, die mit Chromschwefelsäure behandelt wurden.
    Notes: It is demonstrated that both chemical oxidation, e.g. by using acetic acid/hydrogen peroxide or chromosulfuric acid, and plasma treatment of poly(p-phenylene sulfide) (PPS) surfaces introduce polar groups. The changes of the surface chemistry are detected by FTIR spectroscopy, X-ray photoelectron spectroscopy, and contact angle measurements. The increased polarity is partially responsible for better adhesion as verified by lap shear measurements using acrylic adhesive. Another important contribution to the improved adhesion originates from increased surface roughness after surface modification as measured by atomic force microscopy. This effect is very pronounced for PPS surfaces treated with chromosulfuric acid.
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  • 85
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    Angewandte Makromolekulare Chemie 246 (1997), S. 169-181 
    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 durability of a polyurethane-based coating material, used as protecting agent on Sander Sandstone, is investigated after different periods of artificial weathering in an environment simulation chamber (VENUS) by means of surface-sensitive methods (ESCA, infrared spectroscopy) and gel permeation chromatography. Only the outermost 4 millimeters showed decay on the polyurethane-chemistry level.
    Notes: Die Dauerhaftigkeit eines Steinschutzstoffes auf Polyurethanbasis im Sander Schilfsandstein gegenüber chemischen Angriffen wurde nach verschieden langen Bewitterungszeiten in einer Versuchsanlage zur naturnahen Umweltsimulation untersucht. Dabei wurden sowohl die Gelpermeationschromatographie (GPC) als auch oberflächensensible Analysenmethoden (XPS und PAS-FTIR) zur Untersuchung der Polyurethan-Mikroschicht im Stein eingesetzt. Nur im Bereich der ersten vier Millimeter Gesteinstiefe konnten bewitterungsbedingte chemische Veränderungen des Polymeren festgestellt werden.
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  • 86
    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 post-crosslinking of chloromethylated poly(styrene-co-divinylbenzene) to highly crosslinked, porous adsorbent polymers has been studied over a wide range of reaction temperature (50-80°C) and reaction time (up to 24.5 h). The crosslinked materials were characterized by nitrogen adsorption/desorption, mercury porosimetry, determination of the chlorine content, swelling measurements, pyrolysis gas chromatography, and Fourier transform infrared spectroscopy.Surface area, pore size distribution, pore volume, chlorine content, swelling degree, selected peak ratios in the pyrograms and in the FTIR spectrograms are shown to be clear functions of the post-crosslinking time. Therefore the post-crosslinking process can be monitored by physical as well as by chemical characterization methods.Moreover, information on the chemical homogeneity or inhomogeneity of the chloromethylated copolymers and the porous adsorbent polymers can be derived from the swelling and pyrolysis gas chromatographic results. Application of different solvents in the swelling experiments enables the construction of swelling diagrams. Based on these swelling diagrams, the anomalous swelling behaviour of adsorbent polymers during the post-crosslinking can be explained.The surface area and pore volume strongly increase with progressing post-crosslinking, and well-defined correlations between sample texture, pyrolysis and FTIR data are found. In general, changes of physical properties can be attributed to the chemical modification of the material due to the post-crosslinking.
    Notes: Die Nachvernetzung von chlormethyliertem Poly(styrol-co-divinylbenzol) zu hochvernetzten porösen Adsorberpolymeren wurde über einen weiten Temperatur-(50-80°C) und Reaktionszeitbereich (bis zu 24,5 h) untersucht. Die vernetzten Materialien wurden durch Stickstoffadsorption/Desorption, Quecksilberporosimetrie, Bestimmung des Chlorgehalts, Quellungsmessungen, Pyrolyse-Gaschromatographie und Fourier-Transform-Infrarotspektroskopie charakterisiert.Die Oberfläche, die Porengrößenverteilung, das Porenvolumen, der Chlorgehalt, ausgewählte Peakverhältnisse in den Pyrogrammen und den FTIR-Spektrogrammen sind eindeutige Funktionen der Nachvernetzungszeit. Der Nachvernetzungsprozeß kann somit sowohl mit physikalischen als auch mit chemischen Charakterisierungsmethoden verfolgt werden. Darüber hinaus ermöglichen Quellungsmessungen und pyrolysegaschromatographische Untersuchungen Aussagen zur Homogenität und Inhomogenität der chlormethylierten Copolymeren und porösen Adsorberpolymeren.Der Einsatz verschiedener Lösungsmittel bei der Quellung erlaubt die Konstruktion von Quellungsdiagrammen, anhand derer das anomale Quellungsverhalten der Adsorberpolymeren während der Nachvernetzung erklärt werden kann.Im Verlauf der Nachvernetzung werden die Oberfläche und das Porenvolumen stark vergrößert und eindeutige Korrelationen zwischen der Probentextur und den Pyrolyse- und FTIR-Daten gefunden. Die Veränderung der physikalischen Eigenschaften im Verlauf der Vernetzung kann generell auf die chemische Modifikation des Materials zurückgeführt werden.
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  • 87
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    Angewandte Makromolekulare Chemie 247 (1997), S. 61-72 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: UV stabilization of polymer systems containing brominated flame retardants has proven to be a difficult technical challenge. Generation of acidic products during processing or exposure can cause a catastrophic deactivation of the Hindered Amine Light Stabilizer (HALS). An understanding of the mechanism for bromine generation from aliphatic and aromatic based flame retardants has lead to formulation approaches based on flame retardant structure. In formulations containing aromatic brominated flame retardants, combinations of UV absorbèrs and a new class of siloxane HALS provide the highest level of UV stabilization to date. Alternatively, bicomponent fiber spinning technology can also provide outstanding UV resistance at significantly lower levels of stabilizers than that used in the monocomponent formulation approach.
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  • 88
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    Angewandte Makromolekulare Chemie 247 (1997), S. 73-89 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal oxidation (in air between 70 and 150°C) of unstabilised camples of poly(4-methylpentene) (PMP) were studied by infrared spectrometry and by gravimetry. The behaviour was compared to PP exposed in the same conditions.The thermal oxidation was found to exhibit two well differentiated kinetic regimes both for PP as for PMP. The first regime predominates at temperature higher than 90°C. It is characterized by an activation energy of the pseudo induction period of about 100 kJ mol-1. The induction period of mass gain is about 1,8 time shorter than the induction period of carbonyl gain. These characteristics, and the fact that induction periods are of the same order for both polymers, are consistent with a «close loop mechanistic» scheme with unimolecular POOH decomposition. The advantages of this hypothesis compared to other proposed hypothesis (bimolecular POOH decomposition, heterogeneous oxidation...) are discussed. The main theoretical difficulty is that of explaining why the unimolecular process predominates, whereas POOH are obviously hydrogen bonded, even at very low conversions of the oxidation process. This point remains to be explained.The second kinetic regime predominates at temperature lower than 90°C. It is characterized by a considerably lower activation energy. We have examined many hypothesis to explain the existence of a transition at that temperature (where neither PMP nor PP display a physical transition). A first hypothesis is that unimolecular POOH decomposition is replaced by a bimolecular one, which can explain a decrease of the apparent activation energy of about 50%. The bimolecular initiation creates pairs of radicals (POO·+ PO·). It can be imagined that a part of them desactivate mutually by termination after rearrangement of PO· by β scission. In this case, the transition at 90°C could be also a result of the temperature induced change in molecular mobility. Above 90°C, the radicals would diffuse almost freely out of the cage. In contrast, below 90°C, termination would become competitive with diffusion. A supplementary research is needed to fully elucidate the cause of this transition at 90°C.The eventuality of the existence of spatial heterogeneity of the oxidation process has been discussed. It is well known that oxidation is heterogeneous at the morphological scale, but there is no evidence of heterogeneity at smaller scale, where the chemical kinetic would not be applicable.
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  • 89
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    Angewandte Makromolekulare Chemie 247 (1997), S. 179-195 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several aspects of the thermal degradation of polystyrene are highlighted in this communication. The factors involved in determining the ratio of volatile to tar fraction products in the degradation of the pure polymer are examined, leading to the conclusion that the initial melt viscosity plays an important role in determining the balance between intra- and intermolecular transfer. The effect on the degradation of polystyrene of the presence of a second polymer is discussed. For polystyrene-polybutadiene and polystyrene-polyisoprene blends, stabilisation is observed, which is attributed to radical scavenging. The thermal degradation behaviour of polystyrene in the presence of oxygen has been investigated, with and without an antioxidant additive. Products have been characterised for oxidative conditions and the kinetics of degradation have been studied.
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  • 90
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    Angewandte Makromolekulare Chemie 247 (1997), S. 197-211 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A chain cleavage reaction allowing the transformation of high molecular weight polymers in well-defined oligomers can be considered as a step in a synthetic scheme. The control of oligomers with respect to their average molecular weights, their molecular weights distributions and their chain-end microstructures implies the control of the cleavage reaction with respect to its yield, its regiospecificity and its chemiospecificity. Among several examples of efficient uses of this principle for the preparation of liquid oligomers from unsaturated polymers, attention is focused (I) on controlled oxidative degradation of rubber and (II) on metathetical controlled degradation of 1,4-polydienes and polyakenamers. (I.a) The mechanism of the phenylhydrazine accelerated oxidation of rubber in the latex phase is described according to accurate structural studies on molecular model molecules. (I.b) The epoxidation of rubber and periodic acid cleavages of epoxides in the latex phase are interpretated referring to the influence of the biphasic medium. The results are in agreement with interfacial blocky epoxidation by the water-soluble reagent and interfacial arrangement of the epoxidized block to be cleaved. Finally the metathetical degradations resulting from back-bitting cyclisation and cross metathesis with acyclic alkenes are presented as preparative methods to get (II.a) well-defined cyclic oligomers and (II.b) telechclic oligomers (i.e. terminally functionalized oligomers).
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  • 91
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    Angewandte Makromolekulare Chemie 247 (1997), S. 255-268 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two concepts in the chemiluminescence research-the heterogeneous model and the kinetic approach-are discussed. The analysis of published data obtained by a highly sensitive photon-counting system reveals the contradictory nature of the heterogeneous model and proves its inconsistency. On the other hand, the kinetic approach has been successfully applied to evaluation of thermal oxidation in a variety of systems, ABS compositions in particular. Emulsion grade ABS were found to be essentially less stable than ionic mass polymerization products. Among the antioxidants studied, Santonox R is clearly more efficient than Irganox 1076. In emulsion grades the superiority of Santonox R to Irganox 1076 is reflected primarily in larger induction period, while in ionic resin it is mostly due to smaller oxidation rate constant values. The introduction of UV stabilizers by themselves has no influence on durability in either ionic or emulsion resins. Similarly to systems without UV stabilizers, Santonox R is more efficient than Irganox 1076 in mixtures with UV stabilizers as well. The comparative study of various ABS-coloring agent compositions by chemiluminescence and DSC reveals much greater sensitivity of the former. While DSC lets one make only a trivial conclusion that the introduction of an antioxidant improves stability, chemiluminescence shows the differences in durability as large as 3 to 4 times for the samples DSC fails to distinguish. In addition, chemiluminescence furnishes a significant insight on the factors affecting stability. The DSC thermal oxidative stability data can be related to resistance to oxidation during processing, whereas the chemiluminescence results are expected to be useful in predicting materials' lifetime at service temperatures.
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  • 92
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    Angewandte Makromolekulare Chemie 248 (1997), 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: Mit Alkyldihydrogenphosphaten behandeltes Calciumcarbonat unterschiedlicher Teilchenform (sphärisch, kubisch, Nadeln) wurde als Füllstoff für Polypropylen (PP) verwendet. Der Einfluß der Kettenlänge der Alkylgruppe auf mechanische Eigenschaften (Zugdehnung, Zugfestigkeit, Schlagzugfestigkeit, Streckspannung) und die Adhäsion zwischen der PP-Matrix und den verschiedenen CaCO3-Teilchen wurde untersucht, ebenso der Einfluß der Teilchenform auf den Speichermodul des mit unbehandeltem CaCO3 gefüllten und verstreckten PP.Zugdehnung, Schlagzugfestigkeit und Adhäsion des mit kubischem bzw. nadelförmigem CaCO3 gefüllten PP nehmen mit steigender Kettenlänge der Phosphat-Alkylgruppe zu, während das mit sphärischem CaCO3 gefüllte PP keine einheitliche Tendenz zeigt.Die relativen Moduli Edc/Edr (Edc - Speichermodul der verstreckten Komposite; Edr - Speichermodul der ungefüllten verstreckten PP-Matrix) der verstreckten PP/CaCO3-Komposite lassen sich mit einer modifizierten Halpin-Tsai-Gleichung beschreiben, in der die Faktoren (i) Orientierung der Polymermatrix, (ii) Einfluß des Füllstoffes (Gehalt, Modul, Kantenverhältnis) und (iii) Hohlraumvolumen an der Grenzfläche Polymer-Füllstoff enthalten sind.
    Notes: Calcium carbonate of various particle shape (CaCO3, sphere, cube, needle) treated with alkyl dihydrogen phosphate ester (APEN, CnH2n+1OPO(OH)2, n = 1, 4, 8, 10, 12) and poly(propylene) (PP) were mixed on a two roll mill. The effect of carbon number of APEN on the mechanical properties (tensile elongation, tensile strength, impact strength, yield stress) and adhesion between PP matrix and various CaCO3 particles and the effect of CaCO3 shape on the storage modulus of elongated PP/CaCO3 has been investigated.The tensile elongation, impact strength and adhesion of PP-CaCO3 interface increased with carbon number of APEN (n ≦ 10) for needle and cube type, but the dependence of tensile properties on APEN carbon number is not clearly recognized for the sphere type.The relative storage moduli of elongated PP/CaCO3, Edc/Edr Edc - modulus of elongated PP/CaCO3 (untreated); Edr - modulus of elongated PP matrix could sufficiently be described with a modified Halpin-Tsai equation, which contains the factors of (i) polymer matrix orientation, (ii) particle effect (content, modulus, aspect ratio), and (iii) void volume at polymer-filler particle interface.
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  • 93
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    Angewandte Makromolekulare Chemie 248 (1997), S. 85-94 
    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: In der vorliegenden Studie wurde die Permeation und Separation von Kohlendioxid durch eine wassergequollene Chitosanmembran untersucht. Die Chitosanmembran wurde durch in einem Trägergas enthaltenen Wasserdampf gequollen und zeigte nach dieser Behandlung eine hohe Gaspermeabilität. Bei Raumtemperatur durchdrang vorzugsweise Kohlendioxid die gequollene Chitosanmembran mit einer Permeabilität von 2,5·10-8 cm3 (STP) cm(s cm2 cmHg)-1 und einem CO2/N2 Trennfaktor von 70.Diese Trennleistung für Kohlendioxid wird durch die basischen Eigenschaften der Aminogruppen den Chitosanmolekülen hervorgerufen.Die Membranherstellungsbedingungen, wie zum Beispiel die Essigsäurekonzentration der Gießlösung, beeinflußten die Permeationsgeschwindigkeit. Der Einfluß der Arbeitstemperatur wurde ebenfalls untersucht. Um die Trennleistung der Membran zu erhöhen, wurden verschiedene Methoden der Membranbehandlung und Arbeitsbedingungen untersucht.
    Notes: The permeation and separation of carbon dioxide through a water-swollen chitosan membrane was studied. A chitosan membrane was swollen by water vapor contained in a feed gas and, thus treated, exhibited a large gas permeability. Carbon dioxide preferentially permeated through the swollen chitosan membrane with a permeability of 2.5·10-8 cm3 (STP) cm(s cm2 cmHg)-1 and a CO2/N2 separation factor of 70 at room temperature. This separation performance for CO2 resulted from the basic properties of the chitosan amino groups. The membrane preparation conditions, such as acetic acid concentration of the casting solution, affected the membrane permeation rate. The effect of the operation temperature was also measured. To increase the separation performance of the membrane, several methods of membrane treatment and operation were evaluated.
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  • 94
    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: A new conception for modification of textile surfaces by permanent fixation of supramolecular components is explained. The principle of selective complexation is illustrated. Cyclodextrins, aza crown ethers, calixarenes, cyclotriveratrylenes and fullerenes are mainly suggested as suitable ligands for that procedure. The chemical structure and the complexation behaviour of the substances are described. Some surface properties which may be obtained with the ligands are especially emphasized.
    Notes: Ein neues Konzept zur Modifizierung von Faseroberflächen durch permanente Fixierung supramolekularer Verbindungen wird vorgestellt, und das Prinzip der selektiven Komplexierung wird erklärt. Als für die Behandlung grundsätzlich geeignete Liganden werden insbesondere Cyclodextrine, Azakronenether, Calixarene, Cyclotriveratrylene und Fullerene hinsichtlich ihrer chemischen Struktur sowie ihrer komplexierenden Eigenschaften beschrieben. Einige erreichbare Oberflächeneffekte werden hervorgehoben.
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  • 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: Ein neues, wirtschftliches Verfahren zur Herstellung hochmolekularer Poly(amidimid)e (PAIs) basiert auf der direkten Polykondensation von Trimellitsäureanhydrid(TMA) oder Diimid-Disäuren (DIDAs) mit aromatischen Diaminen in Gegenwart von äquimolaren Mengen an Thionylchlorid in N-Methylpyrrolidon bei relativ niedrigen Temperaturen. Die Polyamidierung von Diimid-Disäuren und Diaminen zu Kopf-Kopf-Polymeren (H-PAIs) ist temperaturempfindlich und verläuft rasch; die Reaktionsdauer von 1 h war für die vollständige Umsetzung ausreichend. Der höchste Wert für die inhärente Viskosität ηinh wurde mit 72 mL g-1 bei Polymerisation bei Raumtemperatur erzielt. Durch die Polykondensation von TMA mit Diaminen und anschließende Imidisierung nach verschiedenen Methoden, wie die azeotrope Dehydrierung bzw. die Festphasenimidisierung von Polyamsäuren oder der Einsatz von Triphenylphosphit als Cokondensationsagens, wurden ebenfalls einige statistisch aufgebaute Polymere (R-PAJs) hergestellt. Von den Imidisierungsmethoden ergab die Festphasenimidisierung von Polyamsäuren mit inhärenten Viskositäten ηinh von 58-85 mL g-1 zufriedenstellende Ergebnisse. Imidisierungsgrade und Molekulargewichte wurden im wesentlichen von der Lösungsmittelmenge sowie der Imidisierungstemperatur und -zeit bestimmt. Sowohl H-PAI als auch R-PAI zeigten gute mechanische Eigenschaften, je nach Ausgangsmonomeren lagen die Zugfestigkeiten im Bereich 118-131 MPa und die Glasübergangstemperaturen im Bereich von 263-299°C. Die Schmelzviskositäten der PAIs bewegten sich zwischen 7,4·103 und 4,5·103 Pa s für H-PAI bzw. R-PAI und sind mit dem Wert fur konventionelles PAI, Torlon® 4000T, von 5,6·103 Pa s vergleichbar.
    Notes: A study for the development of a new, economical manufacturing process for high-molecular-weight poly(amide-imide) (PAI) was performed via direct polycondensation of trimellitic acid anhydride (TMA) or diimide diacids (DIDAs) with aromatic diamines using an equimolar amount of thionyl chloride in NMP at relatively low temperatures. The polyamidation of DIDAs and diamines for head-to-head polymers (H-PAIs) was sensitive to the reaction temperature and proceeded very quickly, 1 h was sufficient to complete the reaction. The highest value of inherent viscosity, ηinh, of 72 mL g-1 was obtained by polymerization at room temperature. Also several randomly sequenced polymers (R-PAIs) were prepared by polycondensation from TMA and diamines, followed by imidization with various methods, such as using TPP as a co-condensing agent, azeotropic dehydration of polyamic acid (PAA) and solid-state imidization from PAA. Solid state imidization from polyamic acids at 235°C gave satisfactory results with an inherent viscosity 58-85 mL g-1. Solvent content, imidization temperature and time were major controlling factors for the degree of imidization as well as for the molecular weight. Both H-PAI and R-PAI showed good mechanical properties with tensile strength of 118-131 MPa and Tg ranged between 263-299°C depending on the nature of monomers. The melt viscosity of the PAIs ranged between 7.4 · 103 and 4.5 · 103 Pa s for H-PAI and R-PAI respectively. These values are comparable to that of conventional PAI, Torlon® 4000T of 5.6 · 103 Pa s.
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  • 96
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    Angewandte Makromolekulare Chemie 248 (1997), S. 217-217 
    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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  • 97
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    Angewandte Makromolekulare Chemie 248 (1997), S. 201-215 
    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: In dieser Arbeit werden die durch Oxidation mit Salpetersäure hervorgerufenen Veränderungen der spezifischen Oberfläche, Porosität, Oberflächenfunktionalität und der Faserdimensionen handelsüblicher Kohlenstoffasern untersucht. SEM-Untersuchungen ergaben keine Veränderungen, jedoch konnten durch Kryptonadsorptionsmessungen erhöhte spezifische Oberflächen-und Mikroporositätswerte nachgewiesen werden.Die oxidative Behandlung beeinträchtigt die Faserlänge und verringert, wenn auch nur geringfügig, den Faserdurchmesser und die Festigkeit, wie aus Messungen des Elastizitätsmoduls hervorgeht.Die durch volumetrische Messungen und XPS durchgeführte Funktionalitätsanalyse zeigt eine erhöhte Gesamtoberflächenazidität aufgrund einer Zunahme der Carboxygruppen. Längere Behandlung der Fasern vermindert den Gehalt an Hydroxygruppen an der Faseroberfläche.
    Notes: This work reports on the variations in specific surface, porosity, surface functionality and dimension of commercial carbon fibre subjected to oxidative treatment with nitric acid. Scanning electron microscopy (SEM) observation did not reveal any topographic changes on the fibres, although crypton adsorption evidences increases in specific surface and microporosity.Oxidative treatment has an effect on fibre length, although it also slightly reduces the fibre diameter and the fibre strength, as measured in terms of the elastic modulus.Functional analysis by means of volumetric measurements and X-ray photoelectron spectroscopy (XPS) reveals an increase in the overall fibre surface acidity through carboxy group increase. Prolonged treatment gradually removes hydroxy groups from the fibre surface.
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    Angewandte Makromolekulare Chemie 246 (1997), S. 183-201 
    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 Konzentration von Natriumdodecylsulfat und von 2,2′-Azoisobutyronitril auf die vernetzende Emulsionscopolymerisation von 1,4-Divinylbenzol mit hydrophobem Cyclohexylmethacrylat und mit hydrophilem Methylacrylat wurde untersucht. Um festzustellen, welche Rolle die Diffusion von Monomeren bei der Copolymerisation spielt, wurden die Emulsionen durch gemeinsame und getrennte Solubilisierung hergestellt. Der Monomerumsatz wurde bestimmt. Die erhaltenen Microgele wurden bezüglich Molmasse, Teilchendurchmesser und Grenzviskositätszahl charakterisiert. Beim übergang von einer normalen zu einer mizellaren Emulsion war der Umsatz maximal. Mit dem hydrophoben Comonomeren bildete sich bei Verringerung der Emulgatormenge zunehmend unlösliches Koagulat aus polymerisierten Monomertröpfchen. Mit höherer Emulgatorkonzentrationen entstand zunehmend unlösliches Agglomerat durch Reaktion von Mikrogelteilchen miteinander.
    Notes: The influence of the concentration of sodium dodecylsulfate and 2,2′-azoisobutyronitrile on the crosslinking emulsion copolymerization of 1,4-divinylbenzene with hydrophobic cyclohexyl methacrylate and with hydrophilic methyl acrylate was studied. The emulsions were prepared by joint and by separate solubilization to study diffusion effects. Monomer conversion was measured and the microgels were characterized by molar mass, particle size diameter and intrinsic viscosity. The monomer conversion was maximal in the transition from a normal to a micellar emulsion. With the hydrophobic comonomer increasingly insoluble coagulates from polymerized monomer droplets were formed on decreasing the emulsifier concentration. Toward higher emulsifier concentration increasingly insoluble agglomerates were formed by reactions between microgels.
    Additional Material: 14 Ill.
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  • 99
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 247 (1997), S. 1-18 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A BPA polycarbonate/ABS blend containing 2% TiO2 was exposed to xenon are irradiation under SAE J 1885 conditions (quartz/borosilicate filters). “CRD” conditions (borosilicate/borosilicate filters), and ASTM D4459-86 conditions (borosilicate/soda lime filters). The results are consistent with the conclusion that polycarbonate dominates the photochemistry of polycarbonate/ABS blends under SAE J1885 and CRD xenon are exposure conditions. Exposure under ASTM D4459-86 conditions produced results similar to CRD conditions with some additional contribution attributable to the ABS component. The “activation spectrum” of PC/ABS blends under CRD conditions closely resembled the sum of the activation spectra of ABS and PC determined under similar conditions. The well-known change in mechanism that occurs when polycarbonate is exposed to light with wavelengths 〈 300 nm was manifested by increased rates of yellowing, surface erosion. and loss of gloss under SAE J 1885 conditions. Because of the mechanism change, testing under quartz/borosilicate filtered xenon are exposure cannot be considered to be appropriate for polycarbonate-containing formulations.
    Additional Material: 15 Ill.
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  • 100
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 247 (1997), S. 31-43 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanical and thermal oxidation of UHMWPE used in the preparation of prosthetic implants is studied and the mechanisms of degradation are reported. Oxidation of new and retrieved prosthetic implants are studied by IR microscopy and clear evidence of oxidation in vivo is shown.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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