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  • 1
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of the nature of the polyols used in polyurethane (PUR) synthesis on the structural transformations after ageing by UV irradiation has been studied. The investigations were performed on PUR prepared from polyester and polyether diol oligomers.The characterization of the samples before and after ageing in view of the structural changes, which influence the course of the photooxidative degradation and photocrosslinking as well as in view of changes of mechanical properties has been done. Comparative investigations were performed by spectroscopic and viscometric measurements.The results show pronounced heterogeneity of the degradative reactions, including the existence of crosslinking processes and producing thus very inhomogeneous polymeric material. The course and the intensity of photooxidative degradation of PUR differ together with changes of mechanical properties depending whether polyester or polyether polyol have been used. The processes of photooxidative degradation is less expressed in polyesterurethane then in polyurethane based on polyether, under the same conditions of experiments. Different structures of polyester diols caused the various ageing behaviour of PUR too.
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  • 2
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: QUALIFICATION OF HALS COMPOUNDSA complex method of examination has been developed suitable for the qualification of light stabilizers; by this method, according to experience, the efficacy of HALS compounds can be extensively and expediently characterized.Several light stabilizers of the HALS-type were examined and qualified, used alone or together with a UV-absorber.It has been found that, when selecting the appropriate structure for a given polymer, the weatherability of polyolefine foils is effectively increase to six-eightfold; the increase is even tenfold when the stabilizer is combined with a benzophenone-type compound.As a utilization of these experiences, a contract with the industry, led to the production of an LDPE based agricultural foil with a life-time of several years.
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  • 3
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Natural hail impact tests are scarcely available because hailstorms are limited to a small area and cannot be predicted regarding time, place and intensity. Therefore we relied on laboratory tests simulating natural hailstones by polyamide balls (5-50 mm dia.) whose final velocity could be varied according to meteorological data. So the influence of diameter (weight) and velocity of the artificial hailstones could be taken into consideration independently.The energy of damage or equivalent natural hailstone diameter were determined for 16 mm double skin sheet from PMMA as 0.2 J (14 mm dia.) for star shaped cracks and 2 J (26 mm dia.) for holes. These values do not significantly decrease after 10 years weathering. 10 mm double skin sheets from PC show an extremly high energy of damage of abt. 10 J (38 mm dia.) which decreases to a medium level of 2 J (26 mm dia.) after several years weathering. This decrease is remarkably reduced by weather resistant protective coating.As hailstorms consist to more than 80% of hailstones below 10 mm dia. (0.04 J) the mentioned sheet materials are quite hail resistant also after long weathering periods, but they cannot withstand an extreme hail catastrophe as in Munich July 12, 1984.
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  • 4
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of the specimen temperature on many ageing processes is well known. Two aspects is dealt with: -Measurements of the specimen temperature on several positions of a specimen in commercial weathering devices at different exposure conditions. Technical measures to achieve to uniform ageing at all positions of a planar and homogeneous specimen. Examples from practical use.-Changing specimen temperatures (+60°C to -20°C) during the course of accelerated weathering, i.e. a combination of conventional accelerated weathering with a temperature cycle test.
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  • 5
    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: An Folien (Dicke 100 pm) aus isotaktischem Polypropylen mit verschiedenen Antioxidansgehalten (0,0% bis 0,1%) wird die thermooxidative Alterunq mit der isothermen Langzeit-Differential-Thermo-Analyse (ILDTA) bis zu Temperaturen weit unter dem Kristallitschmelzbereich verfolqt und die Messwerte mit Ergebnissen aus dem Zeitstand-Zugversuch korreliert. Dabei zeigt sich, daß aus Messunqen mit der ILDTA bereits vor Einsetzen der autokatalytischen Zersetzunq sreaktion Ruckschlüsse auf die thermische Vorqeschichte der Proben und Aussagen auf das rnit einem Abfall der mechanischen Eigenschaften verbundene Ende der thermo-oxidativen Stabilität des Polymeren getroffen werden können.Weiters bietet die ILDTA die Moglichkeit, durch den direkten Zusamenhang zwischen Oxidationszeit und Antioxidansögehalt die örtliche Stabilisatorverteilung in Platten und in Folien zu bestimmen und damit Diffusionsvorqange zu verfolgen.
    Notes: Thermo-oxidative ageing processes were investigated in films (100 μm thick) made from isotactic polypropylene with different antioxidant concentrations between 0% and 0.1% using isothermal long-term differential thermal analysis (ILDTA). The end of the oven life of polypropylene coincided with the loss of mechanical properties which was confirmed by tensile tests at temperatures far below the crystallite melting range. Already prior to the beginning of autocatalytic decomposition, ILDTA experiments permits conclusions to be drawn on the thermal history of the specimens and statements made regarding the end of thermo-oxidative stability of the polymer, which is accompanied by a deterioration in the mechanical properties.In consequence of the correlation between oxidation time and antioxidant concentration the local antioxidant concentration in sheets or films can be measured by ILDTA. Thus, investigating the diffusion of an antioxidant in polypropylene using ILDTA is possible.
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  • 6
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Größenverteilungsfunktion von Dispersionen mit extrem breiter Verteilung (Durchmesserbereich 20 〈 D 〈 2000 nm) kann in der analytischen Ultrazentrifuge (AUC) nicht durch eine Standardmethode, z. B. durch Messung der Trübung τ bei einer einzigen Konzentration, bestimmt werden, weil sich die spezifische Trübung τ/c von sehr kleinen und sehr großen Teilchen zu stark unterscheidet. Um dieses Problem zu lösen, haben wir eine neue AUC-Technik, die sogenannte Coupling-PSD-Technik entwickelt. Dabei werden zwei unterschiedliche Konzentrationen derselben Dispersion gleichzeitig in einem einzigen AUC-Lauf vermessen und zwei korrespondierende Lichtintensitiit-Zeit-Kurven aufgezeichnet. Bei einer niedrigen Standardkonzentration cs werden hauptsachlich die größeren Teilchen erfaßt während bei einer 5 bis 30 mal heheren Konzentration ch vor allem die kleineren Teilchen registriert werden. Die beiden I(t)-Kurven werden mathematisch verkniipft und unter Verwendung des Stokeschen Gesetzes und der Streutheorie von Mie für homogene isotrope Kugeln in die gesuchte breite Verteilungsfunktion umgerechnet. Wir benutzen eine mit einem 8-Zellen-Rotor und einem Multiplexer ausgestattete AUC. Da sehr groBe und sehr kleine Teilchen gleichzeitig in einem einzigen Zentrifugenlauf bestimmt werden, kennen wir nicht mehr wie zuvor eine konstante Rotorgeschwindigkeit N anwenden, sondern miissen diese mit Hilfe eines Geschwindigkeitsprogramms N(t) innerhalb einer Stunde von 0 auf 40000 U/min erhehen.
    Notes: The particle size distribution (PSD) of extremely broad distributed dispersions (diameter range 20 〈 D 〈 2000 nm) is not possible to be measured by analytical ultracentrifuge (AUC) using the standard technique, i.e. measuring turbidity τ at a single concentration c, because the specific turbidity τ/c varies too much between very small and very large particles. To solve this problem we have developed a new AUC technique, the so-called Coupling-PSD-Technique. Here two different concentrations of the same dispersion are measured simultaneously by one single AUC run with two corresponding curves of light intensity I vs. time t being registered. At a low standard concentration cs, mainly the larger particles are detected, while at a concentration ch 5 to 30 times higher mainly the smaller particles are registered. Both I(t)-curves are coupled mathematically and transformed into the requested broad distribution curve employing Stokes' law and Mie's light scattering theory for homogeneous isotropic spheres.We use an AUC together with an 8-cells-rotor and a multiplexer. Because very large and very small particles are to be measured simultaneously in one single run, we can no more apply a constant rotor speed N as before, but by means of a time program N(t) we always have to increase the rotor speed from 0 to 40000 rpm within one hour.
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  • 7
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 162 (1988), S. 135-148 
    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 chemische Modifizierung von Polyvinylchlorid (PVC) durch ein Amin verleiht dem Polymeren höhere Reaktivität gegenüber der Pfropfcopolymerisation mit einem Vinylmonomeren. Die Pfropfcopolymerisation von Methylmethacrylat auf mit n-Butylamin modifiziertes PVC wurde thermisch mit Benzoylperoxid (Bz2O2) als Initiator oder photoaktiviert mit Benzophenon (BP) als Photosensibilisator gestartet. Das aus bestimmten Experimenten erhaltene rohe Polymerprodukt wurde durch fraktionierte Fällung in die verschiedenen Bestandteile wie Polymethylmethacrylat (PMMA, Homopolymeres), PVC-g-PMMA (Pfropfcopolymeres) und unverändertes (aminiertes) PVC aufgespalten. Die getrennten Fraktionen wurden mit Hilfe der IR-Spektroskopie und der Thermogravimetrie charakterisiert. Der Mechanismus der Pfropfcopolymerisation von den beiden verschiedenen Systemen wurde erörtert. In beiden Fällen wurden Pfropfausbeuten um 30 - 70%* und Pfropfcopolymerzusammensetzungen, PMMA/PVC (w/w) zwischen 2 und 3 erhalten.
    Notes: Chemical modification of poly(vinyl chloride), PVC, by an amine renders the polymer more reactive towards graft copolymerization with a vinyl monomer. The graft copolymerization of methyl methacrylate (MMA) on PVC modified by treatment with n-butylamine (n-BA) was started thermally at 30° using benzoyl peroxide (Bz2O2) as initiator and under photoactivation at 40° using benzophenone (BP) as photo sensitizer. The gross polymer products from selected experiments were fractionally separated into the constituent polymeric entities viz., poly(methyl methacrylate), PMMA (homopolymer), PVC-g-PMMA (graft copolymer), and unreacted (aminated) PVC following a method of fractional precipitation. The separated fractions were characterized by IR spectroscopy and thermogravimetry. The mechanisms of graft copolymerization for the two different systems have been discussed. In each case, grafting efficiencies of the order of 30-70% and graft copolymers having compositions given as PMMA/PVC (w/w) equal to 2-3 were readily obtained.
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  • 8
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 162 (1988), S. 193-201 
    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: Eine Reihe oberflächensulfonierter, makroporöser Styrol-Divinylbenzol-Copolymerer mit unterschiedlichen Gehalten an SO3H-Gruppen wurden hergestellt. Sowohl von diesen Copolymeren als auch vom nichtsulfonierten Copolymeren wurden Porenstruktur, Oberflächenhydrophilie und -polarität sowie das Sorptionsverhalten gegenüber einigen in Blut vorkommenden Substanzen bestimmt. Der Sorptionsgrad wird umso kleiner, je größer die Oberflächenpolarität ist. Die teilsulfonierten Polymeren könnten eine Anwendung in der Hämoperfusion finden.
    Notes: A series of surface sulphonated macroporous styrene-divinylbenzene (S-DVB) copolymers containing various amounts of  - SO3H groups was obtained. Porous structure, surface hydrophilicity and polarity, and sorption properties of these copolymers as well as those of starting S-DVB resin towards some substances which are present in blood were determined. The sorption degree becomes the smaller the higher is the surface polarity. The partially sulphonated copolymers may find an application in hemoperfusion.
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  • 9
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß einer chemischen Behandlung von dünnen Filmen einer Composit-Membran aus sulfoniertem Polyphenylenoxid wurde untersucht. Über den Einfluß der Konzentration von wáßrigen Lösungen von Formaldehyd, Schwefelsäure, Salzsäure, Phosporsäure, Natriumhydroxid sowie der Behandlungsdauer auf die Trenncharakteristik der inversen Osmose der Composit-Membranen mit einer Ionenaus-tauschkapazität von 2,14 und 2,50 meq/g in verschiedenen Kombinationen wird ausführlich berichtet. Die Ergebnisse zeigen, daß unter den besten chemischen Behandlungsbedingungen eine Erhöhung der Trenncharakteristik der inversen Osmose der sulfonierten Polyphenylenoxid/Polysulfon-Composit-Membran erreicht wird.
    Notes: The effect of chemical treatment on the reverse osmosis (RO) separation characteristics of sulfonated poly(phenylene oxide) (SPPO) thin film composite membranes was investigated. The effects of the concentrations of aqueous solutions of formaldehyde, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, and treatment time on the RO separation characteristics of the composite membranes with ion exchange capacity (IEC) of 2.14 and 2.50 meq/g in various combinations are reported in detail. The results indicate some enhancement in RO separation characteristics of the SPPO/polysulfone (PS) composite membrane under the best conditions of the chemical treatment.
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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: Bei der Herstellung dünner Filme von sulfonierten Polyphenylenoxid/Polysulfon (SPPO/PS)-Composit-Membranen wurde untersucht, daß ein Zusatz von Nitromethan zu einer Lösung von sulfoniertem Polyphenylenoxidnatrium erhöhte Wirkung auf die Trenncharakteristik der inversen Osmose besitzt. Der Einfluß von gamma-Strahlung auf dünne Filme der Composit-Membran unter nassen und trockenen Bedingungen wurde ebenfalls untersucht. Um die maximal mögliche Verbesserung zu erreichen, wurden die Composit-Membranen einer kombinierten chemischen und Gammastrahlen-Behandlung unter nassen und trockenen Bedingungen unterworfen.Die experimentellen Ergebnisse dieser kombinierten Behandlung zeigen, dalß die SPPO/PS Composit-Membran dabei abgebaut wird.
    Notes: The enhancement effect of the addition of nitromethane into the coating solution of sulfonated sodium poly(phenylene oxide) (SPPONa) polymer for the synthesis of sulfonated poly(phenylene oxide)/polysulfone (SPPO/PS) thin film composite membranes on reverse osmosis (RO) separation characteristic was studied. The effect of gamma-ray irradiation on the SPPO/PS thin film composite membranes was also evaluated when the membrane samples were in the wet and dry conditions. The composite membranes were also subjected to a chemical treatment combined with gamma-ray irradiation in both wet and dry conditions in the hope of obtaining the maximum possible enhancement under each treatment. However, the experimental data of this combined treatment indicated the possibility of some degradation of the SPPO/PS composite membranes.
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  • 11
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 37-45 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Mischungen aus Poly(styrol-co-butadien)/Polybutadien, Naturkautschuk/Poly-(ethylen-co-propylen-co-dien und Naturkautschuk/Poly(butadien-co-acrylnitril)) wurden nach drei unterschiedlichen Verfahren compoundiert und Härtungsverhalten sowie Zugfestigkeit und Bruchdehnung der Vulkanisate wurden verglichen.
    Notes: Compounding of styrene-butadiene copolymer/polybutadiene, natural rubber/ethylene-propylene-diene terpolymer and natural rubber/butadiene-acrylonitrile copolymer blends was done in three different ways and their curing behaviour and the tensile properties of the vulcanizates are compared.
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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: Methylmethacrylat (MMA) wurde mit Hilfe von Cerammoniumnitrat als Initiator auf Stärke gepfropft. Die Pfropfcopolymeren wurden durch selektive Lösungsextraktion in einem Soxhlet-Extraktor isoliert. Der Einfluß von Reaktionszeit, Initiatorkonzentration, Temperatur sowie der Monomer- und Särekonzentration auf die Pfropfausbeute wurde untersucht. Eine erste Studie der Kinetik dieser Pfropfcopolymerisationsreaktion zeigt, daß sie dem üblichen kinetischen Verhalten einer Radikalpolymerisation folgt.
    Notes: Methyl methacrylate (MMA) was grafted onto starch using ceric ammonium nitrate as initiator. The graft copolymers were isolated by selective solvent extraction in a Soxhlet apparatus. The effects of reaction time, initiator concentration, temperature, monomer, and acid concentrations on the graft yields were investigated. A preliminary kinetic study of the graft copolymerisation reactions shows that they follow the conventional kinetic behaviour of free radical polymerisation.
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  • 13
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 47-61 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Verwendung von Phenol-Formaldehyd-Harz mit gepreßten Olivenkenen im Gewichtsverháltnis 20/80 wurden kleine zylindrische Formkörper durch Härtung hergestellt. Diese wurden pyrolysiert und einige Proben mit Wasserdampf aktiviert. Für diese Formkörper und für zwei kommerzielle Aktivkohlen für Laboratoriumsbzw. Industrie-Anwendungen wurden folgende Eigenschaften bestimmt: die spezifische Oberfláche, die Struktur, die Adsorptionseigenschaften sowie die Adsorptionskapazität. Die Ergebnisse zeigen, daß die hergestellten kohlenstoffhaltigen Materialien durch Aktivierung höhere Werte für die untersuchten Eigenschaften ergeben als die nur pyrolysierten Proben und die zwei kommerziellen Aktivkohlen. Es wurde festgestellt, daß die Adsorption des 4-Nitrophenols für alle untersuchten kohlenstoffhaltigen Materialien gemäß der Freundlich-Gleichung stattfindet. Die Raster-Elektronenmikroskopie zeigt, daß die hergestellten kohlenstoffhaltigen Materialien andere Porenarten aufweisen als die kommerziellen Aktivkohlen. Die experimentellen Ergebnisse werden durch die molekularen Dimensionen der zur Adsorption verwendeten Substanzen und den Polarisationseffekt der Substituenten am Benzolring erklärt.
    Notes: Mixtures of phenol-formaldehyde-resin and pressed olive stones in a weight ratio of 20/80 were cured as small cylinders and then pyrolyzed. Some samples were also activated by steam. For these specimens and for two commercial activated carbons of laboratory or industrial uses the specific surface area, the structure, the adsorption properties, and the adsorption capacity were determined. The results indicate that the carbonaceous material produced by activation has greater values for the examined properties in comparison to the only pyrolyzed and the two commercial activated carbons, respectively. It was found that the Freundlich-equation is valid for the adsorption of 4-nitrophenol on all carbonaceous materials examined. The produced carbonaceous materials have different kinds of pores than the commercial activated carbons. The experimental results are explained with regard to the molecular dimensions of the adsorptive substances and the polarization effect of the substituents of the benzene ring.
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  • 14
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 101-114 
    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 Anwendung der nichtlinearen Programmiermethode basierend auf der mittleren harmonischen Näherung wurden aus den Kontaktwinkeldaten die freie Dispersions- und polare, freie Oberflächenenergie, γSVd und γSVp, sowie die kritische, freie Oberflächenenergie, γc, von Polymeren bestimmt. Die Komponenten der freien Oberflächenergie der zu untersuchenden Flüssigkeiten, γLVd und γLVp, die die Bedingungen für den maximalen Wechselwirkungsparameter, Φ, wiedergeben, wurden ebenfalls mit Hilfe dieser Methode bestimmt.
    Notes: The dispersion and polar surface free energy components, γSVd and γSVp, and the critical surface free energy, γc, of polymers were determined from contact angle data by the application of a nonlinear programming method using harmonic mean approximation.The surface free energy components of the probe liquids, γLVd and γLVp, which reflect the conditions of the maximized interaction parameter, Φ, were also simultaneously determined by this method.
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  • 15
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 169-193 
    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 condensation reaction of bisphenol A, melamine, and formaldehyde was investigated by gel permeation chromatography, 13C-NMR-spectroscopy, IR-spectroscopy and elemental analysis. Because of the high reaction rates the condensation could be investigated only in the range of pH 6-10. At pH 6 and 7 the reaction of melamine with formaldehyde is dominating.With increasing pH-value the condensation of bisphenol A with formaldehyde is observed preferably. At pH 10 the condensation results in high molecular products. Cocondensation of melamine and bisphenol A through methylene bridges does not take place. But as a separation of the bisphenol A-formaldehyde condensates from the other condensation products was not possible, the three components may be connected through methylene-ether groups and/or intermolecular hydrogen bridges.
    Notes: Die gemeinsame Kondensation von Bisphenol A, Melamin und Formaldehyd wurde mit Hilfe der Gelpermeationschromatographie, der 13C-NMR-Spektroskopie, IR-Spektroskopie und Elementaranalyse untersucht. Wegen der hohen Kondensationsgeschwindigkeit verläuft die Reaktion in Gegenwart der drei Komponenten nur im Bereich von pH 6-10 kontrollierbar. Bei pH 6 und 7 überwigt die Kondensation zwischen Melamin und Formaldehyd. Mit steigendem pH-Wert tritt die Reaktion von Bisphenol A mit Formaldehyd in den Vordergrund und führt bei pH 10 zu hochmolekularen Kondensationsprodukten.Auf direkte Cokondensation hinweisende Methylenverknüpfungen zwischen der phenolischen Komponente und Melamin konnten nicht nachgewiesen werden. Die Kondensationsprodukte des Melamins bzw. des Bisphenol A mit Formaldehyd lassen sich aber nicht mehr vollständig aus den Reaktionsgemischen der Vorkondensation abtrennen, was dafür spricht, daß die Komponenten über Methylenetherbrücken und/oder intermolekularen Wasserstoffbrücken miteinander verknüpft sind.
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  • 16
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 205-207 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cyclodextrin membrane-modified electrodes as sensor materials have been prepared by dipping platinum electrodes in the water suspensions of an oriented cyclodextrin polymer, followed by drying the polymer layers on the electrodes. The polymer is obtained by the solid-liquid reaction between the crystal of cyclodextrin inclusion complex and hexamethylene diisocyanate in anisole. The thickness (2 - 80 μm) of the cyclodextrin membrane is satisfactorily controlled by changing the concentration of the water suspension of the polymer. The cyclodextrin membranemodified electrodes show a significant response to p-nitrophenolate in water which is highly in contrast with no measurable response to o- and m-nitrophenolates.
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  • 17
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Im Zusammenhang mit dem Studium des Wirkungsmechanismus von industriell hergestellten Antidegradantien vom Typus der N-Phenyl-N′-sek-alkyl-1,Cphenylendiamine wurde die Reaktion von N-Phenyl-1,4-benzochinonimin (I) und 4-Hydroxydiphenylamin (II) mit dem Kohlenstoff-Radikal 1-Cyano-l-methylethyl (R·) studiert. Das Gemisch von I und II reagiert mit R· sehr leicht unter Bildung der Verbindungen III, VI und VIII. I allein reagiert wesentlich langsamer, und das Reaktionsgemisch enthält mehrere Produkte. Neben der Verbindung III wurden auch die Verbindungen IV und VII identifiziert. II allein reagiert bei denselben Bedingungen nicht. Die Verbindung IV bildet die zwei isomeren Strukturen syn und anti. Die Verbindung VIII ist ziemlich unbeständig; aus ihren Umwandlungsprodukten wurde XI isoliert. Bei der Reduktion von IV entsteht die Verbindung V, die ähnlich wie VIII unbeständig ist.
    Notes: The reaction of N-phenyl-1,4-benzoquinoneimine (I)Decoding of abbreviations see p. 103/104. and 4-hydroxydiphenylamine (II) with the carbon centred 1-cyano-1-methylethyl radical (R·) was studied in connection with an investigation of the action mechanism of industrial antidegradants, such as N-phenyl-N′-sec-alkyl-1,4-phenylenediamines. The mixture of I and II reacts very readily with R·, giving rise to III, VI, and VIII. I alone reacts much slowlier, and the reaction mixture contains more products. IV and VII were identified along with III. Under the conditions used, II alone does not react at all. IV exists in two isomeric forms, syn and anti. VIII is very labile; XI was isolated from its transformation products. Reduction of IV gives V, which is labile, similarly to VIII.
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  • 18
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 156 (1988), S. 123-137 
    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: Samples of polyoxymethylene (unstabilized and stabilized with the antiozonants N-isopropyl-N′-phenyl-p-phenylenediamin (IPPD) and bis-(1,2,3,6-tetrahydrobenzaldehyd)pentaerithritylacetal (Vulkazon AFS)) were ozonized under mechanical load in a special climate chamber. Surface damages were determined by IR-spectroscopy and scanning electron microscopy. During the ozonolysis a damaged layer is formed, the thickness of which increases with increasing time of ozonization. During this damaging reaction acetal groups are attacked and oligomers are formed.
    Notes: Proben von unstabilisiertem und mit den Antiozonantien N-Isopropyl-N′-phenyl-p-phenylendiamin (IPPD) und Bis-(1,2,3,6-tetrahydrobenzaldehyd)-pentaerithrityl-acetal (Vulkazon AFS) stabilisiertem Polyoxymethylen wurden unter mechanischer Belastung in einer Klimakammer ozonisiert. Die Schädigungen auf der Oberfläche wurden IR-spektroskopisch und rasterelektronenmikroskopisch untersucht. Während der Ozonisierung von POM bildet sich eine geschädigte Schicht, deren Dicke mit zunehmender Ozonisierungszeit wächst. Hierbei wird das Polymere an den Acetalbindungen angegriffen, wodurch Ketten gespalten werden und Oligomere entstehen.
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  • 19
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 156 (1988), S. 105-121 
    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 Hilfe verschiedener Methoden wurde der Einfluß der Entfernung unterschiedlicher porenbildender Verdünner aus porösen Styrol-Ethylstyrol-Acrylnitril-Divinylbenzol-Copolymeren auf die Netzwerkstruktur untersucht. Der günstigste Weg, den ursprünglichen strukturellen Bau des porösen Netzwerkes zu bewahren, welches in Gegenwart von solvatisierenden Verdünnern erhalten wurde, ist das Entfernen des inerten Mediums mit Methanol. Wenn die Wasserdampfmethode angewendet wird, fin det der sog. Kollapseffekt statt, und die aus solchen Harzen hergestellten Anionenaustauscher adsorbieren weniger Farbstoff im Vergleich zu jenen, die aus Perlen hergestellt worden sind, die mit Methanol behandelt wurden; Grund hierfür ist die durch den Kollaps veränderte Porengröße. Es wurde ebenfalls festgestellt, daß die in Anwesenheit von solvatisierenden Verdünnern (Mischungen aus Quellungs- und Fällmitteln) hergestellten Copolymeren in Methanol sehr gut quellen, obwohl dieses ein Fällungsmittel für Polystyrol ist.
    Notes: The influence of the removal of various diluents, pore forming agents from the porous styrene-ethylstyrene-acrylonitrile-divinylbenzene copolymers on the structure of the matrix was investigated by several methods. The most advantageous pathway to preserve the initial structural edifice of the porous networks performed in the presence of solvating diluents consisted in the removal of the inert media with methanol as it was noticed from the experimental data. If the steam treatment is applied, the collapse effect takes place and the anion exchangers prepared from such matrices exchange/adsorb less dye stuff by comparison with ones formed from beads treated with methanol, because the pore size was changed. It was also noticed that the porous copolymers performed in the presence of the solvating diluents (mixtures of solvatings and precipitants) swell very well in methanol though it is a precipitating medium for the polystyrenic macromolecular chains.
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  • 20
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 156 (1988), S. 139-149 
    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: An Styrol-Zinkacrylat-Copolymeren wurde die Abhängigkeit der Glasübergangstemperatur von der Aufheizgeschwindigkeit und der Zusammensetzung mit Hilfe der Differential-Scanning-Calorimetrie untersucht. Die Thermogravimetrie wurde benutzt, um die Pyrolyse dieser Copolymeren an Luft bei drei verschiedenen Aufheizge-schwindigkeiten zu untersuchen. Die thermische Zersetzung von Ionomeren ist ein 3-Stufen-Prozeß. Die Reaktionsordnung und Aktivierungsenergie wurde für jede Stufe der Zersetzung bestimmt unter Verwendung eines Computerprogramms, das auf den Methoden von Kissinger, Freeman-Carrol und Ozawa basiert. Es zeigte sich, daß die thermische Stabilität durch die ionischen Gruppen abnimmt.
    Notes: The dependence of glass temperature on the heating rate and the composition for styrene-zinc acrylate copolymers has been investigated by differential scanning calorimetry. Thermogravimetry was used in order to examine these copolymers undergoing pyrolysis in an atmosphere of air at three different heating rates. Thermal decomposition of ionomers is a three-stage process. The orders and activation energies have been determined for each stage of decomposition using the computer programs based on the methods of Kissinger, Freeman-Carrol, and Ozawa. It was found that the heat stability is lowered by the ionic groups.
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  • 21
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 156 (1988), S. 151-162 
    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 Pfropfung der hydrophilen Monomeren N-Vinylpyrrolidon, 2-Hydroxyethyl-methacrylat und Acrylamid auf ungesättigte segmentierte Polyurethane in N,N-Dimethylformamid mit 2,2′-Azobisisobutyronitril als Initiator wurde untersucht. Die Pfropfcopolymeren wurden von den Homopolymeren durch selektive Extraktion in Soxhlet-Apparaturen abgetrennt. Die kinetische Untersuchung der Pfropfcopolymerisation zeigte, daß die Reaktionen dem gewöhnlichen kinetischen Verhalten radikalischer Polymerisationen folgen. Die Abhängigkeiten der Pfropfungsgeschwindigkeit von der Initiator- und N-Vinylpyrrolidonkonzentration waren von 0,5 bzw. 1,0 Ordnung. Für 2-Hydroxyethylmethacrylat wurden sie zu jeweils 0,5 und 2,0 gefunden. Die Gesamtaktivierungsenergie der Pfropfcopolymerisation des 2-Hydroxyethylmethacrylats und des N-Vinylpyrrolidons betragen jeweilig 21,81 und 16,28 kJ/mol.
    Notes: Grafting of unsaturated segmented polyurethanes with some hydrophilic monomers such as N-vinyl pyrrolidone, 2-hydroxyethylmethacrylate and acrylamide in N,N-dimethylformamide have been studied using 2,2′-azobisisobutyronitrile (AIBN) as initiator. Graft copolymers were isolated from homopolymers by selected solvent extraction using a Soxhlet apparatus. A kinetic study of graft copolymerization reactions showed that the reactions follow the conventional kinetic behaviour of free radical polymerization. The dependencies of the grafting rate on initiator and N-vinyl pyrrolidone concentrations were of 0.5 and 1.00 order, respectively. However, for the 2-hydroxyethylmethacrylate, the dependencies of the grafting rate on initiator and monomer concentrations were found to be of 0.5 and 2.00 order, respectively. The overall activation energy for the graft copolymerization of the 2-hydroxyethylmethacrylate and N-vinyl pyrrolidone were 21.81 kJ/mol and 16.28 kJ/mol, respectively.
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  • 22
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    Angewandte Makromolekulare Chemie 156 (1988), S. 179-185 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ultra fine particles were impregnated by using a finely porous cellulose gel membrane. The impregnated gel membrane is a green transparent one and looks like a solid solution. Highly dispersed Ni catalysts on carbon were obtained from thermal decomposition of these gel membranes. The particle size is in the range of several nm to a few ten nm. They show interesting catalytic properties for hydrogenation of olefins such as cyclooctadiene.
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  • 23
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermo-oxidation resistance and weatherability of LDPE and HDPE compositions, containing up to 45 wt.% calcium carbonate, are investigated. The thermo-oxidation resistance is investigated by dynamic DTA and natural ageing is carried out in an exposure station in a seaside climate. The change in strength and colour after ageing is determined. The behaviours of filled and unfilled polymers are compared. Empirical equations are given, describing the change in the investigated parameters during natural ageing.
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  • 24
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: An Proben aus Polypropylen, die bei sehr unterschiedlichen Einstellungen von Spritzgußmaschinen und Extrudern hergestellt wurden, stellten sich deutliche Abhängigkeiten des Alterungsverhaltens von den thermischen und mechanischen Produktionsparametern ein, die nicht durch unterschiedliche Schmelzetemperaturen bedingt sind. Insbesondere kann ausgesagt werden, daß bei Spritzguß eine hähere Scherbelastung und damit stärkere Orientierungen -eine stärkere Veränderung der Eigenspannungen hervorrufen-einen früheren Glanzabfall und-eine geringere Initialzeit bis zur Rißbildung bewirken.Bei Extrusion fiihrt eine geringere Abkühlgeschwindigkeit und damit ein gröberes Gefüge zu -einer stärkeren Veränderung der Eigenspannungen-einem friiheren und ausgeprägteren Glanzverlust-sowie zu einem früheren Abfall der Reißdehnungen.Unbekannt ist, -ob diese Wirkungen auch bei anderen Thermoplasten als PP auftreten-ob sie auch bei stabilisierten Systemen in relativ gleichem Umfange auftreten-und ob es sich lohnt, die beobachteten Effekte ggf. durch ge zielte Maschineneinstellungen auszunutzen.Auf jeden Fall sollten auf diesem Gebiet weitere Arbeiten durchge-führt werden.
    Notes: Specimens of unmodified polypropylene have been manufactured using extreme adjustings of injection moulding machines and extruders. After artificial weathering, distinct relations of ageing processes to thermal and mechanical production parameters were found, which are not influenced by different melting temperatures. It can be started in particular, that during injection moulding a larger shear stress (resulting in more distinct orientation) results in -a greater change in residual stresses-an earlier gloss reduction-a shorter initial period before cracking.During extrusion a lower cooling rate (resulting in a coarser structure) leads to -a greater change in residual stresses-an earlier and more distinct gloss reduction-an earlier loss of ultimate strain.It remains unknown, whether -these relationships will be similar with other thermoplastic materials than PP-these relationships appear to the same relative extend with stabilized systems-it may be advantageous, to use the observed effects by adjusting the injection moulding and extrusion machines in a special way.It seems to be significant to do more research work in this field.
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  • 25
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    Angewandte Makromolekulare Chemie 160 (1988), S. 1-15 
    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(tetramethylenadipat)diol mit einer Molmasse von 2000 wurde bei Temperaturen von 60 und 80°C in Gegenwart von Wasser bzw. 1,4-Butandiol sowie den gebräuchlichsten PUR-Katalysatoren (Dabco und Dibutylzinndilaurat) gelagert und die Solvolyse untersucht. Die Geschwindigkeit der Solvolyse nimmt mit steigender Temperatur deutlich zu. Die Alkoholyse wird durch Dibutylzinndilaurat weitaus stärker katalysiert als durch 1,4-Diazabicyclo[2.2.2]oktan. Die Hydrolyse verläuft langsamer, da vermutlich die Katalysatoren bei diesem Prozeß desaktiviert werden. Die mechanischen Eigenschaften von Polyurethanen, die mit den partiell abgebauten Diolen hergestellt wurden, korrelieren gut mit der Abnahme der Molmasse.
    Notes: Poly(tetramethylene adipate)diol having a molar mass of 2000 was stored at temperatures of 60 and 80°C in the presence of water or 1,4-butanediol and a common PUR-catalyst like 1,4-diazabicyclo [2.2.2]octane (DABCO) or dibutyltindilaurate (DBTL) and the solvolysis was investigated. The rate of solvolysis is low at 60°C except for DBTL and shows a drastic increase at 80°C. In the alcoholysis reaction DBTL is a much more active catalyst than DABCO. The rate of hydrolysis is slower probably because the catalysts are deactivated by the acidic products formed in this process. The mechanical properties of polyurethanes made from the degraded polyols are in good correlation with the decrease in molar mass.
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  • 26
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 17-28 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß der Zugabe von Bis(allylphenyl) Typ (TM 120)-Monomeren auf die Eigenschaften von unidirektional mit Carbonfasern verstärkten 4,4′-Bismaleimidodiphenylmethan (BM) - 2,4-Tolylendiamin (A) (1:0,3 Molverhältnis) (BM-A)-Verbundkörpern wird vorgestellt. Das Aushärteverhalten sowie das thermische Verhalten in Luft wurde mit Hilfe der Differentialkalorimetrie (DSC) und der Thermogravimetrie (TGA) untersucht. Die thermische Stabilität nimmt mit ansteigenden Konzentrationen von TM 120 deutlich zu. Demgegenüber steht ein Anstieg der Biegefesigkeit, der interlaminaren Scherfestigkeit sowie der Schlagzähigkeit mit zunehmender Monomerkonzentration. Optimale mechanische Eigenschaften wurden bei etwa 20 Tle./100 Tle. TM 120 erreicht.
    Notes: The paper deals with the effect of addition of bis(allylphenyl) type (TM 120) monomer on the properties of unidirectionally carbon fibre reinforced 4,4′ bismaleimidodi-phenyl methane (BM) - 2,4-tolylene diamine (A) (1:0.3 molar ratio) (BM-A) composites. The curing and thermal behaviour of the blends was investigated by using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) in air atmosphere. A marginal decrease in thermal stability was observed with increasing concentration of TM 120. Flexural, interlaminar, and impact strength of the laminates increased in the presence of this monomer. Optimum mechanical properties were observed at ∼ 20 phr of TM 120.
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  • 27
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In dieser Arbeit wurden Veränderungen des verschweisßten Rohr- und Fittingmaterials (isotaktisches Polypropylen Homo- bzw. Copolymer PP-R grau pigmentiert) wührend der für die Praxis relevanten Innendruckversuche untersucht.Bei der technischen Verschweißung von Polyolefinen entstehen charakteristische Gefüigezonen im Schweißnahtbereich, welche vom Fßgematerial und den Fngebedingungen beeinflußt werden. In der vorliegenden Untersuchung wurden sowohl die Materialcbergange im Fiigebereich (mit den Methoden - schichtenweise Differentialkalorimetrie, Polarisations- bzw. Elektronenmikroskopie sowie Fluoreszenzspektroskopie mit extrem hoher Ortsauflösung) als auch die Eigenspannungen hinsichtlich ihrer Verlnderung bei Langzeitpriifung im Innendruckzeitstandversuch bei 95°C bis zu einer Prüfzeit von 18.100h untersucht.Die Abbauvorgänge der Makromoleküle bei der Langzeitprüfung der 364 untersuchten Schweißmuster werden in einer gesonderten Arbeit behandelt (1).Durch die Innendruckversuche bei 950 C findet eine Nachkristallisation und eine Gefügevergrijberung sowohl in der Schweißnaht als auch im Gefüge der Schweißpartner statt. Dabei werden die beim Schweißvorgang eingebrachten Orientierungen und Eigenspannungen unter dem Einfluß von Wärme beim Innendruckversuch weitgehend abgebaut. Durch die unter Druckeinwirkung einsetzenden Flieävorgange jedoch werden neue Eigenspannungen eingebracht.Es konnte gezeigt werden, daß bei guter Verschweißung von PP mit PPCO ein kontinuierlicher Übergang (Mischungsbereich) vom Homopolymeren zum Copolymeren auftritt, der auch beim Langzeiteinsatz im Innendruckversuch erhalten bleibt.
    Notes: The present study deals with changes of welded material of pipes and fittings (isotactic polypropylene homo and copolymer PP-R grey pigmented) during the standardized internal pressure tests, which are commonly used for these products.Technical welding of polyolefines causes characteristic structures, which depend on the natural of the welded material and the welding conditions.In this investigation both the transition of material in the welding seam and the changes of internal stresses during internal pressure tests at 95°C until 18.100h test time were examined. The methods we used were Differential calorimetry of think layers, Polarization- and Electron microscopy, Fluorescence spectroscopy with extreme high local resolution.The effects of decomposition of the macromolecules in the welded samples during the internal pressure tests will be described in a separate paper (1).The internal pressure tests at 95O C cause a recrystallization and an increase of the particle size in the structure of the welding seam and in the structure of the welded parts themselves. Under the above described testing conditions the orientations and internal stresses initiated by the welding procedure will relaxe influenced by heat. However the creep effects that occur in the material when exposed to pressure introduce new internal stresses. It could be shown that in perfectly welded parts a continuous transition from PP to PPCO occurs, which did not change after long time application of internal pressure tests.
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  • 28
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    Angewandte Makromolekulare Chemie 160 (1988), S. 67-81 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurden neue Coordinationspolymere mit Schiffschen Basen aus Terephthalal dehyd und S-Benzyldithiocarbazol als Liganden in DMF-Lösung hergestellt. Die erhaltenen Coordinationspolymeren wurden durch Elementaranalyse, magnetische Suszeptibilität, elektronische und IR-Spektroskopie charakterisiert. Die durch Thermogravimetrie bestimmte thermische Stabilität der Coordinationspolymeren nahm in der folgenden Reihenfolge ab: \documentclass{article}\pagestyle{empty}\begin{document}${\rm Zn} \simeq {\rm Fe} 〉 {\rm Co} 〉 {\rm Ni} 〉 {\rm Min} \simeq {\rm Cu}$\end{document} Mn(II)-, Fe(II)-, Co(II)- und Ni(II)-Coordinationspolymere haben eine Oktaederstruktur mit der Koordinationszahl6, während bei den Cu(II)- und Zn(II)-Coordinationspolymeren eine 4-fach koordinierte quadratisch-planare bzw. eine tetraedrische Struktur gefunden wurde. Ligandenfeld- und nephelawetische Parameter wurden aus den Spektren errechnet. Dam wurde die Ligandenfeldtheorie spin-erlaubter Übergänge angewandt, die sich als konsistent mit einer 6-fach koordinierten Struktur für Mn(II)-, Fe(II)-, Co(II)- und Ni(II)-Coordinationspolymere erwies. Die Elementaranalysen ergaben bei allen Coordinationspolymeren ein Ligand: Metall-Verhältnis von 1 : 1 und deuteten bei den Mn(II)-, Fe(II)-, Co(II)- und Ni(II)-Coordinationspolymeren auf am Zentralatom assoziierte Wassermoleküle hin.
    Notes: New Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) coordination polymers of Schiff base ligand derived from terephthalaldehyde and S-benzyldithiocarbazate have been synthesized in DMF media. The coordination polymers have been characterized by their elemental analysis, magnetic susceptibility, and by electronic and infrared spectral measurements.The thermal stability of each polymer was found out by thermogravimetric analysis. The thermal stability of coordination polymers obtained from thermograms has the following order: \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm Zn} \simeq {\rm Fe} 〉 {\rm Co} 〉 {\rm Ni} 〉 {\rm Min} \simeq {\rm Cu}$\end{document} Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers are of a six-coordinated octahedral structure while Cu(II) and Zn(II) coordination polymers are found to be four-coordinated square planar and tetrahedral structure, respectively. The ligand-field and nephelauxetic parameters have been determined from the spectra, using ligand-field theory of spin-allowed transitions which are found consistent with six-coordinate structure for Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers. Elemental analyses indicates a ligand: metal ratio of 1 : 1 in all the coordination polymers and the association of water molecules with central metal atom in case of Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers.
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  • 29
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    Angewandte Makromolekulare Chemie 160 (1988), S. 91-106 
    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: Emulsionen von aromatischen Polyamidsären (PMPE and PBPPM) in DMF und Methanol wurden benutzt, um gleichmäßige Filme auf Leiteroberflächen durch Elektrophorese abzuscheiden. Die Ausbeute und Qualität der abgeschiedenen Filme hängen von der Art der Polyamidsäre, dem Lösemittel, dem Fällungsmittel, dem oberflächenaktiven Mittel, dem pH-Wert und dem Polymergehalt ab. Die Bedingungen zum Erreichen der höchsten Abscheidungsausbeuten wurden bestimmt.
    Notes: The emulsions of aromatic polyamic acids (PMPE and PBPPM) in DMF and methanol were used to coat uniform films on conductor surfaces by electrodeposition. The deposition yield and quality of the deposited films are dependent on sort of polyamic acid, solvent (DMF), precipitant (MeOH), surfactant (TEA), pH value and solid content. To get maximum deposition yields from PMPE and PBPPM, the best conditions of electrodeposition were required as follows: pH value 5.7 and 5.58, MeOH/DMF weight ratio 3.0 and 2.8, solid content 3.5 and 2.4 wt.-%. Deposition yield was found to obey Faraday's law of electrolysis, and the higher the equivalent weight of the polyamic acid, the higher the coulombic yield.
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  • 30
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    Angewandte Makromolekulare Chemie 160 (1988), S. 107-115 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Ein einfaches Modell von Doppelassoziaten wurde verwendet, um die Doppelschichtsorption von binären Gasgemischen an flexiblen linearen Polymerketten zu beschreiben. Die Isothermengleichung nach diesem Modell ist ein einfaches Produkt der isothermen Gleichung, die die Doppelschichtadsorption von binären Gasgemischen an einer homogenen festen Oberfläche beschreibt und einer Funktion, die die spezifischen Merkmale der Sorption an Polymeren widerspiegelt.
    Notes: A simple model of double associates is used to represent bilayer sorption of binary gas mixtures on a flexible linear chain of a polymer. The isotherm equation derived in terms of this model is a simple product of the isotherm equation describing bilayer adsorption of binary gas mixtures on a homogeneous solid surface and a function reflecting specific features of sorption on polymers.
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  • 31
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    Angewandte Makromolekulare Chemie 160 (1988), S. 131-140 
    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 a polymer system sulfur-styrene containing 10 wt.-% styrene the morphologie depending on the polymerization temperature and time is described. Besides the characteristical orthorhombic phase a monoclinic and a pseudoorthorhombic phase were detected. Moreover amorphous material exists, depending on the polymerisation parameters.
    Notes: Für ein Polymersystem Schwefel-Styrol mit 10% Styrol wird die Abhängigkeit der Morphologie von der Polymerisationstemperatur und -zeit beschrieben. Neben der charakteristischen orthorhombischen Phase wurden röntgenographisch eine monokline und eine pseudoorthorhombische Phase nachgewiesen. Außerdem liegt, abhängig von den Polymerisationsparametern, ein amorpher Anteil vor.
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  • 32
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    Angewandte Makromolekulare Chemie 160 (1988), S. 117-129 
    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: Für eine anionische Polymerisation mit langsamer Start- und schneller Wachstumsreaktion wurde ein analytischer Ausdruck entwickelt, der es erlaubt, mittlere Molekulargewichte und Molekulargewichtsverteilungen von Polymeren vorauszuberechnen, die in einem halbkontinuierlichen Polymerisationsverfahren bei Zulauf einer verunreinigten Monomerlösung zu einer vorgelegten Initiatolösung entstehen. Die Gültig keit des Modells wurde an der Polymerisation von Isopren mit n-Butyllithium in n-Heptan überprüft. Die beobachteten Unterschiede zwischen theoretischen und experimentellen Werten werden auf die Änderungen in den Geschwindigkeitskonstanten von Start- und Wachstumsreaktion zurückgeführt, die dadurch hervorgerufen werden, daß sich die Polarität der Lösung durch die Anreicherung mit polaren Verbindungen ändert. Weiterhin wird gezeigt, daß bimodale Molekulargewichtsverteilungen entstehen, wenn sich an die halbkontinuierliche Verfahrensweise eine diskontinuierliche zur Erhöhung des Monomerumsatzes anschließt.
    Notes: For anionic polymerization with slow initiation and rapid propagation step analytical expressions are presented to calculate average molecular weights and molecular weight distributions for a semi-batch process, in which a monomer solution contaminated by impurities is fed to an initiator solution in the reactor. The validity of the model was checked for the case of the polymerization of isoprene by n-butyllithium in n-heptane. The differences observed between theoretical and experimental values are explained by the changes in the rate constants of the initiation and the propagation step caused by the change in the polarity of the reaction solution by the continuously fed impurities. Furthermore it is shown that polymers with bimodal molecular weight distributions are formed if the semi-batch procedure is followed by a batch one to increase the monomer conversion.
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  • 33
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    Angewandte Makromolekulare Chemie 160 (1988), S. 141-154 
    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: Der Wärmehärtungsmechanismus von zu Anstrichen verwendeten Polyethersulfonen wurde unter Verwendung von FTIR/PAS und ESCA untersucht. Als Ergebnis wurde bestätigt, daß der Luftsauerstoff Einfluß auf den Wärmehärtungsmechanismus hat. Das heißt, die Härtung des Polyethersulfonfilms beginnt an der Oberfläche und verläuft entsprechend Reaktion (4) weiter.
    Notes: Thermosetting mechanism of paint-use polyethersulfones was studied by utilizing FTIR/PAS and ESCA. As a result, it was confirmed that the oxygen in the air has an effect on the thermosetting mechanism. That is, the polyethersulfone film were baked from the surface, and proceeded according to reaction (4).
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  • 34
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    Angewandte Makromolekulare Chemie 160 (1988), S. 155-162 
    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 wurde der Mechanismus der Reaktion von 4-Ethylphenol mit Zimtaldehyd mittels HET 2DJ 13C-NMR Spektroskopie, 1H-NMR Spektroskopie und GPC untersucht. In der ersten Stufe findet die Addition des 4-Ethylphenols an die Carbonylgruppe und an die Doppelbindung des Zimtaldehyds statt. In der zweiten Stufe reagiert die —CH(OH)-Gruppe mit 4-Ethylphenol und bildet verzweigte Produkte in rötlich gefärbten Harzen mit einem Durchschnittsmolekulargewicht on 600. Die Reaktion verläuft bei Temperaturen über 100°C in stark saurem Medium.
    Notes: The mechanisms of the reaction between 4-ethylphenol and cinnamaldehyde were studied by means of HET 2DJ 13C-NMR spectroscopy, 1H-NMR spectroscopy and GPC. In the first step of the reaction the addition of 4-ethylphenol to carbonyl group and to double bond of cinnamaldehyde takes place. In the second step of the reaction the —CH(OH)-group reacts with 4-ethylphenol to form branched products of red coloured resins with an average molecular weight of 600. The reaction takes place at temperatures above 100°C in strong acid medium.
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  • 35
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    Angewandte Makromolekulare Chemie 160 (1988), S. 163-173 
    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 elektrischen und paramagnetischen Eigenschaften des durch eine direkte Methode aus Benzol und Schwefel synthetisierten Poly(phenylensulfid)s wurden untersucht. Die Geichstromdunkelleitfähigkeit dieses Polymeren im nativen Zustand ist 10-10 S/m. Sie nimmt während des Dotierens mit Jod um 8 Größenordnungen zu. Es wurde für undotierte Proben n-Typ- und für die mit Jod dotierten Proben p-Typ-Leitfähigketi beobachtet. Anhand der ESR-Messungen wurden die Zahl der paramagnetischen Zentren und der g-Faktor bestimmt, die entsprechend gleich 0.80 · 1017 Spins/g und 2.0037 für das undotierte Polymere bei Raumtemperatur betragen. Änderungen der Spinkonzentration sowohl für die mit Jod dotierten als auch für die im Temperaturbereich von 513 - 903 K getemperten Proben werden dargestellt. Es wird versucht, die Form der ESR-Linien auf eine quantitative Weise zu diskutieren.
    Notes: Electrical and paramagnetic properties of poly(phenylene sulphide) synthesized by a direct method from benzene and sulphur were investigated. In darkness dc conductivity of the polymer in its pristine state is of the order 10-10 S/m. Upon doping with iodine it increases by 8 orders of magnitude. For undoped samples the n-type conductivity and for those doped with iodine the p-type conductivity was observed. On the basis of ESR experiments the number of spins and g-value were determined, which for undoped polymer at room temperature are equal to 0.80 · 1017 spins/g and 2.0037, respectively. Next, the changes in spin concentration both for the iodine doped samples and these annealed within the temperature range 513 - 903 K were described. An attempt to discuss the ESR lineshape in a quantitative way was also made.
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  • 36
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    Angewandte Makromolekulare Chemie 160 (1988), S. 175-186 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 3-Carboxy-4-hydroxyacetophenon (CHAP) wurde in verschiedenen Mengenverhältnissen mit Formaldehyd unter Verwendung von Alkali als Katalysator polykondensiert. Die erhaltenen Polykondensate (CHAP-F) wurden durch Elementaranalyse, IR-Spektroskopie, Bestimmung des Zahlenmittels der Molmasse (M̄n), Thermogravimetrie und Bestimmung der Grenzviskosität charakterisiert. Es wurden polymere Metallchelate mit Cu2+ -, Fe3+ -, Co2+ -, Ni2+ - und UO2+2 -Ionen hergestellt und charakterisiert. Mit Hilfe der Batch-Austauschmethode wurden Ionenaustauschereigenschaften eines CHAP-F Harzes gegen Fe3+ - Cu2+ - und Ni2+ -Ionen bestimmt.
    Notes: 3-Carboxy-4-hydroxyacetophenone (CHAP) was polycondensed with various proportions of formaldehyde using alcoholic alkali as catalyst. The resin samples, designated as CHAP-F, have been characterized by elemental analyses and IR spectroscopy, by estimation of their number average molecular weights (M̄n), by measurement of intrinsic viscosity, and by TGA. Polymeric metal chelates of one CHAP-F sample with Cu2+, Fe3+, Co2+, Ni2+, and UO22+ ions have been prepared and characterized.Ion-exchanging properties of one CHAP-F resin sample for Fe3+, Cu2+, and Ni2+ metal ions are studied by the application of the batch-equilibration method.
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    Angewandte Makromolekulare Chemie 160 (1988), S. 187-192 
    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 Reaktionsenthalpien für die Addition von Hydroxidanion an substituierte Phenylisocyanate wurden mit MNDO berechnet. Die erhaltenen Werte stimmen sehr gut mit den Reaktionsgeschwindigkeiten der Addition von 2-Ethylhexanol an Phenylisocyanate überein. Dies ermöglicht eine Abschätzung der Reaktionsgeschwindigkeiten für nucleophile Additionen innerhalb vernünftiger Grenzen, ohne daß experimentelle Arbeiten durchgeführt werden müssen.
    Notes: The enthalpies for the addition of hydroxide anion to substituted phenylisocyanates have been calculated with MNDO. The results obtained correlate well with the rates of addition of 2-ethylhexanol to phenylisocyanates. This allows us to estimate the rates for nucleophilic addition within reasonable limits without the need for experiments.
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  • 38
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    Angewandte Makromolekulare Chemie 160 (1988), 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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  • 39
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    Angewandte Makromolekulare Chemie 163 (1988), S. 63-76 
    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 Copolymerisation von Butylacrylat (BA) mit Vinylbenzylglycidylether (VBGE) wurden neue Acrylkautschuke mit Epoxyseitengruppen hergestellt. Um die Zähigkeit eines gehärteten Epoxidharzes (Bisphenol A/Diglycidylether/p,p′-Diaminodiphenylsulfon) zu erhöhen, wurde dieses mit den erhaltenen Acrylkautschuken modifiziert. Eine Zugabe von 20 Gew.-% eines Copolymeren mit 74% BA und 26% VBGE-Einheiten führte zu einer 30proz. Zunahme der Bruchzähigkeit (KIC) des gehärteten Harzes bei einer minimalen Einbuße an Festigkeit und Steifigkeit. Die modifizierten Harze wiesen eine Zwei-Phasen-Morphologie auf, bei der Kautschukteilchen mit einer mittleren Größe von 2 μm in eine Epoxymatrix eingebettet sind. Das Copolymere ohne Epoxyseitengruppen, das aus BA und Vinylbenzylmethoxyethylether hergestellt wurde, war als Modifier unwirksam, was darauf hindeutet, daß die seitenstándigen Epoxidgruppen zu einer guten Zwischenphasenadhäsion zwischen Kautschukteilchen und Matrix, und damit zu erhöhter Zähigkeit führen. Kautschuke, die 55 oder 86% BA-Einheiten enthielten, waren ebenfalls ungenügende Modifier. Zugabe des ersteren ergab Harze mit einer homogenen Phasenstruktur, während die Zugabe des letzteren zu einer Phasentrennung zwischen Kautschuk und Epoxidharz führte.
    Notes: New acrylic rubbers with a pendant epoxy group were prepared by copolymerization of butyl acrylate (BA) with vinylbenzyl glycidyl ether (VBGE). The modification of an epoxy system (bisphenol-A diglycidyl ether/p,p′-diaminodiphenyl sulfone) with the acrylic rubbers was carried out in order to increase the toughness of the cured epoxy resin. The addition of 20 wt.-% of the copolymer containing 74% of BA and 26% of VBGE units resulted in a 30% increase in the fracture toughness (KIC) of the cured resin at minimal expenses of strength and modulus of the resin. The modified epoxy resin had two-phase morphology in which the rubber particles with average diameter of 2 μm are dispersed in the epoxy matrix. The copolymer without the pendant epoxy group, prepared from BA and vinylbenzyl methoxyethyl ether, was ineffective as a modifier, indicating that the reaction of the pendant epoxide with the epoxy matrix resulted in good interfacial adhesion between the rubber particles and the matrix, and in the increased toughness. The epoxide-containing copolymers with 55 or 86% of BA units were also insufficient modifiers. The addition of the former yielded cured resins with homogeneous structure, whereas that of the latter resulted in macroscopic phase separation between the rubber and the epoxy resin.
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  • 40
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    Angewandte Makromolekulare Chemie 163 (1988), S. 77-91 
    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: Lösungen von Polyether/Polyurethan-Kationomeren, die auf Toluoldiisocyanaten basieren, wurden hergestellt und durch Zugabe von Wasser emulgiert. Die Eigenschaften von aus diesen Lösungen und Emulsionen gegossenen Filmen werden mit Hilfe der Infrarot-Spektroskopie, dynamisch-mechanischer Messungen, der Differentialkalorimetrie, der Weitwinkel-Röntgendiffraktometrie und von Zug-Dehnungsmessungen untersucht. Der Einbau eines asymmetrischen, kettenverlängernden Bausteins, wie N-Methyldiethanolamin, führt zu einem Polyurethan (PU), das, ßhnlich wie das mit symmetrischem, kettenverlängerndem 1,4-Butandiol aufgebaute Polyurethan, eine meßbare Ordnung innerhalb der Hartsegmente aufweist. Nach der Quarternisierung mit Glykolsaure haben die PU-Kationomeren erhöhte Werte für Reißdehnung, Zugmodul und -festigkeit. Dies kann auf die Coulomb-Wechselwirkung zwischen benachbarten Hartsegmenten zurückgefiihrt werden. Das Emulgieren der PU-Ionomer-Lösung führt zu einer verstärkten Mischung der Weich-und Hartsegmente, wodurch die ursprünglichen Hartsegmentbereiche mit asymmetrischen 2,4-Urethanisomeren eine höhere Konzentration an 2,6-Isomeren enthalten. Die Hartsegmentbereiche erreichen dadurch höhere Ordnung. Diese erhähte Ordnung und Phasenmischung führt zu einer Verbesserung der mechanischen Eigenschaften. Die Veränderung der Leitfähigkeit und Viskosität wahrend dem Emulgieren zeigt, daß das Wasser zuerst auf der Oberfäche des Mikroionengitters der Hartsegmente adsorbiert wird und dann in die ungeordneten und geordneten Hartsegmentbereiche eindringt.
    Notes: Toluene diisocyanate based polyether polyurethane cationomer solutions are prepared and then emulsified by adding water. Properties of films cast from the solutions and emulsions are studied using infrared spectroscopy, dynamic mechanical analysis, differential scanning calorimetry, wide-angle X-ray diffraction, and tensileelongation testing. It is found that the use of the asymmetric chain extender, N-methyl-diethanolamine, also leads to a polyurethane (PU) with detectable order in the hard domains as in the PU with symmetric chain extender such as 1,4-butandiol. After quaternization with glycolic acid, the PU cationomers have increased elongation and tensile strength and modulus. These can be attributed to the proper Coulomb interaction between two neighboring hard segments. The emulsification of the PU ionomer solution results in an increased mixing between the soft segments and the hard segments with asymmetric 2,4-urethane isomers originally located in the hard domains, and therefore make the hard domains containing a higher concentration of symmetric 2,6-isomer. The hard domains then become more ordered. Such increased order and phase mixing leads to an increase of the three tensile properties. During the emulsification conductivity and viscosity variations show that water is firstly adsorbed on the surface of the hard segment microionic lattices and then enters into the disordered and ordered hard domains successively.
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  • 41
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have tested 21 different basis sets of synthetic DNA circular dichroism spectra and have slected one for use in spectral analyses of natural DNAs. This “standard” set consists of spectra of eight polymers: poly[d(A-A-T)·d(A-T-T)], poly[d(A-G-G)·d(C-C-T)], poly[d(A-T)·d(A-T)], poly[d(G-C)·d(G-C)], poly[d(A-G)·d(C-T)], poly[d(A-C)·d(G-T)], poly[d(A-T-C)·d(G-A-T)], and poly[d(A-G-C)·d(G-C-T)]. This basis set, applied according to the first-neighbor polymer procedure of Gray and Tinoco, allows a more uniformly accurate spectral analysis of six natural complex DNAs and eight (A+T)-rich satellite DNAs for base composition and first-neighbor frequencies than was previously possible. We find that spectra of poly[d(A)·d(T)] and/or poly[d(A-C-T-)·d(A-G-T)] are not generally required for good analysis results but we show in this and the following paper that these spectra are needed for the most accurate analyses of some satellite DNAs.
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  • 42
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of counterions with a suitably long, charged oligomer appears susceptible to treatment in the context of polyelectrolyte theory by the introduction of an end-effect parameter that reflects the reduced association of counterions with the terminal regions of the oligo-ion. Use of a physically reasonable value for the end-effect parameter provides excellent agreement between theory and the experimental data of Elson, Scheffler, and Baldwin [J. Mol. Biol. 54, 401-415 (1970)] on the dependences of melting temperature on salt concentration and chain length for a series of hairpin helices formed by d(TA) oligomers. The differences in behavior expected for hairpin, dimer, and oligomer-polymer helices are discussed. The salt dependence of the end-joining equilibrium investigated for λ DNA by Wang and Davidson [Cold Spring Harbor Symp. Quant. Biol. 33, 409-415 (1968)] is treated as an oligomer-polymer interconversion. The dependence of equilibrium constant for this reaction on counterion concentration is in good agreement with that predicted by theory for an end-region totalling 24 nucleotides, the known length of the λ ends.
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  • 43
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solvent denaturation is developed along thermodynamic lines rather than from multiple-binding theory. Almost all the relations derivable from site-binding theory have their counterparts in the thermodynamic formulation showing that the details of binding models may be sufficient but are not necessary for the general description of solvent denaturation. Equations are derived for the effect of denaturant concentration on stability at constant temperature and on tm. It is recommended that the thermodynamic treatment be used instead of binding models unless stoichiometric interactions are demonstrable experimentally.
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  • 44
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    Biopolymers 17 (1978), S. 1361-1372 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The optical properties of the 1,N6 - etheno derivative of ApA (εApεA) have been studied. Absorbance and CD measurements suggest that (1) neutral salts tend to unstack this molecule and (2) the stacking interaction is weaker than in ApA. εApεA is found to be quenched strongly with respect to the monomer. (εAMP); this quenching is solvent dependent (1M NaCl 〉 5M NaClo4〉40%glycerol) and increases with the ratio of temperature to viscosity (T/η) in each case. Fluorescence lifetime measurements also reveal a temperature- and solvent-dependent decay which is nonlinear on a semilog plot. In the presence of 95% glycerol, this decay return to linearity. These data have been considered from two points of view: (1) two-state pictures which are based on thermodynamic least-squares fit to quatum yield and CD curves, together with two exponential fits to the decay curves and (2) a dynamical model in which relatives fluorophore motion leads to deexcitation via intramolecular collision. A simple model of type (2) gives qualitative agreement with the observed behavior.
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  • 45
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    Biopolymers 17 (1978), S. 1385-1386 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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  • 46
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    Biopolymers 17 (1978) 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 47
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    Biopolymers 17 (1978), S. 1513-1521 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The native antibiotic polymyxin B, carrying five positive charges, displaces the monoacetylated on from its adsorbed state at the interface between negatively charged lipid layers ans water. A simulation model for asdorption, governed by electrostatic forces, is presented. The model adequently representes the competitive adsorption kinetics and equilibria.
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  • 48
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: In order to study the role of D-amino acid residues in keeping the stable β-sheet conformation and in the antimicrobial activity of gramicidin S (GS), the four analogs of GS containing D-Ala, L-Ala, Gly, and Aib (α-aminoisobutyric acid) in place of D-Phe were synthesized. D-Ala-and Gly-containing analogs showed antimicrobial activity, while those containing L-Ala and Aib showed no activity. Conformation of these analogs and their derivatives were studied by comparison of ORD and CD spectra and by slective methylation method. It is concluded that the biologically active analogs have β-sheet conformation while inactive analogs have a much different conformation from that of GS. This indicates that D-Ala-Pro and Gly-Pro sequences favor taking a β-bend form but L-Ala-Pro and Aib-Pro sequences do not because the presence of L-side methyl group on the α-carbon atom of LAla and Aib residues destabilizes the β-bend form. This would explain why the inactive analogs which take a different conformation from that of the active ones result in the loss of activity.
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  • 49
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    Biopolymers 17 (1978), S. 811-814 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Biopolymers 17 (1978), S. 843-855 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Earlier studies by the authors showed that the collagen fibrils in rat-tail tendon have a bi-modal distribution of fibril diameters from a time shortly after birth through to the onset of maturity at about 3-4 months. Present work has extended those observations for rats up to the age of 2 years. Histograms of the fibril diameter distributions for mature tail tendon and direct electron microscope observations show that the fibrils break down as the tendon ages. Further work on the constant diameter subfibrils of diameter 140 Å described previously, has confirmed that these are part of the elastic fibers present in tendon at all ages. It has been shown that there is relatively little variation in the collagen fibril diameter distribution as a function of the position of the specimen in the tail, and as the measured percentage of the area taken by the collagen fibrils present at any particular point. Estimation of the fibrillar collagen content of rat-tail tendon as a function of age indicates that it increases steadily from birth and reaches a maximum at the onset of maturity, beyond which the fibrillar collagen content appears to remain constant.
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    Biopolymers 17 (1978), S. 785-794 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have made quantitative estimates of some of the energetic factors to be considered in packaging of double-stranded DNA in virus particles. Numerical calculations were made using parameters appropriate for T4 bacteriophage. The unfavorable factors, and the Gibbs free energies per mole virus at 20°C associated with them, are bending, 1.5 × 103 kcal/mol; conformational restriction upon condensation, 5.1 × 102 kcal/mol; polyelectrolyte repulsion, 2.1 × 105kcal/mol; and melting or kinking, 6.9 × 103 kcal/mol. These must be counterbalanced in the assembled phage by noncovalent bonding interactions between protein subunits in the phage-head shell; by interactions between the DNA and polyvalent cations, especially putrescine and spermidine; nad perhaps by repulsive excluded volume and electrostatic interaction between the DNA and acidic polypeptides. Indeed, a rough estimate of the standard free energey of interaction between T4 DNA and the putrescine and spermidine contained in the head is --2.1 × 105 kcal/mol. In the absence of the other two sources of stabilization, each head protein subunit must contribute about 210 kcal/mol of binding energy.
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    Biopolymers 17 (1978), S. 815-815 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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  • 53
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    Biopolymers 17 (1978), S. 837-842 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A theoretical basis for thin-film dialysis involving binding between a ligand and nondialyzing species is presented. A general differential equation that applies to the case of equivalent, noninteracting sites is derived relating [A]F, [A]T, [P]T, and K. Numerical solutions to this equation are used to develop a series of escape curves corresponding to specific values of the parameters [P]T, [A]i, K, and k0. A general method for determining an equilibrium binding constant from thin-film dialysis data is given. A comparison of thin-film dialysis results predicted by this theory with literature data shows essential agreement.
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  • 54
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    Biopolymers 17 (1978), S. 887-896 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The normal and vacuum uv spectra of cytosine, 5-azacytosine, and 6-azacytosine thin layers were determined. The spectra were resolved into a series of Gaussian bands and the experimental band positions and oscillator strengths were compared with the calculated values. The calculations were carried out with the PPP-SCF-CI method. The agreement of the calculations with those of others and with the experiment is discussed.
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  • 55
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    Biopolymers 17 (1978), S. 2503-2518 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To obtain information on the solvent-solute interactions in the dinucleoside monophosphates pertaining to the dimeric subunits of RNA and DNA, we have computed the accessibility of a water molecule to the oxygen atoms of the subunits following the method of Lee and Richards [J. Mol. Biol. 55, 379-400 (1971)]. The solute molecules (dimeric unit) is represented by a set of interlocking spheres of appropriate van der Waals radii assigned to each atom, a solvent (water) molecule is rolled along the envelope of the van der Waals surface, and the total surface accessible to the solvent molecule - and hence the solvent accessibility of various atoms of the solute molecule for different conformations - are computed. From the calculated atomic accessibilities, solvation maps in the (ω′,ω) space have been constructed, keeping ψ at 60°, 180°, and -60°. The C(3′)-endo sugar system in the case of DNA subunit have been considered. The solvation maps describing the solvatability of single and groups of atoms give significant information on the backbone conformational domains that are preferred for solvent interaction, thus adding knowledge to the relative stability of the various possible conformations. The B-DNA-type conformer exposes three polar atoms - namely, PO1, O(3′), and O(1′) - to external solvent, whereas the A-DNA- and C-DNA-type conformers expose only one polar atom - O(3′) and O(1′), respectively - to the solvent. The O(2′) atom of the furanose ring system in the RNA subunit could give added stability via solvent association or interunit hydrogen bonding with or without a bridging water. The superposition solvation maps describing the accessibility of a group of polar atoms help to interpret a good number of phosphodiester conformations observed in a energetically less favored conformational domains in the tRNAPhe crystal. Another intresting fact that results from this study is the prediction that the trans oriented of ω is the most favorable conformations of random-coil polynucleotides in solution.
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  • 56
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The Conformational properties of synthetic S-peptide analogs, in which the residues in the N-terminal sequence 1-6 were progressively deleted or replaced with amino acids of lower helical propensity, were studied by CD. Increasing the concentration of guanidine hydrochloride and decreasing the temperature were found to produce progressive destruction of ordered conformations, in the parallel with the increasing solubility of the peptide unit, while increasing the concentration of trifluoroethanol and decreasing the temperature produced the opposite effect. The maximum helicity determined in the these sets of experiments is found equal to or greater than that determined in the formation of the ribonuclease S′ complexes. With some peptides the maximum value of predicted helical conformation is reached, and the tendency of tertiary structure to reduce the maximum possible helicity is evident. We discuss the validity of the procedure by which conformational information, drawn from measurements in helicogenic solvents, is related to the state in native protein.
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  • 57
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: A thermal perturbation curve (TPC) is defined to be the derivative of the fractional degree of saturation, f, with respect to temperature, considered as a function of the natural logarithm of free ligand concentration, y. The theoretical framework for the use of such curves in the thermodynamic analysis of ligand binding to macromolecules is presented. The thermal perturbation curve either provides or complements the information obtained from the derivative binding isotherm ∂f/∂y. For a single set of identical and independent sites the TPC is identical to the derivative binding isotherm. Analysis of such a curve directly yield ΔH0 and ΔG0 for the binding reaction. In actual experimental work, however, the TPC can only be approximated because of “self-buffering” effects relations between the parameter of the approximate curve and the thermodynamic quantities have been developed. This technique is applied to the proflavin-α-chymotryspin system to demonstrate its usefulness. The general features of thermal perturbation curves for cases of multiple sets of independent sites and cooperatively interacting sites have also been developed. The analysis of thermal perturbation curves in combination with other methods should provide a more powerful approach to the characterization of ligand-macromolecule interactions.
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  • 58
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    Biopolymers 17 (1978), S. 1837-1848 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformation of three sequential copolypeptides, poly(L-tyrosyl-L-lysine), poly(L-tyrosyl-L-lysyl-L-lysine), and poly[L-tyrosyl-(L-lysyl)2-L-lysine] have been studied by a variety of techniques, including CD, ir spectroscopy, analytical ultracentrifugation, and x-ray diffraction. Depending upon the pH and sovent composition, poly(L-tyrosyl-Llysyl-L-lysine) and poly [L-tyrosyl-(Llysyl)2-L-lysine] can adopt either the α-helical or random-coil conformation, while poly(L-tyrosyl-L-lysine) forms either inter- or intramolecular β-structures.
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  • 59
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    Biopolymers 17 (1978), S. 1913-1925 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular motion in solid poly(L-alanine), Poly(L-leucine), poly(L-valine), and polyglycine has been investigated through measurement of the portion spin-lattice relaxation time at 30 and 60 MHz between 110 and 350°K. Rapid random reoriention of sied-chain methyl groups provides the dominent source of relaxation in the first three; activation energies are 10.5 ± 1 1, 8.5 ± 1 kJ/mol, respectively, significantly lower than in the monomeric crystals. Relaxation times in poyglycine are two orders of magnitude longer than in the monomeric crystals. Relaxation times in polyglycine, significantly lower than in the monomeric crystals. Relaxation times in polyglycine are two orders of magnitude longer and are attributed mainly to segmental motions of the polymer chains. Evidence of nonexponential recovery of nuclear magnetization was encountered in the first three homopolyamino acids but not in polylycine, and was attributed to the correlated time to characterize these motions gave quite good agreement with the data; some improvement was obtained for two polymers using a Cole-Davidson distribution of correlation times. For biopolymers using a Cole-Davidson distribution of correlation times. For biopolymers generally it is concluded that rapid methyl group reorientation is a common dynamical feature and an important source of nuclear magnetic relaxation.
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  • 60
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    Biopolymers 17 (1978), S. 1957-1972 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The karl Fischer reagent method has been used to study the drying of whale skeletal muscle myoglobin. Drying curves for metmyglobin were obtained by mechanical pumping (moderate vacuum) and diffusion pumping (high vacum) at 20, 10, 0, -10, and -20°C. Strongly held water is present in about the same amounts as were previously observed with lysozyme. Nearly all of this strongly held water is still present during the drying of acid denatured metmyoglobin. This suggest that a core structure containing strongly held water is still present at pH 4.0. Comparison of the drying of metmyoglobin, deoxymyoglobin, and oxymyoglobin indicates that the iron-coordinated water of methyoglobin is the second most strongly held water of the molocule.
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  • 61
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    Biopolymers 17 (1978), S. 2033-2037 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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  • 62
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    Biopolymers 17 (1978), S. 2015-2028 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mixtures of bacteriophage T4D particles with up to six tail fibres attached were seprated and analyzed in a quasielastic light scattering-band electrophoresis apparatus. The electrophoretic mobilities and diffusion coefficients of the seprated bands were determined during the same experiment. Species differing in mobility by 0.05 × 10-4 cm2/V sec were resolved. Henry's electropheresis theory for spheres indicates that each tail fiber contributes about 140 effective positive charges to the phage structure. Estimate of the charge using the permanent dipole moment and the electrophorectic mobility (Bontje et. al. (1977) Biopolymers 16, 551-572) gives an effective charge of + 230 to -250 per tail fiber. The charge distribution on the fiberless particles was estimated to be -3380 on the head and -290 on the tail if the dipole moment was assumed positive and -1400 on the head and -1000 on the tail for a negative dipole. Tail-fiber attachement does not proceed to completion in our invitro system, as substantial distributions as a function of tail-fiber input indicates the reaction is a random, noncooperative process.
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  • 63
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    Topics: Chemistry and Pharmacology
    Notes: The contribution of the 1-6 N-terminal sequence to the conformational properties of the S-peptide (the 1-20 sequence of ribonuclease A) was assessed by determining in the ribonuclease S′ system the helical content and the binding capability of synthetic [Orn10]-S-peptide analogs, in which lysine1, glutamic2 and threonine3 were progressively deleted, alanine4 and alanine5were alternatively replaced by serine, and alanine6 was substituted by serine or proline. Both the deletion of the three N-terminal residues and the alanine6/proline replacement produces the loss of the helical structure up to lysine7. No or minor effects are found in all other cases. From the comparison of the binding data, the energy for the conformational stabilization of the N-terminal region was calculated to amount to 1.4 kcal/mol. The results are discussed in comparison with the known x-ray data of the enzyme, with some predictive rules of secondary structure which were applied to this region and with the known phylogenetic variance of the residues in this region.
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  • 64
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    Notes: In the Polymerization of phenylalanine N-carboxyanhydride (NCA) in No2Oh initiated by MeNHBzl, L-,D-, and DL-NCA As were polymerized at the same rate, and no stereoselectivity was observed. When the same experiment was carried out in HCONEt2, however, L- and D-NCA were both polymerized at a rate which was about twice as large as that of DL-NCA. In this case, the polymerization is stereoselective, ascribable to a preferable reaction between the optical enantiomorphs of the terminal residue of the growing chain and the NCA of the same chirality. On the other hand, the polymerization initiated by SarNMe2 and MeNH(CH2)2CONMe2 were stereoselective in NO2Ph and HCONEt2, but they were not stereoselective in m-(MeO)2Ph. These findings indicate that the polymerizations initiated by a strong base in highly dipolar solvents are stereoselective. Apparently, the reaction between a chiral, cyclic terminal of growing chain and a chiral, cyclic activated NCA in the activated-NCA mechanism is highly stereoselective. In addition, from a kinetic investigation on on the copolymerization between L- and D-NCAs, the penultimate chiral centers were also suggested to contribute to the stereoselection. Stereoselection by the α-helical conformation of the growing chain and by a chiral, linear terminal amine have been considered so far, and the contribution from the present type of stereoselection must have been overlooked.
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    Biopolymers 17 (1978), S. 2689-2702 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transient electric birefringence measurements of the bacteriophages T2L0 and T6 were performed under such conditions that the tail fibers are extended. The data obtained are compared to previously reported data for T4B. For all T-even phages the degree of extension of the tail fibers is a function of pH, ionic strength, and temperature. For T4B, much higher ionic strengths are needed than for T2L0 and T6 to accomplish complete tail-fiber extension. The rotational diffusion coefficients of the phages with fully extended fibers are equal to 120 ± 3 sec-1, 132 ± 5 sec-1, 157 ± 4 sec-1 for T2L0, T4B, and T6, respectively. The respective optical anistropies are - (2.66 ± 0.05) × 10-4, and - (3.07 ± 0.15) × 10-4. The differences in the rotational diffusion coefficient and optical anisotropy arise because the conformation of the fully extended tail fibers is different for the three phages. The tail fibers of T2L0 project further into the solution (away from the head) than do those of T4B and T6. The apparent permanent dipole moments of T2L0 and T6 decrease with increasing ionic strength. This decrease is caused by the screening of the surface charges on the phage body by the counter-ions in the solution. The biological relevance of this decrease is illustrated by the fact that the adsorption rate of T6 phages to E. coli B bacteria shows a similar dependence of ionic strength. Evidence is pressented that the tail fibers may move more or less independently of the phage body when an electric field is applied to the suspension.
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  • 66
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    Topics: Chemistry and Pharmacology
    Notes: The DNA-ligand interactions of a series of phenanthridinium compounds with various combinations of amino, azido, and hydrogen functions at R3 and R8 were examined to determine the contribution of these particular substituents to ligand binding. Spectrophometric titrations using calf-thymus DNA emphasized the importance of amino substituents in conferring a strong interaction and also stabilizing the interaction against reversal by high ionic strength. Although azido groups were not as effective as amino groups, they were more effective than hydrogen functions in enhancing the interaction. Furthermore, an amino substitution at R8 was consistently, though only slightly, more effective than an amino substituent at R3. The results from superhelical titrations using plasmid pBR322 DNA demonstrated that analogs with amino and/or azido functions at both R3 and R8 produced the greatest unwinding, and compounds with an amino or an azido function at R8 proved more effective than those with the corresponding amino or azido substituent at R3.
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  • 67
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    Topics: Chemistry and Pharmacology
    Notes: The magnetic shielding constant of the 31P nucleus of the dimethylphosphate anion is calculated by an ab initio method for different values of the torsion angles about the PO ester bond and different orientations of the methyl groups. The results obtained tend to show that both types of conformational parameters contribute to the value of σ31P. The largest shielding is obtained when the methyl groups are staggered with respect to the PO bond; the smallest, for the eclipsed arrangement. Measurements carried out on the 16 deoxyribodinucleoside monophosphates show that in the majority of cases σ31P is shifted toward lower field for the dimers having large values of 3JPH3′ and 3JPH5′(5″). The theoretical results are discussed in relation to experimental data for polynucleotides and nucleic acids.
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    Biopolymers 23 (1984), S. 471-491 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The optical modes of DNA that displace one strand against the other are modeled by the motion of an oscillator in an asymmetric quartic double-well potential whose minima represent the A- and B-conformations. Assuming that the variation of the polarizability during vibration derives mainly from the tilting of the base rings relative to the helix axis, the total polarizability tensor is shown to possess approximately ellipsoidal symmetry and to depend nonlinearly on the instantaneous displacement of the two strands. The Raman spectrum of a collection of randomly oriented molecules is calculated. It consists of one or more peaks with characteristic shape. The depolarization ratio is 3/4, independent of molecular conformation and frequency. The results are discussed in the light of existing experimental and theoretical information.
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    Biopolymers 23 (1984), S. 511-536 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the semiempirical potential functions, conformational energies of the model compounds DMP-, d(pCp), d(pGp), and d(pCpGpCp) are calculated, and the B → Z transition is discussed along the pseudorotational path of the sugar ring. For dimethylmonophosphate anion, DMP-, the energy contour map is presented and the stabilities of the phosphodiester conformations discussed. For the sugar ring without the base attached, the minimum energies for each sugar-puckering form are calculated along the pseudorotational path. The energy barrier of the interconversion between the C(3′)-endo form and the C(2′)-endo form is calculated to be about 2.0 kcal/mol. From the conformational energy calculations of the interconversions of mononucleoside diphosphates, d(pCp) and d(pGp), between the C(2′)-endo conformer and the C(3′)-endo conformer, the purine sugar segment is known to be more convertible than the pyrimidine sugar segment. The results also support the finding that the pseudorotational transition occurred with the O(1′)-endo form more easily than with the O(1′)-exo form. Based on the results of conformational studies of DMP-, d(pCp), and d(pGp), a topological transition of the handedness of the model compound, d(pCpGpCp), is studied. The left-handed Z-form is found to be less stable by about 8.5 kcal/mol than is the right-handed B-form. The energy barrier of the Z → B transition is calculated to be about 17.4 kcal/mol. The contributions of the electrostatic and nonbonded energies to the energy barrier are discussed in connection with the conformation changes of the model compound, d(pCpGpCp).
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    Biopolymers 23 (1984), S. 593-599 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dielectric properties of aqueous solutions of DNA were measured at frequencies ranging from 0.1 to 12 GHz. The results are analyzed using the Maxwell mixture theory and yield a value for the hydration of the DNA of about 0.4 g/g, which is in the range observed in other investigations. No evidence was found for an additional absorption effect at microwave frequencies, which has been predicted to occur in certain DNA analogs due to the vibrational excitation of the double helix by the applied microwave field.
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  • 71
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    Topics: Chemistry and Pharmacology
    Notes: Self-association of substance P and its C-terminal partial peptide sequences was studied by CD, quasi-electric light scattering, and sedimentation experiments. CD spectra of these peptides are strongly influenced by self-association. They exhibit strong characteristic negative ellipticities, suggesting the formation of a presumably B-type ordered structure. The tendency to form multimers depends on chain length and constitution and has its maximum at the octapeptide (SP 8). The peptide multimers have a broad distribution of sizes in the range of 30- and 800-nm diameter. Subdivision of this distribution into two size classes gives mean diameters of 60-100 nm (predominating)/200-800 nm for substance P and 30-50 nm/200-800 nm for SP 8 multimers.
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    Biopolymers 23 (1984), S. 819-829 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C-nmr chemical shifts of backbone carbonyl and side-chain β-carbons in polypeptides provide structural information. Recent utilization of substituent effects on 13C-nmr chemical shifts (principally γ-effects) has permitted the rationalization of their sequence and conformation dependence when observed in linear, flexible polypeptides. In this report, we apply the γ-effect method to study the 13C-nmr chemical shifts observed in solution and in the solid state for the backbone carbonyl and side-chain β-carbons in conformationally rigid polypeptides, which are usually cyclic. As found previously for flexible, linear polypetides, the relative 13C-nmr chemical shifts observed for the backbone carbonyl and side-chain β-carbons in conformationally rigid polypeptides are predictable from knowledge of their peptide residue sequence (primary structure) and conformation (secondary structure) via the γ-effect method.
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    Biopolymers 23 (1984), S. 847-852 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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  • 74
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    Topics: Chemistry and Pharmacology
    Notes: The CD spectra of the peptides Boc-X-(Aib-X)n-OMe (n = 1, 2, 3) and Boc-(Aib-X)5-OMe, where X = L-Ala or L-Val have been examined in several solvents. The X = Ala and Val peptides behave similarly in all solvents, suggesting that the Aib residues dominate the folding preferences of these peptides. The decapeptides adopt helical conformations in methanol and trifluoroethanol, with characteristic negative CD bands at 222 and 205 nm. In the heptapeptides, similar spectra with reduced intensities are observed. Comparison with nmr studies suggest that estimates of helical content in oligopeptides by CD methods may lead to erroneous conclusions. The pentapeptides yield solvent-dependent spectra indicative of conformational perturbations. Peptide association in dioxane results in an unusual spectrum with a single negative band at 210 nm for the decapeptides. Disaggregation is induced by the addition of methanol or water to dioxane solutions. Aggregation of the heptapeptides is less pronounced in dioxane, suggesting that a critical helix length may be necessary to promote association stabilized by helix dipole-dipole interactions.
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    Biopolymers 23 (1984), S. 831-841 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of poly-5-bromouridylic acid [poly(BU)] with adenosine and 9-methyladenine was studied by equilibrium dialysis, optical melting, and microcalorimetry. The stacking free energy, ω, was estimated as -17.6 kJ/mol for adenosine·2poly(BU) and -18.8 kJ/mol for 9-methyladenine·2poly(BU) from the binding isotherms constructed from equilibrium dialysis results. The binding isotherms constructed from a series of melting curves also gave ω values for adenosine·2poly(BU). The thermal stability of the complex depends on monomer concentration, and the partial molar enthalpies of the complex formation at the midpoint of the transition were evaluated from the Tm coefficients as a function of free monomer concentration. The values of -92.0 and -90.4 kJ/mol were obtained for adenosine·2poly(BU) and 9-methyladenine·2poly(BU) in 0.4M NaCl-0.02M Na-cacodylate-5 × 10-4M EDTA (pH 7.0), respectively. Microcalorimetric measurements provided lower integral heats of reaction values for these complexes, i.e., -73.2 kJ/mol for adenosine·2poly(BU) and -71.5 kJ/mol for 9-methyladenine·2poly(BU). A comparison with a polyribouridylic acid system provided a quantitative understanding of a stabilization by bromination in terms of thermodynamic parameters.
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    Biopolymers 23 (1984) 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 23 (1984), S. 191-194 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 23 (1984), S. 257-270 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A molecular-dynamics simulation was used to carry out an introductory study of the hydration of a section of a rigid single A- or B-DNA helix with one Na+ counterion per nucleotide. Four Na+ ions and four nucleotides and periodic boundary conditions were used to mimic an infinite helix. The atoms of the helix and the Na+ ions were assumed to be Lennard-Jones spheres that also carried charges. Stillinger four-point charge model water molecules were used. We carried out five calculations, for 26 and 46 water molecules in B-DNA and 20, 32, and 46 in A-DNA fragments. The arrangements of the Na+ ions are found to have some similarities to those obtained by Clementi and Corongiu. In the calculations with 46 water molecules, we found that two Na+ ions can be bridged by about two water molecules and form a hydrated bound pair, which in turn forms a bridge between the guanine N7 and a near phosphate group. These bound pairs may be important in stabilizing the helix structure of DNA molecules.
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    Biopolymers 23 (1984), S. 313-323 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ethylurea was used to weaken hydrophobic interactions during collagen fibrillogenesis in vitro. Intact and enzyme-digested type I collagen was studied. In all preparations, ethylurea decreased the extent and rate of fibril formation, inhibition being greatest in the enzyme-digested collagens. With intact collagen (and probably also with carboxypeptidasedigested collagen), there was no evidence the ethylurea altered the mechanism of fibril growth; in pepsin-digested collagen, however, the growth mechanism was altered by ethylurea, possibly reflecting a conformational change of the “hydrophobic cluster” in the C-terminal peptide. Such a structural change could occur in a hydrophobic environment once the distal portion of the C-terminal peptide (presumed to be essential for its structural stability) is removed by pepsin. The results further emphasize the importance of hydrophobic interactions in collagen fibril nucleation and growth in vitro.
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  • 80
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    Biopolymers 23 (1984) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 81
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report the crystal-structure analysis of a complex involving the drug proflavine and the two dinucleoside monophosphates cytidylyl-3′,5′-adenosine (CpA) and uridylyl-3′,5′-guanosine (UpG). The planar drug molecule is intercalated between C⃛G and U⃛A Watson-Crick base pairs, in a double-helical fragmentlike arrangement. Sugar conformations at the 3′-ends of the two strands are dissimilar. The backbone conformations fall within the ranges of values noted previously for dinucleoside intercalation complexes, and some correlations involving these are noted. The separation of the two strands and the basic twist angle of 16°, compared to other reported complexes, are indicative of sequence-dependent effects of the drug binding.
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  • 82
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    Biopolymers 23 (1984), S. 1057-1066 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Helical hydrophobic moment ratios, 〈h2〉/〈H2〉, have been evaluated for 34 polypeptides under conditions where the helix content is dictated solely by the short-range interactions operative in aqueous media. The mean-square helical hydrophobic moment is denoted by 〈h2〉, and 〈H2〉 is the averaged of the squared hydrophobicites. This ratio would be one in absence of any correlation in the hydrophobicities of amino acid residues in helices. The 〈h2〉/〈H2〉 tend to be substantially larger than values of the analogous ratio formulated for the mean-square dipole moments of typical synthetic polymers. For 24 of the 34 polypeptide chains considered, 〈h2〉/〈H2〉 is found to be greater than one, indicating a tendency to form helices with amphiphilic character. The ratio is exceptionally large in the case of the δ-hemolysins. It is also large for two other surface-active peptides, for two of the four apolipoproteins examined, and for myohemerythrin. A much smaller 〈h2〉/〈H2〉 is found for melittins. If melittins is to form helices with large 〈h2〉/〈H2〉, the configurational statistics must be governed by effects in addition to those short-range interactions that occur when water is the solvent.
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  • 83
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    Biopolymers 23 (1984) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 84
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformational-energy computations have been carried out for the N-acetyl-N′-methylamides of the Pro-Pro, Pro-Gly, and Gly-Pro dipeptides and of the Pro-Pro-Gly-Pro tetrapeptide, serving as models for the conformational analysis of single-stranded poly(Gly-Pro-Pro). The probability of β-bend formation for the Pro-Gly sequence is very high, viz., 0.72 for the terminally blocked Pro-Gly dipeptide, and rises to 0.86 in the tetrapeptide. The β-bend conformations of the Pro-Gly sequence are of low energy in single-chain poly(Gly-Pro-Pro) as well. The β-bend structure had been postulated earlier to be a requirement for post-translational proline hydroxylation during the biosynthesis of collagen. The present results lend strong support to this proposal by demonstrating that the β-bend structure is energetically favorable and hence can be accommodated easily in single-stranded poly(Gly-Pro-Pro).
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  • 85
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of Cu(II) with the protamine scylliorhinine Z3 was studied by means of CD measurements. At a 1:1 molar ratio, three complexes are formed. (1) In the pH range 5-6.5, the results suggest the formation of a five-membered chelate ring through the coordination of two nitrogen atoms, the N-terminal and the contiguous peptide nitrogen. (2) At pH ≥ 6.4, there is involvement of the lateral NH2 group of Arg; at pH 6.5-8, the formation of a 3N cupric complex is strongly suggested. (3) At pH ≥ 8, results indicate the formation of a 4N complex as a major species in Cu(II)-Z3 solution. The transformation from a 2N to a 3N complex, and from a 3N to a 4N complex was followed with the help of the σ(αNH2) → Cu(II) charge-transfer dichroic band transitions. At Cu(II):Z3 molar ratios ≥ 2 and at pH 〉 8, a new dichroic band appears, indicating the involvement of the tyrosine residue side chain in metal-ion complexation.
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  • 86
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies of the optical birefringence of solutions of acid-soluble collagen from rat-tail tendon at 22°C in the pH range 1.0-6.0 show that collagen exhibits an isotropic to mesophase transition only between pH 2.4 and 3.0 at 10% weight concentration. Such liquid crystalline order is probably essential for the orientation of collagen in a magnetic field. When solutions of neutral salt-soluble collagen were precipitated at pH 7.0 by warming to 37°C (“heat gelling”) in a magnetic field of ca. 20 kG, the resulting fibrils wee oriented perpendicular to the direction of the field. Heat gelling is shown to be a useful technique for maintaining the orientation induced in precursor solutions even after the sample is removed from the magnetic field.
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  • 87
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    Biopolymers 23 (1984), S. 1295-1306 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyamines are ubiquitous cellular components that interacts strongly with nucleic acids. Although many of the interactions of oligocations with DNA can be rationalized with polyelectrolyte theories that treat counterions as point charges, some structural effects are evident. We have explored the effects of polyamine structure on one important aspect of DNA behavior, its thermal melting transition, by using a series of spermidine analogs NH3(CH2)3NH2(CH2)nNH33+, where n varies from 2 to 8 [Jorstad et al. (1980) J. Bacteriol. 141, 456-463]. For spermidine itself, n = 4. Tm for calf-thymus DNA in the presence of each of these analogs, and the other naturally occurring polyamines putrescine2+ and spermine4+, was measured over a wide range of NaCl concentrations and polyamine:DNA phosphate ratios. There are modest, but significant structural effects. particularly with the shorter n = 2 and 3 derivatives, whose geometry my not allow full electrostatic interaction with DNA. Longer analogs, on the other hand, are not much different than spermidine in their effects on Tm, though a moderate maximum occurs at n = 5. Since polyamines are important in the cellular condensation and packaging of DNA, we have also delineated the critical polyamine and salt concentrations that are required to cause DNA aggregation. Here again, there are significant structural effects, which are not easily rationalized by any simple considerations.
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  • 88
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    Biopolymers 23 (1984), S. 1315-1323 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The observed difference between the CD spectrum of B-DNA mononucleosomes and that of free DNA has been attributed to the tertiary structure of the core DNA. This conjecture is tested here. The tertiary structure is modeled as an optical system consisting of two identical, planar, linear retarders rotated with respect to each other. The retarders have the same linear birefringence and linear dichroism as oriented B-DNA. Such an optical system is circularly dichroic. The predicted wavelength dependence and magnitude of the CD are in reasonably close agreement with the experimental results.
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  • 89
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    Biopolymers 23 (1984), S. 1367-1377 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absorption and CD spectra of the complexes of poly(L-arginine) (PLA) and azo dyes have been measured in aqueous solution. On complexation, Blue-shifted additional absorption bands were observed. In the wide pH 4-11 range, induced CD was observed at the visible wavelengths corresponding to the blue-shifted absorption bands. The induced CD arose from the dimeric dye molecules bound to PLA in the α-helical structure. When a modified analysis of induced CE is made by the excition chirality method, the origin of the induced CD can be assigned to the dipole coupling. The PLA-dye complexes showed the counterlockwise (negative, S) chirality of the transition dipole moments of dyes.
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  • 90
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    Biopolymers 23 (1984), S. 1347-1365 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ionization properties of the tyrosyl groups of bovine plasma albumin in various conformational states - the native state (N), the two acid states (F and E), and the state (B) stable at slightly alkaline pH - were studied by means of a stopped-flow-pH-jump technique. The technique allows us to obtain the tyrosyl titration curve in a conformational state that is unstable in the pH region of the titration. The pH jumps from the N and B states to various alkaline pH's, where the tyrosines ionize to bring about a time-dependent increase in absorption at 296 nm, indicating that a number of the tyrosines buried initially become susceptible to ionization as a result of the alkaline transition occurring above pH 10.8. Extrapolation of the observed absorption change to zero time gives a spectrophotometric titration curve in the initial conformational state. Only 30-401% of the 19 tyrosines of the protein can ionize both in the N and the B state at pH 12. The pH jumps from the F and E states, on the other hand, give a decrease in absorption between pH 9 and 11.7, indicating that the tyrosyl groups initially exposed are remarked by refolding after the pH jumps, and the zero-time titration curves show that essentially all the tyrosyl groups ionize normally in these acid states. The results are discussed in relation to the known results of the tyrosyl exposure of the protein measured by other techniques, and the consistency among them demonstrates the effectiveness of the pH-jump titration method. Hydrogen bonding between the abnormal tyrosyl and carboxylate groups as a mechanism to stabilize native albumin is suggested from characteristics of the alkaline transition, which also involves the exposure of the tyrosyl groups, and from the tyrosyl titration curves in the native and acid states.
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  • 91
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    Biopolymers 23 (1984), S. 1137-1139 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 92
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two series of peptides with hydrophobic side chains, Nps-(L-Leu-L-Leu-L-Ala)n-OEt and Nps-(L-Met-L-Met-LLeu)n-OEt (n = 1-6), were synthesized by the fragment condensation method using dicyclohexylcarbodiimide in the presence of N-hydroxysuccinimide. The tripeptide fragments were prepared stepwise by dicyclohexylcarbodiimide-mediated reaction of Nps-amino acids, which were synthesized by an improved rapid procedure.
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  • 93
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    Biopolymers 23 (1984), S. 1457-1463 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dielectric properties of sonicated calf-thymus DNA sodium salt in aqueous solutions have been studied in the frequency range from 40 MHz to 2 GHz by time domain spectroscopy (TDS). A dielectric dispersion not previously reported was found, which has a characteristic frequency of about 150 MHz. All of the dielectric parameters are insensitive to the size of DNA fragments and to helix-to-coil transitions. The study of this dispersion as a function of DNA concentration and temperature allows us to conclude that it may be due to counterion fluctuation on short sections, probably in a direction transverse to the macromolecular axis.
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  • 94
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    Biopolymers 23 (1984), S. 1465-1479 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of L-adrenaline (epinephrine) in the presence of [Fe(tetpy)(OH)2]+ ions bound to poly(L-glutamate) or to poly(D-glutamate) has been studied at pH 7 (tetpy = 2,2′:6′,2″:6″,2‴-tetrapyridyl). Electron transfer from the substrate to the central metal ion, which is rate-determining, proceeds stereoselectively only when extensive and possibly specific interactions between adrenaline and the peptidic residues of the ordered polymer in the close environment of the active sites occur. This ensures different steric constraints for the two diastereomeric precursor complexes, which are thought to affect the separation and orientation of the redox centers differently, leading to the observed phenomena. Some data on the catalytic oxidation of L-dopa(3,4-dihydroxyphenylalanine) are also presented, showing stereoselective effects similar to those observed with L-adrenaline, despite the diverse distance of the chiral center from the reacting OH groups. A mechanistic interpretation of the results is discussed in the light of a few general considerations concerning the structural features of the catalytic systems. Possible explanations for the finding that stereoselectivity occurs at the expense of the efficiency of catalysis are also considered.
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  • 95
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    Biopolymers 23 (1984), S. 1917-1930 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solution-phase Raman spectra of diastereomeric alanyl dipeptides, D-Ala-L-Ala and L-Ala-L-Ala, and various mono- and dideuterated isotopomers in H2O and D2O, are reported. Spectral differences between the diastereomeric forms are interpreted, using the Raman analog of the coupled oscillator model, in terms of geometric differences between certain vibrations in the diastereomeric forms. Application of the coupled-oscillator formalism allows the determination of a dihedral angle between the coupling vibrations. The results are compared with vibrational coupling employed by other workers in the determination of the vibrational spectra of peptides.
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  • 96
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    Biopolymers 23 (1984), S. 1951-1960 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational equilibria of five β-cellobiose conformers have been studied theoretically in 10 solvents. The stability of the conformers in dilute solution has been compared by using the method that has already been tested for 2-methoxytetrahydropyran, β-maltose, and D-glucose. The solvation energy consists of electrostatic, dispersion, and cavity terms which have been determined from the properties of the solute calculated by the PCILO quantum-chemical method and physicochemical properties of the solvents. The calculated abundance of conformers depends on the solvent (e.g., in dioxane C1:C2:C3:C4:C5 = 60.0:34.1:2.9:2.0:1.0; in dimethylsulfoxide, 75.5:22.1:1.8:0.5:0.2; and in water, 82.2:16.2:1.3:0.2:0.1). The results obtained indicate that the preponderant conformer in the aqueous solution is similar to the one adopted by β-cellobiose in the crystalline form. The role of individual contributions to the solvation energy have been analyzed. Based on the determined abundance of conformers, averaged residual optical activity and nmr parameters have been calculated and compared with observable properties. The marked differences observed between solvent-induced conformational changes for β-cellobiose and β-maltose have been discussed from the viewpoint of the solubility of the cellulose.
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  • 97
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: With a view to understanding the role of hydrogen bonds in the recognition of nucleic acids by proteins, hydrogen bonding between the bases and base pairs of nucleic acids and the amino acids (Asn, Gln, Asp and Glu, and charged residues Arg+, Glu-, and Asp-) has been studied by a second-order perturbation theory. Binding energies have been calculated for all possible configurations involving a pair of hydrogen bonds between the base (or base pair) and the amino acid residue. Our results show that the hydrogen bonding in these cases has a large contribution from electrostatic interaction. In general, the charged amino acids, compared to the uncharged ones, form more stable complexes with bases or base pairs. The hydrogen-bond energies are an order of magnitude smaller than the Coulombic interaction energies between basic amino acids (Lys+, Arg+, and His+) and the phosphate groups of nucleic acids. The stabilities of the complexes of amino acids Asn, Gln, Asp, and Glu with bases are in the order: G-X 〉 C-X 〉 A-X U-X or T-X, and G · C-X 〉 A · T(U)-X, where X is one of these amino acid residues. It has been shown that Glu- and Asp- can recognize guanine in single-stranded nucleic acids; Arg+ can recognize G · C base pairs from A · T base pairs in double-stranded structures.
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  • 98
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    Biopolymers 23 (1984) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 99
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    Biopolymers 23 (1984), S. 2195-2210 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of histone H1 on the conformation and stability of control and acetylated HeLa high-molecular-weight chromatin that had been stripped of H1 and nonhistone proteins was compared by circular dichroism (CD) and thermal denaturation measurements. Two different preparations of H1, originating from rat thymus and chicken erythrocyte, were used in the reconstitution studies. The control and acetylated stripped chromatin had identical CD and thermal denaturation properties, as did their reconstitutes with rat thymus H1. Reconstitutes of the two chromatins with chicken erythrocyte H1 had similar CD properties, but thermal denaturation studies showed that the acetylated reconstitute was destabilized compared to the control reconstitute. Reconstitutes of both chromatins with chicken erythrocyte H1 had a more condensed and stabilized structure than the reconstitutes with rat thymus H1. Thus, acetylation caused a decrease in the stability of chromatin in the presence of erythrocyte H1, but more marked differences were detected in the structure of stripped chromatin after reassociation with different H1 preparations.
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  • 100
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Human fibrinogen was treated with thrombin in the presence of fibrinoligase (Factor XIIIa) and calcium ion at pH 8.5, ionic strength 0.45, and the ensuing polymerization was interrupted at various time intervals (t) both before and after the clotting time (tc) by solubilization with a solution of sodium dodecyl sulfate and urea. Aliquots of the solubilized protein were subjected to gel electrophoresis on polyacrylamide gels after disulfide reduction by dithiothreitol and on agarose gels without reduction. The degree of γ-γ ligation was determined from the former. The latter provided the size distribution of ligated end-to-end sequences produced by splitting the ligated staggered overlapped oligomers down the middle, for degrees of polymerization, x, from 1 to 10. Addition of fibrinoligase (in which the activating thrombin had been inhibited by p-nitrophenyl-p′-guanidinobenzoate, NPGB) to Kabi fibrinogen showed the presence of small amounts of ligatable oligomers. Addition of fibrinoligase to a polymerizing mixture in which the action of thrombin had been stopped before clotting by NPGB produced the same distribution of ligated end-to-end sequences that was obtained when fibrinoligase was originally present, at least for reaction times up to 0.7 of the clotting time. The kinetics of γ-γ ligation by fibrinoligase acting on a polymerized mixture stabilized by NPGB were followed. The reaction was first order in the concentration of ligatable γ-γ junctions and the initial velocity was proportional to the enzyme concentration. The time evolution of size distribution of ligated end-to-end sequences agreed with a theory based on random ligation of ligatable junctions.
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