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  • Polymer and Materials Science  (8,675)
  • Humans  (982)
  • Computational Chemistry and Molecular Modeling  (916)
  • 1995-1999  (5,767)
  • 1990-1994  (4,806)
  • 1985-1989
  • 1950-1954
  • 1995  (5,767)
  • 1990  (4,806)
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  • 1995-1999  (5,767)
  • 1990-1994  (4,806)
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  • 1950-1954
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  • 1
    Electronic Resource
    Electronic Resource
    The solar wind and human birth rate: A possible relationship due to magnetic disturbances (1990)
    Springer
    International journal of biometeorology 34 (1990), S. 42-48 
    Details
    ISSN: 1432-1254
    Keywords: Briths ; Humans ; Solar wind ; Geomagnetism ; Melatonin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geography , Physics
    Notes: Abstract Data obtained from the literature on the annual pattern of human conceptions and plasma melatonin at high latitudes indicated that simple annual rhythms do not exist. Instead, prominent semiannual rhythms are found, with equinoctial troughs and solsticial peaks. A prominent semiannual environmental event is the magnetic disturbance induced by the solar wind. The semiannual magnetic disturbances are worldwide, but most pronounced in the auroral zones where the corpuscular radiation enters the atmosphere. Magnetic indices that predominantly reflect these events were obtained from the literature and correlated with the melatonin and conception data. Significant and inverse correlations were found for Inuit conceptions and the melatonin data. The correlations obtained for 48 contiguous states of the United States indicated that only the extreme northern states exhibited this relationship. These data were compared with a previous correlational study in the United States which established that sunshine was correlated with conceptions in the middle latitude and southern states. An hypothesis of dual control by electromagnetic and magnetic energies is proposed: melatonin is a progonadal hormone in humans controlled by both factors, depending on their relative strength. Other studies are reviewed regarding the possible factors involved in determining the annual pattern of human conceptions. Demographic studies of geographic variation in temporal patterns of conceptions, with particular regard to variations of the magnetic fields on the earth's surface, may provide some insight into the efficacy of these different factors.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01045819
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  • 2
    Electronic Resource
    Electronic Resource
    Modelling the kinetics of the precipitation polymerization of acrylic acid (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 175 (1990), S. 107-116 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Zur Beschreibung der Polymerisationsgeschwindigkeit der radikalischen Fallungspolymerisation von Acrylsäure in Toluol wurde ein Modell entewickelt. Die experimentelle Überprüfung des Modells erfolgte durch Messungen in einem isotherm betriebenen Reaktionskalorimeter. Das Modell beschreibt die Polymerisationsgeschwindigkeit bis zum vollständigen Umsatz in einem Temperaturbereich von 40 bis 60°C.
    Notes: A kinetic model for the free-radical precipitation polymerization of acrylic acid in toluene was developed and verified experimentally by using an isothermal reaction calorimeter. The model predicts the rate of polymerization accurately up to complete conversion in the temperature range of 40 to 60°C.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1990.051750109
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  • 3
    Electronic Resource
    Electronic Resource
    The influence of electron irradiation on the mechanical properties of polypropylene/EPDM rubber blends (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 175 (1990), S. 157-168 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wird über Untersuchungen an Legierungen aus isotaktischem Polypropylen und EPDM-Elastomer berichtet, die mit hochenergetischen Elektronen bestrahlt worden waren. Die Mischungsverhältnisse in den Proben überstrichen sowohl den für elastomermodifizierte Thermoplaste typischen Bereich als auch den der thermoplasticschen Elastomeren. Eine Vernetzung der Komponenten über die Grenzfläche hinweg wurde nachgewiesen. Diese grenzflächenübergreifende Vernetzung bewirkte eine merkliche Verbesserung der mechanischen Eigenschaften insbesondere des thermoplastischen Elastomeren.
    Notes: Blends of isotactic polypropylene and EPDM rubber have been treated by electron irradiation in the composition range of rubber modification and in the thermoplastic rubber composition range as well. Mutual crosslinking of the components through the interface could be detected. This intercrosslinking caused a remarkable improvement of the mechanical properties particularly of the thermoplastic rubber.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1990.051750113
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  • 4
    Electronic Resource
    Electronic Resource
    Mitteilungen (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 175 (1990), S. 205-205 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1990.051750117
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  • 5
    Electronic Resource
    Electronic Resource
    Mechanisms of photooxidation of polyolefinsPaper presented at the 19th Colloquium of Danubian Countries on “Atmospheric Aging and Stabilization of Polymers”, in Prague (Czechoslovakia), July 25 - 27, 1989 (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 176 (1990), S. 27-42 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanisms of photooxidation usually envisaged, are perfected by taking into account photoreactions of peroxy radicals. They involve interaction of a peroxy radical with the polymer to yield a hydroperoxy radical and a pair of macroradicals. After peroxidation, this pair will usually undergo bimolecular termination. The influence of such a reaction on photooxidation kinetics is particularly important for polyethylene. Then, chain termination occurs mainly by interaction of two hydroperoxy radicals or of a hydroperoxy radical with a macroperoxy radical. The reaction does not only affect kinetics of photooxidation but also the nature of the photooxidation products. The latter is more important for polypropylene than for polyethylene.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1990.051760102
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  • 6
    Electronic Resource
    Electronic Resource
    Ageing behaviour of hot-water pipes of polybutene-1Paper presented at the 19th Colloquium of Danubian Countries on “Atmospheric Aging and Stabilization of Polymers” in Prague (Czechoslovakia), July 24 - 29, 1989 (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 176 (1990), S. 55-63 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Isothermal Differential Thermal Analysis was used to test the thermooxidative stability of pipes of polybutene during internal pressure tests at 110°C. At low hoop stresses and long testing times pipe failure was exclusively caused by thermooxidative degradation of the polymer.The stabilizer distribution in the initial state and its alteration during the pressure tests could easily be measured by isothermal DTA. Leaching of antioxidants from pipe walls could be detected. The decrease of residual thermooxidative stability was degressive.Degradation of pipe material started from the exterior pipe wall. Molecular weight of polybutene decreased rapidly after stabilizer exhaustion which could be observed by isothermal DTA.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1990.051760104
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  • 7
    Electronic Resource
    Electronic Resource
    Possibilities for predicting the change in properties of polyolefins at natural ageingPaper presented at the 19th Colloquim of Danubian Countries on “Atmospheric Aging and Stabilization of Polymers” in Prague (Czechoslovakia), July 24 - 29, 1989 (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 176 (1990), S. 79-86 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A base of experimental data on the ageing of commerial grade plastics is created. In includes assorted physical and chemical properties of plastics and their changes at natural ageing. An automated system for storing and processing of the experimental data is designed. Processing involves mathematical modeling of the changes in properties that aids in empirical prediction. The possibilities of the system are verified with experimental results from a 5-year ageing period of PE-LD and PE-HD. The results show a good agreement between the predicted and real data for selected models.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1990.051760106
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  • 8
    Electronic Resource
    Electronic Resource
    Weld lines in injection moulded polypropylene parts. Mechanical properties morphology relationships (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 179 (1990), S. 35-56 
    Details
    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 Morphologie von Polypropylen-Spritzgußteilen mit Bindenaht wurde mit Röntgenweit-und Kleinwinkelstreuung, Lichtstreuung und Polarisationsmikroskopie untersucht. Die erhaltenen morphologischen Daten wurden mit mechanischen Werten aus Zugversuchen korreliert. Es wird gefunden, daß die mechanischen Eigenschaften der untersuchten Proben im wesentlichen von der sphärolithstruktur beeinflußt werden. Anhäufungen von Sphärolithen mit Kristallen der hexagonalen β-Modifikation und eine starke Inhomogenität der Sphärolithstruktur senkrecht zur Bindenaht sind der wesentliche Grund für die verschlechterten mechanischen Eigenschaften. Diese Sphärolithstruktur wird durch die Temperatur des Spritzgußwerkzeugs stark beeinflußt. Die Lamellen-Überstruktur hat dagegen einen vernachlässigbar kleinen Einfluß auf das mechanische Verhalten.
    Notes: The morphology of polypropylene plaques containing a weld line, has been investigated by x-ray wide and small angle scattering, light scattering and polarization microscopy. The results are correlated to mechanical values obtained from tensile tests. While the lamellar morphology is of neglectable influence, it is found, that the mechanical properties of the samples are strongly influenced by the spherulitic structure. Clustering of β-type spherulites and strong morphological inhomogeneities in the vicinity of the weld line are the primary reason for the mechanical weakening of the plaques. The temperature of the mould has a strong effect on the spherulitic structure and thus on the tensile properties of the samples.
    Additional Material: 17 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1990.051790104
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  • 9
    Electronic Resource
    Electronic Resource
    Studies of the surface structure of plasma-modified fillers and their application in PVC and PP compounds (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 179 (1990), S. 77-85 
    Details
    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: Füllstoffe für PVC- und PP-Formmassen wurden mit Mikrowellenplasma behandelt. Photoakustische FT-IR-Spektren zeigen, daß die Plasma-Polymerhülle auf der Füllstoffoberfläche —C=C—, —CH2—, CH3— und andere Gruppen enthält. Aus Röntgenelektronenspektren geht hervor, daß zwischen Siliciumdioxid und der organischen Beschichtung chemische Bindungen existieren. Durch Compoundieren von plasmabehandelten Füllstoffen mit PVC und PP werden Materialien mit guten mechanischen Eigenschaften bei niedrigen Kosten erhalten.
    Notes: Fillers for PVC and PP compounds have been treated by microwave plasma. FT-IR photoacoustic spectroscopy studies show that the plasma polymer sheath on filler's surface contains —C=C—, —CH2—, —CH3 groups, etc. X-ray photoelectron spectroscopy studies reveal that interfacial chemical bondings exist between silica and the organic coating. Application of plasma-treated fillers in PVC and PP compounds gives rise to materials of good mechanical properties and low cost.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1990.051790106
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  • 10
    Electronic Resource
    Electronic Resource
    Alcoholysis of esterlinkages in solution (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 179 (1990), S. 135-148 
    Details
    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-(alkylenadipat)-diole mit Molmassen von 1500, 2000 und 3000 wurden bei Temperaturen von 25 und 60°C in Gegenwart verschiedener Alkohole und unterschiedlicher PUR-Katalysatoren (1,4-Diazabicyclo[2.2.2]octan (DABCO), Dibutylzinndilaurat (DBTL),Dibutylzinndiethoxid (DBTEO) und Dibutylzinnoxid (DBTO)) in Ethylacetat bzw. Toluol gelagert und die Alkoholyse verfolgt. Die erhaltenen Ergebnisse werden mit dem Alkoholyseverhalten verschiedener Dialkyladipate sowie des Lösungsmittels Ethylacetat unter den selben Bedingungen verglichen. Die Alkoholyse verlauft in Gegenwart der zinnorganischen Verbindungen etwa mit gleicher Geschwindigkeit, ohne daß diese selbst signifikant zersetzt werden, wahrend DABCO praktisch inaktiv ist. Die Aktivitat der Alkohole ist starker von ihrer sterischen Struktur als von ihrer Basizitat abhangig. Die Stabilität der Polyalkylenadipate gegenüber einer Umesterung nimmt mit der Lange der Diolalkyleneinheiten des Polyols zu. Die Umesterung von Adipinsäuredialkylestern findet auch partiell in Anwesenheit eines großen Uberschusses an Ethylacetat statt.
    Notes: Poly(alkylene adipate)diols having molar masses of 1500, 2000 and 3000 were stored at temperatures of 25 and 60°C in the presence of low amounts of different alcohols and some polyurethane (PUR) catalysts, such as dibutyltindilaurate (DBTL), dibutyltindiethoxide (DBTEO), dibutyltinoxide (DBTO), and 1,4-diazabicyclo[2.2.2]octane (DABCO). Alcoholysis was studied using either ethyl acetate (EA) or toluene as solvent. The results were compared with those obtained by examining the behaviour of several dialkyl adipates and ethyl acetate under identical conditions. The alcoholysis in the presence of the tin catalysts proceeds at the same reaction rate without significant decomposition of the catalyst, whereas DABCO is practically inactive. The nucleophilic activity of the alcohols depends on their bulk size rather than their basicity. The resistance of polyalkylene adipates to transesterification increases with the increasing alkyl chain length of diol units in polyester. A partial transesterification of dialkyl adipates takes place too, in spite of ethyl acetate being present in excess.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1990.051790110
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  • 11
    Electronic Resource
    Electronic Resource
    Separation of liquid mixtures by using polymer membranes. II. Water-alcohol separation by pervaporation through porous PVA membranesPart 1 cf.25. (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 179 (1990), S. 157-171 
    Details
    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 das Permeations- und Trennverhalten von Alkohol/Wasser-Systemen durch poröse PVA-Membranen untersucht. PVA-Membranen mit unterschiedlicher Anzahl und Große von Poren wurden über Mischungen in Lösung mit verschiedenen synthetisierten Polymeren und Copolymeren, wie Polyacrylsäure, Polyacrylnitril, Polyacrylamid, Poly(Methylmethacrylat-co-Maleinsäureanhydrid) etc., anschließendes Gießen von Filmen und Extraktion der Polymeren oder Copolymeren durch Lösungsmittel hergestellt. Die Abhängigkeit der Durchlässigkeit und Trennwirkung von der Größe und Form der permeierenden Moleköle wurde qualitativ diskutiert. Des weiteren wurde die Selektivität der Trennwirkung in Abhangigkeit von der Zusammensetzung von Alkohol/Wasser-Gemischen und von der Größe und Anzahl der Poren untersucht. Es wurde gefunden, daß die Selektivität von der Menge und dem Molekulargewicht der in die Membranen eingebrachten Polymeren abhängt. Wenn der Gewichtsanteil des verwendeten Polymeren größer als 0,1 war, permeierte bevorzugt der Alkoholanteil bei methanolischen Msungen, wobei der Trennfaktor mit steigender Methanolkonzentration anstieg. In Gemischen mit anderen Alkoholen zeigten die Membranen andererseits eine selektive Durchlässigkeit für Wasser. Der Einfluß der Versuchsbedingungen wurde ebenfalls untersucht.
    Notes: The permeation and separation characteristics of alcohol/water systems through porous PVA membranes were investigated. Porous PVA membranes with different pore size and number were prepared by solution blending of PVA with several synthesized polymers or copolymers, such as polyacrylic acid, polyacrylamide, polyacrylonitrile, and methylmethacrylate-co-maleic anhydride, etc. Then casting, and finally extracting the blended polymers or copolymers by solvent from the membranes. The dependency of both permeation and separation on the molecular size and shape of the permeating species was dicussed qualitatively. Moreover, the permselectivity was investigated with attention to the feed composition of alcohol/water mixture and the effect of pore size and number. The selectivity was found to depend on the weight ratio and the molecular weight of polymer introduced to the membrane. When the weight ratio of polymer introduced into the membrane was larger than 0.1, methanol was permeated through membrane preferentially in methanol/water system, and the separation factor increased with increasing the methanol feed concentration. On the other hand, membrane had a selective permeability for water in the other alcohol/water systems. The influence of operating conditions was also studied.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1990.051790112
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  • 12
    Electronic Resource
    Electronic Resource
    Temperature dependence of proton spin-lattice and spin-spin relaxation times in isotactic polypropylene. Effect of atactic fraction (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 175 (1990), S. 29-38 
    Details
    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 Temperatur des T1-Minimums für die Segmentbewegung in Polypropylen, das einen hohen ataktischen Anteil besitzt, ist niedriger als die in isotaktischem Polypropylen. Ein kurzes T1, T1s, tritt bei beiden Materialien auf. Bei Temperaturerhöhung nimmt T2a (T2 der beweglichen amorphen Bezirke) stark und T2m (T2 der dazwischen liegenden Bezirke) leicht zu, während sich T2c (T2 der steifen kristallinen Bezirke) kaum ändert. T2a in Polypropylen mit hohem ataktischem Anteil ist länger als in isotaktischem Polypropylen.Der Massenbruch der kristallinen Bezirke, Fc, nimmt bei Temperaturerhöhung ab und der der amorphen Bezirke, Fa, zu. Die Relaxationsgeschwindigkeit, 1/ (T1min), steigt linear mit Zunahme des amorphen Anteils an, außer bei der mit siedendem n-Heptan extrahierten Probe. Mit Zunahme der Peaktemperatur von tan δ fällt T2a nahezu linear ab, während die Temperatur des T1-Minimums zunimmt.
    Notes: The temperature of the T1 minimum for the segmental motion in polypropylene containing a lot of atactic fraction is lower than that in isotactic polypropylene. A short T1, T1s, appears for both materials. As the temperature is raised, there is a large increase in T2a (T2 of the mobile amorphous regions), and a mild increase in T2m (T2 of the intermediate regions), while there is no substantial change in T2c (T2 of the rigid crystalline regions). T2a in polypropylene containing a lot of atactic fraction is longer than that in isotactic polypropylene.The mass fraction of crystalline regions, Fc, decreases and that of the amorphous regions, Fa, increases as the temperature is raised. There is a linear increase in the relaxation rate, 1/(T1min), as the amorphous fraction is increased, except for the sample extracted with boiling n-heptane. With increase of the peak temperature of tanδ, T2a decreases nearly linearly, while the temperature of the T1 minimum increases.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1990.051750103
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  • 13
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    Electronic Resource
    Wettability and surface chemistry of irradiated PTFE (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 180 (1990), S. 191-198 
    Details
    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 Bestrahlung von PTFE mit Elektronen niedriger Energie führt zur Abspaltung von Fluor und zum Einbau von Sauerstoff in die Polymeroberfläche. Es wird gezeigt, daß das Ausmaß der Oberflächenveränderungen hauptsächlich von der Zahl und kaum von der Energie der Elektronen abhängt, die die Oberfläche erreichen. Änderungen in der Oberflächenenergie resultieren in unterschiedlichem Benetzungsverhalten. Kontaktwinkelmessungen und Kurvenanalysen der C-1s-Peaks aus Röntgenphotonenspektroskopiemessungen zeigen, daß der am wenigsten benetzbare Teil der bestrahlten Oberflächen in den meisten Fällen aus —CF2 —CF-Einheiten besteht. Werden bei der Bestrahlung nahezu alle Fluoratome abgespalten, bleiben nur isolierte —CF2-oder —CF-Gruppen zurück. Die „receding“-Winkel werden mit zunehmender Sauerstoffkonzentration in der Oberfläche kleiner, was auf die Bildung stark oxidierter Bereiche hinweist. Die Unabhängigkeit der Kontaktwinkel von der Alterungsdauer deutet auf eine sehr geringe Beweglichkeit der Makromoleküle hin, was mit einer starken Vernet-zung an der Oberfläche zusammenhängen könnte.
    Notes: Low energy electron irradiation of PTFE induced fluorine depletion and introduction of oxygen on the surface. The effect on surface chemistry was shown to be dependent mostly on the amount of electrons reaching the sample, rather than on their energy.Changes in surface energy resulted in different wetting behaviors. The measurement of advancing water contact angles and the analysis of XPS C-1s peak shapes showed that the least wettable portion of irradiated surfaces is made in most cases of —CF2—CF — units. When the treatment caused a nearly complete fluorine depletion, only isolated —CF2— or —CF— groups are present. Receding angle values decreased linearly depending on the amount of oxygen introduced on the sample during the treatment, suggesting the formation of strongly oxidized polymer islets. The invariance of contact angles with aging time indicated very low macromolecular mobility, probably related to extensive surface crosslinking.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1990.051800114
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  • 14
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    Herstellung von dispersionen anionischer polyurethane mit COO- -gruppen und NH4+ -gegenionen (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 181 (1990), S. 41-52 
    Details
    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 aqueous dispersions of anionic polyurethanes containing the triethylammonium salt of 2,2-dimethylol propionic acid as chain extender, triethylamine can be largely replaced by ammonia. For electrostatic reasons, NH4+ is namely more tightly bound in the ion pairs located in the Stern layer than NH(C2H5)3+. Thermal treatment of films leads to a loss of base, whereby ammonia is more rapidly released than triethylamine. Therefore, crosslinking with partially methylated hexamethylolmelamine proceeds the faster the more triethylamine is replaced by ammonia.
    Notes: In Dispersionen aus anionischen Polyurethanen, die das Triethylammoniumsalz der 2,2-Dimethylolpropionsäure als Kettenverlängerungsmittel enthalten, läßt sich durch Zugabe von Ammoniak eine weitgehende Verdrängung des Triethylamins erreichen. Aus elektrostatischen Gründen ist nämlich in den in der Sternschen Schicht lokalisierten Ionenpaaren NH4+ fester gebunden als NH(C2H5)3+. Bei der thermischen Behandlung der Filme tritt Basenabspaltung ein, dabei erfolgt die Abgabe von Ammoniak deutlich schneller als die von Triethylamin. Die Spannungswerte der mit teilmethyliertem Hexamethylolmelamin vernetzten Proben sind daher um so höher, je mehr Triethylamin durch Ammoniak ersetzt wurde.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1990.051810103
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  • 15
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    Electronic Resource
    Compression creep of molten polystyrene (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 181 (1990), S. 53-66 
    Details
    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 Viskoelastizitäts-Parameter von geschmolzenem Polystyrol (PS) wurden mit einem Instron-Kapillarrheometer gemessen.Die Drucknachgiebigkeit B(t) zeigt ein Plateau sowohl im Schmelze (B1)- als auch im Glaszustand (Bg); beide nehmen mit abnehmender Spannung ab. Durch Verschiebung der B(t)-Kurven werden Master-Kurven erhalten, mit denen das Gesamtdruckverhalten (überlagerte elastische und viskose Deformationen) analysiert werden kann. Die stationäre Nachgiebigkeit (Bs) erlaubt eine Beschreibung des elastischen Energieanteils und scheint mit der Extrusions-Strangaufweitung (Bcs/Bds) korreliert zu sein. Die Volumenviskosität (ηk) nimmt mit zunehmender Spannung (P), zunehmender Belastungsgeschwindigkeit (k) und abnehmender Temperatur ab.
    Notes: Viscoelastic parameters of polystyrene (PS) melt in compression creep have been measured in an lnstron capillary-rheometer.Bulk compression creep compliance B(t) shows plateau regions in the molten state (B1) and the glassy state (Bg), both decreasing with increasing stress. Shifting of B(t) curves provides master curves suitable to analysing the total (superposed elastic and viscous deformations) bulk compression behaviour. The steady-state creep compliance (Bs) allows to describe the recoverable elastic energy (Be) and seems to be related to the extrusion die swell (Bcs/Bds). Volume viscosity (ηk) decreases with decreasing stress (P), increasing compression rates (k) and decreasing temperature (T).
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1990.051810104
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  • 16
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    Variation in molecular weight and molecular weight distribution of aged iPP filaments as revealed by HTGPC (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 181 (1990), S. 67-74 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurden Untersuchungen über Molekulargewichtsänderungen an physikalisch bei Raumtemperatur gealterten isotaktischen Polypropylenfilamenten (iPP) mit Hilfe der Hochtemperaturgelpermeationschromatographie (HTGPC) durchgeführt. Das Ergebnis der Untersuchungen weist auf eine sehr unbedeutende Änderung des Molekulargewichts des Materials während der Alterung hin.Das Materialgranulat wurde als Bezugsstandard gewählt. Basierend auf der Uneinheitlichkeit D = Mw/Mn des Granulats wurden Filamente der Handelsprodukte GYE 47 und PXC 31399 charakterisiert, deren Alterungsdauer zwischen 2 Wochen und 8 Monaten lag. Bei den Filamenten der Qpe GYE 47 verringerte sich die Breite der Molekulargewichtsverteilung D um durchschnittlich 12%. Andererseits zeigen die Filamente des PXC 31399-vps einen weniger eindeutigen Trend zur Änderung, jedoch im Mittel hat sich die Breite der Verteilung um etwa 20% erniedrigt. Bei letzterem ist die Verteilung iiber die Alterungsdauer stark gestreut. Der GYE 47-Typ zeigt eine nahezu asymptotische Abnahme. Es wird angenommen, daß die Ungleichartigkeit in der Ändenz der Anderung von D zwischen beiden Proben in ihrer unterschiedlichen thermodynamischen Stabilitat liegen ktinnte; PXC 31399 ist weniger stabil.
    Notes: Experiments on the molecular weight variations of physically, room temperature aged isotactic polypropylene (iPP) filaments were done using the High Temperature Gel Permeation Chromatography (HTGPC). Evidence emanating from the studies indicates a very marginal change in molecular weight of the materials during aging.The granules of the materials were chosen as the reference standard. Based on the polydispersity D = Mw/Mn of the granules, filaments of commercial grades GYE 47 and PXC 31399 were characterized between an aging period ranging from 2 weeks to 8 months. The filaments of the GYE 47 grade have their distributions D lowered on the average by about 12%. On the other hand, those of the PXC 31399 grade have a less definite trend in change, but on the average, D is lowered by about 20%. The distributions of this latter grade are highly scattered over the period of aging. The GYE 47 grade shows a reduction in the distribution of a near asymptotic nature. It is believed that the disparity in the trend of change of D between the two samples could be attributed to their relative thermodynamic stability with the PXC 31399 grade being less stable.
    Additional Material: 3 Ill.
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  • 17
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    The photocopolymer rod of ethyleneglycol dimethacrylate with methylmethacrylate (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 174 (1990), S. 1-10 
    Details
    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 Photopolymerisation von Ethylenglykoldimethacrylat (EGDMA) mit Methylmethacrylat (MMA) wurde mit Benzoinmethylether (BME) als Initiator in einem Glasrohr durchgeführt, um einen lichtfokussierenden Plastikstab (Radius Rp) mit parabolischer Brechungsindex-Verteilung (Verteilungskonstante A) in der Nähe der Stabachse (bis zum Radius Rc) herzustellen. Die Abhängigkeit von A und Rc/Rp vom Monomerenverhältnis MMA/EGDMA der Ausgangsmischung, der Einfluß der BME-Konzentration auf die Brechungsindex-Verteilung und die Reproduzierbarkeit der Photopolymerisationen wurden untersucht. Das Rc/Rp-Verhältnis stieg mit dem Monomerenverhältnis MMA/EGDMA bei BME = 1,0 Gew.-% und der Geschwindigkeit der UV-Lampe von V = 0,58 mm/min an. Andererseits stieg Rc/Rp bei BME = 0,6 Gew.-% und V = 0,735 mm/min bis zum Monomerenverhältnis von 0,2 an und fiel dann deutlich zwischen 0,20 und 0,25 ab. Die Plastikstäbe, die hier durch Photopolymerisation hergestellt wurden, haben Linseneigenschaften und sind gut reproduzierbar.
    Notes: The photocopolymerization of ethyleneglycol dimethacrylate (EGDMA) with methylmethacrylate (MMA) containing benzoin methyl ether (BME) as initiator was carried out in a glass tube to fabricate a light-focusing plastic rod (radius Rp) with a parabolic refractive index distribution (distribution constant A) in the region near the center axis (radius Rc). The dependence of A and Rc/Rp on MMA/EGDMA feed ratio, influence of BME concentration on the refractive index distribution, and the reproducibilities of the photopolymerizations were investigated. The Rc/Rp increased with the feed ratio used under BME = 1.0 wt.-% at velocity of UV lamp V = 0.58 mm/min. On the other hand, Rc/Rp increased with the feed ratio to 0.2 and then decreased remarkably with the feed ratio in the range of 0.2-0.25 with BME = 0.6 wt.-% at V = 0.735 mm/min. Plastic rods fabricated in the investigation using photopolymerization have lens characteristics and good reproducibilities.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1990.051740101
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  • 18
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    Effects of drawing conditions on the properties of optical fibers made from polystyrene and poly(methyl methacrylate)Dedicated to Prof. Dr. O. Wichterle on the occasion of his 75th birthday (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 174 (1990), S. 25-39 
    Details
    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: Polystyrol- und Polymethylmethacrylateinzelfäden mit verschiedenen Graden von Doppelbrechung wurden durch die kontinuierliche Änderung der Ziehgeschwindigkeit, der Temperatur der Polymerschmelze und des Molekulargewichts von Polystyrol (PS) und Polymethylmethacrylat (PMMA) gewonnen. Der “brittle to ductile” Übergangspunkt (Übergang des Polymeren vom spröden zum ziehbaren Zustand) wurde für das optisch reine Polystyrol im Bereich der Doppelbrechungszahlen -0,6 · 10-3 bis -2,6 · 10-3 gefunden. Höhe und Lage dieses Punktes werden durch das Molekulargewicht, die Molekulargewichtsverteilung und die Temperatur der Polymerschmelze beeinflußt. Die Werte des Doppelbrechungsindexes von PS sind um zwei Zehnerpotenzen höher als von PMMA. Bei PMMA wurde der “brittle to ductile” Übergangspunkt nicht beobachtet. Die mechanischen und optischen Eigenschaften hängen nicht nur vom mittleren Wert des durch die Doppelbrechung charakteri-sierten Orientierungsgrades ab, sondern auch davon, welcher Teil des Relaxations-spektrums des Polymeren vorzugsweise orientiert ist. Beim Ziehen der PS- und PMMA-Einzelfäden bilden sich in der Mitte des Fadens Risse (crazes), die jedoch nicht an die Oberflache des Fadens treten.
    Notes: Monofilaments possessing various degrees of birefringence were obtained by changing the drawing rate, the molten polymer temperature, and the molecular weight of polystyrene (PS) and poly(methyl methacrylate) (PMMA). The “brittle-toductile” transition point of optically pure PS was found in the range of birefringences of -0.6 · 10-3 to -2.6 · 10-3. Both the height and position of this point are influenced by M̄w, molecular weight distribution, and polymer melt temperature. The birefringence of PS is higher by two orders of magnitude than that of PMMA in which this transition point has not been observed. The mechanical and optical properties depend not only on the average amount of orientation characterized by the birefringence but on what portion of the relaxation spectrum of the polymer is preferentially oriented. During the drawing of PS and PMMA monofilaments crazes are formed in the centre of the fibers and do not reach the surface.
    Additional Material: 14 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1990.051740103
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  • 19
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    Ataktisches polypropylen als pfropfgrundlage für die monomeren vinylacetat und vinylchlorid. Herstellung undeigenschaften der pfropfprodukte (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 174 (1990), S. 105-117 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The possibility of the application of atactic polypropylene is investigated as graft base for the preparation of graft copolymers of vinyl acetate and vinyl chloride respectively graft copolymers from vinyl acetate onto polypropylene as graft base for the preparation of graft copolymers of vinyl chloride in relation to the composition of the original mixture.After compounding of the graft products with polyvinyl chloride or ABS/polyvinyl-chloride mixtures selected mechanical properties are presented in relation to the quantity and composition of the incorporated graft copolymers.
    Notes: Die Möglichkeiten des Einsatzes von ataktischem Polypropylen als Pfropfgrundlage zur Herstellung von Pfropfcopolymerisaten des Vinylacetates und Vinylchlorids bzw. von Polypropylen-Vinylacetat-Pfropfprodukten als Pfropfgrundlage zur Herstellung von Pfropfcopolymerisaten des Vinylchlorids werden in Abhängigkeit von der Ausgangsgemischzusammensetzung untersucht.Nach Abmischung der Pfropfprodukte mit Polyvinylchlorid bzw. ABS/Polyvinylchlorid-Mischungen werden ausgewählte mechanische Eigenschaften sowohl in Abhängigkeit von der Menge des enthaltenen Pfropfproduktes als auch von der Zusammensetzung der Pfropfpolymerisate dargestellt.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1990.051740109
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  • 20
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    Eine spektroskopische Methode zur Messung der Ammoniak-Permeabilität in PolymerfilmenHerrn Prof. Dr. Herward Pietsch zum 60. Geburtstag gewidmet (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 179 (1990), S. 5-19 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: A new spectroscopic method for determining the permeability of ammonia in transparent polymer layers is presented. It is based on the quantitative proof of the ammonia passing the test layer into a sensor layer, containing 4-nitrophenol as an NH3-sensitive probe, which is placed under the test film. The permeability (P) of the test layer is calculated from the slope of extinction with time in the sensor layer. The lag time (t1) gives the diffusion coefficient (D). The suitability of this method is confirmed by comparison with literature values. Diffusion coefficients obtained from t1 correspond well to those obtained by the sorption method.The temperature dependence of P and D in more than five different polymers (CDA, PVB, PVAc, PVC and different polyvinyl alcohols) demonstrates that peculiarities in the temperature dependence of the permeability result from the behaviour of the NH3-solubility (P/D) which is strongly dependent on the polymer structure.
    Notes: Es wird eine neuartige spektroskopische Methode zur Messung der Ammoniak-Permeabilität in transparenten Polymerfilmen vorgestellt. Sie beruht auf dem quantitativen Nachweis des den Testfilm durchdringenden Ammoniaks in einer darunter befindlichen Sensorschicht mit Hilfe der NH3-empfindlichen Sonde 4-Nitrophenol. Aus dem Anstieg der Extinktion mit der Zeit (ΔE/Δt) in der Sensorschicht wird die Permeabilität (P) und aus der Verzögerungszeit (lag time (t1)) der Diffusionskoeffizient (D) berechnet. Die Eignung der Methode wird durch Vergleich mit Literaturwerten belegt. Die aus t1 zugänglichen Diffusionskoeffizienten stimmen sehr gut mit denen überein, die mit der Sorptionsmethode gefunden werden.Die Temperaturabhängigkeiten von P und D in mehr als fünf verschiedenen Polymeren (CDA, PVB, PVAc, PVC und in verschiedenen Polyvinylalkoholen) zeigen, daß Besonderheiten im Temperaturgang der Permeabilität aus dem vom Aufbau des Polymeren stark abhängigen Verhalten der NH3-Löslichkeit (P/D) resultieren.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/apmc.1990.051790102
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  • 21
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    SBS/VP homograft membrane for oxygen enrichment (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 179 (1990), S. 99-111 
    Details
    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 die strahleninduzierte Pfropfung von 4-Vinylpyridin (VP) auf Styrol-Butadien-Styrol-Copolymere (SBS) in Gegenwart von gelöstem Sauerstoff untersucht. Pfropfcopolymer-Membranen mit unterschiedlichen Pfropfgraden wurden durch Gießen aus benzolischer Lösung hergestellt. Die mechanischen Eigenschaften, die Gaspermeabilität sowie der Einfluß der Temperatur auf die Gasdurchlässigkeit wurden untersucht. Der höchste Pfropfgrad von 8,4% wurde bei einer Bestrahlungszeit von 15,5 herreicht. Sowohl bei kürzeren als auch längeren Bestrahlungszeiten war der Pfropfgrad  -  bedingt durch Störung durch den vorhandenen Sauerstoff  -  niedriger. Reißfestigkeit und Reißdehnung von SBS-g-VP waren vergleichbar rnit SBS. Die Spannungsrelaxation von SBS-g-VP war langsamer als bei SBS, was auf der Bildung von starren Polyvinylpyridin(DVP)-Mikrophasen beruhen könnte, die als permanente Vernetzungspunkte wirken und die Spannungsrelaxation beeinträchtigen könnten.Da SBS eine hohe Gasdurchlässigkeit und PVP eine hohe O2/N2-Selektivität aufweisen, wurde die Gasdurchlässigkeit der Pfropfmembranen untersucht. Die Selektivitat der SBS-g-VP-Membranen stieg mit steigendem Pfropfgrad, allerdings auf Kosten der Permeabilität, Bei Erhöhung der Temperatur nahm die Durchlässigkeit zu, das Verhältnis O2/N2, aber ab. Die Aktivierungsenergie (Ep) der Gasdurchlässigkeit stieg mit dem Pfropfgrad. Für eine nichtgepfropfte SBS-Membran betrug Ep 5,5 kcal/mol für Sauerstoff und 7,2 kcal/mol für Stickstoff. Für eine SBS-g-VP-Membran mit einem Pfropfgrad von 8,4% waren die Ep-Werte für Sauerstoff und Stickstoff 6,5 bzw. 8,1 kcal/mol.
    Notes: The grafting of 4-vinyl pyridine (VP) onto styrene-butadiene-styrene triblock copolymers (SBS) by homografting irradiation with dissolved oxygen was studied. Homograft membranes of various degree of grafting were prepared from a casting solution of grafted copolymer in benzene. The mechanical properties of membranes, gas permeability, and the effect of operating temperature on gas permeation were investigated.The degree of grafting of 8.4% was the largest at an irradiation time of about 15.5 h. It was smaller at both shorter and longer duration because of the interference of dissolved oxygen. It was found that the tensile strength and elongation of SBS-g-VP were similar to those of SBS. The stress relaxation of SBS-g-VP was slower than that of SBS, and this might be due to the formation of rigid microphase separation domain of poly(4-vinyl pyridine), which acted as permanent crosslinking points to reduce the stress relaxation.Using the properties of high flux of SBS and high O2/N2 selectivity of poly(4-vinyl pyridine), the performance of gas permeation of 4-vinyl pyridine homografted SBS membrane was studied. The selectivity of SBS-g-VP membrane increased with increasing degree of grafting. However, it was done at the expense of a decrease in the gas permeability.When the operating temperature of gas permeation increased, the permeability of oxygen and nitrogen increased, and the O2/N2 permeability ratio decreased. The activation energy (Ep) for gas permeation through different degree of grafting of SBS-g-VP membrane (obtained by the Arrhenius law) increased with increasing degree of grafting. For ungrafted SBS membrane, Ep was 5.5 kcal/mol for oxygen and 7.2 kcal/mol for nitrogen. For 8.4% grafting degree SBS-g-VP membrane, Ep for oxygen and nitrogen, were 6.5 and 8.1 kcal/mol, respectively.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1990.051790108
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  • 22
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    Anhäufung von bruchstellen in polydispersen polymeren unter dauerbelastung (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 175 (1990), S. 13-27 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The change of molecular mass and long-term strength of high and low density polyethylene under tensile load in surface-active medium was studied. It is shown that long-term strength of polyethylene depends on the molecular mass. The influence of polydispersity on strength was investigated.
    Notes: Es wird über die Untersuchungsergebnisse von Lebensdauer und Molmassenänderung an polydispersen Proben von HDPE und HDPE in einem breiten M̄v-Bereich im Zugversuch in einem oberflächenaktiven Medium berichtet.Die Arbeit enthält auch die Darstellung der quantitativen Änderung der Molmasse von Hochdruck- und Niederdruck-Polyethylen unter Dauerbeanspruchung und die Analyse der Lebensdauer in Abhängigkeit von den unterschiedlichen Molmassen (MM) (M̄w, M̄n, M̄v); die Unterschiede in Abhängigkeit von der Lebensdauer von M̄v für Proben und polydisperse Muster sowie die Vorstellungen über den dualen Einfluß der Polydispersität auf die Lebensdauer mit einer Interpretation der auftretenden Erscheinungen werden beschrieben.
    Additional Material: 9 Ill.
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    Partikelgrößenanalyse von dispersen farbstoffsystemen I. Grundlagen zur partikelgrößenanalyse mittels photonen-korrelations-spektroskopieHerrn Dr. Gerhard Heidemann zum 60. Geburtstag gewidmet (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 175 (1990), S. 51-67 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: One constitutive property for the description of dyeing polyester-materials with disperse dyes is the particle size distribution in the dye bath. To measure particle sizes below one micrometer in situ, special techniques are required. One of these is the so called photon-correlation-spectroscopy, depending on the scattering of laser light by suspended small particles in a fluid. The mathematical and physical principles of the photon-correlation-technique are explained in this article.
    Notes: Eine zur Beschreibung des Färbevorganges von Polyestermaterialien mit Dispersionsfarbstoffen wesentliche Größe stellt die Partikelgrößenverteilung im Farbebad dar. Partikelgrößen unterhalb eines Mikrometers lassen sich in situ nur mit wenigen Meßtechniken bestimmen. Dazu zählt u. a. die Photonen-Korrelations-Spektroskopie, die auf Streuung von Laserlicht an kleinen, in einer Flüssigkeit suspendierten Teilchen basiert. Die mathematischen und physikalischen Grundlagen dieser Meßtechnik werden in diesem Artikel erläutert.
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  • 24
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    SAXS and WAXS investigations of the crystallinity in polymers (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 175 (1990), S. 81-97 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Kristallinität von Polyethylen, Polyethylenterephthalat und Polypropylen wurde mit Hilfe der Röntgenweitwinkel(WAXS)-und-kleinwinkel(SAXS)streuung gemessen. Die mittels der letzteren Methode erhaltenen Kristallinitätswerte sind deutlich größer als die durch WAXS. Es wird vermutet, daß die Unterschiede mit der Schicht zusammenhängen, die zwischen den amorphen und kristallinen Bereichen liegt. Daraus wurde geschlossen, daß die Röntgenkleinwinkelstreuung nicht als unabhängige Routinemethode zur Kristallinitätsbestimmung angewendet werden kann.
    Notes: The crystallinity of polyethylene, polyethyleneterephthalate, and polypropylene was measured with the aid of wide angle (WAXS) and small angle (SAXS) X-ray scattering methods. The values of crystallinity evaluated using the latter method are distinctly larger than those ones given by the WAXS method. The differences are supposed to be associated with the transition layer existing between the amorphous and crystalline regions. It was concluded that small angle X-ray scattering cannot be employed as an independent routine method of crystallinity determination.
    Additional Material: 11 Ill.
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    SEC on cellulose nitrate: DP-Ve relationship and evaluation of different methods to determine the calibration parameters (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 175 (1990), S. 117-128 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Für das System Cellulosenitrat-μ-Styragel-THF wurde die DP-Ve-Beziehung sowie die Ausarbeitung der betreffenden Eichparameter einer genaueren Betrachtung unterzogen. Die etwa dreißig Eichpräparate waren durch definierten säurekatalysierten Abbau von Baumwollcellulose und anschließende Nitrierung hergestellt worden und umfaßten einen DP-Bereich von 150 〈 DP 〈 8000. Es wird gezeigt, daß mit steigendem DP die DP-Ve-Beziehung drei verschiedene Phasen aufweist. Bei der Anwendung der SEC auf Cellulosenitrat müssen daher bezüglich der Eichung zwei Fehlerquellen in Betracht gezogen werden: eine bezieht sich auf die Methode der Ausarbeitung der Eichparameter als solche, und die andere auf die Nichtbeachtung des Vorhandenseins dreier Abschnitte in der DP-Ve-Beziehung. Die Auswirkung dieser Fehler auf die Genauigkeit der aus den Elutionsdiagrammen abgeleiteten Verteilungskurven und DP-Mittelwerte wird diskutiert.
    Notes: The calibration behaviour of the system cellulose nitrate-μ-Styragel-THF has been studied using about 30 different calibration samples prepared by defined acid catalyzed degradation of cotton cellulose. The samples covered a range of DP between 150 〈 DP 〈 8000. It is shown that the DP-Ve relationship is characterized by the existence of three subsequent stages. Consequently, two sources of errors in the DP-Ve calibration must be taken into consideration. One refers to the methods as such to elaborate the calibration parameters, and the other one arises by neglecting that the DP-Ve relationship involves 3 distinct stages. The extent of the two classes of errors in regard to the exactness of the determined molecular weight averages and molecular weight distributions is discussed.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1990.051750110
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    Water-Soluble polyamides as potential drug carriers. I. Poly(α,β-D,L-asparthydrazide-CO-D,L-ornithine) (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 175 (1990), S. 141-156 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Bei der Polycondensation von d,l-Asparaginsäure mit Nδ-phthaloyl-L-ornithin in Phosphorsäure bei 185°C entstehen statisticsche Copolymere (Ausbeute 60  -  70%) aus Poly(d,l-succinimid-co-Nδ-phthaloyl-d,l-ornithin), Formel 6, mit inhärenten Viskositäten (DMF) von 5 bis 15 ml g-1. Copolyimide der selben Zusammensetzung 6 und vergleichbarer Kettenlänge werden aus Asparaginsäure und dem Kupferchelat des Phthaloylornithins erhalten. Die Behandlung des Copolymeren 6 mit Hydrazinhydrat fuhrt zur Öffnung der Succinimid-Kettenglieder unter Bildung von Hydrazid-Seitengruppen. Die resultierenden Polyamide sind Poly(α,β-d,l-asparaginsäurehydrazid-co-d,l-ornithin), Formel 7. Kürzere Reaktionszeiten bedingen unvollständige Ringöffnung, und die verbleibenden Succinimid-Gruppen werden bei der folgenden Aufarbeitung hydrolytisch gespalten unter Bildung von Asparaginsaüre-Gruppen; die sogebildeten Polyamide besitzen die Struktur 8. Beide Polymere, 7 und 8, sind in Wasser loslich und zeigen in Wasser inharente Viskositiiten von 5 bis 14 ml g-l. Die Fahigkeit dieser Polyamide zur Arzneimittelverankerung wird durch Ankoppeln von Carbonsau- ren als Modellsubstanzen gezeigt.
    Notes: The polycondensation of d,l-aspartic acid with Nδ-phthaloyl-l-ornithine in phosphoric acid at 185°C gives rise to the formation, in 60  -  75% yield, of random copolymers of the poly(d,l-succinimide-co-Nδ-phthaloyl-D,L-ornithine) type 6 possessing inherent viscosities (DMF) in the range of 5  -  15 ml g-1. Copolyimides of the same compositions 6 and comparable chain lengths are obtained from aspartic acid and the copper chelate of the phthaloylornithine. Treatment of copolymers 6 with hydrazine hydrate in DMF leads to N-deprotection and opening of the intrachain succinimide rings with formation of hydrazide side groups. The resultant polyamides are of the poly(α,β-d,l-asparthydrazide-co-d,l-ornithine) type 7. Shorter reaction periods give incomplete hydrazinolytic ring opening, and the remaining succinimide units are cleaved hydrolytically during the subsequent aqueous workup, thereby transforming into aspartic acid units. The polyamides so formed possess the general poly(α,β-d,l-asparthydrazide-co-α,β-d,l-aspartic acid-co-d,l-ornithine) structure 8 Both types 7 and 8 are soluble in water and, in this medium, give inherent viscosities of 5  -  14 ml g-1. The potential drug-anchoring capabilities of these amine-functionalized polyamides are demonstrated by coupling reactions with model carboxylic acids.
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    Antioxidants and stabilizers, 111Part 110 cf. Polym. Degrad. Stab., in press.. Regeneration mechanism of the antioxidant action of N-isopropyl-N′-phenyl-1,4-phenylenediamine (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 175 (1990), S. 169-180 
    Details
    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 Arbeiten über den Wirkungsmechanismus von Antioxidantien in Kohlenwasserstoffpolymeren unter Sauerstoffmangel wurde die Abfangreaktion des Modellradikals 1-Cyano-1-methylethyl (R°) mit N-Isopropyl-N′-phenyl-1,4-phenylendiamin (Ia) und seinem Oxidationsprodukt IIa untersucht. Reines Ia und IIa reagieren kaum mit R′, eine Mischung aus beiden ist jedoch ein effektiver Fänger fur R′, wobei R′ entweder am Stickstoffatom zwischen den aromatischen Ringen unter Bildung von VIa gebunden wird, oder unter Substitution mit dem Phenylenring reagiert, wobei VIIIa entsteht. Verbindung VIa ist labil, bei Vulkanisationstemperatur spaltet sie im neutralen Medium Olefin unter Regenerierung von Ia ab. In Gegenwart von Säuren lauft diese Reaktion auch bei niedrigerer Temperatur ab. Im Produkt VIIIa ist R′ fest gebunden, durch die Nitrilgruppe tritt jedoch eine säurekatalysierte Cyclisierung zum Indolinderivat X ein. Die Bildung von VIIIa ist ein Modell für die Entstehung einer „nichtextrahierbaren Fraktion“ des Antioxidants Ia bei der Stabilisierung von Kohlenwasserstoffpolymeren.
    Notes: In connection with the investigation of the mechanism of antioxidant action of antidegradants in hydrocarbon polymers under the conditions of a relative deficiency of oxygen, scavenging of a model alkyl (1-cyano-1-methylethyl,R°) was studied with Nisopropyl-N′-phenyl-1,4-phenylenediamine (Ia)For abbreviations see p. 11. and its oxidation product, i.e. Nisopropyl-N′-phenyl-1,4-benzoquinonediimine (IIa). While pure Ia and IIa do not react with the radical R° almost at all, their mixture is able to scavenge R° effectively. The reaction is further accelerated with acids. The alkyl R° combines with the antidegradant molecule in two ways, one of which leads to the substitution at the nitrogen atom between the aromatic rings, giving rise to VIa, while the other consists in the substitution of phenylene, leading to VIIIa. The product VIa is labile, and at vulcanization temperatures it readily splits off olefin in a neutral medium, being regenerated to Ia. In the presence of acids this reaction proceeds even at lower temperatures. In the other product, i.e. in VIIIa, the alkyl R° is bound firmly, but due to the presence of the nitrile group, VIIIa is readily cyclized by the effect of acids, and an indoline derivative X is formed. The formation of VIIIa is a model of the formation of an “unextractable fraction” of antidegradant Ia in the stabilization of hydrocarbon polymers. Investigations based on the isolation of reaction products bear at the same time evidence of the possibility of regeneration of an effective antioxidant in the stabilized substrate.
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    Wetterbeständigkeit von polymeren: Messung der photochemischen abbauprozesse und der schutzwirkung anorganischer pigmente mittels physikalischer untersuchungsmethodenHerrn Prof. Dr. Hans Rudolph zum 60. Geburtstag gewidmetVortrag anläßlich des 19. Donauländergesprächs über “Atmosphärische Alterung und Stabilisierung von Polymeren” in Prag (Tschechoslovakei) vom 24. - 29. Juli 1989 (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 176 (1990), S. 1-25 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The photochemical degradation of polymers (commonly known as UV degradation) takes place in two stages: First, there is the primary process comprising the rapid formation of radicals caused by quanta of visible light; this involves the dissociation of polymer chain molecules and/or the activation of polymer chain molecules respectively of additives, colorants and impurities contained in the polymer. The secondary process consists in oxidation reactions with singulett-oxygen generated by energy-transfer and/or between the polymer radicals thus formed and adsorbed oxygen, as a result of which gradual degradation of the polymer takes place.An investigation of these individual reactions using a combination of selected physical test methods leads to an unterstanding of the entire reaction sequence involved in photo-oxidative degradation. This knowledge provides a basis for systematically improving the weather-resistance of polymers by modifying their basic polymeric structure or through the controlled use of UV absorbers, quenchers, radical interceptors and antioxidants.The physical test methods themselves are divided into two categories: techniques used for investigating the primary processes (ultra short-time spectroscopy, ESR) and those used to investigate the secondary processes (XPS, FT-IR, UV/VIS et al.).With pigmented polymers, attention is focussed on borderline cases in the use of photoactive and photoinactive pigments: as a result of “photocatalytic oxidation”, photoactive pigments (e.g. TiO2 anatase) lead to additional degradation reactions which take place at the same time as the UV degradation reaction. Photoinactive pigments (e.g. high-grade TiO2-rutile and iron oxide pigments), on the other hand, exhibit negligible or no photocatalytic oxidation and, by absorbing UV radiation, provides better protection for the polymer against UV degradation.This paper gives an overview of the above-mentioned physical methods of investigating primary and secondary photochemical processes, taking a thermoplastic material (Polycarbonate) as an example. A description is also given of the photocatalytic oxidation reations which can take place if pigmented polymers are used, and there is a discussion of the degradation-inhibiting effects of inorganic pigments.
    Additional Material: 7 Ill.
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    Investigation of the thermal ageing of polyethylene and polystyrene with the purpose of predicting their shelf-lifePaper presented at the 19th Colloqium of Danubian Countries on “Atmospheric Aging and Stabilization of Polymers” in Prague (Czechoslovakia), July 24 - 29, 1989 (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 176 (1990), S. 87-92 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The aim of the present work is to predict the warehouse storage life of polyethylene low-density, polyethylene high-density and polystyrene impact-resistent, using the method of temperature-time superposition. The properties, most representative for thermal ageing, are the relative elongation at break for polyethylene and the impact resistance for polystyrene. The validity of the predicted shelf-life is verified by estimating the change of these properties under real conditions of warehouse storage.
    Additional Material: 3 Ill.
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    Thermal and UV degradation of impact-resistant polystyrene (II)Paper presented at the 19th Colloquium of Danubian Countries on “Atmospheric Aging and Stabilization of Polymers” in Prague (Czechoslovakia), July 24-29, 1989 (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 176 (1990), S. 105-112 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A commercial type of impact-resistant polystyrene was investigated. Two types of antioxidants, Irganox 245 and Irganox PS-800 were added to polystyrene in ammounts of 0,05 to 0.20%. Films, dumbbells and straight test pieces were subjected to thermal and u.v. ageing. Films of 250 μ thickness were thermally treated at 100°C and separately u.v. irradiated at 360 nm for 24, 72, 120 and 168 hours. Dumbbells and straight test pieces were only thermally aged at 100°C for 7, 14, 21, 28 and 35 days. Mechanical properties were determined. The spectra of samples were recorded using Perkin-Elmer, model 1750 FTIR and Perkin-Elmer data station 7700. Colour changes of all dumbbells were measured using Elrepho apparatus in u.v.-visible region. (Changes of the content of carbonyl and hydroxyl groups, as well as of polybutadiene (PB) unsaturation in films were recorded on i.r. spektrophotometer Perkin-Elmer 257 between 4000 and 625 cm-1 and were published in the first part of this study1).
    Additional Material: 7 Ill.
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    New resin system for low-pressure moulding compounds with special properties (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 181 (1990), S. 85-91 
    Details
    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: Formstoffe aus aromatischen Polyepoxiden, aromatischen Polyaminen mit hochtemperaturbeständigen Strukturelementen sowie pulverförmigen Füllstoffen besitzen hervorragende Eigenschaften, wie hohe Glasübergangstemperatur, hohemechanische Festigkeit, kleinen thermischen Ausdehnungskoeffizienten und Schwerbrennbarkeit ohne Zugabe von Flammschutzmitteln. Über die Synthese dieser aromatischen Polyamine, die Herstellung und Verarbeitung der Niederdruckpreßmassen sowie die Eigenschaften der Formstoffe wird berichtet.
    Notes: Moulded materials produced from aromatic epoxide resins, aromatic polyamines with high-temperature-resistant structure units and powdered mineral fillers possess outstanding properties like high glass transition temperatures, high mechanical strength, low linear thermal expansion coefficient, and reduced flammability without the addition of flame retardants. An account is given of the synthesis of aromatic polyamines, the preparation and working of moulding materials and the properties of the finished products.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1990.051810107
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    Lichtinduzierte Umorientierung der optischen Achse in LC-Farbstoff-CopolymerenHerrn Prof. Dr. D. Braun zum 60. Geburtstag gewidmetVortrag anläßlich der Tagung der Fachgruppe “Makromolekulare Chemie” der Gesellschaft Deutscher Chemiker über “Polymere und Licht”. in Bad Nauheim vom 7. bis 9. Mai 1990. (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 183 (1990), S. 103-113 
    Details
    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 influence of linearly and circularly polarized light on the state of order of nematic dye-copolymers is investigated. For a nematic model system we have shown that the optical axis of these systems can be reorientated with linearly polarized light in a well defined manner. Furthermore these investigations prove that the isomerisation cycles of the azo dye is responsible for the described properties. By selection of circularly polarized light the same transmission behaviour as shown by selectively reflecting materials, i. e. cholesteric liquid crystals, was observed.
    Notes: Untersucht wird der Einfluß von linear und zirkular polarisiertem Licht auf den Ordnungszustand von nematischen Farbstoff- Copolymeren. Am Beispiel eines Modellsystems wird gezeigt, daß mit linear polarisiertem Licht die optische Vorzugsachse dieser Systeme gezielt reorientiert werden kann. Die Untersuchungen zeigen, daß der Isomerisierungszyklus des Azofarbstoffes für diese Eigenschaft des Materials verantwortlich ist Nach Bestrahlen der Probe mit zirkular polarisiertem Licht wird für das Polymere das gleiche Transmissionsverhalten beobachtet. Wie es auch selektivreflektierende Materialien, z. B. cholesterische Flüssigkristalle, aufweisen.
    Additional Material: 16 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1990.051830105
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    Anwendung organischer Resistmaterialien in der SynchrotronlithographieVortrag anläßlich der Tagung der Fachgruppe “Makromolekulare Chemie” der Gesellschaft Deutscher Chemiker über “Polymere und Licht”. in Bad Nauheim vom 7. bis 9. Mai 1990. (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 183 (1990), S. 123-132 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1990.051830107
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    HERSTELLUNG VON MIKROSTRUKTURPRODUKTEN DURCH TIEFENLITHOGRAFIE UND SPRITZGUSSPaper presented at the meeting of the GDCh-Fachgruppe “Makromolekulare Chemie” on “Polymers and Light” in Bad Nauheim (West Germany), May 7 - 9, 1990. (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 183 (1990), S. 133-150 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: For fabricating microstructures with extreme structural heights a technology has been developed which is based on deep-etch lithography and subsequent replication processes. A particularly high precision is achieved if the lithographic process is carried out by means of synchrotron radiation. Electroforming and molding processes are used for the replication of microstructures from a large variety of materials. The field of application comprises micromechanics, microoptics, electrical and optical microconnectors as well as sensors and actuators.
    Additional Material: 9 Ill.
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    Critical requirements for non linear optical polymeric materials in active optical devices: The present state and prospects for the futurePaper presented at the meeting of the GDCh-Fachgruppe “Makromolekulare Chemie” on “Polymers and Light” in Bad Nauheim (W-Germany) May 7 - 9, 1990. (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 183 (1990), S. 151-166 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1990.051830109
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    Photoconductive polymers: Structure, mechanisms and propertiesPaper presented at the meeting of the CDCh-Fachgruppe “Makromolekulare Chemie” on “Polymers and Light” in Bad Nauheim (W-Germany) May 7-9, 1990. (1990)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 183 (1990), S. 197-220 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Charge carrier transport properties of organic polymers can vary over a wide range. The paper shows that the electron- and hole mobilities of polymers with pendant photoconductive groups (i. e. carbazole) are on the order of 10-6 cm2/Vs. In these materials the flow of electronic charge is maintained by the overlap of the π-orbitals of the pendant molecular groups. The large variation of this short-range interaction, depending on the local configurations encountered in polymer glasses, leads to a large variation of hopping probabilities and, hence, to wide rate-distributions. These distributions are reflected in the slow algebraic decay characteristics of the observed photocurrents. The typical time exponents α (α 〈 1) are shown to carry a great deal of physical information, if the dynamical range of the experiments is sufficiently large. The paper also refers to quasi-conjugated polymers (polysilanes) whose dynamic transport parameters are about 103 times better (faster) as compared to polymers with pendant groups. These new materials open interesting aspects for the development of new polymeric materials with better transport parameters and, hence, shorter 'switching times'.
    Additional Material: 17 Ill.
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    Optimization of mechanical strength of reinforced composites. 1. Study on the effect of reactive bismaleimide on the mechanical performance of CaCo3-filled polypropylene (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 224 (1995), S. 9-20 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß von 3-Phenylenbismaleimid auf die Werkstoffeigenschaften von CaCO3 gefüllten Polypropylen-Verbundstoffen wurde untersucht. Die Verarbeitungstemperatur spielte eine entscheidende Rolle bei der Herstellung der Verbundwerkstoffe. Bei Verarbeitungstemperaturen oberhalb der Bismaleimid-Zersetzungstemperatur zeigte die Bismaleimid-Verbindung einen positiven Effekt. Die chemische Zusammensetzung der modifizierten Verbunde wurde mit den mechanischen Eigenschaften korreliert. Basierend auf ESCA-Analysen werden Wechselwirkungen zwischen dem Polymeren und CaCO, diskutiert.
    Notes: The effect of 3-phenylene bismaleimide on the mechanical performance of an inorganic filler-based polypropylene composite was studied. The selection of processing temperature played a significant role in the preparation of such composites. A positive effect of the bismaleimide compound was obtained for a processing temperature above the decomposition temperature of bismaleimide. The chemical composition of the modified composite was correlated to its mechanical strength by experimentation involving a rotatable design. An interaction between polymer and CaCO3 has been proposed based on ESCA analysis.
    Additional Material: 9 Ill.
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    The effect of the processing steps on the oxidative stability of polyethylene tubing crosslinked by irradiation (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 224 (1995), S. 33-48 
    Details
    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: Chemische und mechanische Eigenschaften von Zwischenprodukten der PE-Schrumpfschlauch-Produktion wurden bei unterschiedlichen Compound-Zusammensetzungen (PE, ein aromatisches Amin oder Phenolderivat als Antioxidans und in einigen Fällen ein Flammschutzmittel und/oder eine Elastomerkomponente) untersucht.Während der Herstellung, besonders während der durch Elektronenstrahlung initiierten Vernetzung, nimmt die thermooxidative Stabilität des Materials gegenüber der des compoundierten Granulats ab. Das aromatische Amin scheint bei gleicher Zusammensetzung das wirksamere und strahlungsbeständigere Antioxidans im Vergleich zum Phenolderivat zu sein. Die Oxidationsstabilität der hergestellten Schrumpfschläuche wird nicht von der Qualität des eingesetzten PE-Ausgangsgranulats beeinflußt.Durch die Alterung des Materials ändern sich die mechanischen Eigenschaften geringfügig. Die Elastomerzugabe bewirkt keine Änderung von Zugfestigkeit und Reißdehnung. Die Stabilität des Endprodukts ist bei weitem ausreichend, um den Spannungen, die beim Schrumpfen während des Gebrauchs auftreten, standzuhalten. Die gute Zugfestigkeit des Materials wird durch die Alterung ebenfalls nicht beeinträchtigt.Bei der Extrusion des Granulats tritt keine nennenswerte Änderung des Molekulargewichts bzw. der Molekulargewichtsverteilung auf. Durch die Bestrahlung wird das Material vernetzt und zu mehr als 50% unlöslich, und seine thermooxidativen Eigenschaften ändern sich deutlich gegenüber dem ursprünglichen PE und dem daraus compoundierten Material.
    Notes: Some chemical and mechanical properties of intermediate products obtained in the production of PE heat-shrinkable tubes were studied at different compositions of the material containing PE, antioxidant (aromatic amime or phenol) and, in some cases, flame retardant and/or an elastomer.In the course of the production phase, the thermooxidative stability decreases compared to that of compounded granulate. The greatest decrease is caused by irradiation. The aromatic amine seems to be a more effective antioxidant at similar compositions than the phenol derivative, and it shows a better resistance against irradiation. The oxidative stability of the finished shrinkable tubes is not affected by the quality of commercial granulate (initial polyethylene).Mechanical properties change slightly upon ageing, and the introduction of the elastomer did not alter the tensile strength and elongation at break. The remaining stability of the end product was still high enough to bear the stress of shrinking in use, and the good tensile strength of the material did not decrease upon thermal ageing either.In the extrusion of the granulated compound no significant change in the distribution and average molecular weight took place. Irradiation produced more than 50% insoluble fraction and the thermooxidative properties of the crosslinked sample changed significantly compared to the original PE and to the compound prepared from it.
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    Thermogravimetrie als brennbarkeitsbestimmungs-methode für lineare polyurethane (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 224 (1995), S. 89-96 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In the present work oxygen index (OI) measurements and thermogravimetric analysis (TG) for a series of polyurethanes based on diols and isocyanate were conducted. It was found that a correlation exists between some of the thermal degradation parameters obtained from TG and OI-values. Analysis of experimental results confirms that the amount of mass loss at 250°C is directly proportional to the OI-value. It was also found that the logarithmic temperatures of maximal decomposition rates are directly proportional to the OI-values.
    Notes: In der vorliegenden Arbeit wurden für eine Serie von Polyurethanen auf der Basis von Diol und Isocyanat der Sauerstoffindex (SI) gemessen und die thermische Zersetzung mittels thermogravimetrischer Analyse (TG) untersucht. Dabei wurde ein Zusammenhang zwischen einigen Parametern der thermischen Zersetzung und den SI-Werten gefunden. Die Auswertung der experimentellen Ergebnisse zeigte, daß die Höhe des Massenverlustes bei 250°C und die SI-Werte direkt proportional zueinander sind. Derselbe Zusammenhang besteht auch zwischen dem Logarithmus der Temperatur bei der maximalen Zersetzungsgeschwindigkeit und den SI-Werten.
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    Studies on thermal stability of modified polycarboxylate cements (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 224 (1995), S. 109-114 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Poly(acrylsäre-co-acrylamid) wurde mit Zinkoxid und Kryolith (Na3AlF6) in unterschiedlichen Verhältnissen gemischt und bei Raumtemperatur zu Zahnzementen ausgehärtet. IPDT, Temperaturen bei maximaler Abbaugeschwindigkeit, Aktivierungsenergien und Frequenzfaktoren des thermischen Abbaus der Proben wurden aus thermogravimetrischen Messungen ermittelt. Die Probe mit 20 Gew.-% Kryolith in der Füllstoffmischung ist thermisch sehr stabil.
    Notes: Dental cement compositions made by mixing poly(acrylic acid-co-acrylamide) and mixtures of zinc oxide and cryolite (Na3AIF6) in various proportions of 10-50 wt.-% (w/w) were cured at room temperature. From thermogravimetric analyses of the samples, the integral procedural decomposition temperatures (IPDT), maximum decomposition temperatures, activation energies and frequency factors were evaluated. The cured cement sample containing 20 wt.-% cryolite in the filler mixture is thermally very stable.
    Additional Material: 2 Ill.
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    Synthesis and characterization of water-soluble diazonium salts as contrast-enhancement materials (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 224 (1995), S. 133-144 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die wasserlöslichen aromatischen Diazonium-Doppelsalze p-Diazodiphenylaminchlorid/Zinkchlorid (DZS-1) und p-Diazoanisolchlorid/Zinkchlorid (DZS-2) wurden auf ihre Verwendbarkeit als photobleichbare Farbstoffe in der Kontrastverstärkungslithographie untersucht. Nach Untersuchung der Bleicheigenschaften der hergestellten Salze wurde DZS-1 in wäßrigen Lösungen mit Poly(vinylalkohol) als Kontrastverstärkungssystem eingesetzt. Die thermische Stabilität, der Resistkontrast, die Bestrahlungsparameter und andere Bleicheigenschaften wurden untersucht. Im Vergleich zu einem handelsüblichen i-Linien-Photoresist beträgt das Kontrastverhältnis der DZS-1/PVA CEL-Schicht 1,67.
    Notes: Water soluble aromatic diazonium double salts, p-diazodiphenylamine chloride zinc chloride (DZS-1) and p-diazoanisol chloride zinc chloride (DZS-2), have been evaluated as photobleachable dyes for contrast enhancement lithography. After testing the bleaching characteristics, aqueous solutions of DZS-1 and poly(vinyl alcohol) were used as a contrast enhancement material. Thermal stability, resist contrast, exposure parameters and other bleaching characteristics of the photobleachable membranes were investigated. A. commercial i-line photoresist was used to evaluate the contrast ratio of the DZS-1/PVA CEL layer. The contrast ratio obtained in this investigation is 1.67.
    Additional Material: 10 Ill.
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    Comparison of the coupling behaviour of diisocyanate and bisoxazolines in modification of liquid crystalline poly(ethylene terephthalate-co-oxybenzoate)s (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 224 (1995), S. 167-178 
    Details
    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: Methylen-4,4′-diphenyldiisocyanat und zwei unterschiedliche Bisoxazoline wurden für Kopplungsreaktionen in mit Carboxygruppen terminierten flüssigkristallinen Poly(ethylenterephthalat-co-oxybenzoat)en eingesetzt. Um definierte Bedingungen zu gewährleisten, erfolgte die Synthese von Copolyestern mit unterschiedlichen Carboxygruppenkonzentrationen. Die Bestimmung des Carboxygruppengehalts wird beschrieben.Es erfolgt ein Vergleich des Kopplungsverhaltens beider Arten von Kettenverlängerern. Es konnte nachgewiesen werde, daß die Bisoxazoline bedeutend schneller reagieren als das Diisocyanat. Durch einen geringen Überschuß and Bisoxazolin in der Reaktionsmischung konnte einer thermischen Schädigung vorgebeugt werden. Abhängig von der Menge an zugegebenem Koppler wurden bei den modifizierten Copolyestern Oxazolinendgruppen beobachtet. Außerdem werden mögliche Vernetzungsreaktionen und die thermische Stabilität diskutiert.
    Notes: Methylene-4,4′-diphenyldiisocyanate and two different bisoxazolines were used for coupling reactions in carboxy-terminated liquid crystalline poly(ethylene terephthalate-co-oxybenzoate). In order to guarantee defined conditions, copolyesters with different carboxylic group concentrations were synthesized. The determination of the carboxylic group content is described.The coupling behaviour of both types of chain extenders has been compared. It was evidenced that the bisoxazolines reacted significantly faster than the diisocyanate. A slight excess of bisoxazoline in the reaction mixture prevented thermomechanical degradation. Depending on the amount of coupling agent added, an oxazoline termination of the copolyester was observed. Additionally, probable crosslinking reactions and the thermal stability have been discussed.
    Additional Material: 7 Ill.
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    Announcements (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 224 (1995), S. 201-201 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    URL: http://dx.doi.org/10.1002/apmc.1995.052240120
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    Optimization of mechanical strength of reinforced composites. 2. Reactive bismaleimide-modified polypropylene composites filled with talc and zeolitePart 1 cf.2. (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 225 (1995), S. 11-20 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß von 3-Phenylenbismaleimid auf die Werkstoffeigenschaften von mit Talkum und Zeolith gefüllten Polypropylen-Verbundstoffen wurde untersucht. Durch geeignete Planung des Aufbaus kann die Produkteigenschaft optimiert werden. Die Kapazität zur Füllstoffaufnahme schwankt bei Polypropylen je nach Art des Füllstoffs. Ein hochbelastbarer Verbundstoff kann aus einem geeignet modifizierten, mit Zeolith gefüllten Polypropylen hergestellt werden, auch wenn der Füllstoff in der Verbundmatrix dominiert. Als Ursache dieser Verstärkung wird eine verbesserte Wechselwirkung zwischen dem Polymeren und dem Füllstoff angenommen.
    Notes: The effect of 3-phenylene bismaleimide as a modifier for talc and zeolite-filled polypropylene composites has been studied. The usefulness of the experimental design to assure best product properties has also been illustrated. Polypropylene shows a variable degree of filling capacity depending on the type of filler. A high-strength composite can be prepared with suitably modified zeolite-filled polypropylene even if filler is the dominant phase in the composite matrix. An improved interfacial interaction between polypropylene and filler is proposed to be the reason for this improvement of strength.
    Additional Material: 3 Ill.
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    Oligomerization of 1-decene with Ziegler-Natta catalysts (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 225 (1995), S. 51-61 
    Details
    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 katalytische Oligomerisation von 1-Decen wurde mit Komplexverbindungen mehrerer Übergangsmetalle (Co(II), Co(III), Zr(IV), Ti(IV), Cr(III), V(V)) und Alkyl-aluminiumhalogeniden als Cokatalysatoren durchgeführt. Mit einem Chrom(III)-Et3Al2Cl3-Katalysatorsystem konnten Dimere (C20), Trimere (C30) und Tetramere (C40) von 1-Decen erhalten werden. Die kinematischen Viskositäten und Fließpunkte der hydrierten Oligomere wurden bestimmt und mit den Werten handelsüblicher Proben verglichen. Ein Mechanismus für die Oligomerisation von 1-Decen mit diesem Katalysatorsystem wird vorgeschlagen.
    Notes: The catalytic oligomerization of 1-decene has been carried out employing several transition metal complexes of Co(II), Co(III), Zr(IV), Ti(IV), Cr(III), V(V) in combination with alkyl aluminum halides as cocatalysts. The chromium(III)-Et3Al2Cl3 system exhibits good oligomerizing activity yielding dimers (C20), trimers (C30) and tetramers (C40) of 1-decene. The kinematic viscosities and pour points of hydrogenated oligomers have been determined and compared with those of commercial samples. The probable mechanism of oligomerization of 1-decene on this catalyst is described.
    Additional Material: 3 Ill.
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    Zur Häurtung von Bisphenol-A-diglycidether mit Dicyandiamid in Gegenwart von Beschleuniger-Addukten (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 225 (1995), S. 99-107 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Single-component formulations of epoxy resins with reactive accelerators must be storable. The preparation of several blocked accelerators is described. The basicity of tertiary amines, which correlates with accelerating effects, as well as acidity and structure of polyphenols and modified novolacs influences the extend of blocking. The curing process was investigated by measurements of gel time and viscosity.
    Notes: Einkomponentige Epoxidharzsysteme mit effizienten Reaktionsbeschleunigern müssen lagerstabil sein. Daher wurden Versuche unternommen, Beschleuniger auf Basis von tertiären Aminen mit modifizierten Phenolnovolaken zu blockieren. Das Ausmaß der Blockierung ist sowohl von der Basizität der Amine, die mit der beschleunigenden Wirkung korreliert, als auch von der Acidität und dem strukturellen Aufbau der modifizierten Phenole abhängig. Die Bewertung der Härtungseigenschaften erfolgte über Gelzeitbestimmungen und Viskositätsmessungen.
    Additional Material: 2 Ill.
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    Comparison of the crack growth method and the crack stress whitening zone method for the fracture toughness determination of phenolphthalein poly(ether ketone)Key Project of the National Natural Science Foundation of China. (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 225 (1995), S. 131-138 
    Details
    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 Bruchzähigkeit von Phenolphthalein-Poly(etherketon) bei 190°C wurde mit zwei verschiedenen Methoden bestimmt, der konventionellen Rißwachstumsmethode und der „stress whitening zone“-Methode. Die gute Übereinstimmung der Ergebnisse zeigt, daß letztere Methode zur Bestimmung der Rißinitiierung einiger Polymerer herangezogen werden kann, für die das „blunting line concept“ nicht geeeignet ist.
    Notes: Fracture toughness values of phenolphthalein poly(ether ketone) (PEK-C) at 190°C were determined by two different methods, i.e. the conventional crack growth method and the crack stress whitening zone method, which show consistent results. This indicates that the crack stress whitening zone method can be used to determine the crack initiation of some polymers for which the blunting line concept is unsuitable.
    Additional Material: 7 Ill.
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    Thermodynamic studies on some interpolymer interactions and stability of polycomplexes (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 226 (1995), S. 13-22 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Stabilitätskonstanten und zugehörige thermodynamische Parameter (ΔH°, ΔS°) eines intermakromolekularen Komplexes aus Poly(acrylsäure-co-acrylamid), Poly(methacrylsäure-co-acrylamide) und Poly(N-vinylpyrrolidon) wurden mit bekannten Methoden bei verschiedenen Temperaturen bestimmt. Dabei wurde eine stufenweise Auflösung des Komplexes in Abhängigkeit von der Temperatur beobachtet, die mit den Stabilitätskonstanten und den thermodynamischen Parametern korreliert wurde.
    Notes: Stability constant and related thermodynamic parameters (ΔH° and ΔS°) of a multicomponent intermacromolecular complex consisting of poly(acrylic acid-coacrylamide), poly(methacrylic acid-co-acrylamide) and poly(N-vinylpyrrolidone) have been determined using known methods. A distinct stepwise disintegration of the complex at different temperatures has been observed, and this could be correlated with the stability constant and thermodynamic parameters calculated at various temperatures.
    Additional Material: 2 Ill.
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    The effect of ultrasound in ethyl methacrylate polymerization and depolymerization reactions (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 226 (1995), S. 53-57 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß von Ultraschall auf die Polymerisation und Depolymerisation von Ethylmethacrylat und der Mechanismus des Kettenabbruchs wurden untersucht. Der Polymerisationsumsatz war unabhängig von den verwendeten Ultraschallbedingungen (800 W, 35 kHz). Depolymerisationsversuche mit Ultraschall bei 20°C zeigten, daß Kettenabbruch im wesentlichen durch Disproportionierung stattfindet; dabei werden Molekulargewichte nicht unter ca. 500000 erreicht.
    Notes: The effect of ultrasound in ethyl methacrylate polymerization and depolymerization and the chain termination mechanism for ethyl methacrylate have been studied. Polymerization conversion at 60°C did not depend on energy (80 W) and frequency (35 kHz) of ultrasound applied. In ultrasound depolymerization studies at 20°C the governing termination mechanism was found to be disproportionation and the lower limiting molecular weight was Mn = 500 000.
    Additional Material: 2 Ill.
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    Reaktive membrancopolymere auf acrylbasis (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 226 (1995), S. 71-87 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The copolymerization of acrylonitrile with maleic anhydride was investigated to synthesize acylic reactive polymers for manufacture of membranes that serve as support for covalent enzyme immobilization. The free-radical copolymer synthesis was carried out in solution (N,N-dimethylformamide (DMF), dimethylacetamide (DMAC), γ-butyrolactone, ethylene carbonate), by precipitation polymerization (dioxane) as well as bulk polymerization. The polymers were characterized using IR spectroscopy, elementary analysis, NMR spectroscopy, gel permeation chromatography, viscosity measurements, osmometry and potentiometry.The kinetic parameters were followed by dilatometric measurements up to high conversions. The anhydride content in the monomer mixtures showed a significant influence on the rate of polymerization and the molecular weight. With raised concentration of anhydride the polymerization rate and molecular weights decreased. Film forming polymers (M̄η 〉 30 000 g/mol) can be obtained by all copolymerization procedures with exception of solution polymerization in DMF and DMAC, respectively. The content of maleic anhydride in the membrane polymers did not exceed 5 mol-%, even though the maleic anhydride content in the monomer mixtures was raised up to the equimolar mixture. Nevertheless, such low maleic anhydride content of prepared membranes is enough for successful enzyme immobilization with amyloglucosidase (copolymer was prepared in γ-butyrolactone, M̄η = 49 000 g/mol, cPMSA = 0,3 mol-%).
    Notes: Die Copolymerisation des Acrylnitrils mit Maleinsäureanhydrid (MSA) wurde mit dem Ziel untersucht, acylfunktionalisierte Reaktivpolymere mit Filmbildungseigenschaften herzustellen, um diese in der Anwendung als Membran für kovalente Enzymfixierungen zu nutzen. Die radikalinitiierte Synthese der Copolymeren wurde in Lösung (Dimethylformamid (DMF), Dimethylacetamid (DMAC), γ-Butyrolacton, Ethylencarbonat), durch Fällungscopolymerisation (Dioxan) sowie in Substanz durchgeführt.Die Polymercharakterisierung erfolgte durch IR-Spektroskopie, Elementaranalyse, Kernresonanzspektroskopie, Gelpermeationschromatographie, Viskosimetrie, Osmometrie und Potentiometrie.Die Kinetik wurde durch dilatometrische Untersuchungen bis zu hohen Umsätzen verfolgt. Danach weist der Anhydridgehalt im Monomergemisch einen signifikanten Einfluß auf die Bruttopolymerisationsgeschwindigkeit und die Molmasse der Polymeren auf. Mit steigendem Anhydridanteil wird die Bruttopolymerisationsgeschwindigkeit herabgesetzt und eine Verringerung der Molmasse herbeigeführt. Die Copolymerisation von Acrylnitril und Maleinsäureanhydrid führt mit Ausnahme der Lösungspolymerisation in DMF bzw. DMAC zu Polymeren mit Molmassen oberhalb 30 000 g/mol, was ihre Anwendung als Membran ermöglicht. Die Einbaurate an Maleinsäureanhydrid in den Membranpolymeren ist bis einschließlich einer äquimolaren Zusammensetzung des Monomergemischs nicht größer als 5 mol-%. Derartig niedrige MSA-Reaktivgruppenanteile erweisen sich jedoch als ausreichend, um an einer aus einem Lösungspolymerisat (γ-Butyrolacton, M̄η = 49 000 g/mol, cPMSA = 0,3 mol-%) formierten Membran eine Enzymimmobilisierung mit Amyloglucosidase nachzuweisen.
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    Synthesis and characterization of photopolymers with azo units. Interfacial polyaddition, photolysis, photodegradation (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 226 (1995), S. 143-160 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Synthesen einer Aryl-alkyl-azodiisocyanat-Verbindung und einer Azoharnstoff-Modellsubstanz werden beschrieben. Aus dem Azodiisocyanat wurden durch Grenzflächen-Polyaddition neuartige Azoharnstoff-Polymer hergestellt. Die zahlenmittleren Molekulargewichte, bestimmt mit der Gelpermeationschromatographie (GPC), lagen zwischen 6000 und 9000. Die Photolyse- und Thermolysereaktionen der Modellsubstanzen und der Polymeren wurden mittels UV-Spektroskopie und Differentialkalorimetrie (DSC) verfolgt und mit den Ergebnissen von ähnlichen Azoamiden verglichen. Der photochemische Polymerabbau wurde mittels GPC untersucht.
    Notes: The synthesis of an aryl alkyl azo diisocyanate and a model azo urea is described. From the azo diisocyanate new azo polyureas were created by interfacial polyaddition. Molecular weights Mn in the range of 6000 to 9000 were determined by gel permeation chromatography (GPC). Photolysis and thermolysis of both, model compounds and polymers, were studied by UV-spectroscopy and differential scanning calorimetry (DSC), respectively, and the results were compared with those of similar azo amides. Photochemical polymer degradation was followed by GPC.
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    Announcements (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 226 (1995), S. 219-219 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1995.052260120
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    Molecular structure of liquid-crystalline copolyesters of vanillic acid, 4-hydroxybenzoic acid and poly(ethylene terephthalate) (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 227 (1995), S. 69-85 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Thermotrop flüssigkristalline Copolyester aus Vanillinsäure (V), 4-Hydroxybenzoesäure (B) und Polyethylenterephthalat (E) wurden mittels 1H-NMR-Spektroskopie und Gelpermeationschromatographie (GPC) untersucht. Die neun möglichen Diaden konnten detektiert und zugeordnet werden. Die Abfolge der Grundeinheiten der V/B/E-Copolyester ändert sich mit zunehmendem B-Anteil von statistischer Verteilung zur Blockbildung und ist außerdem geringfügig von der Katalysatorkonzentration und der Polykondensationsdauer abhängig. Die GPC-Ergebnisse deuten darauf hin, daß die V/B/E-Copolyester engere Molekulargewichtsverteilungen aufweisen als die B/E-Copolyester. Mit von 0 bis 5 mol-% steigendem V-Anteil verengt sich die Molekulargewichtsverteilung. Die Gelpermeationschromatogramme der meisten V/B/E-Copolyester weisen im Unterschied zu den Einzelsignalen der B/E-Copolyester Dublett-Peaks auf.
    Notes: Thermotropic liquid-crystalline copolyesters made from vanillic acid (V), 4-hydroxybenzoic acid (B) and poly(ethylene terephthalate) (E) were examined by 1H-NMR and GPC investigations. Nine possible diads could be identified and assigned. The sequence distribution of V/B/E copolyesters tends to change from random to block with an increase of B content in the copolyesters. The sequence distribution also varies slightly with catalyst concentration and polycondensation time. GPC results suggest that the V/B/E copolyesters have narrower molecular weight distribution (MWD) than B/E copolyesters. The MWD of the copolyesters narrows gradually with increasing V content from zero to 5 mol-%. The GPC chromatograms of the most V/B/E copolyesters show double peaks, which is different from the single peak of the GPC chromatograms of the B/E copolyesters.
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    Effect of pre-irradiation on radiation stability of co-polypropylene (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 227 (1995), S. 111-120 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Strahlungsbeständigkeit von vorbestrahltem Polypropylen mit 2,5 Gew.-% Ethylenanteil wurde mitr einem Copolymeren aus Polypropylen und einem nukleierenden Agens im Hinblick auf die Strahlungssterilisation von medizinischen Geräten verglichen. Die Transparenz des Propylen-Ethylen-Copolymeren wurde durch die Vorbehandlung verbessert. Im Vergleich mit der ebenfalls verbesserten Transparenz des Copolymeren aus Polypropylen und dem nukleierenden Agens wurde durch die Vorbestrahlung die Strahlungsbeständigkeit während der Bestrahlung und bei der Lagerung des bestrahlten Materials verbessert. Dies wird auf die geringere Kristallinität des vorbestrahlten Polypropylens aufgrund von bei der Bestrahlung gebildeten Verzweigungen zurückgeführt.
    Notes: The radiation stability of the pre-irradiated copolymer of polypropylene containing 2.5 wt.-% ethylene units is compared with a copolymer of polypropylene with a nucleating agent with regard to radiation sterilization of medical devices. It is found that transparency property of the propylene-ethylene copolymer is improved through pre-irradiation processes. This finding was compared with the co-polypropylene with nucleating agent which also gives a better transparency property. In comparison, it is found that pre-irradiated copolymer exhibits better radiation stability during irradiation and during storage after irradiation. The radiation stability of the pre-irradiated copolymer is due to its lower crystallinity caused by the formation of branches during the pre-irradiation process.
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    Mitteilungen/Announcements (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 227 (1995), S. 193-193 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    URL: http://dx.doi.org/10.1002/apmc.1995.052270117
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    Poly(diaryl diazosulfide)s  -  synthesis and photolysisThis topic is part of the Ph.D.-Thesis of A. Lang.. Photopolymers, diazosulfides, interfacial polycondensation, photolysis (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 228 (1995), S. 73-92 
    Details
    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: Polydiaryldiazosulfide wurden durch Grenzflächenpolykondensation aus aromatischen Bisdiazoniumionen und Benzol-1,3-dithiol erhalten. Auf diese Weise wurden Molekulargewichte Mn von 3400 bis 11700 erreicht (GPC).Die neue Polymerklasse zeichnet sich durch hohe Photolabilität und relativ geringe Thermostabilität aus. Mittels UV-Spektroskopie wurde die Photolyse von Modellver-bindungen und Polymeren verfolgt, wobei in nahezu allen Fällen ein Zerfall 1. Ordnung beobachtet wurde. Der photochemische Kettenabbau konnte durch GPC-Untersuchungen verfolgt werden. Die thermische Stabilität der polymeren Diazosulfide wurde durch DSC-Messungen untersucht.
    Notes: Poly(diaryl diazosulfide)s were synthesized from aromatic bisdiazonium ions and benzene-1,3-dithiol via interfacial polycondensation. Number-average molecular weights Mn in the range of 3400 to 11700 were determined by gel permeation chromatography (GPC).The new polymer class is distinguished by high photosensitivity and low thermostability. First order kinetics during photolysis of nearly all polymers and model compounds under investigation was observed by means of UV spectroscopy. Polymer degradation upon irradiation was verified by GPC measurements. Thermal decay was followed by differential scanning calorimetry (DSC).
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052280107
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    Methoden zur bestimmung des maleinsäureanhydridgehaltes in acrylnitril-copolymeren in gegenwart initialer carboxygruppen (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 228 (1995), S. 161-178 
    Details
    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: Three different titration methods were proved with respect to accuracy, reproducibility and handling for the determination of maleic anhydride (MSA) content in acrylonitrile (AN) copolymers in form of poly(AN-co-MSA) and poly(AN-co-styrene-co-MSA). The comparison comprises (i) the combined method A/H characterized by the reaction of anhydride groups (AG) with aniline and titration of the formed monoacid with methanolic KOH (A) and the complete hydrolysis of AG and titration of acid groups (SG) with aqueous NaOH (H), (ii) method B based on the conversion of AG with n-butylamine (BA) and back-titration of unreacted amine with HClO4 in glacial acetic acid and (iii) method C consisting of the reaction of AG with p-chloroaniline (pCA) followed by Cl-determination after the Schöniger-decomposition. Whereas all mentioned methods are suitable for the determination of AG in the presence of initial SG, the combination of A/H additionally allows the simultaneous determination of AG and SG. In comparison with the other methods the combination of A/H is to be favoured due to the possibility to obtain additional information about SG and because of the better results in accuracy, reproducibility and handling. By means of FTIR spectroscopy the content of AG and SG was estimated qualitatively and a correlation between the spectroscopic and potentiometric data of AG was discovered.
    Notes: Zur Bestimmung des Maleinsäreanhydrid(MSA)-Gehaltes in Acrylnitril(AN)-Copolymeren des Typs Poly(AN-co-MSA) bzw. Poly(AN-co-Styrol-co-MSA) wurden drei verschiedene Titrationsmethoden hinsichtlich ihrer Richtigkeit, Reproduzierbarkeit sowie ihres Zeitaufwandes geprüft. Miteinander verglichen wurden (i) eine Methodenkombination A/H bestehend aus dem Teilschritt A, einer Umsetzung der Anhydridgruppen (AG) mit Anilin einschließlich der Titration der Monosäuregruppen mit methanolischer KOH, und dem Teilschritt H, einer vollständigen Hydrolyse der AG und Titration der Säuregruppen (SG) mit wäßriger NaOH, (ii) Methode B basierend auf der Reaktion der AG mit n-Butylamin (BA) und der Rücktitration des nicht umgesetzten Amins mit Perchlorsäure (HClO4) in Eisessig und (iii) Methode C, beruhend auf der Umsetzung der AG mit p-Chloranilin (pCA) und nachfolgender Chlorbestimmung durch Schöniger-Aufschluß. Während sich alle genannten Methoden prinzipiell für die AG-Bestimmung in Gegenwart initialer SG empfehlen, ist darüber hinaus über A/H eine simultane Bestimmung von AG und SG möglich. Wegen dieses zusätzlichen Informationsgewinns, ihrer besseren Reproduzierbarkeit, der erhöhten Richtigkeit sowie des geringeren zeitlichen und apparativen Aufwandes ist die Kombination A/H zu favorisieren. Mit Hilfe der FTIR-Spektroskopie wurde der Gehalt an AG und SG qualitativ verfolgt und eine Korrelation zwischen den Bandenintensitäten der AG und den potentiometrisch erhaltenen Werten gefunden.
    Additional Material: 6 Ill.
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    Curing of unsaturated polyester resins with low exotherm peak (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 229 (1995), S. 15-27 
    Details
    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 Härtung eines ungesättigten Polyesterharzes mit niedrigem Exotherm-Peak wurde mit der Standardmethodik und der Differential-Kalorimetrie (DSC) untersucht. Ein Kupfersalz und α-Methylstyrol wurden als Polymerisationsverzögerer benutzt. Der Einfluß der Verzögerer auf die Temperatur des exothermen Peaks, die Gelzeit, die Härtungsenthalpie und die Polymerisationskinetik wurden untersucht.
    Notes: The curing behavior of an unsaturated polyester resin with low exotherm peak was studied by a standard procedure and by differential scanning calorimetry (DSC). A copper salt and α-methylstyrene were used as the polymerization retarders. The influence of the retarders on the exotherm peak temperature, gelation time, exothermic heat and the polymerization kinetics was investigated.
    Additional Material: 8 Ill.
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    Modified syndiotactic polypropene: Poly(propene-co-octene) and blends with atactic oligopropene (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 229 (1995), S. 93-112 
    Details
    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: Propen und 1-Octen wurden mit dem syndiospezifischen Metallocen-Katalysator Me2C(Cp)(Flu)ZrCl2/MAO copolymerisiert. Es wurde ein hoher, statistischer Octeneinbau beobachtet. Niedrige Octenkonzentrationen beeinflußten die Aktivität des Katalysators nur wenig; Molekulargewicht, Kristallinität, E-Modul und Glastemperatur wurden dagegen mit ansteigendem Octengehalt erniedrigt. Blends aus ataktischem Oligopropen und syndiotaktischem Polypropen bzw. Poly(propen-co-octen) wurden aus einer Toluol-Lösung hergestellt. Diese Lösungsblends wurden mit einem Reaktorblend verglichen, der mit einem Hybrid-Katalysator bestehend aus einer Mischung von syndiospezifischem Me2C(Cp)(Flu)ZrCl2/MAO und unspezifischem Cp2ZrCl2/MAO hergestellt wurde. Das ataktische Oligopropen wirkte als Weichmacher, der E-Modul und Glastemperatur der Blends erniedrigte.
    Notes: Propene and 1-octene were copolymerized with the syndiospecific homogeneous metallocene catalyst Me2C(Cp)(Flu)ZrCl2/MAO. Large amounts of octene were incorporated randomly. While catalyst activity was not affected markedly by low octene content, molecular weight, crystallinity, Young's modulus, and glass transition temperature were reduced with increasing octene content. Blends of atactic oligopropene with syndiotactic polypropene and poly(propene-co-octene) were prepared from toluene solution and compared with a reactor blend prepared with a hybrid catalyst containing a mixture of syndiospecific Me2C(Cp)(Flu)ZrCl2/MAO and non-specific Cp2ZrCl2/MAO. Atactic oligopropene acted as plasticizer reducing Young's modulus and glass transition temperature of the blends.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052290106
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    Inner surface and void system of regenerated cellulose fibers (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 229 (1995), S. 175-184 
    Details
    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 innere Oberfläche und das Hohlraumsystem von verschiedenartigen Celluloseregeneratfasern werden mit Röntgenkleinwinkelstreuung untersucht. Dabei wird gefunden, daß alle Fasern ein Hohlraumsystem von 0,01 bis 0,1% (Volumenanteil 10-4-10-3) aufweisen. Es zeigt sich jedoch, daß die Größe des Hohlraumsystems für die mechanischen Eigenschaften wenig Bedeutung hat. Es ist vielmehr die Gestalt der Hohlräume und ihre Orientierung, die hier wesentlich sind. Es wird gefunden, daß langgestreckte Hohlräume, vermutlich orientiert, für gute mechanische Eigenschaften verantwortlich sind. Damit können auch verbesserte textile Eigenschaften von Lyocellfasern des NMMO-Typs erklärt werden.
    Notes: Both the inner surface and the void system of different cellulose regenerate fibers are investigated with X-ray small angle scattering. Thereby it turns out that all fibers have a void system of 0.01 to 0.1% (volume fraction 10-4-10-3). However, the amount of the void system has little influence on the mechanical properties. Rather, it is the shape of the voids and their orientation which proves essential. It is found that elongated voids, probably well oriented, are responsible for superior mechanical properties. This explains also improved textile properties of lyocell fibers of the NMMO type.
    Additional Material: 6 Tab.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052290112
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    Radiation-induced copolymerization of methacrylic and acrylic acid with acrylamide (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 230 (1995), S. 1-12 
    Details
    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 mit γ-Strahlen induzierte Polymerisation von Methacrylsäure (MA) und Acrylsäure (AA) mit Acrylamid (AAm) (M2) in Substanz wurde untersucht. Die nach Kelen-Tüdős berechneten Copolymerisationsparameter betragen r1 = 1.35 und r2 = 0.22 für MA-AAm bzw. r1 = 1.75 und r2 = 0.10 für AA-AAm. Die Polymerisationsgeschwindigkeit hängt sowohl von der Temperatur als auch von der Comonomerzusammensetzung ab. Die differentialkinetischen Kurven sind unimodal, was darauf hinweist, daß nur der Copolymerisationsprozeß abläuft. Ein zweites Maximum in diesen Kurven wird mit Vernetzung und der Bildung wasserunlöslicher Bestandteile erklärt. Die Copolymeren sind weiße Pulver; die wasserlöslichen Fraktionen sind im Gegensatz zu den wasserunlöslichen nicht giftig, aber als Immunmodulatoren weniger aktiv.
    Notes: A study was made of the γ-radiation-induced bulk copolymerization of the methacrylic acid-acrylamide (M2) (MA-AAm) and acrylic acid-acrylamide (M2) (AA-AAm) monomeric pairs. The copolymerization reactivity ratios deterined according to the Kelen-Tüdő method were: r1 = 1.35, r2 = 0.22 for the MA-AAm pair, and r1 = 1.75, r2 = 0.10 for the AA-AAm pair. It has been established that the polymerization rate depends both on the composition of the starting reaction mixture and on the reaction temperature. The differential kinetic curves obtained are unimodal ones, suggesting the occurrence of only one process, i.e. copolymerization. A second maximum in these curves, appearing at elevated temperature, is explained by crosslinking and formation of a water-insoluble fraction. The copolymers obtained are white powders; in contrast to their water-insoluble fractions, the water-soluble ones are not toxic but they are less active as immunomodulators.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052300101
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    Synthesis and hydrolytic stability of model poly(ester urethane ureas) (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 228 (1995), S. 201-219 
    Details
    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 Hydrolyse von Poly(ester-urethan-harnstoffen) (PURUs) wurde untersucht. Es handelt sich dabei um einen komplexen Vorgang, der die Analyse der Beziehung zwischen der Zusammensetzung der PURUs und ihrer Hydrolysebeständigkeit erschwert. Es wurde gefunden, daß die Hydrolysebeständigkeit mit Zunahme (i) der Polyol-Acidität, (ii) des Estergruppen-Gehaltes, (iii) der Beweglichkeit der Hauptketten und (iv) deren Hydrophilie abnimmt; die Molmasse des Polyols scheint keinen merklichen Einfluß darauf zu haben. Der negative Einfluß von Ethergruppen (obwohl hydrolysebeständiger als Estergruppen) ist möglicherweise auf eine Zunahme der Hauptkettenbeweglichkeit und den dadurch leichteren Zugang von Wassermolekülen zu Estergruppen zurückzuführen. Der positive Effekt von aromatischen Ringen in Polyolen kann einer erhöhten Steifigkeit der Hauptkette als auch einer ansteigenden Hydrolysebeständig-keit benachbarter Estergruppen durch Resonanzeffekte zugeschrieben werden. Insgesamt kann angenommen werden, daß die beschriebenen Effekte sich überlagern und gleichzeitig die resultierende Hydrolysebeständigkeit vorherbestimmen. Es sollte daher möglich sein, qualitative Vorhersagen bezüglich der Hydrolysebeständigkeit in Abhängigkeit von der Zusammensetzung der PURUs zu treffen.
    Notes: Hydrolysis of poly(ester urethane ureas) (PURUs) is a complex phenomenon which impedes the analysis of the relationships between their composition and hydrolytic stability. Hydrolytic stability of PURUs decreases due to rising (i) polyol acidity, (ii) content of ester groups, (iii) flexibility and (iv) hydrophilicity of the backbones; molar mass of polyols does not seem to have any appreciable effect on it. Negative influence of ether groups (which have better hydrolytic stability than ester groups) is probably linked to the increase in the backbone flexibility and, consequently, to easier access of water molecules to ester groups. Positive effect of aromatic rings in polyols can be ascribed to enhanced rigidity of the backbones as well as to increased hydrolytic stability of adjacent ester groups due to the resonance effect. It can be presumed that the mentioned effects will superpose and simultaneously predestine the resulting hydrolytic resistance. Considering the observed tendencies, it is possible to qualitatively predict the trends how the hydrolytic stability will respond to changes in PURUs composition.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052280116
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    Synthesis and characterization of a naphthoquinonediazide positive photoresist derived from bis(hydroxymethyl)phenol (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 229 (1995), S. 63-72 
    Details
    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 neuartige lichtempfindliche Naphthochinondiazid-Verbindung (NQD) wurde aus 2,6-Bis(hydroxymethyl)-3,4-dimethylphenol und Toluoldiisocyanat synthetisiert und mit IR-, NMR- und Elementaranalyse identifiziert. Die Bleicheigenschaften unter Lichteinwirkung wurden mit UV-Spektrophotometrie bestimmt. Die Anwendung von NQD in der Photolithographie als positiver Photoresist sowie einer wäßrigen Lösung von NQD, Novolak, Cellosolve-Acetat und DMF als lichtempfindliches Material wurde untersucht. Das hergestellte NQD erwies sich als effektive Komponente in positiven Photoresists. Die optimalen Bedingungen der UV-Dosis, Schichtdicke und Resistzusammensetzung wurden abgeschätzt. Die Auflösung des positiven Photoresists wurde durch Rasterelektronenmikroskopie bestimmt. Außerdem wurde der Einfluß von UV-Dosis und -Wellenlänge, Einwirkungsdauer und Entwicklungszeit auf die Empfindlichkeit und die Auflösung des Photoresists untersucht.
    Notes: A new photosensitive naphthoquinonediazide (NQD) was synthesized from 2,6-bis-(hydroxymethyl)-3,4-dimethylphenol and toluene diisocyante. NQD was identified by using IR, NMR and elemental analyses. Photobleachable characteristics were evaluated by UV spectrophotometry. Applications of the NQD on the photolithography as a positive working photoresist were investigated. The aqueous solution of NQD, novolak, cellosolve acetate, and DMF was used as a photosensitive material. It was found that NQD synthesized in this investigation can be used as an effective component in a positive photoresist. Optimal conditions of the UV dose, coating thickness, and development of the resist system were estimated. Resolution of the positive resist was evaluated by SEM technique. Effects of UV dose, exposure time, development time, and exposure UV wave length on the sensitivity and resolution of the photoresist were investigated.
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    Investigations on free radical polymerization of phenyl-substituted 2-methylene-1,3-dioxanes (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 229 (1995), S. 123-132 
    Details
    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 radikalinduzierte Polymerisation von phenlysubstituierten 2-Methylen-1,3-dioxanen wurde untersucht. Es kann gezeigt werden, daß die grundlegende Polymerisationstendenz derartiger Ketenacetale darin besteht, über die Doppelbindung zu hochmolekularen Polyacetalen ohne eine nennenswerte Ringöffnung zu polymerisieren. Einflußfaktoren, wie z. B. resonanzstabilisierte Kettenenden oder sterische Hinderungen während des Wachstumsschrittes sind nicht in der Lage, die Polymerisation in die Richtung der gewünschten Ringöffnung zu lenken.Mittels Dichtemessungen wurden Informationen über das Schrumpfungsverhalten gewonnen. Es konnte gezeigt werden, daß raumerfüllende Substituenten am 2-Methylen-1,3-dioxansystem bei der Homopolymerisation grundsätzlich eine geringe Volumenschrumpfung bewirken und die Schrumpfung von herkömmlichen Monomeren bei der Copolymerisation herabsetzen können.
    Notes: We have investigated the free radical polymerization of phenyl-substituted 2-methylene-1,3-dioxanes. It was shown that there is a basic tendency of such ketenacetals to undergo exclusively a vinyl polymerization forming high-molecular polyacetals without any detectable ring opening. The polymerization with the desirable ring opening reaction cannot be controlled by factors like resonance stabilized chain ends or steric hindrance in the growing step.From densitometric measurements we got new information about the shrinkage behaviour. It was demonstrated that bulky substituents attached to the 2-methylene-1,3-dioxane system result in a significant low shrinkage in homopolymerization and the shrinkage of common comonomers can be decreased by copolymerization.
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    Acrylamide polymerization in concentrated bicontinuous systems (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 229 (1995), S. 133-143 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Polymerisation von Acrylamid (AAM) in einer konzentrierten bikontinuierlichen Mikroemulsion wurde studiert. Die Initiierungsstelle bei Verwendung von radikalischen Initiatoren mit verschiedener Wasserlöslichkeit wurde untersucht. Es wurde festgestellt, daß ein vollständig oder teilweise wasserlöslicher radikalischer Initiator die Acrylamidpolymerisation in der untersuchten Mikroemulsion effektiv initiieren kann. Die dadurch entstandenen Polymeren weisen eine Spezialstruktur auf, die von der Zusammensetzung der ursprünglichen Mikroemulsion abhängig ist.
    Notes: The polymerization of acrylamide (AAM) in concentrated bicontinuous microemulsion systems was studied. The locus of initiation using radical initiators with various water-solubility was investigated. It was found that water-soluble and partially water-soluble initiators initiate the AAM polymerization in the reaction systems under investigation very effectively. The polymers thus formed have special structures dependent on the composition of the original concentrated bicontinuous microemulsion.
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    Mitteilungen/announcements (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 229 (1995), S. 209-209 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1995.052290115
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    Orientierung von Bacteriorhodopsin in einer Polymermatrix (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 229 (1995), S. 185-198 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Bacteriorhodopsin is a component of the purple membrane of Halobacterium halobium. It shows photochemical activity and undergoes a series of photocyclic-associated conformational changes. Incorporated in a matrix it is suitable as a light energy/electrical current transducer. Very important is an orientation of purple membrane fragments.The reaction between solutions of a polyelectrolyte and multivalent ions leads to a ionotropic gel, that is a gel with an ordered structure. If the gel formation was carried out in the presence of purple membrane fragments, the Bacteriorhodopsin is highly oriented and produces a photoelectrical signal. It consists a correlation between the light direction and the orientation of the purple membrane due to the gel formation.
    Notes: Bacteriorhodopsin ist Bestandteil der sogenannten Purpurmembran des Mikroorganismus Halobacterium halobium. Es zeigt photochemische Aktivität und kann als biologischer Lichtwandler fungieren. Voraussetzung hierfür ist eine orientierte Anordnung der Purpurmembran in einer Matrix.Das Prinzip der ionotropen Gelbildung, d. h. die geordnete Strukturbildung einer Polyelektrolytlösung infolge eines gerichteten Diffusionsstromes von mehrwertigen Ionen gestattet die orientierte Anordnung der Purpurmembran. Durch Lichteinwirkung werden elektrische Signale induziert. Es besteht ein Zusammenhang zwischen der Richtung des Strahlungseinfalls und der durch die Gelwachstumsrichtung festgelegten Orientierung der Purpurmembran.
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    Stabilizer consumption and lifetime prediction in ageing of crosslinked polyethylenePaper presented at the “16th International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland), June 14-17, 1994. (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 232 (1995), S. 1-12 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal oxidation of β ray-crosslinked polyethylene (XLPE) was studied in temperatures ranging from 90 to 180°C. Various analytical methods were used for determination of an end of the induction period on bulk samples: gravimetry, ultimate tensile properties, density and color change. On microtome slices of ∼30 μm thickness the depth distribution of oxidation products, phenolic antioxidant, density and tensile ultimate properties were followed as a function of exposure time by respectively IR and UV spectrophotometry, densitometry and Microfoil Tensile Testing.Depending on the testing method different durations of induction period (DIP) were obtained. They increase in following order:Phenol depletion 〈 Ultimate elongation 〈 Density 〈 Carbonyl build-up ≤ Color change 〈 Weight loss.The difference between phenol depletion DIP and carbonyl build-up DIP can be considered as negligible at temperatures higher than the melting point (about 30%) but it reachs more than 100% at T〈 Tm.Different kinetic regimes of phenol consumption were observed depending on the exposure temperature. A mechanistic interpretation is proposed explaining the role of the stabilizer system in initially homogeneous and later heterogeneous oxidation of the bulk material.The Arrhenius law was applied to different durations of induction period. A discontinuity appeared in the melting point region (120-130°C) which is tentatively interpreted in terms of different stabilizer concentration in amorphous phase of semicrystalline material (T 〈 Tm) and in melt material (T 〉 Tm). On the basis of the presented complex study of polyethylene thermo-oxidation, different aspects of lifetime predictions are discussed.
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    Pyrolysis with respect to recycling of polymerPaper presented at the “16th International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland), June 14-17, 1994. (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 232 (1995), S. 151-165 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Most plastics are produced from oil and have a high potential as hydrocarbon sources for the chemical industry. Pyrolysis is a practicable way to pyrolyze mixed plastics. The fluidized bed pyrolysis has turned out to be particularly advantageous. 25 to 45 percent of product gas with a high heating value and 30 to 50 percent of an oil rich in aromatics, could be recovered. The oil is comparable to that of a mixture of light benzene and bituminous coal tar. Up to 60 percent of ethene and propene are produced by using mixed polyolefins as feedstock. Under appropriate conditions the pyrolysis could be successful on the market.
    Additional Material: 1 Ill.
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    Photodegradation of UV absorbers: Kinetics and structural effectsPaper presented at the “16th International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland), June 14-17, 1994. (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 232 (1995), S. 229-238 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When poly(methyl methacrylate) films containing UV absorbers are exposed to UV light, the absorbers undergo photodegradation resulting in loss of absorbance. If the data extend for less than one half-life, both zero and first order kinetic treatment give fairly linear fits, but the rate constants so derived are dependent on the initial absorbance of the films. When the zero order rate constants are corrected to account for the higher rate of degradation near the surface compared with the bulk that occurs in highly absorbing films, consistent “infinite absorption” zero order rate constants are derived. The inhomogeneous degradation is due to only the highly absorbed, higher energy light contributing significantly to the degradation. For the benzophenone and benzotriazole classes of absorber, at least 65% of the degradation is due to light with wavelengths 〈 350 nm. Structural variations generally caused only small differences in the rates of degradation of these classes of absorbers unless the substitutions disrupted the intramolecular hydrogen bonds that are critical for stability. If the hydrogen bond is weakened, the absorber is less stable.
    Additional Material: 3 Ill.
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    Polymers from renewable resources, VI. Synthesis and characterization of thermosetting resins derived from cashewnut shell liquid/formaldehyde/substituted aromatic compounds (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 233 (1995), S. 1-13 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Aus Cardanol, einem Bestandteil der Schale der Cashewnuß, wurde durch Kondensation mit Formaldehyd und substituierten aromatischen Verbindungen unter saurer oder basischer Katalyse eine Reihe von Harzen hergestellt und anhand ihrer IR-Spektren charakterisiert. Sie lassen sich als selektive Ionenaustauscher für bestimmte Ionen verwenden, was mittels einer Gleichgewichtsmethode geprüft wurde. Das thermische Verhalten der Harze wurde untersucht, und ein plausibler Abbaumechanismus wird vorgeschlagen.
    Notes: A large number of resins have been synthesized by reacting cardanol, a constituent of cashewnut shell liquid, with formaldehyde and substituted aromatic compounds in the presence of acidic and basic catalysts. The resins have been characterized by IR spectra. They were shown to be selective ion exchangers for certain metal ions. A batch equilibrium method was used for studying the selectivity of the metal ions. The thermal behaviour of the resins has been studied and a plausible degradation mechanism has been suggested.
    Additional Material: 3 Ill.
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    Search for the sources of color in thermally aged, weathered and γ-ray irradiated bisphenol a polycarbonatePaper presented at the “16th International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland), June 14-17, 1994. (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 232 (1995), S. 27-43 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Bisphenol A polycarbonate (BPA-PC) is an important high performance engineering thermoplastic well known for its outstanding combination of toughness, transparency and heat resistance. These properties make it an idel material for demanding applications where it is exposed to external stresses such as elevated temperatures, ultraviolet light and γ-ray sterilization. However, on extended exposure to these conditions, BPA-PC slowly degrades, turning progressively more yellow, eventually leading to a decrease in its physical properties. Over the years, there has been numerous studies made to understand these degradative processes so as to better design more stable BPA-PC formulations. In this paper, this chemistry is briefly reviewed along with more recent work in this area with a special emphasis on the efforts made to identifying the actual chemical species responsible for the observed yellow color and the chemistry responsible for their formation.
    Additional Material: 7 Ill.
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    Model studies on the mechanism of hals stabilizationPaper presented at the “16th International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland), June 14-17, 1994. (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 232 (1995), S. 65-83 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hindered Amine Light Stabilizers (HALS) are know to inhibit the photo-oxidation of polymers. A key reaction in their stabilization mechanism is believed to be the conversion of a hindered aminoether into a nitroxyl radical. Several different possible mechanisms for this conversion were explored. One, the elimination of the aminoether to form an olefin and hydroxylamine (an intermediate in the formation of a nitroxyl), while possible at high temperatures, cannot account for the inhibitory activity we observed for secondary and primary aminoethers. Direct radical displacement by peroxy radicals was also considered. However, the products predicted by this reaction pathway were not observed. Finally, oxidation of the nitrogen by a peroxy radical, by either electron transfer or a radical attack on the nitrogen, was investigated. While electron transfer was shown to be unlikely, direct oxidation of the aminoether nitrogen was supported by our results. A detailed mechanism for the reaction of both alkyl- and acyl-peroxy radicals with aminoethers is proposed.
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    Physical, dynamic-mechanical and thermogravimetric analysis of aromatic and cycloaliphatic-based poly(urethaneurea)s (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 231 (1995), S. 79-89 
    Details
    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 thermischen und dynamisch-mechanischen Eigenschaften einiger linearer kautschukelastischer Polyurethane mit chemisch unterschiedlichen starren Segmenten wurden untersucht und zur chemischen Zusammensetzung in Beziehung gesetzt. Interessante Zusammenhänge wurden zwischen der Kristallinität der elastischen Polyurethanharnstoffe und der aromatischen oder cycloaliphatischen Natur der Diisocyanat-Komponenten gefunden. Darüber hinaus scheinen die Ergebnisse bei einem bestimmten Verhältnis zwischen starren und flexiblen Segmenten und bei gegebener Zusammensetzung der flexiblen Gruppen auf eine bessere Phasenseparation bei den Polyurethanharnstoffen mit cycloaliphatischen starren Segmenten als bei solchen mit aromatischen, starren Einheiten hinzuweisen.
    Notes: Experimental batches of linear rubber-like polyurethanes characterized by the presence of chemically different hard segments are studied and their thermal and dynamic-mechanical properties are related to the differences in chemical compositions. Interesting correlations are found between the development of crystallinity in such elastomeric poly(urethaneurea)s and the aromatic or alicyclic nature of the diisocyanate. Moreover, for a fixed ratio between hard and soft segments, and for a given composition of the soft segment, the results seem to indicate a better degree of phase separation in cycloaliphatic-based hard segment poly(urethaneurea)s than in aromatic-based hard segment poly(urethaneurea)s.
    Additional Material: 7 Ill.
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    Dispersion polymerization of styrene and methyl methacrylate initiated by poly(oxyethylene) macromonomeric azoinitiators (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 231 (1995), S. 135-144 
    Details
    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: Makromonomere Polyethylenoxid-Azoinitiatoren (Makroinimere) MIM-400 und MIM-1500 wurden synthetisiert und IR- und NMR-spektroskopisch sowie mit Hilfe der DSC-Analyse charakterisiert. Die mit diesen Makroinimeren initiierte Dispersions-polymerisation von Styrol bzw. Methylmethacrylat (MMA) in Ethanol/Wasser bei 60°C wurde untersucht. Dabei wurde gefunden, daß die Polymerisationsgeschwindig-keit mit zunehmender MIM-Konzentration ansteigt, wobei der Anstieg im Styrolsystem ausgeprägter war. Im Bereich von mittleren Umsätzen konnte gezeigt werden, daß die Polymerisationsgeschwindigkeit von MMA proportional der Potenz 1,7 bzw. 1,6 von [MIM-400] bzw. [MIM-1500] ist, während für Styrol eine Potenz von 2,5 bezüglich [MIM-400] gefunden wurde.
    Notes: Macromonomeric poly(oxyethylene) azoinitiators (macroinimers) MIM-400 and MIM-1500 were synthesized and characterized by IR and NMR spectroscopy and DSC techniques. The dispersion polymerizations of styrene and methyl methacrylate (MMA) initiated by poly(oxyethylene) macroinimers (MIM-400 and MIM-1500) in water/ethanol were investigated at 60°C. The rate of polymerization was found to increase with increasing concentration of MIM and the increase was more pronounced in the styrene system. In the range of medium conversions the rate of polymerization was found to be proportional to the 1.7th and 1.6th power of [MIM-400] and [MIM-1500] for MMA and to the 2.5th power of [MIM-400] for styrene, respectively.
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    Modell zur beschreibung der glasübergangstemperaturen binärer und ternärer mischungen von poly(styrol-co-n-butylmethacrylat)en (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 231 (1995), S. 187-198 
    Details
    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: Glass transition temperatures of binary and ternary blends of chemically uniform poly(styrene-co-n-butyl methacrylate)s with a mean content of 30.8 wt.-% of n-butyl methacrylate and number-average molar masses in the range of 4900 and 67000 g/mol have been investigated in relation to their composition. The blends showed significant deviations from an ideal behaviour with reference to a linearity between glass transition temperature and composition.This phenomenon is described by a mathematical model where polynoms are particularly well suited to represent the glass transition temperatures of the blends, partly exceeding those of the pure components. Finally, various reasons of these deviations were discussed. Here, energetical interactions seem to be of considerable importance combined with a nonadditivity of volumes.
    Notes: Die Glasübergangstemperaturen binärer und ternärer Mischungen chemisch einheitlicher Poly(styrol-co-n-butylmethacrylat)e mit einem mittleren n-Butylmethacrylat-Anteil von 30,8 Gew.-% und unterschiedlichen zahlenmittleren Molmassen im Bereich von 4900 bis 67000 g/mol wurden in Abhängigkeit von der Zusammensetzung untersucht. Es wurden wesentliche Abweichungen vom idealen Verhalten bezüglich einer linearen Abhängigkeit zwischen Glasübergangstemperatur und Zusammensetzung festgestellt.Dieses Verhalten konnte mit einem mathematischen Modell dargestellt werden, wobei sich insbesondere Polynome zur Beschreibung der teilweise über den Werten der Ausgangskomponenten liegenden Glasübergangstemperaturen der Mischungen als geeignet erwiesen. Schließlich wurden verschiedene Ursachen für diese Abweichungen diskutiert, wobei offensichtlich energetische Wechselwirkungen verbunden mit einer Nichtadditivität der Volumina von wesentlicher Bedeutung sind.
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    Zur bildung von polyepoxid-polyamid-netzwerken. Modelluntersuchungen am system phenylglycidether-ε-caprolactam (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 233 (1995), S. 133-148 
    Details
    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: ε-Caprolactam (CL) and phenyl glycidyl ether (PGE) were homopolymerized using the initiator/accelerator-systems Na-caprolactam/N-acetyl-caprolactam (NaCL/AcCL) and Na-caprolactam/N-acetyl imidazole (NaCL/AcImi). In a one-pot reaction both monomers gave different oligomeric reaction products depending on the reaction temperature (100°C to 140°C, max. 240°C) but no regular copolymers. Soluble products were separated by HPLC and identified by means of spectroscopic methods. In acetone insoluble products were investigated by IR- and NMR-spectroscopy, mass spectrometry and elemental analysis.
    Notes: Es wurden Versuche zur Homopolymerisation von ε-Caprolactam (CL) und Phenylglycidether (PGE) mit den Initiator/Beschleuniger-Systemen Na-Caprolactam/N-Acetylcaprolactam (NaCL/AcCL) und Na-Caprolactam/N-Acetylimidazol (NaCL/AcImi) durchgeführt, um die für eine mögliche Copolymerisation von CL und PGE geeigneten Reaktionsbedingungen zu ermitteln. CL und PGE wurden in unterschiedlichen molaren Verhältnissen (CL : PGE = 1 : 5 bis 1 : 0,05) und bei Temperaturen zwischen 100°C und 140°C (max. 240°C) in einer Eintopfreaktion polymerisiert.Die löslichen Produkte wurden mittels HPLC getrennt und spektroskopisch identifiziert. Die in Aceton unlöslichen Produkte wurden mit IR- und NMR-Spektroskopie, Massenspektrometrie (MS) und Elementaranalyse untersucht.
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    Synthesis and characterization of copolymers from acrylic and methacrylic acid with 2-methylaziridine by spontaneous copolymerization (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 231 (1995), S. 199-211 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 2-Methylaziridin (MAz) wurde als nukleophiles Monomeres mit den elektrophilen Monomeren Acrylsäure (AA) bzw. Methacrylsäure (MA) in unterschiedlichen Verhältnissen ohne Initiator copolymerisiert. Die Copolymeren wurden mittels Elementaranalyse, FT-IR- und 1H-NMR-Spektroskopie charakterisiert. Die Copolymerisationsparameter wurden mit den Methoden nach Fineman-Ross bzw. Kelen-Tüdős bestimmt. Für r1 und r2 wurden die Copolymerpaare MAz-AA und MAz-MA jeweils Werte 〈 1 ermittelt, was auf statistische Copolymere mit einer Tendenz zu alternierenden Copolymeren hinweist. Thermische Zersetzung mit einem Gewichtsverlust von 10% tritt bei den Copolymeren erst oberhalb 430 K auf. Der thermische Abbau verläuft nach einer Reaktion nullter Ordnung. Die kinetischen Parameter der Zersetzung der Copolymeren wurden bestimmt.
    Notes: 2-Methylaziridine (MAz) as a nucleophilic monomer and acrylic acid (AA) and methacrylic acid (MA), respectively, as electrophilic monomers were copolymerized in the absence of initiator at various feed ratios. Copolymers were characterized by elemental analysis, FT-IR and 1H-NMR spectroscopy. The monomer reactivity ratios were determined by the Fineman-Ross and Kelen-Tüdős methods. Values of r1 and r2 were found to be less than unity for MAz-AA, and MAz-MA, corresponding to random copolymers with the tendency to the alternance. For all the copolymers the thermal decomposition with 10% weight loss is higher than 430 K. The reaction order for degradation of all copolymers was zero. The kinetic parameters of the decomposition were determined for all copolymers.
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    New trends in epr and epr kinetics studies in the stabilization mechanism by N-oxyl radicalsPaper presented at the “16th International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland), June 14-17, 1994. (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 232 (1995), S. 45-63 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanism of the solid state oxidation of isotactic polypropylene films and the the mechanism of inhibition by HALS have been investigated by kinetic-ESR and kinetic modelling with derivation of the rate constants for the sensitive steps in the reaction scheme. The results have shown the inadequacy of the Denisov cycle to account for the observed experimental kinetics of the intermediate nitroxyl radicals. The molecular dynamics associated with the oxidation inhibited by HALS in the polypropylene matrix has been investigated by applying the Liouville stochastic method to the analysis of the temperature effects of the ESR spectra of the intermediate nitroxyl radicals used as spin probes. The investigation on the nature and characteristics of the molecular motions available at the oxidation sites has also been carried out with nitroxyl spin labels bound to the PP chains. For this application a novel method of spin labelling was developed based on reactions with some of the oxidation products, namely the terminal and intrachain ketones (keana method), alcohols, peroxides and macroalkyl radicals.
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    Aspects of stabilization with phosphorous antioxidants in polymersPaper presented at the “16th International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland). June 14-17, 1994. (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 232 (1995), S. 119-131 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: As plastics are being used in a variety of applications, demands on a greater level of processing stability are increasing. Phosphites are noteworthy as effective processing stabilizer and the performance of phosphite antioxidants can be correlated to the chemical structure of phosphites. Cyclic phosphite esters derived from 2, 2′ methylene bis-2, 4-di-tert-butylphenol and some commercially available phosphites were submitted to comparative studies. Decomposition of cumene hydroperoxide, melt flow of polypropylene and consumption of additives after multiple extrusions were investigated to understand the activity of phosphites as process stabilizers in polypropylene.This study suggests that phosphites play an important role in process stabilization when used in combination with sterically hindered phenols, and that the activity of phosphites may be predicted by their reactivity on hydroperoxide.
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    Conformational analysis of the immunodominant epitopes of the circumsporozoite protein of Plasmodium falciparum and knowlesi (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 123-130 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: All of the coat proteins of the sporozoite and merozoite stages of Plasmodium, determined to date, contain tandem repeats and most of these contain at least one proline residue. These tandemly repeated segments of the circumsporozite (CS) proteins of P. falciparum and P. knowlesi have been shown to constitute an immunodominant epitope. Antibodies to these peptide segments have been shown to be protective and cause the shedding of the CS protein, known as the CSP reaction. In this study, four synthetic peptides were prepared by solid-phase peptide synthesis. The first peptide corresponds to the tetrapeptide tandem repeat in the CS protein of P. falciparum, repeated eight times, (NANP)8. The second peptide is an analogue of the first in which glycine is substituted for proline, (NANG)8. The third peptide corresponds to the tandem repeat of P. knowlesi, PK(1-24), which is repeated twice (QAQGDGANAGQP)2. The fourth peptide is a tetrapeptide repeat, corresponding to the C-terminal tetrapeptide of PK(1-24) and is repeated eight times, (AGQP)8. It is shown by CD measurements that the presence of proline in these repeats induces an increase in β-sheet (β-turn) content in the (NANP)8 peptide relative to the repeat of (NANG)8 and PK(1-24) peptide in aqueous media. The (AGQP)8 peptide has the highest β-sheet (β-turn) content in the synthetic peptides. It is concluded that this increase in defined structure correlates well with and hence may contribute to the increased antigenicity in these repeats.
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    Synergism through direct covalent bonding between agents: A strategy for rational design of chemotherapeutic combinations (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 247-262 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Self-assembling chemotherapeutic agents are mixtures of relatively nontoxic precursors that can combine chemically under physiological conditions to form products with greater cytotoxic and/or antimicrobial activity than either of the precursors. Combinations that form products more rapidly in or near the target (tumor, pathogen, virally infected cell) than in normal tissues will exhibit target-selective synergism, thus exhibiting an antitarget selectivity that is greater than the selectivities of the product (e.g., a hydrazone) and of either precursor (e.g., a hydrazine derivative or ketone) used singly.This paper describes the target-selective cytotoxic synergism of a cationic aldehyde (A) and a cationic acylhydrazine (B) containing a triarylalkylphophonium moiety against Ehrlich ascites carcinoma cells (ELA) in culture, in addition to reviewing previous work on self-assembling cytotoxins. The synergism between A and B is carcinoma selective when the ELA cells (the target) are compared to CV-1, A, B and the hydrazone C resulting from their reaction are lipophilic delocalized cations that selectively inhibit ELA growth relative to CV-1 growth. The hydrazone C is more growth inhibitory than either A or B for both cell lines. A combination of A with an unreactive analogue of B and a combination of B with an unreactive analogue of A did not synergistically inhibit ELA proliferation. The degree of synergism is greater against the ELA cells than against the CV-1 cells. These data, together with hydrazone formation kinetics, suggest that A and B are both concentrated together selectively inside the ELA due to the transmembrane potentials, reacting inside the ELA cells at a higher velocity than inside the CV-1 cells to form the more growth-inhibitory hydrazone C.
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    URL: http://dx.doi.org/10.1002/bip.360290129
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    Masthead (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990) 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360290201
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    Cyclic pentapeptides as models for reverse turns: Determination of the equilibrium distribution between type I and type II conformations of Pro-Asn and Pro-Ala β-turns (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 263-287 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyclic pentapeptides are excellent models for reverse turns and have been used extensively in our laboratory to explore the influence of different amino acid sequences on turn preference. This paper is divided into two parts: In the first, we review our previous studies of cyclic pentapeptides. We summarize work that demonstrates the range of conformations possible within the cyclic pentapeptide backbone, the importance of sequence chirality in determining the backbone fold, and the utility of these cyclic pentapeptides as models for various turns. In the second, we present new results on two cyclic pentapeptides that contain β-turns with Pro-Ala or Pro-Asn sequences in the i + 1 and i + 2 positions. By stereochemical criteria, a type I β-turn is expected to be preferred by such L-L sequences. On the other hand, in proteins Asn occurs frequently in the i + 2 position of type II turns. We asked whether the same propensity would be manifest in an isolated model peptide, and if so, what the interactions were that influenced the relative stability of the type I and type II turns. To address these questions we have compared the conformational behavior of two peptides: cyclo(Gly-Pro-Ala-D-Phe-Pro) and cyclo(D-Ala-Pro-Asn-Gly-Pro). From previous studies, we anticipated that both peptides would contain an inverse γ-turn and a β-turn which consisted of either Gly-Pro-Ala-D-Phe or D-Ala-Pro-Asn-Gly in positions i to i + 3, respectively. Nuclear magnetic resonance analysis confirms this overall backbone conformation. Furthermore, quantitative nuclear Overhauser effect measurements in combination with molecular dynamics simulations and torsionally-forced energy minimizations have enabled us to determine that both type I and type II β-turns are present in equilibrium in these peptides. The introduction of Asn in position i + 2 shifts this equilibrium significantly towards type II. We have done preliminary assessment of the possible side-chain/backbone conformations that contribute to the shift in populations.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/bip.360290130
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    Fourier transform infrared spectroscopy for the characterization of a model peptide-DNA interaction (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 289-299 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To better understand the structural basis of protein-DNA interactions, the conformational changes that accompany these interactions need to be described. In order to develop a methodological approach to this problem, Fourier transform infrared spectroscopy (FTIR) with derivative resolution enhancement has been used to identify conformational changes that occur when a 29-residue synthetic peptide binds nonspecifically to heterogenous cellular DNA in aqueous solution. The peptide sequence was chosen de novo, in order to rationally design a peptide model that would allow the relationship between DNA binding and the stability of protein secondary structure to be studied. Peptide at a concentration of 100-200 μM produces 50% saturation of heterogenous phage DNA sequences as well as of short synthetic oligonucleotides. FTIR spectra reveal significant changes in peptide and DNA upon binding. Second-derivative spectra resolve the amide I band of native peptide into components located at 1627 (β-strand), 1658 (α-helix), and 1681 (turn or β-strand) cm-1, with a distinct shoulder at 1647 cm-1 (disordered structure). Assignment of the 1681 cm-1 vibration to a turn conformation is supported by uv CD studies, which indicate significant amounts of turn structure in unbound peptide. Ultraviolet CD also confirms the existence of disordered and β-strand regions in the free peptide. Upon interacting with DNA the band at 1681 cm-1 (turn) is no longer seen; a new band appears at 1675 cm-1; the 1627 cm-1 band (β-strand) is considerably reduced in intensity; the position of the α-helical (1658 cm-1) component remains unchanged; the shoulder at 1647 cm-1 (disorder) disappears. The new vibration at 1675 cm-1 is characteristic of β-strand structures. The asymmetric stretch (vAS) of the DNA phosphates shifts from 1223 (unbound) to 1229 cm-1 (bound); the relative intensities of νAS and the PO2- symmetric stretch (vs) are altered upon peptide binding. The data is consistent with the following conclusions: (a)DNA binding changes the secondary structure of the peptide, (b) disordered region(s) are only observed in free peptide, i.e., DNA binding stabilizes and increases order in the peptide secondary structure, (c) turn(s) change into β-strand and/or α-helical conformations(s) when peptide binds to DNA, (d) a β-strand conformation that is characterized bya 1627 cm-1 vibration is present in free and bound peptide, (e) there is a particular β-strand vibration/conformation that is only present in the bound peptide, (f) an α-helical region exists in both free and bound peptide, (g) DNA remains in a B-family conformation upon peptide binding, and (h) DNA phosphates participate in peptide binding and/or subtle changes occur in the DNA conformation upon complex formation.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/bip.360290131
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    Masthead (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990) 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360290101
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    Side-chain interactions in the C-peptide helix: Phe 8 ⃛ His 12+ (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 1-11 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Previous studies have demonstrated that His 12 plays a major role in the pH-dependent stability of the helix formed by the isolated C-peptide (residues 1-13 of ribonuclease A). Here, amino acid replacement experiments show that His 12+ stabilizes the C-peptide helix chiefly by interacting with Phe 8. The Phe 8 ⃛ His 12+ ring interaction is specific for the protonated form of His 12 (His 12+) and the interaction is not screened significantly by NaCl, unlike the charged group ⃛ helix dipole interactions studied earlier in C-peptide. Analogs of C-peptide that are unable to form the Phe 8 ⃛ His 12+ interaction show large increases in helix content for Phe → Ala and His → Ala. Therefore, the helical tendencies of the individual residues Phe, His, and Ala are important in determining the result of a replacement experiment. Since the side chains of Phe 8 and His 12 probably interact within the N-terminal helix of ribonuclease A, the existence of the Phe 8 ⃛ His 12+ interaction in the isolated C-peptide helix adds to the evidence that the C-peptide helix is an autonomous folding unit.
    Additional Material: 8 Ill.
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    CD of the synthetic RNA duplexes poly[r(A-T)] and poly[r(A-U)] in salt and ethanolic solutions (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 385-392 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthetic RNA poly[r(A-T)] has been synthesized and its CD spectral properties compared to those of poly[r(A-U)], poly[d(A-T)], and poly[d(A-U)] in various salt and ethanolic solutions. The CD spectra of poly[r(A-T)] in an aqueous buffer and of poly[d(A-T)] in 70.8% v/v ethanol are very similar, suggesting that they both adopt the same A conformation. On the other hand, the CD spectra of poly[r(A-T)] and of poly[r(A-U)] differ in aqueous, and even more so in ethanolic, solutions. We have recently observed a two-state salt-induced isomerization of poly[r(A-U)] into chiral condensates, perhaps of Z-RNA [M. Vorlíčková, J. Kypr, and T. M. Jovin, (1988) Biopolymers 27, 351-354]. It is shown here that poly[r(A-T)] does not undergo this isomerization. Both the changes in secondary structure and tendency to aggregation are different for poly[r(A-T)] and poly[r(A-U)] in aqueous salt solutions. In most cases, the CD spectrum of poly[r(A-U)] shows little modification of its CD spectrum unless the polymer denatures or aggregates, whereas poly[r(A-T)] displays noncooperative alterations in its CD spectrum and a reduced tendency to aggregation. At high NaCl concentrations, poly[r(A-T)] and poly[r(A-U)] condense into ψ (-) and ψ (+) structures, respectively, indicating that the type of aggregation is dictated by the polynucleotide chemical structure and the corresponding differences in conformational properties.
    Additional Material: 5 Ill.
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    Electrostatic forces at helix-coil boundaries in DNA (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 393-405 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Tm of internal loop-forming (dA · dT)N domains in pBR322 DNA has been measured over a tenfold range of [Na+]. The slopes SN = dTm/d log[Na+] are linear and decrease in magnitude with decreasing loop size N, signaling a reduction in Na+ released during the transition of these domains to the coil state. Values of SN decrese linearly with increasing N-1 in accordance with the expectation of a simple model for the occurrence of a gradient of long-range electrostatic forces at helix-coil boundaries, and extrapolate almost precisely to the value of S∞ observed for (dA · dT)∞. These results indicate (1) less counterion is released per phosphate residue from the finite loop than from the infinitesized loop, and (2) the difference in binding is constant for each boundary formed and independent of the size of the loop within the range examined: ∼ 350 base pair (bp) 〉 N 〉 71 bp. The slope of the dependence of SN on N-1 indicates the region of higher charge density at the boundary extends at least 18 Å into the coil and probably 40-50 Å before dropping to a value characteristic of the unperturbed coil. The free energy for excess counterion binding at boundaries can be expressed by \documentclass{article}\pagestyle{empty}\begin{document}$$ {{ - \Delta G} \mathord{\left/ {\vphantom {{ - \Delta G} {RT}}} \right. \kern-\nulldelimiterspace} {RT}} = 10.47{\rm log}\left[{{\rm Na}^ + } \right] + 5.234 $$\end{document} When the loop entropy function in a statistical mechanical algorithm for the dissociation of DNA is weighted by this quantity, calculated Tm are seen to vary by only ±0.09°C from observed.
    Additional Material: 7 Ill.
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    Synthesis and conformational studies by 1H- and 13C-nmr spectroscopy of a novel, sterically constrained analogue of thyrotropin-releasing hormone (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 407-422 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel thyrotropin-releasing hormone (TRH) analogue, [2, 4-MePro3]-TRH (2, 4-MePro: 2-carboxy-2, 4-methanopyrrolidine), has been synthesized using a rapid solid phase peptide synthesis method, and its conformational properties investigated by one- and two- dimensional (2D) nmr spectroscopy and by proton Overhauser measurements. Following a published approach, calibrated interproton Overhauser effects were used together with distance geometry analysis to deduce that the single conformation of the His-2, 4-MePro tertiary amide bond is trans in aqueous solution. This conclusion was corroborated by 2D dipolar-correlated (NOESY) spectroscopy. A preferentially extended conformation is indicated by the nmr data, similar to that of TRH. The φ, ψ conformational space of 2, 4-MePro is, however, significantly different from that of trans proline and the structural consequences of these differences at the C-terminus are discussed. The distribution of histidine side-chain conformation in the TRH analogue was deduced from coupling constants and from the short-range interaction between the imidazole ring and one of the prochiral faces of the 2, 4-MePro side chain.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/bip.360290212
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    Light scattering studies of the effect of Ca2+ on the structure of porcine submaxillary mucin (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 441-448 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of calcium ions on the solution properties of porcine submaxillary mucin (PSM) have been investigated by static and dynamic light scattering. The weight average molecular weights of PSM fractions are unaffected by the addition of up to 0.5M CaCl2: these data are within experimental error of those for solutions in 0.1M NaCl. The distribution of relaxation frequencies derived from the dynamic data shows the existence of two distinct relaxation modes. The average relaxation times have been interpreted to yield the z-average translational diffusion coefficient and the longest intramolecular relaxation time τ1. A plot of τ1 vs 〈1/Rh〉z-3 is linear, and consistent with plots of such data recorded for PSM in 0.1M NaCl and 6M GdnHCl solutions. However, the τ1 values and the associated results for 〈Rh-1〉z-1 in 0.5M CaCl2 are smaller than those determined in 0.1M NaCl. This suggests that the conformation of PSM in CaCl2 solution is more contracted than those in the other two solvents. These results are consistent with the compact packaging of mucin in the secretary granules that have elevated Ca2+ levels.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/bip.360290214
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    Temperature dependence of enthalpy changes for ethidium and propidium binding to DNA: Effect of alkylamine chains (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 449-459 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Calorimetric titrations have been performed on the binding of ethidium and propidium to calf thymus DNA at temperatures in the 15-60°C range. Enthalpy changes (ΔHB) derived from these experiments performed with the new Omega reaction calorimeter have a precision of ±0.10 kcal/mol or less at all temperatures. For ethidium (a monocation), ΔHB varies little with temperature, and the heat capacity change (ΔCP) for the binding reaction derived from these parameters is 10 cal/deg/mol. In contrast, ΔHB changes from -6.5 to -8.1 kcal/mol for DNA binding of propidium (a dication due to a charged amine group at the end of an alkyl chain attached to the phenanthridine ring nitrogen), and ΔCP is -57 cal/deg/mol. At 21°C a plot of ΔHB vs mole ratio is curved downward for propidium in the 0.08-0.25 range, whereas the same plot at 45°C is a straight line from 0.05 to 0.15 and sharply downward thereafter. Similar plots for ethidium follow the latter pattern between 25 and 50°C. These observations and our analyses of ΔHB and ΔSB are consistent with the hypothesis that the location in the DNA complex and the rotational motion of the alkylamine chain change substantially over the temperature range in this study. Only near 50°C is ΔHB equal for the binding of these two cations to DNA, and caution must be used in analyses of enthalpic effects when the temperature dependence for ΔHB is not available.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/bip.360290215
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    Inhibition of protein kinase C and calmodulin by the geometric isomers cis- and trans-tamoxifen (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 97-104 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The triphenylethylene antiestrogen trans-tamoxifen is an effective antitumor agent used in the treatment of human breast cancer. While the antiestrogenic activity of trans-tamoxifen clearly plays an important role in its tumoricidal action, some of the biological effects of trans-tamoxifen are independent of estrogen. Therapeutic concentrations of trans-tamoxifen inhibit protein kinase C (PKC) and calmodulin-dependent enzymes. PKC and calmodulin play critical roles in growth regulation, and there is evidence that inhibition of PKC and calmodulin by trans-tamoxifen may contribute to the antiumor activity of the drug in vivo.The geometric isomers cis- and trans-tamoxifen have a number of opposing biological activities that have been attributed to their interactions with the estrogen receptor, Cis-tamoxifen is generally estrogenic, whereas trans-tamoxifen is generally antiestrogenic. In this report, we compared the effects of cis- and trans-tamoxifen on PKC activity and on calmodulin-dependent cAMP phosphodiesterase activity. Cis- and trans-tamoxifen inhibited the Ca2+- and phosphatidylserine- (PS-) dependent activity of purified rat brain PKC with indistinguishable potencies, but cis-tamoxifen was somewhat more potent than the trans isomer in the inhibition of the Ca2+- and PS-independent activity of PKC. In addition, cis-tamoxifen was the more potent isomer in the inhibition of T lymphocyte activation, an event that entails a PKC-requiring signal transduction pathway. A modest preference of the cis isomer was also observed in the inhibition of a calmodulin-dependent cAMP phosphodiesterase. These results suggest a congruence between triphenylethylene binding sites on PKC and on the activated calmodulin-cAMP phosphodiesterase complex. We conclude that the interactions of cis- and trans-tamoxifen with PKC and the activated calmodulin-cAMP phosphodiesterase complex offer a criterion for distinguishing biological effects of triphenylethylenes that are due to interactions with the estrogen receptor from the biological effects resulting from their inhibitory activities against PKC and calmodulin-dependent processes.
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    Inactivation of the catalytic subunit of bovine cAMP-dependent protein kinase by a peptide-based affinity inactivator (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 131-138 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A peptide affinity inactivator, Ac-Leu-Arg-Arg-Ala-(BrAc)Orn-Leu-Gly, was used as a tool to probe for active site residues in the catalytic subunit of bovine cAMP-dependent protein kinase. The peptide inactivated the catalytic subunit in an active site-directed and monophasic manner with a first-order rate constant of 0.03 min-1 and a dissociation constant of 675 μM. Studies with radioactive peptide indicated that approximately one equivalent of peptide was incorporated into each protein molecule. Protein sequencing identified the modified residue as Cys-199. A possible location for Cys-199 within the active site is suggested.
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    URL: http://dx.doi.org/10.1002/bip.360290118
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    A comparative analysis of single- and multiple-residue substitutions in the alkaline phosphatase signal peptide (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 139-147 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The alkaline phosphatase signal peptide participates in transport of the enzyme to the periplasmic space of Escherichia coli. The signal sequence, like that of other signal peptides, is composed of a polar amino-terminal segment, a central region rich in hydrophobic residues and a carboxy-terminal region recognized by signal peptidase. We have previously shown that an alkaline phosphatase signal peptide mutant containing a polyeucine core region functions efficiently in transport of the enzyme [D. A. Kendall, S. C. Bock, and E. T. Kaiser (1986) Nature 321, 706-708]. In this study, some of the amino acid changes involved in the polyleucine sequence are examined individually. A Phe to Leu substitution as the sole change results in impaired transport properties in contrast to when it is combined with three other amino acid changes in the polyleucine-containing sequence. A mutant with a Pro to Leu substitution in the hydrophobic core region is comparable to wild type while the same type of substitution (Pro to Leu) in the carboxy-terminal segment results in substantial accumulation of the mutant precursor. Finally, introduction of a basic residue into the hydrophobic segment (Leu to Arg substitution) results in a complete export block. These results exemplify the spectrum of properties produced by individual residue changes and suggest there is some interplay between hydrophobicity and conformation for signal peptide function.
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    URL: http://dx.doi.org/10.1002/bip.360290119
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    The most highly amphiphilic α-helices include two amino acid segments in human immunodeficiency virus glycoprotein 41 (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 171-177 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A search for highly amphiphilic α-helices has been made in a data base of protein sequences, using the helical hydrophobic moment as a criterion of amphiphilicity. The protein segments of largest hydrophobic moment have been analyzed. For the segments whose structures are known, they are in fact α-helices. Two of the segments having very large hydrophobic moments are from the smaller C-terminal portion of the human immunodeficiency virus (HIV) envelope glycoprotein gp41. Also, among segments having large hydrophobic moments, but not among the most extreme, are lytic peptides such as melittin. Melittin seeks surfaces between polar and apolar phases, including the membrane-water interface. It is conceivable that the gp41 segments of extreme hydrophobic moment may participate in one of the membrane-related functions of the HIV virus.
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    URL: http://dx.doi.org/10.1002/bip.360290122
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    Enkephalin analogues containing β-naphthylalanine at the fourth position (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 179-196 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To examine the importance of the aromatic side chains of enkephalin on opiate activity, we report the synthesis and conformational analysis of a series of analogues related to enkephalin with β-naphthylalanine in place of phenylalanine at the fourth position. Three linear analogues (Tyr-D-Ala-Gly-(L and D)-β Nal(1)-Leu-NH2 and Tyr-D-Ala-Gly-β Nal(2)-Leu-NH2) were initially synthesized to examine the effect of the substitution on biological activity. The increased activity of these peptides at the μ-opiate receptor, compared to native Leu-enkephalin, prompted us to examine the more conformational constrained analogues, Tr-c[D-A2bu-Gly-(L and D)-β Nal(1)-Leu], incorporating a α,γ-diaminobutyric acid at the second position and cyclization to the carboxylic end of the leucine. These two cyclic analogues provide insight into the necessity for the L chirality of the aromatic residue at position 4. The Tyr-c[D-A2bu-Gly-L-β Nal(1)-Leu] analogue is highly potent and displays a slight preference for the μ receptor. The conformational analysis indicates that despite the high flexibility of the tyrosine side chain, the aromatic rings of the tyrosine and naphthylalanine are relatively distant from each other. The presence of two intramolecular hydrogen bonds help maintain the conformation of the 14-membered backbone ring that keeps the side chains directed away from each other. These findings are in agreement with our model of an extended structure required for μ selectivity and a folded form with close aromatic ring placement for δ selectivity.
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    Masthead (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990) 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360290301
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    Assessment of protien reorientational diffusion in solution by 13C off-resonance rotating frame spin-lattice relaxation: Effect of anisotropic tumbling (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 469-480 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 13C off-resonance rotating frame spin-lattice relaxation technique is applicable to the study of protien rotational diffusion behaviour in a variety of experimental situations. The original formalism of James and co-workers (1978) (J. Amer. Chem. Soc. 100, 3590-3594) was constrained by the assumption of random isotropic reorientational motion. Here we include in the formalism anisotropic tumbling, and present the results of computer simulations illustrating the differences between anisotropic and isotropic reorientational motion for the off-resonance rotating frame spin-lattice relaxation experiment. In addition, We have included chemical shift anisotropy of the peptide carbonyl carbon as an additional relaxation mechanism contribution, to permit high field nmr protein rotational diffusion measurements.
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    A unique binding cavity for divalent cations in the DNA-metal-chromomycin A3 complex (1990)
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 481-489 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Binding of chromomycin A3 (CRA) to calf thymas DNA was investigated in the presence of divalent cations using visible absorption and 1H-nmr spectroscopies. An apparent equilibrium binding constant (∼ 1011M-1) was obtained from metal competition experiments using EDTA to remove the metal cation from the DNA-M-CRA (M: metal) complex. The large binding constant of the drug to DNA enabled us to obtain essentially complete complexation of CRA to the short homogeneous d(ATGCAT)2 duplex using stoichiometric amounts of the metal cation. Large induced chemical shifts were observed in the 1H-nmr spectrum of the above complex using the paramagnetic Co2+ cation indicating that the metal occupies a unique binding site. Since no induced 1H-nmr chemical shifts were observed for the drug-Co2+ mixture, it was concluded that no metal-drug complex is formed. In addition, it was found that bound CRA is negatively charged at physiological pH and binding to the DNA could be affected only by using metal cations whose ionic radius size (〈 0.85 Å) and charge (2+) were simultaneously satisfied. Stringent metal cation selectivity for the DNA-M-CRA complex may be intimately connected with the antitumor selectivity of CRA, since different types of cells generally possess widely differing molar concentrations of metal cations.
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    URL: http://dx.doi.org/10.1002/bip.360290303
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