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  • Chemistry  (20,568)
  • 1990-1994  (9,496)
  • 1980-1984
  • 1970-1974  (11,072)
  • 1930-1934
  • 1990  (9,496)
  • 1973  (5,599)
  • 1971  (5,473)
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  • 1990-1994  (9,496)
  • 1980-1984
  • 1970-1974  (11,072)
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 7 (1971), S. 150-162 
    ISSN: 1432-0827
    Keywords: Uranium ; Bone ; Distribution ; Fission ; Chemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Une concentration moyenne de 2.4×10−8 g U/g de cendre a été obtenue à partir de l'os humain normal. La microdistribution de l'uranium dans l'os indique que cet élément est surtout limité à surface de l'endoste et, en particulier, aux surfaces de l'os lamellaire et aux parois des canaux de Havers, ouverts dans l'os corticol. Cette répartition suggère que l'uranium se présente sous une forme chimique impropre à son incorporation dans l'apatite osseux: il ne semble donc pas exister une distribution diffuse significative de l'uranium dans l'os.
    Abstract: Zusammenfassung Eine mittlere Konzentration von 2,4×10−8 g Uran/g Asche wurde in normalen menschlichen Knochen gefunden. Die Feinverteilung von Uran im Knochen zeigt, daß dieses Element hauptsächlich an der endostalen Oberfläche vorkommt, insbesondere an der Oberfläche des trabeculären Knochens und an den Wänden der offenen Haversschen Kanäle im kortikalen Knochen. Diese Verteilung läßt vermuten, daß Uran in einer chemischen Form vorliegt, welche sich für den Einbau in das Knochenapatit nicht eignet. Daraus folgt, daß keine signifikante diffuse Verteilung des Urans innerhalb des Knochens vorliegt.
    Notes: Abstract A mean concentration of 2.4×10−8 g U/g ash has been obtained for normal human bone The microdistribution of uranium in bone indicates that this element is mainly restricted to endosteal surfaces; in particular the surfaces of trabecular bone and the walls of open Haversian canals in cortical bone. This distribution suggests that uranium is present in a chemical form that is not acceptable for incorporation into bone apatite and consequently there does not appear to be a significant diffuse distribution of uranium throughout bone.
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  • 2
    ISSN: 1432-0827
    Keywords: Morphology ; Glycosaminoglycans ; Cartilage ; Chemistry ; Audioradiography ; Healing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Une perte de substance ostéo-cartilagineuse, de taille limitée et identique, est réalisée chez le lapin adulte et la cicatrisation est étudiée histologiquement et par autoradiographie après marquagein vitro au35S-sulfate. Une analyse microchimique est pratiquée pour le contenu et la composition en glycosaminoglycanes. 1. Entre la première semaine et la 4ème et 8ème semaine, un tissu conjonctif non-métachromatique se différencie en un cartilage métachromatique et la quantité de sulfate de chondroitine augmente de façon significative aux dépens des glycoprotéines. 2. Jusqu'à la 4ème semaine, la perte de substance est surtout comblée par de l'os néoformé: après cette période, la région est comblée au delà de la limite de la surface articulaire. 3. Le cartilage hyalin, ressemblant morphologiquement, autoradiographiquement et chimiquement au cartilage articulaire, en ce qui concerne la distribution en glycosaminoglycanes, constitute la surface articulaire de la perte de substance comblée dans un tiers des cas après 8 semaines. Le cartilage hyalin s'observe surtout dans les régions où de l'os néoformé a comblé la cavité médullaire. 4. Dans les deux tiers des cas, après 8 semaines, les surfaces articulaires des zones comblées comportent, non seulement du cartilage, mais aussi du tissu fibreux se formant essentiellement sur les parties latérales et dans les régions, où la cavité médullaire, fliant face, à la surface articulaire, n'a pas été comblée par du tissue osseux. La fraction glycoprotéique augmente par rapport à la fraction chondroitine sulfate. 5. Dans la majorité des cas, après 20 semaines, le cartilage néoformé subit des phénomènes dégénératifs, qui se traduisent par une diminution en chondroitine sulfate.
    Abstract: Zusammenfassung Bei ausgewachsenen Kaninchen wurde ein begrenzter, standardisierter, osteochondraler Defekt hervorgerufen, und das regenerierte Gewebe wurde histologisch und autoradiographisch durch Markierung in vitro mit35S-Sulfat und durch mikrochemische Bestimmung des Gehaltes und der Zusammensetzung der Glykosaminglykane untersucht. Die wichtigsten Befunde waren: 1. Zwischen 1 und 4–8 Wochen veränderte sich nichtmetachromatisches Bindegewebe zu metachromatisch gefärbtem Knorpel, und der Anteil an Chondroitin-Sulfat nahm auf Kosten der Glykoproteine signifikant zu. 2. Bis zu 4 Wochen war der Hauptteil des defekten Gebietes mit neugebildetem Knochen gefüllt; nach dieser Zeit lag dieser Bezirk oberhalb der Verknöcherungsgrenze in Richtung der Gelenkoberfläche. 3. Nach 8 Wochen bestand die Gelenkoberfläche des defekten Gebietes in einem Drittel der Fälle aus hyalinem Knorpel, der morphologisch, autoradiographisch und chemisch dem Gelenkknorpel in Bezug auf die Verteilung von Glykosaminoglykanen glich. Hyaliner Knorpel wurde hauptsächlich an Stellen beobachtet, wo neugebildeter Knochen die Markhöhle geschlossen hatte. 3. Nach 8 Wochen bestand die Gelenkoberfläche des defekten Gebietes in einem Drittel der Fälle aus hyalinem Knorpel, der morphologisch, autoradiographisch und chemisch dem Gelenkknorpel in Bezug auf die Verteilung von Glykosaminoglykanen glich. Hyaliner Knorpel wurde hauptsächlich an Stellen beobachtet, wo neugebildeter Knochen die Markhöhle geschlossen hatte. 4. Nach 8 Wochen bestanden Teile der Gelenkoberfläche des Defektes in zwei Dritteln der Fälle nicht nur aus Knorpel, sondern auch aus fibrösem Gewebe, welches vor allem in den seitlichen Teilen des Defektes und an Stellen vorlag, wo die Markhöhle gegenüber der Gelenkoberfläche nicht mit Knochengewebe verschlossen worden war. Die Glykoproteinfraktion nahm im Vergleich zur Chondroitin-Sulfatfraktion zu. 5. Nach 20 Wochen zeigten sich in den meisten Fällen bei neugebildetem Knorpel degenerative Veränderungen, welche durch eine gewisse Abnahme des Chondroitin-Sulfats wiedergegeben wurden.
    Notes: Abstract A limited, standardized osteochondral defect was created in adult rabbits and the regenerated tissue was examined histologically and autoradiographically after labellingin vitro with35S-sulphate, and microchemically for its content and composition of glycosaminoglycans. The principal findings were: 1. Between 1 week and 4 to 8 weeks, non-metachromatic connective tissue differentiated to metachromatically stained cartilage, and the proportion of the chondroitin sulphate increased significantly at the expense of the glycoproteins. 2. Up to 4 weeks, the major part of the defect area was filled with newly formed bone; after this time, the area lay above the level of the “tidemark”, towards the articular surface. 3. Hyaline cartilage with morphological, autoradiographic and chemical resemblance to the articular cartilage in terms of the distribution of glycosaminoglycans constituted the articular surface of the defect area in one-third of the cases at observation times after 8 weeks. Hyaline cartilage was observed mainly in areas where newly formed bone had closed the medullary cavity. 4. In two-thirds of the cases, after 8 weeks, parts of the articular surface of the defect consisted not only of cartilage but also of fibrous tissue, occurring mainly in the lateral parts of the defect and in areas where the medullary cavity facing the articular surface had not been sealed by bone tissue. The glycoprotein fraction increased relative to the chondroitin sulphate fraction. 5. In most cases after 20 weeks, newly-formed cartilage underwent degenerative changes, which were reflected in some reduction of the chondroitin sulphate.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 8 (1971), S. 228-236 
    ISSN: 1432-0827
    Keywords: Skin ; Calcinosis ; Keratin ; Chemistry ; X-ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Des études histologiques antérieures ont montré que le follicle pileux est particulièrement susceptible de se calcifier, lorsque la peau de rats hypercalcémiques est lésée. Des analyses chimiques et par diffraction aux rayons X du follicule ont confirmé ce résultat. — En se basant sur l'augmentation du calcium et du phosphore, les calcifications débutent dans le tissue folliculaire 6–12 h après une blessure d'intensité moyenne de la peau de rats, ayant reçu du dihydrotachysterol (DHT), et 24–48 h après une blessure similaire chez des rats non injectés. Les diagrammes de diffraction aux rayons X sont diffus. Trois heures après la blessure, on note une augmentation du calcium du tissu folliculaire qui ne semble pas en rapport avec le DHT qui traduit probablement une liaison de calcium plutôt qu'un dépot minéral.
    Abstract: Zusammenfassung Frühere histologische Untersuchungen haben gezeigt, daß der Haarfollikel besonders anfällig für Verkalkungen ist, wenn die Haut von hypercalcämischen Ratten verletzt wird. Dieses Resultat wurde nun durch direkte chemische Bestimmungen und Röntgendiffraktions-analysen von Follikelgewebe bestätigt. Aufgrund der erhöhten Calcium- und Phosphatwerte kann gesagt werden, daß nach einer leichten Quetschung der Haut von Ratten, die mit Dihydrotachysterol (DHT) behandelt wurden, im Haarfollikelgewebe nach 6–12 Std Mineral-ablagerungen stattfanden, wogegen Kontrollratten mit der gleichen leichten Hautverletzung diese Ablagerungen erst nach 24–48 Std zeigten. Röntgendiffraktionsanalysen ergaben ein diffuses Apatit-Muster. Innerhalb 3 Std nach der Verletzung wurde ein Anstieg des Calcium-gehaltes im Follikelgewebe beobachtet, der nicht im Zusammenhang mit der DHT-Behandlung stand, also nicht eine Mineralablagerung, sondern eher eine Bindung von Calcium widerspiegelte.
    Notes: Abstract Previous histological investigations have shown that the hair follicle is particularly susceptible to mineralization when the skin of hypercalcaemic rats is injured. Direct chemical and X-ray diffraction analyses of follicle tissue have now confirmed this finding. As judged by increases in both calcium and phosphorus, mineral deposits began to form in hair follicle tissue 6–12 h after a mild crush injury to the skin of rats dosed with dihydrotachysterol (DHT), and 24–48 h after a similar injury to the skin of non-dosed rats. X-ray diffraction gave a diffuse apatite pattern. Within 3 h of injury there was a rise in the calcium content of follicle tissue which was not related to DHT-dosing and which was probably a reflection of calcium binding rather than mineral deposition.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 8 (1971), S. 304-319 
    ISSN: 1432-0827
    Keywords: Chemistry ; Calcium ; Phosphate ; Solubility ; Computer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Un programme d'ordinateur a été mis au point pour calculer les activités ioniques du calcium et l'orthophosphate dans un grand nombre de solutions. Dans le cas de solutions synthétiques, les calculs sont vérifiés en comparant les valeurs de pH, obtenues par ordinateur, avec celles observées expérimentalement. Des essais de ce type, avec des solutions possèdant des concentrations de calcium et d'orthophosphate trouvées dans les liquides biologiques et à des valeurs de pH variant de 3.00 à 10.00, indiquent que le programme est adapté pour des applications biologiques. Le programme n'est pas effectif pour des solutions, dans les lesquelles l'ion bromure est la source principale de la force ionique, sans doute, par manque d'équation étendue de Debye-Hückel dans ces circonstances. Aucune formation de complexe de phosphate de sodium n'a été notée à des concentrations biologiques normales.
    Abstract: Zusammenfassung Es wurde ein Computer-Programm ausgearbeitet, um die Ionenaktivitäten von Calcium und Orthophosphat in einer breiten Varietät von Lösungen zu berechnen. Die Berechnungen wurden bei synthetischen Lösungen durch Vergleiche zwischen den auf diese Weise errechneten pH-Werten und den experimentell gefundenen kontrolliert. Diese Art Kontrollen mit Calcium-und Orthophosphatkonzentrationen, wie sie in biologischen Flüssigkeiten gefunden werden, und mit pH-Werten zwischen 3,0 und 10,0 wies darauf hin, daß das Programm für biologische Anwendungen geeignet war. Das Programm konnte nicht benützt werden für solche Lösungen, bei welchen hauptsächlich das Bromidion zur Einstellung der Ionenstärke verwendet wurde, vermutlich weil die erweiterte Debye-Hückel-Gleichung unter diesen Umständen nicht anwendbar ist. Die Bildung eines Natriumphosphat-Komplexes unter normalen biologischen Konzentrationen konnte nicht nachgewiesen werden.
    Notes: Abstract A computer program has been designed to calculate the ionic activities of calcium and orthophosphate in a wide variety of solutions. In the case of synthetic solutions the calculations were checked by comparing the computed pH values with those observed experimentally. Tests of this type with solutions having the concentrations of calcium and orthophosphate found in biological fluids and with pH values ranging from pH 3.0–10.0 indicated that the program was suitable for biological applications. The program was not effective for solutions in which the bromide ion was a principal source of ionic strength probably because of the failure of the extended Debye-Hückel equation under those circumstances. No evidence for the formation of any sodium phosphate complex at normal biological concentrations could be found.
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  • 5
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    Electronic Resource
    Springer
    Calcified tissue international 8 (1971), S. 197-210 
    ISSN: 1432-0827
    Keywords: Fluorescence ; Calcium ; Collagen ; Chemistry ; Bone ; Dentine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Des composants fluorescents de l'os et la dentine sont séparés des hydrolysats alcalins de leur marice sur des colonnes Sephadex C25 CM d'échange cationique. Les concentrations en fluorescence et le spectre d'excitation (λ max 330 nm) et d'émission (λ max 395 nm) sont les mêmes que ceux observés au niveau des matrices intactes et gélatinisées. Les paramètres de fluorescence ne sont pas altérés par hydrolyse. La filtration sur gel à l'aide de colonnes Sephadex G 10 perment de différencier le matériel isolé en deux composants, ayant la même fluorescence et la même absorption UV. La fluorescence est indépendante de pH de 3.5–9.5. Des études de dialyse et de filtration sur gel de matrices gélatinisées indiquent une association étroite du matériel fluorescent avec les chaines polypeptidiques de collagène.
    Abstract: Zusammenfassung Fluorescierende Bestandteile aus Knochen und Dentin wurden in Sephadex C25 CM Kationen-Austauschersäulen von alkalischen Hydrolysaten ihrer Matrices getrennt. Die Fluorescenzintensitäten sowie die Erregungs- (λ max 330 nm) und Emissions- (λ max 395 nm) Spektren waren dieselben wie bei intakten und gelatinisierten Matrices. Die Fluorescenzparameter wurden durch die Hydrolyse nicht verändert. Eine Gelfiltration über Sephadex-G10-Säulen trennte das isolierte Material in 2 Komponenten auf, welche gleiche Fluorescenz- und UV-Absorptionseigenschaften zeigten. Im pH-Bereich zwischen 3,5 und 9,5 war die Fluorescenz unabhängig vom pH. Dialysierversuche sowie Gelfiltrationsexperimente mitden gelatinisierten Matrices zeigten eine starkgefügte Bindung des fluorescierenden Materials mit den Polypeptidketten des Kollagens.
    Notes: Abstract Fluorescent components in bone and dentine were separated from alkaline hydrolysates of their matrices on Sephadex C25 CM cationic exchange columns. The fluorescence levels, and the excitation (λ max 330 nm) and emission (λ max 395 nm) spectra, were the same as those observed in the intact and gelatinised matrices. The fluorescence parameters were unaltered by the hydrolysis procedure. Gel filtration on Sephadex G. 10 columns further resolved the isolated material into two components with the same fluorescence and UV absorption properties. The fluorescence was independent of pH over the range 3.5–9.5. Dialysis and gel filtration studies on the gelatinised matrices indicated a firmly-bonded association of the fluorescent material with the collagen polypeptide chains.
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  • 6
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    Springer
    Calcified tissue international 12 (1973), S. 125-136 
    ISSN: 1432-0827
    Keywords: Mineralization ; Molt ; Isopod ; Chemistry ; Light microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Au cours de la phase inhabituelle de mue d'un isopode d'eau courante,Lirceuts brachyrus, la moitié postérieure de l'exosquelette est éliminée 24 heures avant la moitié antérieure. A ce stade, une reminéralisation se développe dans la partie postérieure alors que la partie antérieure est dans un stade de pré-mue. Le pourcentage de différence en calcium dans les deux moitiés à mi-mue et mue complète est respectivement de 22% (p〈0.01) et 33% (p〈0.01), indiquant une complexation du calcium pendant la mue. La rapidité de la reminéralisation est illustrée par le fait que le contenu minéral total double dans la partie postérieure entre la mi-mue et la mue totale et dans la partie antérieure entre la fin de la mue et un jour après. Le carbonate de calcium, sous forme de calcite, a pu être identifié par diffraction électronique de coupes fines des téguments.
    Abstract: Zusammenfassung Während der ungewöhnlichen Häutungssequenz des Frischwasser-IsopodenLirceus brachyurus (Harger) wird die hintere Hälfte des äußeren Skeletts 24 Std vor der vorderen Hälfte abgestoßen. In der halbgehäuteten Phase erfolgt Remineralisation im hinteren Teil, während der vordere Teil in einem Vorhäutungszustand ist. Der prozentuale Unterschied des Calciums in den zwei Hälften bei Halb- und Vollhäutungszustand ist 22% (p〈0,01) bzw. 33% (p〈0,01), was andeutet, daß Calcium während der Häutung abgesondert wird. Die Geschwindigkeit der Remineralisation erhellt aus der Tatsache, daß sich der Gesamtmineralgehalt im hinteren Teil zwischen Halt- und Vollhäutung, in der vorderen Hälfte jedoch zwischen Endhäutung und einem Tag nach der Häutung verdoppelt. Calciumcarbonat in kristalliner Calcitform wurde mittels Elektronendiffraktion von dünnen Hautschnitten nachgewiesen.
    Notes: Abstract During the unusual molt sequence of the fresh-water isopod,Lirceus brachyrus (Harger), the posterior half of the exoskeleton is shed 24 hours before the anterior half. At the half-molt stage, occurs in the posterior part while the anterior portion is in a pre-molt condition. The percentage difference in calcium in the two halves at half-molt and full-molt is22 (p〈0.01) and33 (p〈0.01) respectively, an indication that calcium is sequestered during The rapidity of remineralization is illustrated by the fact that the total mineral content doubles in the posterior part between half and full molt and in the anterior half between the end of molt and one day after ecdysis. Calcium carbonate in the calcite cystalline form was demonstrated by electron diffraction of thin sections of the integument.
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  • 7
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    Springer
    Calcified tissue international 13 (1973), S. 259-270 
    ISSN: 1432-0827
    Keywords: Fluorapatite ; Exchange ; Chemistry ; Crystallography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Un échantillon minéral provenant de Burgess, Canada s'est révélé être un speciment exceptionnellement pur de fluoroapatite après analyse chimique et cristallographique. La composition globale de cet échantillon est la suivante: $$(Ca^2 )9.98(Sr^{2 + } ,Na^ + ,K^ + ,Mg^{2 + } )0.02(PO_4^{3 - } )5.98(HCO_3^ - ,CO_3^{2 - } )0.02(F^ - )2$$ . L'axe cristallographique C est de 6.865 A et l'axe a de 9.374 A. Des expériences d'échanges réalisés à l'aide de45Ca,32P et18F indiquent la présence de gros cristallites de surface spécifique de l'ordre de 1 m2/g. Il apparait que l'interprétation physique des processus d'échange ne nécessite pas l'existence de compartiments séparés, avec chacun son propre facteur cinétique, les échanges semblent être simplement liés à un changement exponentiel dans l'énergie libre de la réaction. Pour la réaction suivante: $$(Ca)_5 (PO_4 )_3 OH solide + (F^ - ) \rightleftarrows (Ca)_5 (PO_4 )_3 F solide + (OH^ - )$$ , la constante thermodynamique de 101.26 a été calculée, suggérant que le fluorapatite se forme toujours aux dépens de l'hydroxyapatite dans des conditions physiologiques. Cette transformation se continue en abaissant le pH.
    Abstract: Zusammenfassung Eine Mineralprobe aus Burgess, Kanada, erwies sich nach chemischer und kristallographischer Analyse als außergewöhnlich reines Fluorapatit. Die Gesamtzusammensetzung entspricht: $$(Ca^{2 + } )_{9,98} (Sr^{2 + } ,Na^ + ,K^ + ,Mg^{2 + } )_{0,02} (PO_4^{3 - } )_{5,98} (HCO_3^ - ,CO_3^{2 - } )_{0,02} (F^ - )_2 $$ . Die kristallographische c-Achse wurde bestimmt und ergab 6,865 Å, und die a-Achse ergab 9,374 Å. Austauschwerte, welche durch Anwendung von45Ca,32P und18F erhalten wurden, deuteten auf große Kristalliten mit einer spezifischen Oberfläche von ca. 1 m2/g. Die Befunde deuten darauf hin, daß für die physikalische Erklärung des Austauschvorganges keine separaten Kompartimente mit eigenen kinetischen Faktoren nötig sind, sondern daß der Austausch mit dem exponentiellen Wechsel in der freien Energie der Reaktion in einfacher Beziehung steht. Für die Reaktion $$(Ca)_5 (PO_4 )_3 OH_{in fester Form} + (F^ - ) \rightleftarrows (Ca)_5 (PO_4 )_3 F_{in fester Form} + (OH^ - )$$ wurde als thermodynamische Konstante 101,26 errechnet, was darauf deutet, daß unter physiologischen Bedingungen immer Fluorapatit auf Kosten von Hydroxyapatit entsteht. Diese Umwandlung wird erhöht, wenn das pH erniedrigt wird.
    Notes: Abstract A mineral specimen from Burgess, Canada, proved upon chemical and crystallographic analyses to be an exceptionally pure sample of fluorapatite. The over-all composition corresponds to $$(Ca^{2 + } )_{9.98} (Sr^{2 + } ,Na^ + ,K^ + ,Mg^{2 + } )_{0.02} (PO_4^{3 - } )_{5.98} (HCO_3^ - ,CO_3^{2 - } )_{0.02} (F^ - )_2 $$ . The crystallographic c-axis was determined to be 6.865 Å, and the a-axis 9.374 A. Exchange data obtained by employing45Ca,32P, and18F indicate the presence of large crystallites with a specific surface of the order of 1 m2/g. It is indicated that the physical interpretation of the exchange process does not require the existence of separate departments, each with its own kinetic factor, but that the exchange may be simply related to the exponential change in the free energy of the reaction. For the reaction $$(Ca)_5 (PO_4 )_3 OH_{solid} + (F^ - ) \rightleftarrows (Ca)_5 (PO_4 )_3 F_{solid} + (OH^ - )$$ the thermodynamic constant has been calculated to be 101.26, implying that fluorapatite always will form at the expense of hydroxyapatite under physiologic conditions. This transformation will be furthered by lowering the pH.
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  • 8
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    Plant systematics and evolution 171 (1990), S. 1-14 
    ISSN: 1615-6110
    Keywords: Angiosperms ; Compositae ; Chemistry ; systematics ; evolution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The broad knowledge of the chemistry of theCompositae allows the discussion of its relevance for the systematics and evolution within the family. Furthermore a separation into subfamilies can be supported by the observed differences in the distribution of the main constituents in the tribes.
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  • 9
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 175 (1990), S. 107-116 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
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  • 10
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 175 (1990), S. 157-168 
    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.
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  • 11
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 175 (1990), S. 205-205 
    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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  • 12
    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.
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  • 13
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    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.
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  • 14
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    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.
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  • 15
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    Angewandte Makromolekulare Chemie 179 (1990), S. 35-56 
    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.
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  • 16
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    Angewandte Makromolekulare Chemie 179 (1990), S. 77-85 
    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.
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  • 17
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    Angewandte Makromolekulare Chemie 179 (1990), S. 135-148 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
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  • 18
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    Angewandte Makromolekulare Chemie 179 (1990), S. 157-171 
    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.
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  • 19
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    Angewandte Makromolekulare Chemie 175 (1990), S. 29-38 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die 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.
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  • 20
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    Angewandte Makromolekulare Chemie 180 (1990), S. 191-198 
    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.
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  • 21
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    Angewandte Makromolekulare Chemie 181 (1990), S. 41-52 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
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  • 22
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    Angewandte Makromolekulare Chemie 181 (1990), S. 53-66 
    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).
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  • 23
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    Angewandte Makromolekulare Chemie 181 (1990), S. 67-74 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
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  • 24
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    Angewandte Makromolekulare Chemie 174 (1990), S. 1-10 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
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  • 25
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
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  • 26
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    Angewandte Makromolekulare Chemie 174 (1990), S. 105-117 
    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.
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  • 27
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
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  • 28
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 179 (1990), S. 99-111 
    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.
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  • 29
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 175 (1990), S. 13-27 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
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  • 30
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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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  • 31
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 175 (1990), S. 81-97 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
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  • 32
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 175 (1990), S. 117-128 
    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.
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  • 33
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 175 (1990), S. 141-156 
    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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  • 34
    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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  • 35
    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.
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  • 36
    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.
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  • 37
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    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).
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  • 38
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    Angewandte Makromolekulare Chemie 181 (1990), S. 85-91 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
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  • 39
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
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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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  • 41
    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.
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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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    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'.
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    Biopolymers 10 (1971), S. 1049-1057 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ultrastructural morphology and x-ray and electron diffraction of poly (Gly-Gly-Ala) have been studied. The polymer has two forms; the first, form I possesses a super-folded cross-β structure, long fibers of which show some twisting and intertwining. Form II precipitates in a less distinct fibrous form from aqueous solution. The x-ray diffraction and oriented electron diffraction data suggest that form II is a polyglycine II helix situated in a monoclinic cell with dimensions a = 8.86 Å, b = 22.0 Å, c = 9.42 Å, and β = 90°. Combined with the morphological evidence it appears likely that form II is also in an antiparallel superfolded array.
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    Biopolymers 10 (1971), S. 1099-1101 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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  • 46
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: A statistical mechanical model was developed for use in connection with the problem of preferential binding of solvent components to proteins and of conformational transition in water-organic solvent systems. The model is a statistical one for the conformational transition of globular proteins induced by the adsorption of solutes in the solution, considered as a nearest-neighbor problem in statistical mechanics. Although a few illustrative examples are given, the actual interpretations of the experimental data using this theory are reserved for a later paper.
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    Biopolymers 10 (1971), S. 1103-1103 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 10 (1971), S. 1121-1138 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The concept and representation of a logical tree as defined in computer science is applied to obtain a suitable representation of protein molecules in computer programs which handle or calculate atomic coordinates of protein molecules. On the basis of this analysis and of the analysis of the calculation and modification of the structure of a protein from bond lengths, bond angles, and dihedral angles, which is reproduced in an appendix, program modules which accomplish the various required computations are described. Three such modules are given in Iverson notation; in fact, it is hoped that this article will serve as a reasonably complete basis for the preparation of machine programs by moderately proficient programmers.
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    Biopolymers 10 (1971), S. 1207-1212 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The circular dichroism spectrum obtained from a dilute aqueous solution of poly (ala-gly-gly) resembles that described for charged polypeptides such as the salt form of poly glutamic acid. A similar spectrum is found for films cast from aqueous solution where x-ray studies reported elsewhere have indicated a poly-glycinc II conformation. Evidence is presented for a heat induced poly-glycine II to unordered state transition similar to that described for collagen. The interpretation of this, the first observation of the optical properties of a poly-amino acid in the poly glycine II conformation, is further rationalized on the basis of spectra obtained from a number of polypeptides whose conformation approaches that of a 31 helix.
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    Biopolymers 10 (1971), S. 1229-1242 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of cupric ion on the emission of tryptophan, tyrosine, and serum albumins is studied by emission spectroscopy and lifetime measurements. It is found that whenever cupric ion is bound to tryptophan or tyrosine, their emissions are quenched completely. The quenching may be due to an electron transfer mechanism. The fluorescence of complexes of cupric ions with serum albumins is partially quenched; this is because energy is transferred from tryptophan to the complexed cupric ions by a dipolar energy transfer mechanism. It is deduced from the present study that the tryptophan in the human serum albumin molecule is between 11 and 16 Å from the nearest eupric ion binding sites (assumed to be at the surface of the protein) and that one of the tryptophan in the bovine serum albumin molecule is very close to the cupric ion binding sites and the other is near the center of the bovine serum albumin molecule. It is also found that the deuterium solvent effect on serum albumin fluorescence is very small, and that the quenching of bovine serum albumin fluorescence at the N-F transition is the result of quenching of the fluorescence of both tryptophans. The phosphorescence lifetime apparatus, capable of measuring decay times of signals with intensities changing over a few orders of magnitude, and the ratio spectrofluorometer, both of which were constructed in this laboratory, are also described.
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    Biopolymers 10 (1971), S. 1253-1260 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The measurements were made for the volume and the sound velocity changes (ΔV and ΔU) on titrating the sodium salt of poly (S-carboxymethyl L-cysteine) with dilute HCl. For the reaction, —COO- + H+ → —COOH, ΔV per mole of H+ bound was + 12. 7 ml and +11. 4 ml in salt-free and 0. 2 M NaCl solutions, respectively. Corresponding ΔU was about -13 cm/sec in salt-free polymer solution where 11.5 mM carboxylate ion reacts with equimolar hydrogen ion. ΔV associated with the coil-to-β transition was found to be +2. 35 ml in H2O and +1. 90 ml in 0. 2 M NaCl per mole of amino acid residue, respectively. These values are larger than those obtained for the coil-to-helix transition of poly (L-glutamic acid). ΔU for the transition was about -30 cm/sec in salt-free solution of polymer concentration 0.0115 mole/liter. Possible sources of ΔV and ΔU for reaction; coil → β, are (1) the formation of void volume and (2) the changes in the extent of solvation in amide linkage and in side chain.
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    Biopolymers 10 (1971), S. 1317-1329 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The binding of three aromatic molecules to apomyoglobin has been investigated. In each case equilibrium dialysis studies and tryptophan fluorescence quenching studies indicate that a one to one complex has been formed. The fluorescence quenching studies further suggest that the binding of the aromatic molecules is at the heme site with possible involvement of the arginine CD3. Xenon, which is known to quench the fluorescence of aromatic hydrocarbons, is found to be bound to apomyoglobin-aromatic molecule complexes and quenches the emission of the aromatic molecule in the complexes. Oxygen quenches pyrene fluorescence in water solution but does not quench the pyrene fluorescence from the apomyoglobin-pyrene complex. This is explained by a slower rate of diffusion of oxygen to pyrene in the apomyoglobin-pyrene complex.
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    Biopolymers 10 (1971), S. 1365-1369 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The rotor speed-dependent aggregation of T4 DNA in the analytical ultracentrifuge is studied in the presence of high pressure generated by compressed nitrogen gas in the cell. The extents of aggregation at various speeds are found to be practically the same in the presence and absence of pressure.
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    Biopolymers 10 (1971), S. 1331-1349 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The time-dependent theory developed in Part I is specialized to treat tetrameric hemoglobin, and the results of the theory for dimeric-and tetrameric hemoglobin are compared with data on the kinetics of the reactions of hemoglobin with carbon monoxide and oxygen at various salt concentrations for the case of large concentration of ligand relative to that of hemoglobin. The fit of the theoretical results to the data suggests that hemoglobin at a 2 M salt concentration is predominantly dimeric and that the tetramer should be taken as the functional unit to explain the kinetics of the reactions of normal hemoglobin. A relationship is established between the time-dependent theory arid Adair's Intermediate Compound Hypothesis (I.C.H.) for hemoglobin, as brought to its present state by Gibson and Roughton. A generalization (G.I.C.H.) of the I.C.H. is presented and is shown to be equivalent to the time-dependent theory in the limit of infinite ligand concentration. The I.C.H. is shown to be an excellent approximation to the centralized theory (G.I.C.H.) in this limit.
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    Biopolymers 10 (1971), S. 1421-1425 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 10 (1971), S. 1427-1428 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 10 (1971), S. 1429-1454 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The ability of oligodesoxyribonucleotides of various chain lengths to form complexes has been compared with that of oligoribonucleotides. Four series of oligonucleotidcs were prepared and investigated, i.e., dCn at acid pH versus rCn, dAn and dTn versus. rAn and rUn at neutral pH. The results indicate that in dilute solution, the formation of complexes is greatly facilitated in the case of desoxyoligomers and occurs for shorter oligomere than in the corresponding ribooligomers. The spectrophotometric titration of deoxyribooligo C indicates the appearance of two pK values in the 4-5 pH region characteristic of the double-stranded form, which occurs for much shorter dCn than rCn. The circular dichroism (CD.) spectra of deoxycytidylies in dilute solution starting from the trimer are conservative, characteristic of the double-stranded helical form of poly C at acid pH. In contrast, the CD spectra of a series of corresponding ribo Cn, under identical conditions is of nonconservative character similar to that of the single-stranded form of poly C at neutral pH, but differs in the band position. This spectrum is called intermediate. Only at higher concentrations of oligonucleotidcs (i.e., 10-3Minstead of 10-4M) does the circular dichroism spectrum of longer ribocytidylics assume conservative character. Thermal denaturation of deoxycytidylces at acid pH are strongly dependent on chain length and concentration, its one would expect for a cooperative helix-coil transition. The circular dichroism spectra measured at different temperatures shows one isosbestic point. In dilute solution, the standard-state enthalpy change found was 5-6 kcal/mole for higher oligomers (dC7). These properties are all in agreement with a structural transition from the d-Cn double-stranded form to a coil for n 〉 3. Studies of dAn and dTn in solutions of high ionic strength at low temperature indicate that complex formation occurs already at the level of trimer and for high oligomers. Under identical conditions a complex between rAn and rUn is detected only for oligomers longer than the hexamer. The nature of the “intermediate” form of oligoribo C at acid pH and low temperature was investigated by sedimentation and circular dichroism. A model of rCn is proposed of linear molecules which are partially double-stranded and partially single-stranded, which probably are slowly rearranged by “slippage” into a regular-double-stranded helical form.
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    Topics: Chemistry and Pharmacology
    Notes: The number average molecular weight, Mn, of low molecular weight dextran was determined through endgroup analysis, and the intrinsic, viscosities of these materials in aqueous solution were determined at 25°C. The ultrasonic velocities in their aqueous solutions were also measured at 25 and 45°C. As concerns the molecular weight dependence of the intrinsic viscosity, partial specific compressibility of solute and the hound water around the solute, the following results were obtained. (1) log [η]-log Mn and [η]/Mn0.5 - Mn0.5 plots were in accord with the Mark-Houwink and Stockmayer-Fix-man equations respectively for Mn 〉 2, 000, but these plots deviated from the equations for Mn 〈 2, 000. (2)The partial specific compressibility, β1°, of dextran is expressed by following equation for Mn 〈 2,000: β1° = 10-12 × (13.6 log Mn - 51.7) (cm2/dyne). In contrast, it, becomes the constant value, -- 7.3 × 10-12 cm2/dyne, for Mn 〉 2,000. (3) The amount of bound water of dextran calculated from the sound velocity measurement lakes constant value of 0.17 ml g for Mn 〉 2, 000, but the amount of hydration increase with decreasing molecular weight for Mn 〈 2,000. From these results, a dextran molecule in aqueous solution is expected to change its conformation from random coiling to uncoiling stretched form at the molecular weight of around 2, 000 or about 12 glucose units.
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    Biopolymers 10 (1971), S. 1559-1581 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optical rotation studies were performed on five compounds containing two peptide groups. Four of the molecules were confined to restricted regions of conformational space by the presence of closed rings. Solvent and temperature were varied, and theoretical calculations were done for each compound covering the appropriate conformational space. The interpretation which results is qualitatively successful over the conformational regions covered by the compounds. Quantitative correlation between theory and experiment will require compounds of high rigidity.
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    Biopolymers 10 (1971), S. 1617-1623 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformational energy maps have been calculated for α-D-mannuronic acid (1-4) α-L-guluronic acid and for α-L-guluronic acid (1-4) β-D-mannuronic acid. These have been used, together with maps previously calculated for the homomonomeric dimers, to estimate the characteristic ratios and Kuhn lengths of the alternating copolymer and of a stochastic copolymer similar in composition to that extracted from L. digitata.The results show that the alternating copolymer is less extended than either homopolymer. Kuhn lengths calculated for the stochastic copolymer agree well with experimental results on high ionic strength solutions of alginate isolated from L digitata.
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    Biopolymers 10 (1971), S. 1635-1648 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-S-carboxyethyl-L-cysteine, a higher side-chain homolog of poly-S-carboxymethyl-L-cysteine, has been prepared from poly-S-carbobenzoxyethyl-L-cysteine with hydrogen bromide in chloroform or acetic acid. The polymer is found to be in the β-conformation of an antiparallel arrangement of polypeptide chains in solid films, both in acid and salt forms, when examined by infrared spectra. Aqueous solutions of t he polymer have been investigated by measurements of rotatory dispersion and circular dichroism as well as by infrared spectra in D2O. These properties show sharp changes around pH 5.5, as the pH of solution is varied. At higher ionization the polymer is randomly coiled, but at lower ionization it is in the β-conformation. Dependence of the rotatory properties upon polymer concentration as well as on ionic strength has been observed even at the lowest degree of ionization attained, and this has been attributed to the formation of intermolecular β-conformation in solutions. The β-structure is characterized by a negative circular dichroic band at 223 mμ and a positive dichroic band at a wavelength lower than 200 mμ, and furt her by a negative bo value, -140°. The pH-induced coil-β transition of the polymer is compared with that of poly-S-carboxymethl-L-cysteine.
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    Biopolymers 10 (1971), S. 1681-1699 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The specific heat, of rat tail tendon at various water contents was measured as a function of temperature. The resulting graphs showed peaks arising from the melting, near 50°C, of helical material in the collagen, and from the melting of absorbed water in the range -40°C to 0°C. The heat of melting of helical material was 11.7 cal per gram of dry tendon. Determination of the heat and temperature of fusion of the absorbed water allowed resolution of the water into four states in the case of tendon before denaturation, and three states after denaturation. The four states are (1) water not freezable on cooling to - 70°C, (2) freezable water with-both heat and temperature of fusion different from the values for ordinary water, (3) freezable water with the heat of fusion of ordinary water, but a different temperature of fusion, and (4) water not distinguished from ordinary water. The fourth state was absent in denatured tendon. The results are discussed in terms of increasing size of clusters of absorbed water molecules.
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    Biopolymers 10 (1971) 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 10 (1971), S. 1743-1757 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absorption and rotatory properties of acridine orange-poly-S-carboxymethyl-L-cysteine system in water and in 0.2 M NaCl have been measured at different pH and polymer-to-dye mixing ratios. The absorption spectra indicate that the dyes are bound to the polymer in dimeric or highly aggregated forms. At neutral pH where the polymer is randomly coiled, no optical activity is induced on the absorption bands of bound acridine orange. At acid pH where the polymer has the β-conformation, a pair of positive and negative circular dichroic bands occur at each of the absorption bands, centered around 458 and 261 mμ. The signs of those bands are opposite to those found for α-helical poly-L-glutamic acid. A model for the binding of dye to the β-form polymer is presented, in which dimeric dyes are attached to ionized carboxyl groups and slack one another to form linear arrays on both sides of an extended polypeptide chain. The observed circular dichroism spectra can be explained by the Tinoco's exciton mechanism, based on this model. Low molecular weight poly-S-carboxymethyl-L-cysteine induces quite a different circular dichroism on bound acridine orange.
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    Biopolymers 10 (1971), S. 1853-1863 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The circular dicrosim (CD) spectra of complexes of DNA with ethidiun bromnide, profiavine, 9-aminoacridine and 4-etliyl-9-amino-acridine have been determined between 220 and 450 nm, the range lieing extended to 600 nm for ethidiufm bromide. The variation of the magnitude of the visible and near - ultraviolet CD spectra of ethidium bromide - DNA complexes with the amount of ligand bound (r) suggests a common binding position with profiavine. On the other hand, 4-ethyl-9-aminoacndine complexed to DNA shows CD spectra not distinguishable from those of 9-aminnoacnidmc in both the visible and ultraviolet. The interpretation of these results with respect to the stereochemistry of the DNA-ligand complexes is discussed.
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    Biopolymers 10 (1971), S. 1901-1924 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The various treatments of sedimentation equilibrium are compared on a theoretical and an experimental basis. Particular attention is paid to the polyelectrolyte nature of the problem and the choice of a neutral component. The effective density gradients of several cesium salts for DNA are measured. Two previous theories for the effective density gradient are shown to be equivalent, and the experimental values are interpreted with respect to these theories. It is clear t hat sedimentation equilibrium in a density gradient may be used for the determination of unambiguous molecular weights.
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    Biopolymers 10 (1971), S. 1949-1972 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The theory of friction-limited DNA unwinding is developed explicitly for moderate tind large perturbations. This extension of the earlier theory of the relaxation kinetics is necessary because of the complex nature of the rate limitation for small perturbations. The assumption of the theory that is violated under relaxation conditions is that base pairing reactions occurring at a constant local degree of twist of the strands are fast compared to the net unwinding of the molecule. However, these reactions that are slow for small perturbations have a large activation energy, and become faster than friction-limited un winding for large enough temperature jumps and sufficiently large DXA molecules. Thus only the rate for moderate and large perturbations is clearly limited by frictional resistance to turning the molecule in solution. The model used is a diffusional unwinding of the two strands, driven by the accompanying decrease in free energy. For large perturbations a numerical solution of the diffusion equation is required, since the diffusion coefficient is not constant. Two new parameters must be introduced into the equilibrium statistical theory to describe friction-limited unwinding kinetics. These are the force constant b, for winding up coil regions and the frictional coefficient per base pair βcfor rotating coil regions in solution. We find by fitting the theory to experiment that b = 1.8 × 10-13 ergs/ rad2- and βc = 3.5 × 10-21 erg see/base pair, both for DNA melted in alkali at 0.4.M Na + and ∼30 °C. The latter value is in agreement with predictions based on the viscosity of single stranded DNA in alkali. The quoted value of bcan be interpreted to mean that the number of conformational states of a nucleolide is reduced by an average factor of 1.55 when it is wound around another strand to the degree of twist in a double helix, but without forming a base pair.
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  • 68
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The properties of oligonucleotide helices of adeuylic- and uridylic acid oligomers have been investigated by measurements of hypo-and hyperchromieity. High ionic strengths favor the formation of triple helices. Thus, the double helix-coil transition can be studied (without interference by triple helices) only at low ionic-strength. A “phase diagram” is given representing the Tm-values of the various transitions at different ionic strengths for the system A(pA)17 + U(pU)17. Oligonucleolides of chain lengths 〈8 always form both double and triple helices at the nucleotide concentrations required for base pairing. For this reason the double helix-coil transition without coupling of the triple helix equilibrium can only be measured for chain lengths higher than 7. Melting curves corresponding to this transition have been determined for chain lengths 8, 9, 10, 11, 14 and 18 at different concentrations. An increase in nucleotide concentration leads to an increase in melting temperature. The shorter the chain length the lower the Tm-value and the broader the helix-coil transition. The experimental transition curves have been analysed according to a staggering zipper model with consideration of the stacking of the adeuylic acid single strands and the electrostatic repulsion of tlip phosphate charges on opposite strands. The temperature dependence of the nucleation parameter has been accounted for by a slacking factor x. The stacking factor expresses the magnitude of the stacking enthalpy. By curve fitting xwas computed to be 0.7, corresponding to a stacking enthalpy of about S kcal/mole. The model described allows the reproduction of the experimental transition curves with relatively high accuracy. In an appendix the thermodynamic parameters of the stacking equilibrium of poly A and of the helix-coil equilibria of poly A + poly U at neutral pH are calculated (ΔHA = -7.9 kcal/mole for the poly A stacking and ΔH12 = -10.9 kcal/mole for the formation of the double helix from the randomly coiled single strands). A formula for the configurational entropy of polymers derived by Flory on the basis of a liquid lattice model is adapted to calculate the stacking entropies of adenylic oligomers.
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    Biopolymers 10 (1971), S. 2049-2049 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 10 (1971), S. 2071-2077 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The data on the band widths and band shapes of several DNA's at various concentrations in sedimentation equilibrium in a CsCl density gradient have recently become available. In the present report, these literature data are treated in the following manner: (1) based on a theory of isotope-substitution, calculations are made of the molecular weights at infinite dilution, and (2) to explain the concentration dependence of band widths and band shapes, a theory of charge and hydration is put forth, and it is shown that by retaining the terms involving the charge of the macromolecules, it is possible to account for most of the concentration dependence.
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    Biopolymers 10 (1971), S. 2083-2094 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The mechanism of the unique and specific association of a given amino acid to its t-RNA is investigated by theoretical methods. Several possible schemes are proposed to explain specificity. The physical forces which act within these mechanisms are illustrated by the computer simulation of probable interactions between glycine and nucleotide bases and base pairs. It is demonstrated that glycine has direct and selective affinities for the nucleotide bases and that these interactions are principally determined by the polar groups. Energies have been calculated for the interaction of glycine with several base pairs. From these, the possibility that specificity arises through direct complexing of an amino acid with its anticodon is evaluated.
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    Biopolymers 10 (1971), S. 2147-2160 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Equations are developed to describe the shift in the temperature of the helix-coil transition when small molecules bind to nucleic acids. Included are high polymers, oligonucleotides, and oligomer-polymer interactions. The equations prescribe simple ways of plotting experimental data to evaluate transition and binding parameters.
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    Biopolymers 10 (1971), S. 2181-2197 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The helix-coil transitions for poly-L-lysine (PL) were investigated by the methods of spectropolarimetry, viscometry and potentiometric titration in 0.2M NaCl at different temperatures as well as in 0.2MNaBr, 1MKCl, and in mixtures of 0.2MNaCl or NaBr with methanol at room temperature. The enthalpy and entropy differences between the helical and coillike states of uncharged PL molecules in 0.2.M NaCl were determined from the potentiometric titration curves. The cooperativity parameters σ for PL in different solvents were determined by two methods (from the sharpness of the transition and from the dependence of the intrinsic viscosity on the helical content in the transition region). In 0.2MNaCl σ has a value of (2.3 ± 0.5) × 10-4 and does not depend on temperature, i.e., the cooperativity of the helix-coil transition, as for PGA, is mainly of an entropy origin (the initiating of the helical region is accompanied by the entropy decrease ΔSi = -12 eu/mole of helical regions). A comparison of the obtained results for PGA and PL with the molecular theories of the helix-coil transitions shows that the role of dipole-dipole interactions of nonneighboring peptide groups is greatly overestimated in these theories, leading to a considerable enthalpy contribution to the free energy of initiating helical regions which is not observed in the experiment.
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    Biopolymers 10 (1971), S. 2029-2037 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The variation of the polarized components of fluorescence of a rodlike particle bearing a fluorescent label upon partial orientation is calculated for some special geometry of the dye macromolecules complexes. Explicit expressions are given for the case where the energy of the molecule in the field depends only on one angle θ, showing that the result is a function of both 〈sin2θ〉 and 〈sin4θ〉. For the case of orientation in an electric field through an anisotropic induced moment, the expressions allow the calculation of this anisotropy of polarizability. The method is applied to the measurement of the polarizability of rodlike fragments of DNA labeled by intercalated molecules of Acridine Orange.
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    Biopolymers 10 (1971), S. 2039-2048 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: As the temperature of solid poly(β-benzyl-L-aspartate) (PBLA), (CO.NH.CH.-CH2COOCH2C6H5)n, in the α-helieal form is raised from -150 °C, tlie line width and second moment of the proton magnetic resonance (PMR) signal decrease in stages until the conformational transition to the ω-helix occurs at about 90 °C. A similar temperature dependence of the PMR parameters is observed as the transformed polymer is cooled. Below -100°C (where the lattice is presumed to be rigid), the measured second moments are 9.5 Oe2 and 10.7 Oe2 for the α and ω forms, respectively. Second moments, calculated from the Van Vleck formula for the rigid lattice and also estimated for possible motional cases in which the polymer is taken to be in the ω form, are compared with the PMH data. By combination with the results of X-ray diffraction and infrared spectroscopic measurements, a tentative explanation can be made of the types of motion occurring in PBLA.
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    Biopolymers 10 (1971), S. 2133-2145 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have performed potentiometric titrations of poly-L-lysine. From these data we have calculated the free energy and enthalpy changes for the folding of the random coil to the α-helix in 10% ethanol (-120 and -120 cal/mole) and from the random coil to the β-structure in water (-140 and 870 cal/mole) and in 10% ethanol (-180 and 980 cal mole). Comparison of these values with each other and with values for the coil → α- helix transition in water (-78 and -880 cal/mole) led to the following conclusions. The stabilization by ethanol of ethanol of the α-helix with respect to the coil is that predicted from the known free energy of transfer of the peptide group from water to 10% ethanol. Similar data to explain the enthalpy difference are not available. The thermodynamic functions for the transition from α-helix to β-structure, obtained by subtracting those for the coil → α-helix and coil → β-structure transitions, are explained from a consideration of the structural differences: non bonded interactions of the polypeptide backbone are less favorable in the β-structure than in the α-helix, causing an increase in the energy, while hydrophobic contacts between side chains raise the entropy of the β-structure as compared with the α-helix, so that the free energy difference between the two structures is small, but enthalpy and entropy differences are large. The observation of only small differences in the free energy and enthalpy changes for the transition from coil β-structure upon going from water to 10% ethanol is expected by considering both the free energy of transfer of the peptide group (as for the α-helix) and the free energy and enthalpy of transfer of the apolar part of the side chain involved in hydrophobic bond formation.
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    Biopolymers 10 (1971), S. 2209-2221 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Valine specific transfer RNA (tRNAVal) was isolated from Bacillus stearothermophilus and Escherichia coli by chromatography on benzoylated DEAE-cellulose (BD-cellulose). Likewise isoleucine specific transfer RNA (tRNAIle) was isolated from B. stearothermophilus and from Mycoplasma sp. Kid. The thermal denaturation profiles (melting curves) of the two tRNAVal species in the presence of Mg+ + were nearly identical. However, the Tm for the Kid tRNAIle was about 10°C lower than that for the B. stearothermophilus tRNAIle. A nuclease and tRNA-free aminoacyl-tRNA synthetase (AA-tRNA synthetase) preparation from B. stearothermophilus was able to function efficiently at temperatures up to 80°C in the aminoacylation of all four tRNA species. Determination of the amino acid-acceptor activity of each tRNA species as a function of temperature of the aminoacylation reaction showed in each case a strong correlation between the loss of acceptor activity and the thermal denaturation profile of the tRNA. Evidence is presented that the loss in acceptor activity is most likely due to a change in structure of the tRNA as opposed to denaturation of the enzyme. These results further support the idea that correct secondary and/or tertiary structure must be maintained for tRNA to be active as a substrate for the AA-tRNA synthetase.
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    Biopolymers 10 (1971), S. 2275-2281 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The Cotton effects of N-acetoacetyl amino acids and derivatives were examined by a circular dichroism technique. A correlation has been established between the sign of the Cotton effect and the absolute configuration of the asymmetric center. The L derivatives show, in dioxane, negative circular dichroism curves, whereas the D antipodes present positive curves. The effect of solvent and pH and influence of alkylation at the amide nitrogen are also discussed.
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    Biopolymers 10 (1971), S. 2345-2358 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The anisotropy of electrical polarizability of rodlike fragments of DNA has been studied by a number of electro-optical methods: Kerr effect (combined with flow birefringence), light scattering, diehroism, and fluorescence in an electric field. The most sensitive technique (Kerr effect) has been used to study the variation of the polarizability with the nature and concentration of counteroins. DNA fragments constitute a truly rigid polyelectrolyte of known structure. The value obtained can then be quantitatively compared to the predictions of those of the theories of the longitudinal polarizability of rigid polyelectrolytes which are based on true molecular parameters. The comparison emphasizes the role of the counterion-counterion repulsion. Oosawa's theory seems to represent the best approach but fails to explain the differences observed between monovalent and divalent ions.
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    Biopolymers 10 (1971) 
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    Biopolymers 10 (1971), S. 2537-2553 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The MCD (magnetic circular dichroism) spectra of Ap, ApA, ApApA, poly A, Up, UpU, poly U and double-stranded poly A:U alternating copoly A-U and alternating deoxyribopoly A-T were measured with a Cary 61 spectropolarimeter fitted with a Varian superconducting magnet at a field strength of 50 Kgauss. The MCD spectra of T2 and T5 DNA at various stages of heal denaturation were measured as a function of hyperchromicity of the sample. MCD spectra of the intact and degraded T2 and T5 phages were used to study the degree of alteration of the DNA inside the phages versus the DNA in vitro. The results for the adenine polymers show that the main MCD bands, B2u(271 nm), B1u(252 nm), and E1u(212 nm), show a decrease in specific magnitude as the length of the polymer is increased, reflecting the degree of stacking of the polymer. In contrast, the uridine series of polymers shows little change of the MCD bands, indicating that there is little interaction between the bases regardless of the length of the polymers. The MCD spectra of poly A:U, alternating poly r(A-U): (A-U), and alternating poly d(A-T):(A-T) show significant differences among themselves in the magnitude of the B2u band and when compared with the sum of the spectrum for the poly A plus poly U. This may indicate the selective effect of hydrogen bonding on the B2u band. Alternatively, the difference may be due to the absence of an n → π* transition in the double-stranded polymer. Measurements of denatured T2 and To DNA's show increases in all MCD bands. The T2 DNA internally packed in phage shows an increase of the B2u and E1ubands, the B2u remaining unchanged. The internal T5 DNA shows an increase of the B1u band only. Thus, the internal DNA structure is altered in a manner quite different from a simple denaturation caused by hydrogen bond breaking. Furthermore, different MCD bands indicate that different modes of DNA packing exist for T2 and T5 phages.
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    Biopolymers 10 (1971), S. 2591-2596 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The infrared absorption of poly-L-proline in concentrated aqueous salt solutions was measured in the fundamental region. Of primary interest were the carbonyl absorption of the peptide linkage and the methylene C-H bending absorption of the pyrrolidine ring. These spectral regions each show an additional component in the concentrated salt solutions. Using the position of the absorptions of poly-L-proline I (cis) and II (trans) as models, we conclude that both cis-trans linkages are present in the peptide in salt solutions. Increasing the temperature shifts the equilibrium slightly in favor of cis.
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    Biopolymers 10 (1971), S. 2619-2621 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 10 (1971), S. 2635-2638 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 10 (1971), S. 221-224 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 10 (1971) 
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    Notes: The base-stacking patterns in over 70 published crystal structures of nucleic acid constituents and polynucleotides were examined. Several recurring stacking patterns were found. Base stacking in the solid state apparently is very specific, with particular modes of interaction persisting in various crystalline environments. The vertical stacking of purities and pyrimidines in polynucleotides is similar to that observed in crystals of nucleic acid constituents. Only partial base overlap was found in the majority of the structures examined. Usually, the base overlap is accomplished by positioning polar substituents over the ring system of an adjacent base. The stacking interactions are similar to those found in the crystal structures of other polar aromatic compounds, but are considerably different from the ring-ring interactions in nonpolar aromatic compounds. Apparently, dipole-induced dipole forces are largely responsible for solid-state base stacking. It is found that halogen substituents affect base-stacking patterns. In general, the presence of a halogen substituent results in a stacking pattern which permits intimate contact between the halogen atom and adjacent purine or pyrimidine rings. Considering differences in the stacking patterns found for halogenated and nonhalogenated pyrimidines, a model is proposed to account for the mutagenic effects of halogenated pyrimidines.
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    Biopolymers 10 (1971), S. 225-242 
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    Topics: Chemistry and Pharmacology
    Notes: The desorption and melting with temperature of proflavine-DNA complexes has been studied by spectrophotometry and spectrofluorometry. Two methods are described to determine at each temperature the concentration of free and bound dye. The first one is based on the quenching of fluorescence of the free dye by the iodine ion, the second on fluorescence polarization measurements. It is shown that the sites where the bound dye fluoresces are thermally less stable than those where it is quenched, in such a way that a redistribution of the dye between the two types of sites occurs at intermediate temperatures, leading to a drop in the total fluorescence. This confirms the nature of the “emitting” sites which correspond to AT-rich region, while “quenched” sites correspond to GC-rich region. The first have a larger binding constant at room temperature, but only the latter are stabilized by dye intercalation. The desorption and melting have also been followed through the relative changes of absorption. The curves obtained at different wavelengths are not superimposed which is at variance with what is observed with complexes of proflavine with poly dAT and poly dG.dC. The beginning of the desorption process corresponds to minor variations at 445 nm, the maximum of absorption of the free dye, but large changes occur at 460 nm, the maximum of the difference spectrum of the complexes proflavine-poly dAT and proflavine-poly dG.dC. The spreading of the melting curves for different wave lengths must therefore reflect the dependence of the absorption spectra of the dye on the nature of the neighboring bases. However, the action spectrum of the fluorescence, which gives the absorption spectrum of the “emitting” sites only, is identical with the total absorption spectrum of the bound dye.
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    Biopolymers 12 (1973), S. 121-125 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Notes: Despite its being weaker base poly(2-vinylpyridine) polymerized DL-β-phenylalanine NCA at a much faster rate than pyridine and α-picoline. Poly(2-vinylpyridine) adsorbs NCA by hydrogen bonding with the cooperation of a few pyridine groups. This results in a high local concentration of NCA. The syndiotactic configuration of pyridine group seemed to be least suitable for the cooperative hydrogen bonding. Adsorbed NCA is activated to form an “activated” NCA which in turn reacts with an NCA adsorbed on the same polymer chain. Since the polymer chain is flexible, this intramolecular reaction takes place frequently, resulting in the acceleration of polymerization. The intramolecular reaction along the polymer chain is dependent on the degree of polymerization of polymer catalyst. A suitable model was proposed for the intramolecular reaction to explain the effect of degree of polymerization.
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    Notes: 5-Bromouracil-substituted DNA was isolated form B. Subtilis and phage PBSH. The three DNA fractions of Different densities (TT, TB, and BB) were irradiated with u.v. (313nm). The number of single-strand and double-strand breaks was determined. The breakage rates are given. It was found that in hybrid DNA (TB) double-strand breaks occur depending linearly on dose. In BB-DNA the observed double-Strand bresks can be divided into two fractions with a linear and quadratic dose dependence respectively. The results can be explained by assuming intramolecular energy transfer from the BU-containing strand to its complementary strand.
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    Biopolymers 12 (1973), S. 229-235 
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    Topics: Chemistry and Pharmacology
    Notes: Differential enthalpic analysis of a series of 3′,5′-cyclic nucleotides indicates that homolytic cleavage of the six-membered phosphate ring occurs either immediately prior to or concurrent with decomposition of the crystal lattice. Homolysis is followed by a rapid polymerization to yield oligonucleotides. The enthalpies of these reactions have, with the exception of guanosine 3′,5′-cyclic phosphate, almost identical values of 25 kcal/mole. The anomalous case is attributed to a more stabilized phosphate ring as a result of hydrogen bonding through the two position of the purine ring. The pair of overlapping exothermic peaks observed in each of the thermograms for cAMP and cIMP is related to the presence of two conformational arrangements within the unit cell of each compound.
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    Notes: The total energy and the electronic properties of some syn purine nucleosides have been determined as a function of the rotation angle around the C-N glycosidic linkage. Invariably, the crystallographic coordinates provide a state lying at or very near the minimum on the potential energy curve according to the extended Hückel parametrization here employed. The ribose moiety always carries a net positive charge whereas the base is always negatively charged. Changes in dipole moment magnitudes for the overall structure as well as in net atomic charges are noted upon rotation around the glycosidic linkage indicating that potential functions for polynucleotides may be in error if such changes are ignored.
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    Biopolymers 12 (1973), S. 341-352 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Measuring the equivalent noise resistance of Na-DNA solutions in NaCl provides in formation about the free ino atmosphere. In an Arrhenius type diagram, the helix → coil transition is clearly brought Out. A Calculation of the number of free ions in the solution as function of temperature, reveals once more the process of ejection of compensating Na+ ions form the macromolecules during the thermal transconformation.
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    Biopolymers 12 (1973), S. 423-433 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Optical properties in different solvents of gramicidin-bis (salicylaldimine) Cu(II) and (5-I-salicyladimine) Cu(II) chelates are intercepted in terms of their molecular structure. A molecular model for the inversion of Contton effects in two different classes of solvents is proposed. This explanation is supported by the study of optical properties of model compounds.
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    Biopolymers 12 (1973) 
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    Notes: Syntheses are described for two N-benzyloxycarbonylpeptide tert-butoxycarbonylhydrazides which correspond to positions 24-34 and 35-44, respectively, of the primary structure of baker's yeast iso-1-cytochrome c. The two peptide derivatives were coupled via the azide procedure to form the N-benzyloxycarbonylheneicosapeptide tert-butoxycarbonylhydrazide (sequence 24-44).
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    Biopolymers 10 (1971), S. 337-355 
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    Topics: Chemistry and Pharmacology
    Notes: The optical and hydrodynamic properties of T2 bacteriophage DNA have been determined by steady-state flow birefringence and viscosity in glycerol-aqueous buffer solvents at 25°C. Flow birefringence and extinction angle data were obtained over a velocity gradient range of 0.1 to 5 sec-1 and at concentrations from 3 to 55 μg/ml in solvents containing approximately 30, 42, and 48 vol-% glycerol. Large optical backgrounds were observed in the mixed solvent flow birefringence studies which presented special experimental difficulties; these are described and their effect upon the flow birefringence data are discussed. The data on extinction angle provide no evidence for an internal viscosity effect on the stationary-state hydrodynamic properties of high molecular weight DNA over a range of solvent viscosity from 0.9 to 4.6 cP. Both the optical and hydrodynamic properties under present conditions of measurement appear to be self-consistent in terms of the values for these quantities in neutral aqueous buffer solution. Interpretation of the birefringence is complicated by uncertainties inherent in calculating the form anisotropy of DNA in non-aqueous solvents, but the data imply no large changes in helical structure with increasing glycerol concentration. Both intact and slightly degraded DNA samples were investigated, and no significant polydispersity effects were observed under the experimental conditions described.
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    Biopolymers 12 (1973), S. 647-654 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The primary amine initiated homopolymerization of γ-benzyl-L-glutamate NCA in dioxane at 25°C, 35°C, 50°C, and 65°C has been investigated. The reactions were virtually independent of temperature indicating an activation energy of less than 1 kcal/mole. The entropy of activation was estimated to be -65 entropy units at 300°K. The reaction proceeded in two stages. The first stage was zero-order with respect to monomer, whereas the second was first-order with respect to monomer. Both stages were first-order with respect to initiator. These results were interpreted by assuming that the rate constant for propagation was not independent of the degree of polymerization up to the point where a conformational transition to α-helix occurred.
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