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  • Chemistry  (14,880)
  • 1990-1994  (9,407)
  • 1980-1984
  • 1970-1974  (5,473)
  • 1930-1934
  • 1991  (9,407)
  • 1971  (5,473)
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  • 1990-1994  (9,407)
  • 1980-1984
  • 1970-1974  (5,473)
  • 1930-1934
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  • 1
    Publication Date: 1991-10-25
    Description: The presence of clathrate hydrates in cometary ice has been suggested to account for anomalous gas release at large radial distances from the sun as well as the retention of volatiles in comets to elevated temperatures. However, how clathrate hydrates can form in low-pressure environments, such as in cold interstellar molecular clouds, in the outer reaches of the early solar nebula, or in cometary ices, has been poorly understood. Experiments performed with the use of a modified electron microscope demonstrate that during the warming of vapor-deposited amorphous ices in vacuo, clathrate hydrates can form by rearrangements in the solid state. Phase separations and microporous textures that are the result of these rearrangements may account for a variety of anomalous cometary phenomena.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Blake, D -- Allamandola, L -- Sandford, S -- Hudgins, D -- Freund, F -- New York, N.Y. -- Science. 1991 Oct 25;254:548-51.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Planetary Biology Branch, Ames Research Center, Moffett Field, CA 94035, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/11538372" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; Crystallography ; Earth (Planet) ; Hydrocarbons/chemistry ; Ice/*analysis ; *Meteoroids ; Microscopy, Electron ; *Solar System
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 2
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1991-07-12
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Baskin, Y -- New York, N.Y. -- Science. 1991 Jul 12;253(5016):140-2.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/1853198" target="_blank"〉PubMed〈/a〉
    Keywords: *Academies and Institutes ; Biology ; California ; Chemical Phenomena ; Chemistry ; Research Support as Topic
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 3
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1991-05-03
    Description: Immunochemistry has historically focused on the nature of antigenicity and antibody-antigen recognition. However, in the last 5 years, the field of immunochemistry has taken a new direction. With the aid of mechanistic and synthetic chemistry, the vast network of molecules and cells of the immune system has been tapped to produce antibodies with a new function--catalytic antibodies. Because antibodies can be generated that selectively bind almost any molecule of interest, this new technology offers the potential to tailor-make highly selective catalysts for applications in biology, chemistry, and medicine. In addition, catalytic antibodies provide fundamental insight into important aspects of biological catalysis, including the importance of transition-state stabilization, proximity effects, general acid and base catalysts, electrophilic and nucleophilic catalysis, and strain.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Lerner, R A -- Benkovic, S J -- Schultz, P G -- New York, N.Y. -- Science. 1991 May 3;252(5006):659-67.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry, Scripps Research Institute, La Jolla, CA 92037.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2024118" target="_blank"〉PubMed〈/a〉
    Keywords: Animals ; *Antibodies/chemistry/immunology/metabolism ; Antibodies, Monoclonal/immunology/metabolism ; Antibody Specificity ; Antigens/chemistry/immunology/metabolism ; Binding Sites, Antibody ; *Catalysis ; Chemical Phenomena ; Chemistry ; Haptens ; Hydrogen-Ion Concentration ; Hydrolysis ; Metals ; Molecular Conformation ; Recombinant Proteins ; Thermodynamics ; Zinc
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 4
    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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  • 5
    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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  • 6
    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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  • 7
    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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  • 8
    Electronic Resource
    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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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Pharmacy world & science 13 (1991), S. 109-118 
    ISSN: 1573-739X
    Keywords: Chemistry ; Consumer product safety ; Drug packaging ; Environmental pollution ; Plasticizers ; Polyvinyls
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this report the state of the art with respect to PVC as pharmaceutical packaging material is described. A general introduction into the applications of PVC is followed by a description of its production process. The metabolic effects of the monomer of PVC, vinyl chloride and of the most commonly used plasticizer diethylhexylphthalate are mentioned. Special attention is given to the pharmaceutical properties of plasticized PVC bags in comparison to other plastics and the environmental aspects of waste PVC disposal. Although there are emotional and political queries regarding the future use of PVC as a (pharmaceutical) packaging material, we conclude that there is no scientific justification for a total or partial ban of PVC. PVC will remain a fact of life as a cheap, versatile, high-performance and well-investigated plastic material for medical and pharmaceutical applications, to be replaced by newer plastics only for certain well-defined indications where the requirements of the plastic to be used are so specific that it will economically and technically be justified to use another polymer. Community and hospital pharmacists have to be prepared for a role in intake of waste plastic disposables, probably against deposit money, in order to fulfil the logistics needed for recycling.
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  • 10
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The properties (squared dimensions, anisotropy, numbers of intra- and intermolecular contacts) of a single five-way cubic lattice chain embedded into an environment (matrix) of chains of the same length n = 50 were evaluated as a function of matrix volume fraction (matrix density) v and intermolecular interaction between the matrix polymer and the minority chain segments, characterized by a parameter φ. No convincing evidence was found for the occurrence of a coil-globule transition in the range of matrix densities (v ≤ 0.7) and repulsive interactions between matrix and minority chain (φ ≤ 0.2) investigated. For moderate attractive interaction (φ ≈ -0.17) a compensation of the chaincompressing action of the matrix and the chain-expanding interaction with the matrix was observed resulting in a zero-dependence of the size and shape of the minority chain on matrix density. It further turned out that there are fixed relations among the various size and shape data irrespective of the specific combination of matrix density and thermodynamic interaction by which a particular polymer dimension is produced. These interrelations are fairly the same as those evaluated for isolated chains the size of which is varied by an intramolecular energy parameter φi.
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  • 11
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: New three phases composite materials made of glassbeads as filler, water as liquid dispersed phase and polystyrene as matrix were obtained by polymerization of a water in oil emulsion formed by water dispersed in styrene in which glass beads are added. For this purpose glass beads have to be modified by silanization by a coupling agent 3-(Trimethoxysilyl)propylmethacrylate (TPM) or a silane Octadecyltrichlorosilane (ODMS), in order to prevent the wetting of the glass by water. Only low coverage of the glass surface by the coupling agent (0,05% of TPM) are convenient for the preparation cellular materials having good mechanical properties. At higher coverage ratio, strong hydrophobic glass beads are obtained which destabilize the water / styrene emulsion and lead to macroporous products. Study of the rheology of the filled emulsion appears to be the more simple and more sensitive method to determine the level of wettability of the glass bead by the emulsion which is the most significant parameter for the preparation of such three phases composite materials. Composite materials made of glass beads, air and polystyrene are simply obtained by evaporation of water under vacuum.
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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: To test the molecular parameters concerning gas sorption in polymers, the concentration of CO2, N2O, CO, N2, CH4 and the noble gases Ne, He in glassy poly(butylene terephthalate) films (PBTP) has been studied gravimetrically with a recording microbalance at 25°C. The sorption isotherms exhibit downward curvature to the pressure axis. As neither solubility nor adsorption can explain the experimental results, analysis was carried out based on the dual-sorption model: gas dissolution and microvoid filling are considered as independent sorption mechanisms. The parameters of the dual-sorption model for the mentioned penetrants are determined. The results indicate that for parameter correlation the Lennard-Jones potential parameters give a rough idea, but size exclusion of gases in small diameter microvoids is proposed and special chemical interactions must be considered.
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  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 185 (1991), S. 283-292 
    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 ring opening metathesis polymerisation (ROMP) of 5-cyano-2-norbornene with tungsten hexachloride, tungesten oxytetrachloride, bis(dichloralkoxo)tungsten tetrachloride and bis(dichloralkoxo)tungsten oxydichloride as transition metal component was studied. Methylaluminoxan, diethylaluminium ethoxide, tetraisobutyldialuminoxan and tetrabutyltin served as cocatalyst. Toluene, Chlorobenzene and dichloromethane were used as solvents. The concentration of the tungsten components was in the range from 5 × 10-4 to 5 × 10-3 mol/l. Among the catalyst studied, tungsten hexachloride with diethylaluminium ethoxide proved to be the best. The polymerisation was highly selective with this system even at high monomer/tungsten ratios (e.q. 10200:1) and let to high conversions (≥82%).
    Notes: Die ringöffnende metathetische Polymerisation (ROMP) von 5-Cyano-2-norbornen wurde unter Einsatz von Wolframhexachlorid, Wolframoxidterachlorid, Bis(dichloralkoxo)wolframtetrachlorid und Bis(dichloralkoxo)wolframoxiddichlorid als Übergangsmetallkomponente untersucht. Als Cokatalysatoren dienten Methylaluminoxan, Diethylaluminiumethoxid, Tetraisobutyldialuminoxan und Tetrabutylzinn. Als Lösungsmittel wurden Toluol, Chlorbenzol und Dichlormethan verwendet. Die Konzentration der Wolframkomponente lag im Bereich 5 × 10-4 - 5 × 10-3 mol/l. Unter den geprüften Katalysatoren erwies sich Wolframhexachlorid in Verbindung mit Diethylalumiumethoxid als der geeignetste. Mit diesem System verlief die Polymerisation auch bei großen Monomer/Wolfram-Verhältnissen (10200 :1) hochselektiv und führte zu großen Umsätzen (≥82%).
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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: The dependence of dilution on the chain propagation and termination rate constants was investigated in the polymerization of ethyl acrylate in benzene solution at 50°C, with the rotating sector method. The errors of the above rate constants were determined and, by our method applied to decrease these errors, the errors of the propagation rate constant was reduced to its half value. By the application of our earlier results in polymerization kinetics, we found that in this system the chain propagation step is exclusively responsible for the solvent effects observed. Our experimental results can be quantitatively described in terms of the hot redical theory.
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  • 15
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    Angewandte Makromolekulare Chemie 185 (1991), S. 329-334 
    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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  • 16
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    Angewandte Makromolekulare Chemie 190 (1991), S. 1-14 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch gemeinsame Reaktion von Benzophenontetracarbonsäuredianhydrid, Maleinsäureanhydrid und Diaminen mit 1,3,5-Triazingruppen wurden niedermolekulare Prepolymere mit Amin-Endgruppen erhalten, die sowohl 1,3,5-Triazingruppen als auch Etherbindungen enthalten. Diese reaktiven Prepolymeren sind in niedrigsiedenden Lösemitteln wie z. B. Chloroform und Tetrahydrofuran löslich. Sie wurden durch Elementaranalyse, IR- und NMR-Spektroskopie, Dampfdruckosmometrie und Viskosimetrie charakterisiert. Beim Erhitzen der Prepolymeren auf Temperaturen zwischen 180 und 190°C tritt Kettenverlängerung durch Michael-Addition auf; gleichzeitig vernetzen sie durch Reaktion der Amin- mit den Maleimid-Endgruppen. Die vernetzten Polymeren sind thermisch stabil; ihr thermisches Verhalten wurde durch TGA, DTA und isotherme Alterung untersucht. Die Biegefestigkeit und interlaminare Scherfestigkeit von aus den Prepolymeren und Carbonfasergeweben hergestellten Laminaten wurden gemessen.
    Notes: Low molecular weight amine-terminated monomaleimide prepolymers containing 1,3,5-triazine groups as well as ether linkages were synthesized by reacting benzophenone tetracarboxylic dianhydride, diamines having 1,3,5-triazine group and maleic anhydride. These reactive prepolymers are soluble in low boiling solvents such as chloroform, tetrahydrofuran etc. They were characterized by elemental analyses, IR and NMR spectroscopy, vapour pressure osmometry, and viscosity. On heating at 180-190°C these prepolymers undergo simultaneous chain extension by Michael addition reaction and crosslinking by mutual reaction between their amine-terminated and maleimide-terminated ends. The cured polymers are thermostable and the thermal behaviour was studied by TGA, DTA, and isothermal aging. Laminates fabricated using these prepolymers and carbon fiber as reinforcing agent were evaluated by their flexural strength and interlaminar shear strength.
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  • 17
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    Angewandte Makromolekulare Chemie 190 (1991), S. 15-32 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Ein Epoxidharz wurde durch Reaktion mit Anilin bzw. Benzylamin in unterschiedlichen molaren Verhältnissen modifiziert. Die modifizierten Harze wurden dann mit Diethylamin und anschließend mit teilblockiertem Toluylendiisocyanat umgesetzt, wobei thermisch vernetzbare Harze mit tertiären Aminen in und am Ende der Polymerkette erhalten wurden. Die partielle Ansäuerung mit Essigsäure lieferte thermisch vernetzbare kationische Harze, aus denen durch Lösen in geeigneten Lösungsmitteln und Zugabe von entionisiertem Wasser Emulsionen hergestellt wurden. Diese wurden hinsichtlich ihrer Eignung zur elektrolytischen Abscheidung untersucht und verglichen. Die Ergebnisse zeigen, daß die Abscheidungsausbeute und das Streuvermögen der Emulsionen aus Benzylamin-modifizierten Epoxidharzen besser sind als die der Anilin-modifizierten Epoxidemulsionen. Ein hohes, vom pH-Wert der Emulsion abhängiges Streuvermögen ist für diese kationischen Harze charakteristisch.
    Notes: Aniline/benzylamine-modified epoxy resins with different molecular weights, which contain tertiary amines in the middle of the polymer chain, were synthesized by the reaction of aniline/benzylamine with epoxy resin at various molar ratios. The resulting aniline/benzylamine-modified epoxy resins were reacted with diethylamine and subsequently reacted with 2-ethylhexanol-blocked toluene diisocyanate to obtain thermally crosslinkable resins which contain tertiary amines at the end and in the middle of the polymer chain. These resins were partially neutralixed with acetic acid to give thermally crosslinkable cationic resins. The resulting cationic resins were dissolved in suitable solvents and mixed with deionized water to form various emulsions. The emulsion and electrodeposition properties of these resins were studied in some detail to compare the properties of these cationic resins. The results show that the deposition yields and throwing power of the emulsions prepared from benzylaminemodified epoxy resins are higher than those of the emulsions prepared from anilinemodified epoxy resins. The emulsion having proper pH values can give a high throwing power. High throwing power is the characteristic property of these modified cationic resins. Factors determining the throwing power and deposition yield of the emulsions were also investigated.
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  • 18
    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: Arylacrylsäuren, wie Furylacrylsäure und Thienylacrylsäure können durch Knoevenagel-Reaktion der Arylcarbaldehyde mit Malonsäure in Pyridin dargestellt werden. Durch einfache Veresterung der Arylacrylsäuren in Methanol/Schwefelsäure werden die entsprechenden Arylacrylsäuremethylester mit guten Ausbeuten erhalten. Diese isomerisieren bei Bestrahlung mit UV-Licht (λ ≥ 280 nm) in methanolischer Lösung. Bei der Photoreaktion in Lösung wurde keine Photodimerisierung beobachtet. Die Reaktionskinetik der Photoreaktionen wurde untersucht.
    Notes: Aryl acrylic acids, e. g. furyl acrylic acid or thienyl acrylic acid are readily formed by the Knoevenagel condensation reaction of arylcarbaldehydes and malonic acid in pyridine. Esterification of these acids with methanol/sulfuric acid gives the corresponding aryl acrylic acid methyl esters in good yields. In methanolic solution these methyl esters isomerize upon irradiation (λ 280 nm). No photodimerization was observed. Kinetic data are given.
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  • 19
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    Angewandte Makromolekulare Chemie 190 (1991), S. 67-80 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Different composite materials, with retified or natural poplar and polyester resin were prepared by molding. The influence of the filler granulometry on certain physicochemical (density, humidity, hardness) or mechanical properties of the materials was studied. The density and the increase of mass in humid atmosphere were always found to be less when the wood was thermally treated. On the other hand, the hardness of the composites made from natural poplar was much higher. The mechanical properties were found to be weak when the wood was retified.When the wood was thermally treated, it was possible to optimise the three parameters, namely, density, water retention capacity and mechanical properties. The optimal granulometry of poplar was determined between 0.75 and 1.5 mm.The results obtained are discussed considering the physico-chemical properties of the different varieties of wood studied and the interactions which exist between the polar resin and the wood.
    Notes: Divers matériaux composites à base de peuplier rétifié ou naturel et de résine polyester insaturée ont été préparés par moulage. L'influence de la granulométrie de la charge a été étudiée sur quelques propriétés physico-chimiques (densité, reprise d'humidité, dureté) ou mécaniques des matériaux obtenus. La densité et la reprise de masse en milieu humide sont toujours plus faibles si la charge est traitée thermiquement sous atmosphère inerte. Par contre, la dureté des composites issus du peuplier naturel est plus importante. Les propriétés mécaniques sont inférieures si la charge est rétifitée.Si la charge lignocellulosique est traitée thermiquement, il est possible d'optimiser les trois paramètres: densité, reprise d'eau et propriétés mécaniques; la granulométrie optimale du peuplier est ainsi comprise entre 0,75 et 1,5 mm.Les résultats obtenus sont expliqués en tenant compte des propriétés physico-chimiques des charges et des interactions existant entre la résine polaire et le bois.
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die vorliegende Arbeit untersucht das Wasserdurchlässigkeitsverhalten von vier Arten verschieden modifizierter Chitosanmembranen zur Abtrennung von Wasser aus wäßrigen Ethanolmischungen. Chitosan wurde aus Chitin von Krebstierschalen durch Verseifung (Deacetylierung) gewonnen. Die in dieser Arbeit untersuchten modifizierten Chitosanmembranen enthielten Carboxymethyl-, Carboxyethyl-, Cyanethyl- und Amidoxim-Chitosan. Die Einführung hydrophiler funktioneller Gruppen in der 6-O Position des Chitosans erhöht die Selektivität der modifizierten Membranen im Vergleich zu den mit Essigsäure komplexierten Chitosanmembranen. Die Untersuchungen zeigen, daß Chitosanmembranen, die Carboxygruppen enthalten, die höchste Wasserdampfdurchlässigkeit aufweisen. Carboxymethyl-Chitosanmembranen zeigen eine maximale Quellung und den höchsten Ethanoldurchfluß bei einer Ethanolkonzentration von ca. 15 Gew.-% im Zulauf aufgrund von Bindungs- und Weichmachereffekten.
    Notes: The present study investigates the pervaporation performance of four kinds of modified chitosan membranes to separate water from aqueous ethanol solution. Chitosan was prepared from chitin abstracted from the crab shell and subsequently deacetylated with aqueous NaOH solution. Modified chitosan membranes examined in this study include carboxymethyl chitosan, carboxyethyl chitosan, cyanoethyl chitosan, and amidoxime chitosan. The incorporation of hydrophilic functional groups into the 6-O position of chitosan enhances the selectivity of modified chitosan membrane compared to the previously reported chitosan-acetic acid complex membrane. Among the modified chitosan membranes, membranes containing carboxy groups show the best pervaporation performance. Carboxymethyl chitosan membranes show the maximum swelling and ethanol flux at approx. 15 wt.-% feed ethanol concentration due to the coupling and plasticizing effect.
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  • 21
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The tensile properties of self reinforced poly(propylene)/poly(1-butene) composites, obtained by rapid extension of the melt, have been measured and correlated to morphological parameters derived from x-ray experiments. Critical fiber lengths as a function of sample composition and the elastic modulus and yield stress of the fibers could be determined. It is shown, that, applying a load to the system, the forces are fully taken up by the fibers and the system breaks by fail of the fibers. The longitudinal structure of the fibers is found to be independent of sample composition.
    Notes: Mechanische Parameter wie Elastizitätsmodul, Fliß- und Bruchspannung von aus der hochorientierten Schmelze hergestellten nadelkristallinen Mischungen aus Poly(propylen) und Poly(1-bute) wurden mit morphologischen Parametern, die aus Röntgenmessungen abgeleitet wurden, korreliert. Es wird gezeigt, daß der Elastizitätsmodul des Verbundes aus den E-Moduln der Fasern und der Matrix berechnet werden kann (Mischungsregel). Die an der Probe angreifenden Kräfte werden voll auf die Fasern übertragen; der Verbund kann daher als eigenfaserverstärktes System angesehen werden. Die Abschätzung der kritischen Faserlänge ergibt, daß die Festigkeit der FAsern voll ausgenutzt wird; der Bruch des Systems bei Belastung ist daher auf das Versagen der Fasern zurückzuführen. Das mechanische Verhalten des Verbundes wird stark beeinflußt durch die Komponentenzusammensetzung. Die longitudinale Struktur der Nadeln beider Komponenten bleibt unbeeinflußt von der jeweiligen Co-Komponente.
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  • 22
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    Angewandte Makromolekulare Chemie 192 (1991), S. 199-211 
    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: Lösliche kationische Polyelektrolyte mit quartären Stickstoffatomen in der Hauptkette wurden durch Polykondensation von Epichlorhydrin (ECH) mit Dimethylamin (DMA) und N,N-Dialkylaminoakylaminen erhalten. Die Reaktionsparameter, die die Polymereigenschaften hauptsächlich beeinflussen, sind: Molverhältnis DMA/asymmetrische Diamine, Ausgangskonzentration der Aminlösung, Molverhältnis ECH/Amine und die Struktur der asymmetrischen Diamine. Das viskosimetrische Verhalten verdünnter wäßriger Lösungen mit oder ohne Zugabe neutraler Salze veranschaulicht die flexible Natur der Polyelektrolyten.
    Notes: Water soluble cationic polyelectrolytes containing quaternary nitrogen atoms within the main chain were prepared via condensation polymerization of epichlorohydrin (ECH) with dimethylamine (DMA) and N,N-dialkylaminoalkylamines. The main parameters of the reaction that influence the polymer properties are: DMA/asymmetrical diamine molar ratio, the initial concentration of amine solution, NaOH/amine molar ratio, ECH/amine molar ratio, and asymmetrical diamine structure. The feature of flexible polyelectrolyte own to the investigated polymers was emphasized by the viscosimetric behaviour in dilute aqueous solutions with and without salt presence.
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    Angewandte Makromolekulare Chemie 192 (1991), S. 213-213 
    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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  • 24
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    Angewandte Makromolekulare Chemie 193 (1991), S. 1-11 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Antioxidantien wurden in einer modifizierten Friedel-Crafts-Reaktion mit wasserfreiem Zinkchlorid als Katalysator an Flüssig-Naturkautschuk mit Hydroxy-Endgruppen gebunden. Die immobilisierten Antioxidantien waren weniger flüchtig und extrahierbar als konventionelle Antioxidantien. Sie wurden sowohl einem Latex als auch trockenem Kautschuk zugesetzt; die daraus hergestellten Vulkanisate zeigten eine bessere Alterungsbeständigkeit als Vulkanisate mit konventionellen Antioxidantien.
    Notes: Antioxidants were attached to hydroxy-terminated liquid natural rubber by modified Friedel-Crafts alkylation reaction using anhydrous zinc chloride as catalyst. The rubber bound antioxidants were found to be less volatile and less extractable compared to conventional antioxidants. The bound antioxidants were tried both in latex compounds and dry rubber compounds. The vulcanizates showed improved ageing resistance compared to vulcanizates based on conventional antioxidants.
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    Angewandte Makromolekulare Chemie 193 (1991), S. 13-20 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Strom-Spannungs-Charakteristik eines Bisphenol-A-Polycarbonats im Span-nungsbereich 50-1000 V und der Einfluß von UV-Bestrahlung (λ = 225 und 300 nm) und Tempern auf die elektrische Leitfähigkeit (σ) des Polycarbonats wurden untersucht. Die Abhängigkeit von σ gegen 1/T deutet auf zwei verschiedene Leitfähigkeits-mechanismen hin. Aus den Ergebnissen wurden die Aktivierungsenergien der Leitfähigkeit und die Sprungdistanzen berechnet.
    Notes: Current-voltage characteristics of polycarbonate samples (PC) have been studied in the voltage range 50-1000 V. The effect of UV-irradiation at λ = 225 and 300 nm, and thermal annealing on the electrical conductivity (σ) of PC was studied. The σ vs. 1/T relationship shows two slopes, i.e. two possible conduction mechanisms. The obtained results made it possible to determine a complete set of conduction parameters including activation energy and jump distance.
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    Angewandte Makromolekulare Chemie 193 (1991), S. 21-28 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Suspensionspolymerisation wurden Terpolymere aus Acrylnitril (AN), Vinylacetat (VA) (7,5-30 mol-%, bezogen auf AN) und Divinylbenzol (DVB) (10 Gew.-%) hergestellt. Als Verdünner wurden Mischungen von Toluol oder Cyclohexanol (90 Vo1.-%) mit Hexadecan, Octan, Dodecan, 2-Ethylhexanol oder Benzylalkohol (jeweils 10 Vo1.-%) verwendet.Die Porosität der AN-VA-DVB-Terpolymeren ist mit 0,61-0,68 größer als die der entsprechenden AN-DVB-Copolymeren. Die übermolekulare Struktur der Terpolymeren hängt vom verwendeten Verdünner ab, obwohl sich die Porositäten nicht sehr voneinander unterscheiden. Die beim Erhitzen der Terpolymeren auf Temperaturen über 200°C auftretenden thermischen Effekte sind signifikant größer als die bei der Cyclisierung von AN-Polymeren gemessenen.
    Notes: Terpolymers of acrylonitrile (AN), vinyl acetate (VA) (7.5-30 mol-%, related to AN), and divinylbenzene (DVB) (10 wt.-%) were prepared by suspension polymerization. The diluents used were mixtures of toluene or cyclohexanol (90 vol.-%) with solvents (10 vol.-%) such as hexadecane (HD), octane (O), dodecane (D), 2-ethylhexanol (E) or benzyl alcohol (B).It has been found that AN-VA-DVB terpolymers have a higher porosity, about 0.61-0.68, than corresponding AN-DVB copolymers. The terpolymers obtained with mixtures of various diluents differ in their supermolecular structure although they had similar porosity characteristics.The thermal effects accompanying heating of the terpolymers above 200°C significantly exceed that of nitrile groups cyclization observed of the other AN polymers.
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    Angewandte Makromolekulare Chemie 193 (1991), S. 39-49 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die rheologischen und mechanischen Eigenschaften von Blends aus PE-HD und zwei verschiedenen PE-LLD-Typen wurden im gesamten Mischungsbereich gemessen. Die Polymeren sind im festen Zustand und in der Schmelze ausreichend verträglich, so daß ihre vorteilhaften Eigenschaften genutzt werden können.
    Notes: A high density polyethylene grade is blended with two selected grades of linear low density polyethylene and the mechanical and rheological properties of the blends are evaluated over the entire composition range. The blends show sufficient compatibility in the solid phase and in the melt and hence they can be advantageously used to capitalize on their useful properties.
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    Angewandte Makromolekulare Chemie 192 (1991), S. 51-55 
    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: N,N-Dimethylacrylamid (DMA) und Isopropylmethacrylat (IPM) wurden in Dimethylformamid mit Azoisobutyronitril als Initiator copolymerisiert. Die Copolymerzusammensetzung wurde 1H-NMR-spektroskopisch ermittelt. Die Copolymerisationsparameter (rDMA = 0,58, rIPM = 2,76) wurden nach Kelen-Tüdős berechnet.
    Notes: Copolymers of N,N-dimethyl acrylamide (DMA) and isopropylmethacrylate (IPM) were prepared in dimethyl formamide using azoisobutyronitrile as initiator. The composition of copolymers was determined by 1H-NMR analysis. Reactivity ratios (rDMA = 0.58, rIPM = 2.76) were calculated from these values by using the Kelen-Tüdős differential linear equation.
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  • 29
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    Angewandte Makromolekulare Chemie 192 (1991), S. 69-79 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wird ein allgemeines numerisches Verfahren vorgestellt, um die Modifikation der Grundgleichung für hydrodynamische Schmierung, die von mit Polymeren versetzten Schmierölen mit scherabhängiger Viskosität erbracht wird, zu berechnen.Das Verfahren basiert auf dem verallgemeinerten Newtonschen Fileßmodell und erlaubt, alle Fileßregionen zwischen dem rein Newtonschen und dem Exponentialgesetzverhalten kontinuierlich zu behandeln. Die Ergebnisse zeigen, daß der Einfluß der scherspannungsabhängigen Viskosität durch eine dimensionslose Zahl vollkommen charakterisiert wird, nämlich U · τ*/h*, wobei U die relative Gleitgeschwindigkeit, h* die charakteristische Filmdicke und τ* die Relaxationszeit des Schmieröles darstellen.Als praktisches Beispiel wird die Anwendung des Verfahrens aufgezeigt, um den Einfluß des Molekulargewichts und der Konzentration der Polymerkomponente des Schmieröls auf die hydrodynamische Schmierung zu bestimmen. Dieser Einfluß ist durch die starke Beziehung zwischen Polymereigenschaften und τ* verursacht.
    Notes: A general numerical procedure is presented to calculate the modification of the basic equation for hydrodynamic lubrication brought about by the use of polymeric fluids with shear depending viscosity. The procedure is based on the generalized Newtonian fluid model and allows to treat continuously all the flow regions between the pure Newtonian and the power law behavior. The results show that the influence of the viscosity depending on shear stress is completely characterized by one dimensionless number, namely U.·τ*/h*, where U is the relative sliding velocity, h* is the characteristic film thickness, and τ* is a characteristic time of the lubricant. The procedure is exemplified by applying it for the determination of the influence of the molecular weight and concentration of the polymeric component of the lubricant on the hydrodynamic lubrication. This influence is brought about by the strong relation between the polymer properties and τ*.
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    Angewandte Makromolekulare Chemie 192 (1991), S. 57-67 
    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 Morphologien von spritzgegossenem und formgepreßtem Poly(1-buten) (PB-1) wurden im Polarisationsmikroskop und im Transmissionselektronenmikroskop untersucht. Eine dünne Oberflächenhaut und bis in den Kern der Probekörper reichende abgeplattet-sphärolithische Strukturen werden bei spritzgegossenem PB-1 beobachtet, während in formgepreßtem PB-1 typische Sphärolithe vorliegen. Das Bruchbild des spritzgegossenen PB-1 zeigt unter der Oberflächenhaut viele aufgereihte streifenartige Hohlräume, die senkrecht zur Spritzrichtung zur Mitte des Probekörpers wachsen. Aus diesen Beobachtungen kann geschlossen werden, daß eine beim Spritzgießen durch den Schmelzefluß induzierte Scherspannung nicht nur die Entstehung der Oberflächenhaut verursacht, sondern auch bis in die Mitte des Probekörpers hinein die Bildung abgeplatteter Sphärolithe bewirkt. Diese abgeplattet-sphärolithischen Strukturen sind für die beim Dehnen des spritzgegossenen PB-1 entstehenden, streifenartigen Hohlräume verantwortlich, während die Oberflächenhaut und die abgeplatteten Sphärolithe im Kern die Sprödigkeit und die im Vergleich zu formgepreßtem PB-1 geringere Bruchdehnung bewirken. Diese kann durch Tempern oberhalb des Schmelzpunktes erhöht werden.
    Notes: The injection-molded poly(1-butene) (PB-1) is found to be more brittle than the compression-molded PB-1. The morphologies of these specimens are examined by use of polarized optical microscopy and scanning electron microscopy (SEM). A skin layer and an oblate spherulitic structure extended to the core region are observed in the injection-molded PB-1, while typical spherulites exist in the compression-molded PB-1. Below the skin layer of the injection-molded PB-1, the fracture surface is found to consist of many aligned strip-like voids with ribbon edges propagating to the center of the specimen and perpendicular to the flow direction of injection-molding. Based on these observations, it can be inferred that shear stress induced by the melt flow during the injection-molding does not only cause the formation of skin layer, but also penetrates deeply into the central region of the injection-molded specimen causing the formation of oblate spherulites. The oblate spherulitic structure is responsible for the aligned voids during elongation of PB-1, while the existence of the skin layer and the oblate spherulites in core region is responsible for the brittleness of the injection-molded PB-1. The elongation of the injection-molded PB-1 is found to be lower than that of the compression-molded. This can be attributed not only to the presence of the skin layer but also to the oblate spherulites in the core region. The elongation can be improved by annealing at a temperature above the melting point of PB-1.
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    Angewandte Makromolekulare Chemie 192 (1991), S. 103-111 
    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: Durch Kondensation von p-Xylol mit Chloracetylchloride, 1,2-Dichlorethan und Dichlormethan mit Aluminiumtrichlorid in Schwefelkohlenstoff wurden Polyketone hergestellt und IR-spektroskopisch sowie bezuglich des Molekulargewichtes charakterisiert. Die thermischen Eigenschaften wurden thermogravimetrisch und mittels DSC untersucht. Die Prüfung der Harze auf ihre biologische Aktivität gegen Pseudomonas fluorescens, Bacillus subtilis and Aspergillus niger ergab, daß deren Wachstum durch die Polyketonharze kontrolliert werden kann.
    Notes: Some polyketones were prepared from p-xylene, chloroacetylchloride, 1,2-dichloroethane and dichloromethane using anhydrous aluminiumtrichloride and carbon disulfide as solvent. The resins thus obtained have been characterized by IR spectra and number average molecular weight. The thermal properties have been studied by thermogravimetry and differential scanning calorimetry. All the resins were tested for their biological activity against Pseudomonas fluorescens, Bacillus subtilis and Aspergillus niger. The results show that the growth of the tested organisms can be controlled by the polyketone resins.
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  • 32
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    Angewandte Makromolekulare Chemie 192 (1991), S. 145-153 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In der Arbeit wurde die homogene Polyaddition von Pyromellitsäuredianhydrid und 4,4′-Diaminodiphenylmethan untersucht. Die Abhängigkeit des zahlenmittleren Molekulargewichts (M̄n) von der Zeit weist ein Maximum auf. Die Ursache der niedrigen Gleichgewichtswerte von M̄n beruht auf einer durch Wasserspuren im Lösungsmittel verursachten Dianhydridhydrolyse und damit einer gestörten Äquimolarität der funktionellen Gruppen. Im Laufe der Stabilisierung des M̄n-Gleichgewichtswertes entsteht auch die wahrscheinlichste Molmassenverteilung.
    Notes: The homogeneous polyaddition reaction of pyromellitic dianhydride with 4,4′-diaminodiphenylmethane was investigated. The dependence of the number average molecular weights on time has a maximum; low equilibrium values of M̄n are caused by a disturbed equimolarity of functional groups due to the hydrolysis of dianhydride with water present in the solvent. In the course of establishment of the equilibrium M̄n value, the molecular weight distribution changes to the most probable value.
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  • 33
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    Angewandte Makromolekulare Chemie 192 (1991), S. 133-144 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Das Phasen- und Mischbarkeitsverhalten der binären und ternären Polymermischungen von Polyarylat (PAR), Phenoxid und Poly(butylenterephthalat) (PBT) wurde untersucht. Die Mischungen wurden durch Ausfällen aus gemeinsamen Lösungen hergestellt, und die Mischbarkeit wurde durch DSC-Messungen und Transparenz der Schmelze beurteilt. Im Falle der binären Blends zeigten PAR/PBT und Phenoxid/PBT Mischbarkeit, während sich PAR/Phenoxid nicht mischen ließ. Die Mischbarkeitstendenz der unmischbaren PAR/Phenoxid-Mischungen konnte jedoch durch Zugabe von PBT erhöht werden; eine ausreichende Menge PBT machte die ternären Mischungen mischbar, so daß diese eine einzige Tg in der DSC-Kurve zeigten. Im ternären Phasendiagramm war das Maximum der Mischbarkeitsgrenze in Richtung auf die Phenoxidseite hin verschoben, was auf die bessere Mischbarkeit von PAR/PBT im Vergleich zu Phenoxid/PBT zurückgeführt wird.
    Notes: The phase and miscibility behavior of binary and ternary blends containing polyarylate (PAR), polyhydroxyether of bisphenol AIUPAC: poly[oxy(2-hydroxytrimethylene)oxy-1,4-phenylene-isopropylidene-1,4-phenylene]. (Phenoxy), and poly(butylene terephthalate) (PBT) were studied. The blends were prepared by solution-precipitation method and miscibility was examined by DSC and melt transparency. In binary blends, PAR/PBT and Phenoxy/PBT blends show miscibility, while PAR/Phenoxy appeared to be immiscible. However, the miscibility of incompatible PAR/Phenoxy blend was enhanced by addition of PBT. The addition of sufficient amount of PBT caused the ternary blend to have a single glass transition temperature. The shape of miscibility boundary of ternary blend was skewed to the apex of Phenoxy, which was attributed to the better miscibility of PAR/PBT than that of Phenoxy/PBT.
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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: Die Festphasen-Polykondensation von amorphen, unorientierten Poly(ethylenterephthalat)-Folien (PET) (Vorstufe der Du Pont Mylar® -Polyesterfilme), die mit einem speziellen Katalysator-und Monomer-System hergestellt wurden, war Gegenstand dieser Arbeit. Der Einfluß verschiedener Reaktionsparameter, wie Reaktionstemperatur und -zeit, auf die inhärente Viskosität (ηinh) und auf die Anzahl der Carboxy-und Hydroxy-Endgruppen wurde untersucht. Aus den Messungen von ηinh wurde eine empirische Gleichung erstellt, die die Berechnung von M̄n der PET-Folien nach der Festphasen-Polykondensation bei gegebener Zeit und Temperatur erlaubt. Das Schmelzverhalten verschiedener Festphasen-Polykondensate wurde ebenfalls untersucht.
    Notes: The solid-state polycondensation of poly(ethylene terephthalate) (PET) amorphous and unoriented films from Du Pont (precursor for their Mylar® Du Pont's registered trade mark for the polyester film. polyester film) prepared from a specified catalyst and monomer system has been studied. The effect of various reaction parameters such as reaction temperature and time on inherent viscosity (ηinh) and number of carboxy and hydroxy end-groups has been investigated. From ηinh measurements an empirical equation was taken which allows the calculation of (M̄n) of PET film after solid-state polycondensation at a certain temperature and time. The melting behaviour of the solid-state polycondensated samples was also studied.
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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
    Description / Table of Contents: Sphärische makroporöse Partikel, die als Trägermaterialen für verschiedene Säulen-Operationen eingesetzt werden sollen, wurden mittels Suspensions- und Mikrosuspensionspolymerisation von Trimethylolpropan-trimethacrylat (TRIM) in Gegenwart verschiedener Mengen porogener Reagenzien (Toluol bzw. Mischungen von Toluol und Isooktan) hergestellt. Textur und Eigenschaften der Partikel variierten deutlich mit dem Anteil und der Zusammensetzung des porogenen Reagens und wurden zusätzlich durch die Wahl des Suspensionstabilisators beeinflußt. Die makroporösen Partikel wiesen ein Gesamtporenvolumen von 0,4 bis 3,6 cm3/g und eine spezifische Oberfläche von 7 bis 〉 450 m2/g auf. Alle Partikel enthielten Makroporen und, außer den Teilchen mit sehr niedriger spezifischer Oberfläche, einen gewissen Anteil an Mikroporen (Durchmesser 〈 60 Å). Durch Erniedrigung der Monomerkonzentration und Erhöhung des Isooktan-Gehaltes im porogenen Reagens auf 50 Gew.-% konnte das Auftreten von Mikroporen vollständig unterdrückt werden. Das Erhöhen des Isooktan-Gehaltes führte zu einem vergrößerten Gesamtporenvolumen und zu einem verringerten Quellvermögen der Polymermatrix in Toluol. Der Einfluß einer Hitzebehandlung bei 130°C und eines Aufpfropfens von Polymethylmethacrylat auf die Partikeleigenschaften wurde ebenfalls untersucht.Die Menge an nicht umgesetzten Doppelbindungen in den Partikeln konnte durch Variation der Polymerisationstemperatur verändert werden. Das Vorhandensein leicht zugänglicher Doppelbindungen ist wichtig, da sie zur Funktionalisierung der festen makroporösen Partikel verwendet werden können.
    Notes: Spherical macroporous particles, intended for use as carrier particles in various types of column operations, were prepared by suspension and microsuspension polymerization of trimethylolpropane trimethacrylate (TRIM), in the presence of various amounts of porogenic agents (toluene or mixtures of toluene and isooctane). The texture and properties of the particles varied markedly with the amount and composition of the porogenic agent, and were also affected by the choice of suspension stabilizer. Macroporous particles were prepared, ranging in total pore volume from 0.4 to 3.6 cm3/g, and in specific surface area from 7 to 〉450 m2/g. All of the particles contained macropores, and except for those with very low specific surface area, contained a certain fraction of micropores (diameter 〈60 Å). The presence of micropores could be eliminated completely by decreasing the monomer concentration and increasing the isooctane content of the porogenic agent to 50 wt.-%. Increasing the isooctane content also resulted in an increase in the total pore volume and a decrease in the tendency of the polymer matrix to swell in toluene. The effect on properties of particles by heat treatment at 130°C and by grafting poly(methyl methacrylate) onto the particles was also studied.The amount of unreacted double bonds of the particles could be varied by varying the polymerization temperature. The presence of easily accessible double bonds is important as they can be utilized for functionalization of the rigid macroporous particles.
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  • 36
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    Angewandte Makromolekulare Chemie 191 (1991), S. 31-38 
    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: Eine einfache Methode für die Bestimmung der Grenzflächenhaftung in kurzfaserverstärkten Polymeren, beruhend auf der Längenverteilung von aus der Bruchfläche herausgezogenen Faserteilen, wurde entwickelt. Die Messungen mit Faserverbundwerkstoffen von isotaktischem Polypropylen mit 32 Gew.-% Kurzglasfasern bestätigen die Brauchbarkeit dieser Methode für eine empfindliche Beurteilung von Unterschieden in der Grenzflächenhaftung. Die Einflüsse von Temperatur, Polymer- und Glasfasermodifizierung sowie Faserorientierung auf die Grenzflächenhaftung wurden untersucht.
    Notes: For the evaluation of the interfacial adhesion in short-fibre composites, a simple method based on fibre pull-out length distribution was proposed. The experiments with three composites of isotactic polypropylene with 32 wt.-% of short-glass fibres confirm the potentials of the method for a sensitive determination of differences in the interfacial adhesion. The effects of temperature, crystallinity and fibre orientation angle on the interfacial adhesion were investigated.
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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
    Description / Table of Contents: PE und EPDM-Kautschuk wurden durch Aufpfropfen von Dibutylmaleat (DBM) mit Dicumylperoxid (DCP) als Initiator in Substanz im Temperaturbereich von 140-220°C funktionalisiert. Der Pfropfungsgrad wurde IR-spektroskopisch und durch DSC-Messungen ermittelt. Die für die Pfropfung optimalen DBM- und DCP-Konzentrationen betragen 0,5 bzw. 0,2 Gew.-%. Die Kinetik der Pfropfreaktion ist für PE und EPDM vergleichbar; die Aktivierungsenergien betragen ca. 145 bzw. 130 kJ/mol. Die Pfropfungsgrade sind für PE höher als für EPDM; bei PE/EPDM-Blends steigt der Pfropfungsgrad mit zunehmendem PE-Anteil. Ein Pfropfungsmechanismus, der Nebenreaktionen berucksichtigt, wird vorgeschlagen.
    Notes: Functionalization of polyethylene (PE) and ethylene propylene diene terpolymer (EPDM) in the bulk through dicumyl peroxide (DCP) initiated grafting of dibutyl maleate (DBM) has been studied in the temperature range from 140 to 200°C. The degree of grafting has been determined by infrared spectrophotometry and DSC. The concentration of DBM and DCP has been optimized. 0.5 wt.-% and 0.2 wt.-% DCP for PE and EPDM, respectively, and 10% DBM for both have been found to be the optimum. The kinetics of the grafting reaction is comparable for PE and EPDM. The activation energy of grafting is ca. 145 kJ/mol for PE and ca. 130 kJ/mol for EPDM. The influence of structure of polyolefins on the degree of grafting has also been studied. A higher degree of grafting is obtained for PE than for EPDM. For PE/EPDM blends, the degree of grafting increases with increasing PE content in the blends. A through discussion and proposed mechanism for grafting and other competitive secondary reactions has been provided.
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  • 38
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    Angewandte Makromolekulare Chemie 191 (1991), S. 71-80 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die dynamisch-mechanischen Eigenschaften von gehärteten Epoxidharzen, gefüllt mit porösen Siliciumdioxid-Mikrokugeln mit unterschiedlichen spezifischen Oberflächen, Porenradien, Porenvolumina und adsorbierter Wassermenge, wurde untersucht. Die Glasubergangstemperaturten (Tg) der Composite sind 12-14°C niedriger als die des ungefullten Harzes, was auf die bevorzugte Adsorption von Härter an den porösen Mikrokugeln zurückgeführt wird. Mit zunehmender adsorbierter Wassermenge steigt die Tg der Composite an. Der Speichermodul ist mit der mit Quecksilber bestimmten spezifischen Oberfläche (Hg-Oberfläche) der Mikrokugeln, die der Summe der Oberfläche von Poren mit einem Durchmesser größer als 4 nm entspricht, korreliert.Das Verbältnis tan δc/tan δm nimmt mit zunehmender Hg-Oberfläche ab.
    Notes: Dynamic mechanical properties were studied for epoxy resin filled with porous silica microballoons with varying surface area, pore radius, pore volume and adsorbed water. The glass transition temperature (Tg) of the composites is 12-14°C lower than the Tg of the unfilled epoxy resin. This Tg depression is attributed to the preferential adsorption of curing agents on the porous silica microballoons. Tg of the composite increases with increase in the adsorbed water on fillers. The storage modulus has a distinct correlation with the Hg-surface area of silica microballoons, which corresponds to the sum of the surface area of pores with radii larger than about 4 nm.Tan δc tan δm decreases with increasing Hg-surface area.
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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: Membranen aus Blends von Nylon 6 mit Poly(acrylsäure) (PAA) mit PAA-Gehalten zwischen 25 und 45 Gew.-% wurden durch Filmgießen hergestellt und anschließend durch Eintauchen in eine Aluminiumsalzlösung ionisch vernetzt. Die Glasübergangstemperaturen (Tg) der Membranen wurden mit der DSC-Methode bestimmt. Alle Proben zeigen eine einzige Tg oberhalb der Tg der Homopolymeren, die sich mit zunehmender Scanzeit verschiebt; dies wird auf die Eliminierung von Wasser und die Bildung von Anhydriden im nicht vernetzten PAA-Anteil zurückgeführt.Die Morphologie wurde rasterelektronenmikroskopisch untersucht; die Membranen zeigen eine dichte, porenfreie Struktur ohne Phasenseparation, was auf eine völlige Mischbarkeit der beiden Homopolymeren im untersuchten Zusammensensetzungsbereich schließen läßt. Die Festigkeit der Membranen liegt je nach PAA-Gehalt zwischen 5 und 26 MPa; Membranen mit hohem PAA-Anteil zeigen trotz höherer Vernetzungsdichte eine geringere Zugfestigkeit, was mit der geringen Festigkeit von PAA und der mit größerem PAA-Anteil zunehmenden Quellung zusammenhängt. Letztere wurde durch Messen der Wasseraufnahme trockener Membranen bestimmt; sie steigt von 23,6 Gew.-% bei einem PAA-Gehalt von 25 auf 76,3 Gew.-% bei einem PAA-Gehalt von 45 Gew.-%.
    Notes: Ionically crosslinked blended membranes were prepared from blends of nylon 6 and poly(acrylic acid) (PAA) with the proportion of PAA ranging from 25 to 45 wt.-%. The technique consists of casting a film of the blend, followed by drying and immersion in an aluminum salt crosslinking solution for a predetermined time. The glass transition temperature (Tg) of the membranes was determined by differential scanning calorimetry (DSC). All the samples exhibited a single Tg, which is higher than that of either polymer. There is also a shift in the Tg with increasing scanning time. This phenomenon is attributed to the elimination of water molecules and the formation of anhydrides in the non-crosslinked PAA portion of the membrane. The membrane morphology was studied using scanning electron microscopy (SEM) and shows a dense structure without any pores. No phase separation is observed by scanning cross-sections of the samples, indicating that nylon 6 and PAA are completely miscible in the ranges studied. The membrane material strength lies in the range of 5 to 26 MPa and varies with the amount of PAA in the membrane. Samples with higher PAA content show lower tensile strength in spite of increased crosslinking density. This is due to the inherent low strength of PAA, coupled with increasing swelling of the membrane with increasing PAA content. The latter is confirmed by the measurement of water uptake into a dry membrane which increases from 23.6% to 76.3% with the membrane PAA content increasing from 25 to 45 wt.%.
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  • 40
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    Angewandte Makromolekulare Chemie 191 (1991), S. 81-107 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Practically no adhesion is observed at the interface poly(tetrafluoroethylene)/glass fiber. We have investigated methods to improve adhesion between these interfaces. We have also discussed the question of possible reinforcement, i.e. increase of tensile strength and a simultaneous decrease of elongation.In this first part we present some calculations demonstrating the prerequisites for reinforcement using existing theoretical models. We describe the influence of modification of the glass fiber surface by dispersion coating or by plasma polymerization.In a second part the influence of polymer surface modification and of additives will be dealt with.
    Notes: In Mehrphasensystemen aus Poly(tetrafluorethylen) (PTFE) und Glasfasern besteht praktisch keine Haftung zwischen Matrix und Füllstoff. Es wurde der Frage nachgegangen, ob es Wege zur Verbesserung der Grenzflächenhaftfestigkeit gibt und ob diese Verbesserungen ausreichen, eine Verstärkung, d. h. Anhebung der Reißfestigkeit bei gleichzeitigem Rückgang der Dehnung des Gesamtsystems zu erzielen.In diesem ersten Teil wird den theoretischen Voraussetzungen und der Modifizierung der Füllstoffoberflächen mittels Dispersionsbeschichtungen sowie Plasmaätzen und Plasmapolymerisation nachgegangen.In einem zweiten Teil werden Möglichkeiten zur Verbesserung der Grenzflächenhaftung durch Modifizierung der Polymer-Oberfläche und durch Additive untersucht.
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  • 41
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    Angewandte Makromolekulare Chemie 191 (1991), S. 109-126 
    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: Practically no adhesion is observed at the interphase of poly(tetrafluoroethylene)/glass fiber. We have investigated methods to improve this adhesion and discuss the influence of this improved adhesion on the mechancial properties of the multiphase system.In this paper the influence of a modified polymer surface and of additives is described.
    Notes: In Mehrphasensystemen aus Poly(tetrafluorethylen) (PTFE) und Glasfasern besteht praktisch keine Haftung zwischen Matrix und Füllstoff.Es wurde die Frage untersucht, ob es Methoden gibt, diese Grenzflächenhaftung zu erhöhen und welchen Einfluß diese Erhöhung auf die Eigenschaften des Verbundsystems hat.In dem hier vorliegenden Teil 2 wird speziell auf den Einfluß der Modifizierung der Polymeroberfläche und des Zusatzes von Additiven eingegangen.
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  • 42
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    Angewandte Makromolekulare Chemie 191 (1991), S. 127-144 
    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: Due to the very strong variation of the viscosity of the reaction mass with increasing monomer conversion, three stationary states for the tubes of a multitubular system with cooling vessel can be found. As a consequence, a maldistribution of the fluid arises, so that the reactor stability and the polymer quality are negatively influenced. The recycling of the reaction mass is a helpful method to increase the reactor stability. In this paper some fundamental aspects of the use of multitubular reactors for the polymerization of styrene are studied.
    Notes: Infolge der sich mit steigendem Monomerumsatz stark verändernden Viskosität der Reaktionsmasse existieren im Multirohrreaktor mit Kühlung mindestens drei stationaäre Punkte bezüglich des Einzelrohrmassenstromes gleichzeitig. Als Konsequenz ergibt sich eine Ungleichverteilung der Rohrbelastung, die sowohl die Reaktorstabilität als auch die Polymerqualität negativ beeinflußt. Das Betreiben einer Rückführung kann das Reaktorverhalten stabilisieren. In der vorgelegten Arbeit werden einige fundamentale Aspekte der Anwendung von Multirohrreaktoren für die Massepolymerisation von Styrol untersucht.
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  • 43
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    Angewandte Makromolekulare Chemie 191 (1991), S. 171-176 
    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 nucleophile Substitution von verschieden substituierten Phenoxygruppen in Polyphenylacrylaten durch Ethanolamin in Dioxan wurde bei 60, 80 und 100°C untersucht. Der Umsatz wurde IR- und 1H-NMR-spektroskopisch und elementaranalytisch bestimmt; er hängt sowohl von der Temperatur als auch von der Art der Substituenten am Phenylring ab.
    Notes: The nucleophilic substitution reaction of differently substituted phenoxy groups with ethanolamine in various poly(phenyl acrylate)s was investigated in dioxane at 60, 80, and 100°C. The conversion, as determined from IR- and 1H-NMR spectroscopy and elemental analysis, depends on the temperature and the kind of substituents at the phenyl ring.
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  • 44
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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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  • 45
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    Biopolymers 10 (1971), S. 1099-1101 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 46
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    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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  • 47
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    Biopolymers 10 (1971), S. 1103-1103 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 48
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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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  • 49
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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 
    ISSN: 0006-3525
    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
    Source: Wiley InterScience Backfile Collection 1832-2000
    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 
    ISSN: 0006-3525
    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 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    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 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    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 
    ISSN: 0006-3525
    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 
    ISSN: 0006-3525
    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 
    ISSN: 0006-3525
    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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    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
    Source: Wiley InterScience Backfile Collection 1832-2000
    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
    Source: Wiley InterScience Backfile Collection 1832-2000
    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
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    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 
    ISSN: 0006-3525
    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 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    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 
    ISSN: 0006-3525
    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 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    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 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    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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  • 79
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    Biopolymers 10 (1971), S. 2345-2358 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    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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  • 80
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    Biopolymers 10 (1971) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 81
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    Biopolymers 10 (1971), S. 2537-2553 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    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 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    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 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Biopolymers 10 (1971), S. 2635-2638 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Biopolymers 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 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    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 10 (1971), S. 337-355 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    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 10 (1971), S. 379-389 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper extends a previous study in which a discontinuity in the specific rotation of open chain α-l,4-linked glucopyranosides in the water-dimethyl sulfoxide (H2O-DMSO) system was attributed to a symmetry change about a polymer chain segment. Optical rotation of amylose, cyclohexamylose, methyl β-maltoside, and dextran was measured in the following mixed solvent systems: formamide-dimethyl sulfoxide (F-DMSO), ethylenediamine-dimethyl sulfoxide (E-DMSO), and hexamethylphosphoramide-dimethyl sulfoxide (HMPA-DMSO). Refractive index measurements were used in an attempt to detect hydrogen bonding between solvent components. The specific rotation of amylose corrected for variation in refractive index (CSR), as a function of solvent composition, showed a discontinuity at solvent compositions corresponding to about 1 mole F to 2 moles DMSO and to 1 mole E to at least 8 moles DMSO. A discontinuity in the CSR function of amylose in the H2O-DMSO mixed solvent that occurs at 25°C is not observed at 70°C. The CSR function of methyl-β-maltoside exhibits a discontinuity in solvent composition corresponding to mole ratios between 2F-DMSO and 3F-DMSO. Present results indicate that an amylose chain segment may undergo a symmetry change in solvent compositions corresponding to mole ratios between F-DMSO and F-2DMSO. Our CSR measurements of amylose and model compounds in E-DMSO and HMPA-DMSO do not permit us to distinguish between possible changes in amylose chain segment symmetry and solvent interactions that could affect symmetry properties of the glucopyranose ring.
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    Biopolymers 10 (1971), S. 547-564 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have studied the effect of polypeptide concentration on the helix-coil transition of poly(γ-benzyl L-glutamate) (PBLG) in both dichloroacetic acid (DCA) and DCA-chloroform (CHF) mixtures. In agreement with other reports, we find the van't Hoff transition enthalpy to be strongly dependent on PBLG concentration. Also, an apparent effect of polypeptide concentration was noted on the transition temperature; however, corrections for finite PBLG concentration on the mole fraction of DCA seem to remove this effect. In order to explain our data, as well as some calorimetric data in the literature, we consider the transition free energy and enthalpy as a sum of three partial terms. These represent the thermodynamic parameters associated with: (1) conformational changes of the polypeptide, e.g. formation or disruption of intramolecular hydrogen bonds; (2) binding by the strong acid to the nonhelical segments of the polypeptide; (3) an overall (weak) interaction of the polypeptide with the nonbound solvent giving rise to dilution parameters that are dependent on the polypeptide conformation. The latter effect is generally ignored, since it is assumed that solvent interactions, other than specific binding, are similar for both the helical and the nonhelical conformation. Striking effects of water (small amounts) and solution aging on the formation of PBLG helices was observed. Water, as expected, acts as a helicogenic solvent when combined with DCA. The processes occurring during solution aging are not known, although the net effect is to stabilize the helical conformation. Finally, we present some rather unique thermally induced transitions of concentrated PBLG (about 200 mg/ml) in DCA. At low temperatures the soluble randomly coiled conformation is present. Heating produces first an isotropic gel, followed at higher temperatures by an isotropic solution consisting of about 70% α-helicity.
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  • 93
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    Topics: Chemistry and Pharmacology
    Notes: Potential energies of conformation of a dipeptide unit with butyl, seryl, threonyl, eysteinyl, and valyl side groups have been computed by using classical energy expressions. The presence of a γ-atom introduces characteristic restrictions on the backbone rotational angles φ and ψ the γ-atom itself is restricted to three staggered positions about the Cα - Cβ bond. The important results are that a γ-carbon in position I (χ1 ≃ 60°) cannot be accommodated in the standard right-and left-handed α-helices, whereas a γ-oxygen or sulfur could easily be accommodated in the right-handed α-helix. Further, a γ-carbon or a heteroatom in position II (χ1 ≃ 180°) does not favor a conformation ψ ≃ 180°, compared to two other positions. The valyl side group significantly reduces the allowed φ and ψ values and energetically prefers a β-conformation compared to right-or left-handed α-helical conformations. The less favorable α-helical conformation is possible only for γ (III, II) combination of the valyl residue. The observed φ, ψ, and χ1 values of all the amino acid residues in the three protein molecules, lysozyme, myoglobin, and chymotrypsin are compared with the theoretical predictions and the agreement is excellent. The results bring out the important fact that even in large molecules, the conformation of local segments are predominantly governed by the short-range intramolecular interactions.
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    Biopolymers 10 (1971), S. 593-599 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three methods are described for the preparation of oriented samples of DNA molecules in films. The methods involve simple equipment and produce films of good optical qualities, suitable for the determinations of dichroic spectra, for example. To illustrate the quality of the films the dichroism of DNA and of acridine orange-DNA complex are described. Evidence is given that native DNA structure is stabilized by poly-(vinyl alcohol).
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    Biopolymers 10 (1971), S. 699-710 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A molecular conformation of Gramicidin S was derived on the basis of conformational calculations taking into account the available experimental data.The conformation is characterized by a dyad axis which relates the two chemically equivalent halves of the molecule and contains four hydrogen bonds; other structural features agree with experimental results. X Ray Crystallographic evidences for the relative position of the Ornithine residues is also reported which supports an important feature of the structure of Gramicidin S.
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    Biopolymers 10 (1971), S. 657-680 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The heat ΔH° for converting an uncharged lysine residue from a coil to an α-helical state in poly-L-lysine in 0.1N KCl has been determined calorimetrically to be -1200 cal/mole at both 15°C and 25°C. Essentially the same value has been obtained for the conversion of an uncharged residue from a coil to a β-pleated sheet state. Titration data provided information about the state of charge of the polymer in the calorimetric experiments, and optical rotatory dispersion data about its conformation. In order to compute ΔH°, the observed Calorimetric heat was corrected for the heat of breaking the sample cell, the heal of dilution of HCl, the heat of neutralization of OH- ion, and the heat of ionization of the ε-amino group in the random coil. The latter was obtained from similar Calorimetric measurements on poly-D,L-lysine, which was shown to be a good model for the random coil form of poly-L-lysine. The measured transition heat was ∼0.7 cal., which is only 7% of the total heat liberated when a 40 ml solution of 0.25% w/v poly-L-lysine is brought, from pH 11 to pH 7; nevertheless it could be determined with a precision of ±8%. The conformation of poly-L-lysine at pH 11 appears to be completely helical at 15°C, but a mixture of 90% α-helix, 5% β form, and 5% coil at 25°C. Since ΔH° ∼ 0 for the α ⇌ β conversion, the polymer behaves like one of 95% α-helix and 5% coil in the calorimeter at 25°C. At neutral pH, poly-L-lysine is an extended coil, like poly-D,L-lysine.
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  • 97
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    Topics: Chemistry and Pharmacology
    Notes: Four fragments (named K, L, M, and N) of Escherichia coli formylmethionine transfer RNA have been prepared by a partial digestion with ribonuclease T1 followed by a chromatographic separation with a DEAE-Sphadex (A-25) column and then a DEAE-cellulose column. The fragment K is the anticodon fragment with 19 nucleotides (previously reported). L is a fragment with 57 nucleotides involving the 3′-terminal (CCA). M is a fragment with 51 nucleotides which is equal to L except that M lacks 6 nucleotides at the 3′-terminal. N is a fragment with 20 nucleotides which involved the 5′-terminal and corresponds to the complementary half to L. The infrared absorption spectrum has been observed of each of these fragments and two equimolar mixtures L + N and M + N in D2O solutions at several temperatures. The results indicate that at 37°C, K has about 4 hydrogen-bonded base-pairs, L about 11, and M about 13. On the other hand, fragment N is found to have only three weak G-C pairs. For both L + N and M + N, 15-17 strong base pairs are found. The observations give direct support to the clover-leaf structure and at the same time provide information on the stability of each of the four arms in the structure.
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    Biopolymers 10 (1971) 
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    Biopolymers 10 (1971), S. 767-775 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The matrix method is used for calculating the grand partition function for the reaction: 2 polymer + solute = complex. The homogeneous polymers are assumed to have two types of sites within each nucleotide unit: sites for the polymer-polymer association, i.e., (p-p) sites; sites for polymer-solute association i.e., (p-s) sites. The respective binding parameters, P and F, and nearest-neighbor interaction parameters, W and S, are assumed independent. Complications due to ring entropy are avoided by rest riding the model to one-solute-stack systems, which are physically realizable when the reciprocal of the solute cooperativity parameter is much larger than the number of nucleotides in the polymer. The 4 × 4 generating matrix is shown to be a tensor product of two 2 × 2 matrices, each the generating matrix of a particular type of site. The scalar product of the 4 × 4 matrix is shown to be equivalent to the scalar product of a 2 × 2 matrix in the weak interaction limit, W ≈ 0. Calculations are presented for the general case which restricts the (p-s) association to occur only with (p-p) associated nucleotide units. The nature of the binding curve in relation to partitioning the total interaction energy (F + P + S + W) among the parameters is discussed. Also presented is a criterion for neglecting possible states in the calculation of the grand partition function.
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    Biopolymers 10 (1971), S. 777-788 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The x-ray scattering method has been used to investigate the structure in two amorphous crosslinked polymers which are regarded as test systems to establish the power of the method as applied to amorphous biologically significant polymer associations. It is shown that structural information can be determined about the rigid regions within the polymer systems, i.e., those regions held in particular configuration by stereochemical effects. Models of such regions extending over distances with dimensions of ca 18 Å are proposed for an Araldite polymer and for crosslinked poly (methyl/butyl methacrylate). The results allow some general statements about the usefulness and limitations of the amorphous x-ray method.
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