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  • Chemistry  (86,273)
  • PROPULSION SYSTEMS
  • 1990-1994  (50,842)
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  • 201
    Electronic Resource
    Electronic Resource
    Blends of polyamide 6 and poly(etheraroylhydrazide)s prepared concurrently with polyhydrazide polymerization (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 214 (1994), S. 101-113 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polyhydrazid/Polyamid-Blends (PEHZ12/PA6) wurden durch Niedrigtemperatur-Polykondensation von 4,4′-Dichlorformyl-α,ω-diphenoxydodecan und Terephthaloyldihydrazid (TDH) zu Poly(etheraroylhydrazid) in Gegenwart von Polyamid 6 synthetisiert. Die DSC-Analysen lassen vermuten, daß die zwei Polymerkomponenten nicht wechselwirken. Bei der Extraktion des PA6-Anteils der Blends mit Ameisensäure zeigt die Charakterisierung des PEHZ12-Extraktionsrückstands aber, daß zumindest bei bestimmten Zusammensetzungen Wechselwirkungen zwischen den Komponenten auftreten. Modellreaktionen erlauben die Annahme, daß die PEHZ12-Polymerisation zwischen den Amino-Endgruppen des PA6 und den wachsenden PEHZ12-Polymerketten abläuft.
    Notes: Poly(etheraroylhydrazide) is synthesized in the presence of PA6 by means of low-temperature condensation polymerization of 4,4′-dichloroformyl-α,ω-diphenoxydodecane with terephthaloyl dihydrazide (TDH) in order to prepare polyhydrazide/poly-amide 6 (PEHZ12/PA6) blends. The thermal analysis of the blends by DSC seems to indicate that the two polymers are not interacting. Nevertheless, when the blends are subjected to an extraction process with formic acid in order to remove the PA6, the characterization of the residual PEHZ12 reveales that some interactions do occur between the constituent polymers, at least for selected compositions. Model experiments permit to hypothesize that the polymerization of PEHZ12 proceeds with a chemical interaction between amino end groups of PA6 and growing PEHZ12 chains.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052140110
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  • 202
    Electronic Resource
    Electronic Resource
    Die kristallisation von polybutylenterephthalat (PBT) und polycarbonat (PC) im polymerblend PBT/PC (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 214 (1994), S. 179-196 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The crystallization behavior of PBT as well as PC is changed in the controlled-processed blend due to intermolecular interactions between the different macromolecules in molten state.If the kinetics of the crystallization process prevents a crystallization-induced separation, the partial miscibility of the amorphous phases, measured by the glass transition temperatures, will lead to a decrease of the crystallinity of PBT. The crystallinity, normalized to the concentration of PBT in the blend, is independent from the concentration of PC at low coolling rates.At high cooling rates, PBT is crystallizing stepwise in the blend PBT/PC 40/60 wt.-%. The crystallization temperature in the anisothermic crystallization process is increased at low contents of PC due to a changed nucleation mechanism. The half-time of crystallization is increasing in blends with an increasing PC-content in isothermic crystallization experiments.The normally amorphous PC crystallizes considerably fast in presence of PBT in PC-rich blends. The crystallization or change in the state of order of PC was measured in situ by X-ray diffraction. Calorimetric experiments confirm this result and allow a quantitative estimation of the PC-crystallinity, which amounts to some 20% in the blend PBT/PC 5/95 wt.-%.
    Notes: Das Kristallisationsverhalten sowohl von PBT als auch von PC ist im definiert verarbeiteten Blend infolge intermolekularer Wechselwirkungen zwischen den unterschiedlichen Molekülen in der Schmelze verändert.Die über die Glasübergangstemperaturen gemessene teilweise Mischbarkeit der amorphen Phasen führt bei PBT zu einer Erniedrigung des Kristallinitätsgrades, wenn die kinetischen Bedingungen des Kristallisationsprozesses keine kristallisationsbedingte Entmischung zulassen. Der auf den PBT-Anteil normierte Kristallinitätsgrad ist bei kleinen Abkühlgeschwindigkeiten vom PC-Anteil unabhängüg.In der Mischung PBT/PC 40/60 Gew.-% kommt es bei hohen Kühlraten zu einer fraktionierten Kristallisation. Die Kristallisationstemperatur bei anisothermer Kristallisation ist bei geringen PC-Gehalten durch Änderung des Keimbildungsmechanismus erhöht. Bei isothermer Kristallisation steigt mit zunehmendem PC-Anteil die Kristallisationshalbwertszeit des PBT an.Das normalerweise amorphe PC kann in Gegenwart von PBT in den PC-reichen Mischungen besonders schnell kristallisieren, wobei der Kristallisations- bzw. Ordnungsprozeß des PC in situ mittels der Röntgenbeugung gemessen wurde. Kalorimetrische Untersuchungen bestätigen dieses Ergebnis und erlauben eine quantitative Abschätzung des PC-Kristallinitätsgrades zu ca. 20% im Blend PBT/PC 5/95 Gew.-%.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052140116
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  • 203
    Electronic Resource
    Electronic Resource
    Photoreactions in halogen-containing negative-tone novolac resists (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 214 (1994), S. 197-210 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Elementaranalytische sowie NMR-, IR- und UV-spektroskopische Untersuchungen zeigen, daß die Photolyse von Halogenphenolnovolaken zur Substitution der Halogenatome durch Wasserstoff, der Bildung chinoider Gruppen und intermolekularen Vernetzung führt. Die Geschwindigkeit der Halogeneliminierung hängt von der Art des Halogens ab. Sie steigt in der Reihenfolge F 〈 Cl 〈 Br 〈 I. Die Chloreliminierung aus der 4-Position ist gegenüber der aus der 2- und 3-Position begünstigt. Außerdem verläuft die Abspaltung para-ständiger Chloratome aus Dimeren schneller als aus Trioder Tetrameren. ESR-Messungen bei 77 K sowie die Laserblitzphotolyse bei 296 K deuten auf die intermediäre Bildung von Phenoxyl- und Arylradikalen. Lithographische Tests belegen die hohe UV-Empfindlichkeit von Resisten auf der Basis von Halogenphenolnovolaken. Im Vergleich zu nichthalogenhaltigen Novolakresisten wird eine 6 - 10fache (System: 4-Chlorphenolnovolak/4,4′-Bisazidobiphenyl (5%)) bzw. eine ca. 25fache (System: 4-Chlorphenol-/m-Cresolnovolak/Hexamethoxymethylmelamin (5%)) Steigerung der Empfindlichkeit erreicht. Zur Interpretation wird ein Mechanismus postuliert, demzufolge die durch Halogenabspaltung hervorgerufene Sekundärradikalbildung zu einer zusätzlichen Vernetzung beiträgt. In den melaminhaltigen Resisten katalysiert der gebildete Halogenwasserstoff (Hal· + RH → H-Hal + R·) außerdem die Reaktion der Melaminverbindung mit der Novolakmatrix.
    Notes: The photolysis of halogenophenol novolacs is determined by the substitution of halogens by hydrogen and the formation of quinoid groups and intermolecular crosslinks. This is concluded from elemental analysis, NMR, IR and optical absorption measurements. The rate of halogen release depends on the chemical nature of the halogen. It increases in the order F 〈 Cl 〈 Br 〈 I. Chlorine elimination from 4-position is favored over that from 2- and 3-position. Moreover, dimers release chlorine from 4-position much more readily than trimers and tetramers. ESR measurements at 77 K and flash photolysis studies at 296 K yielded evidence for the intermediate existence of phenoxyl and aryl radicals. Lithographic tests demonstrated the high UV-sensitivity of resist formulations based on halogen-containing novolacs. The increase in sensitivity relative to that of formulations based on nonhalogenated novolacs is 6 to 10fold system: 4-chlorophenol novolac/4,4′-bisazidobiphenyl (5%) and ca. 25fold system: 4-chlorophenol/m-cresol novolac/hexamethoxymethylmelamine (5%). A postulated reactions mechanism concerning the sensitivity increase takes into account that halogen elimination results in the formation of additional radicals that accelerate the rate of crosslinking. Moreover, hydrogen halide generated by hydrogen abstraction of halogen radicals (Hal· + RH → H-Hal + R·) provides for the acid required to catalyze the reaction of the melamine compound with the novolac matrix.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052140117
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  • 204
    Electronic Resource
    Electronic Resource
    Crystallization behavior of polypropylene filled with calcium carbonate of various shape (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 215 (1994), S. 11-24 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Calciumcarbonate unterschiedlicher Teilchenform (sphäarisch, kubisch und nadelfäormig) wurden mit Polypropylen (PP) in einer Zwei-Walzen-Mäuhle gemischt und anschließend zu Platten gepreßt. Der Einflußder Teilchenform auf das Kristallisationsverhalten der PP/CaCO3-Composite, d.h. Kristallisationspeaktemperatur (Tmax), Kristallisationsverlauf usw., wurde mittels Differentialkalorimetrie untersucht. Der Wert von Tmax häangt von der Größe der Gesamtoberfläache der CaCO3-Teilchen ab; Tmax ist bei nadelfäormigen Teilchen gräoßer als bei kubischen oder sphäarischen und hauangt in allen Fäallen der nicht-isothermen Kristallisation von der Abkäuhlgeschwindigkeit und der vorher erreichten maximalen Temperatur ab.
    Notes: Calcium carbonate of various particle shape (spheric, cubic, needle-shaped type) and polypropylene (PP) were mixed on a two roll mill and the mixture was pressed into plates. The effect of particle shape on the crystallization behavior of PP/CaCO3 composites, such as crystallization peak temperature (TMAX), crystallized pattern, etc., was investigated with differential scanning calorimetry measurements. The value of TMAX is explained by the total surface area of added CaCO3 particles; TMAX of needle-shaped series is larger than that of cubic or spheric ones. TMAX of various shaped CaCO3-filled PP totally depends on the cooling rate and maximum temperature in the non-isothermal crystallization, respectively.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052150102
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  • 205
    Electronic Resource
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    Cationic polyelectrolytes, XIIPart. XI cf.8.. PEG-precursor for water-soluble cationic polymers with tertiary n-atoms in the main chain (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 215 (1994), S. 107-119 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Polyaddition von Polyethylenglykol (PEG) Oligoglycidylethern (Mn (PEG): 396,587, 1437 und 3554) mit asymmetrischen Diaminen, wie N,N-Dimethylund N,N-Diethyl-1,3-diaminopropan, wurden wasserläosliche kationische Polymere erhalten. Die Eigenschaften der kationischen Polymeren sind vom urspräunglichen PEG-Molekulargewicht und der Diaminreaktivitäat abhäangig. PEG mit Mn = 396 zeigt das beste Verhalten. In verdäunnten wäassrigen Läosungen und in wäassrigen 2M NaCl-Läosungen der Polymeren wurde das Polyelektrolytverhalten veranschaulicht. Die Gegenwart der PEG Kette bestimmt das Polyelektrolytverhalten in den 2M NaCl Läosungen.
    Notes: Water-soluble cationic polymers were obtained by polyaddition of poly(ethylene glycol) (PEG) diglycidylethers (M̄n of PEG were 396, 587, 1437 and 3554, resp.) with asymmetrical diamines such as N,N-dimethyl-1,3-diaminopropane and N,N-diethyl-1,3-diaminopropane. The cationic polymer properties depend on the PEG initial molecular weight and on the diamine reactivity too. PEG with M̄n = 396 had the best behaviour in these reactions. The polyelectrolyte feature of cationic polymers was emphasized both in dilute aqueous solutions and in 2M aqueous NaCl solutions. The polyelectrolyte behaviour in 2M aqueous NaCl solution is determined by the PEG chain presence.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052150109
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  • 206
    Electronic Resource
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    Untersuchungen zur reaktion von o-kresol mit formaldehyd unter verwendung tertiärer amine (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 215 (1994), S. 139-145 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Reaktion von o-Kresol mit Formaldehyd wurde unter Verwendung verschiedener tertiäarer Amine als Katalysatoren untersucht. Der Einfluß der Reaktionsparameter Basizitäat, Temperatur, Reaktionszeit und Formaldehydkonzentration wird diskutiert. Für die bevorzugte Bildung von 2,4-Bis(hydroxymethyl)-6-methylphenol wurden optimierte Synthesebedingungen erarbeitet. Die Bildung von Zwei-bzw. Mehrkernprodukten konnte nicht ausgeschlossen werden.
    Notes: The reaction between o-cresol and formaldehyde was investigated using various tertiary amines as catalysts. The influence of the reaction parameters basicity, temperature, reaction time and concentration of formaldehyde was discussed. To yield preferentially 2,4-bis(hydroxymethyl)-6-methylphenol the conditions of synthesis were optimized. The formation of bi- and polynuclear products cannot be avoided.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052150112
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  • 207
    Electronic Resource
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    Effect of addition of cellulose powder on the viscometric behavior of liquid crystalline solutions of ethyl cellulose in m-cresol (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 215 (1994), S. 189-200 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Scherviskositäat fläussigkristalliner Ethylcellulose, die mit Cellulosepulver unterschiedlicher Partikelgräoße gefäullt war, wurde bei konstantem Schergefäalle mit einem Kegel-Platte-Viskosimeter bestimmt. Der Einfluß des Cellulosepulvergehalts, des Läange/Breite-Verhäaltnisses der Pulverteilchen und der Temperatur auf das viskose Verhalten und die Phasenäubergäange wird diskutiert. Der Zusatz von Cellulosepulver erhäoht die Viskositäat und verringert die Aktivierungsenergie des Fließens(Ea), ohne jedoch die Phasenäubergäange zu beeinflussen. Die Viskositäat und die Aktivierungsenergie sind abhäangig vom Läange/Breite-Verhäaltnis der Pulverteilchen; mit zunehmender Gräoße dieses Verhäaltnisses wird die Viskositäatszunahme beschleunigt und die Aktivierungsenergie des Fließens erhäoht, wäahrend die Aktivierungsenergie mit steigendem Pulvergehalt abnimmt. Die Phasenumwandlungen sind unabhäangig von der Partikelform. Der Einfluß des Pulvergehalts auf Viskositäat und Aktivierungsenergie ist abhäangig von der Art der fläussigen Phase; in der anisotropen Phase ist der Einfluß geringer als in der isotropen Phase. Dies scheint von der Ausrichtung der Pulverteilchen und der stäabchenfäormigen Molekäule herzuräuhren.
    Notes: Steady-state shear viscosity for the liquid crystalline ethyl cellulose solution filled with cellulose powders was determined using a cone-plate-type viscometer and the effects of cellulose powder content, powder aspect ratio and temperature on the viscometric behavior and phase transformation were discussed. The addition of powder increased the viscosity and decreased the activation energy (Ea) for flow, but did not affect the phase transformation. The viscosity and Ea depended on the aspect ratio; with greater aspect ratio, the viscosity enhancement was accelerated and Ea as well as the decrease in Ea with powder content increased. The phase transformation did not depend on the aspect ratio, the dependences of viscosity and of Ea on powder content depended on the solution phase; the dependences for the anisotropic phase were smaller than those for the isotropic one. The findings appeared to originate from the alignments of powders and rod-like molecules.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052150116
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  • 208
    Electronic Resource
    Electronic Resource
    Oxygen uptake methods as a tool to determine the mechanism of action of hindered amine light stabilizers1Paper presented at the “15th Annual International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland), June 2-4, 1993. (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 216 (1994), S. 37-44 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The UV-degradation of an unstabilized and two HALS stabilized polyethylene (PE) films is described. The degradations are characterized by measuring the oxygen uptake, the formation of CO and CO2, the FT-IR spectra, the mechanical properties, the stabilizer concentration and the oxygen content of the film.The oxygen uptake of the unstabilized PE film led to the expected changes in the IR spectra and embrittlement of the film, while the oxygen uptake by the HALS stabilized films caused only minor changes. The differences between the results for the unstabilized and the HALS stabilized polymers are explained assuming that the initiation of the photodegradation of PE is due to charge transfer complexes.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052160103
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  • 209
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    Current of status of exploitation of radical scavenging stabilizers in advanced polymer stabilizationPaper presented at the “15th Annual International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland), June 2-4, 1993. (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 216 (1994), S. 135-146 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Principal chemical pathways characteristic of active participation of radical scavenging polymer stabilizers (phenols, aromatic, hydroaromatic and hindered aliphatic amines) are outlined. Pathways resulting in a partial depletion or distortion of activity of stabilizers, in formation of polymer discolouring products, or in interactions in bifunctional stabilizers are involved.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052160109
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  • 210
    Electronic Resource
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    Poly(butyleneterephtalate) photolysis and photooxidation : Identification of the ir-absorbing productsPaper presented at the “15th Annual International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland), June 2-4, 1993. (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 216 (1994), S. 155-167 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Irradiations (λ≥300 nm) of poly(butyleneterphtalate) films were carried out in both vacum and air. Photoproducts were investigated by FTIR spectroscopy, chemical derivatization reactions and physical treatments. The repartition of photoproducts in the polymer was shown to be heterogeneous. A scheme accounting for the main routes of PBT photolysis was found on the basis of photoproducts identification. Most of oxidation products were analogous to vacum photolysis species; the mechanism of photooxidation proposed implied both pure photolytical processes and a photo-induced oxidation route.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052160111
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  • 211
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    Photo- and radiation-induced degradation of synthetic polymers: Polymer structure and stabilityPaper presented at the “15th Annual International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland), June 2-4, 1993. (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 216 (1994), S. 225-241 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of polymer density, processing conditions (quenching of annealing), degree of crystallinity, size of crystallite and mobility of polymer chains on the photo-and radiation-induced degradation and the polymer stability have been studied by UV, FTIR spectroscopic, viscosity and mechanical property measurements. Four kinds of annealed or quenched polyethylene (PE) films varying densities were used to the studies. Polystyrene (PSt) films were used to investigate the effect of chain mobility on polymer degradation. The following results were obtained. 1.In linear low density (LLD) PE, greater amounts of crosslinking (irradiated in vacuum) and chain scission (irradiated in air) were noticed than in mediun density (MD) PE and high density (HD) PE samples.2.Polyene formation is favored in the case of the irradiation in vacuum for LLDPE.3.Polymer stability evaluated by mechanical property such as elongation at break (%) is superior in LLDPE to MDPE and HDPE for annealed and quenched samples.4.Segmental motion of polymer chain also affects the polymer stability
    Additional Material: 19 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052160115
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  • 212
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    Eigenschaften von binären mischungen aus polyethylenen hoher dichte mit ultrahoher und normaler molmasse (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 217 (1994), S. 43-49 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The study is on two component blends of high density polyethylenes, having normal and ultra-high molecular weight. The polyethylenes were homogenized by two routes: in powder state or by rolling in melt, then pressed at temperatures in the range from 140°C to 220°C. Comparative studies showed that the way of homogenizing of the components does practically not affect the main mechanical properties of the blends when pressed at temperatures ≥ 160°C. Of special interest are the characteristics of those systems where ultra-high molecular weight polyethylene is the matrix component.
    Notes: Untersucht wurden binäre Mischungen von Polyethylenen hoher Dichte rnit normaler und ultrahochmolekularer Molmasse, die auf zweierlei Weise - in Pulverform oder durch Walzen im Schmelzezustand - homogenisiert und bei Temperaturen zwischen 140 und 220°C gepreßt waren.Es wurde festgestellt, daß die Art der Homogenisierung der Komponenten praktisch keinen Einfluß auf die Eigenschaften bei Preßtemperaturen ≥ 160°C hat. Von besonderem Interesse sind die Eigenschaften der Systeme, in welchen das ultrahochmolekulare Polyethylen die Rolle der Matrixkomponente spielt.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052170105
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  • 213
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    Removal of escherichia coli from water by systems based on polystyrene-g- and poly(glycidyl methacrylate)-g-amines (1993)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 207 (1993), S. 31-41 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Aktiviertes Aluminiumoxid wurde mit den Produkten der Reaktionen von chlormethyliertem Polystyrol mit Diethylamin, von Poly(styro1-co-chlormethylstyrol) mit Diethanolamin und von Poly(styro1-co-glycidylmethacrylat) mit Diethanolamin belegt und zur Adsorption von Escherichia-coli-Bakterien aus Wasser eingesetzt. 100 mg belegtes Trägermaterial wurden mit einer E.-coli-Suspension (20 ml, 107-8 Zellen/ml) gerührt, wobei die Zahl der lebensfähigen Zellen durch Adsorption abnahm; das Adsorptionsgleichgewicht wurde nach etwa 2 h erreicht. Der Abnahme-Koeffizient D (entspricht der Adsorptionsgeschwindigkeitskonstante) wurde aus der Abnahme der Zahl der lebensfähigen Zellen nach 2 h Adsorption gemessen.
    Notes: Reaction products of soluble chloromethylated polystyrene with diethylamine, poly(styrene-co-chloromethylstyrene) with diethanolamine, and poly(styrene-co-glycidyl methacrylate) with diethanolamine were prepared and supported on activated alumina granules. A study was made of removal of Escherichia coli cells from water by these supported alumina granules. When these granules (0.100 g) were stirred in a viable cell suspension (107-8 cells/ml, 20 ml), the viable cell number decreased by the adsorption of the cells to the granules. The adsorption attained approximately to the equilibrium (saturated adsorption) after about 2 h from the start of the adsorption. The decrease coefficient (D, which corresponds to the adsorption rate constant) was determined from the decrease in the viable cell number in the adsorption for about 2 h from the start.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1993.052070104
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  • 214
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    Radical polymerization of mono- and di-methacrylic esters containing bisphenol-S (1993)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 207 (1993), S. 43-52 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die radikalische Polymerisation von Bisphenol-S enthaltenden Mono- und Dimethacrylsaureestern (BPS-M und BPS-DM) wurde bezüglich Polymerisationsgeschwindigkeit, Läsungsmitteleinfluß, Copolymerisation und Kinetik der Photovernetzung untersucht. Es zeigte sich, daß das Lösungsmittel die Polymerisationsgeschwindigkeit signifikant beeinflußt; polare Lösungsmittel wie DMSO und Acetonitril verlangsamen die Polymerisationsgeschwindigkeit. Die Copolymerisation von BPS-M (M1) mit MMA (M1) wurde in Aceton bei 60°C untersucht. Die Copolymerisationsparameter wurden nach der Fineman-Ross-Methode zu r1 = 3,72 ± 0,0l und r2 = 0,80 ± 0,0l berechnet. Die hohe Reaktivität von BPS-M in diesem Copolymerisationssystem kann vermutlich dem „Matrix-Effekt“ zugeschrieben werden. Funktionelle Polymere mit Methacrylat- Seitengruppen wurden erfolgreich modifiziert und durch Bestrahlung in Gegenwart von Benzoinisopropylether photovernetzt. Die Kinetik der Photovernetzung ist zweiter Ordnung.
    Notes: Radical polymerizations of mono- and di-methacrylic esters containing bisphenol-S (BPS-M and BPS-DM) were studied in terms of polymerization rate, solvent effect, copolymerization and kinetic measurements of photocrosslinking. The solvents were found to affect significantly the polymerization rate. Polar solvents such as DMSO and acetonitrile were found to slow down the polymerization rate. Copolymerization of BPS-M(M1) with MMA(M2) was studied in acetone at 60°C. The monomer reactivity ratios were calculated to be r1 = 3.72 ± 0.01 and r2 = 0.80 ± 0.01 by the Fineman-Ross method. The high reactivity of BPS-M observed in this copolymerization system may be due to the “matrix effect”. Functional polymers containing methacrylate side-groups were successfully modified and photocrosslinked by irradiation in the presence of benzoin isopropyl ether. The photocrosslinking process is found to be of second order kinetics.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1993.052070105
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    Supported titanium catalyst for propylene polymerization. Convenient synthesis of unsolvated anhydrous magnesium chloride from MgCl2 · 6 H2OIPCL Communication No. 220. (1993)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 207 (1993), S. 53-63 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Reaktion von Chlorsilanen (Me3SiCl, R2SiCl2, SiCl4; R=Me, Ph) mit MgCl2 · 6 H2O wurde bezüglich der Entfernung des Kristallwassers untersucht. Die Dehydratisierungsgeschwindigkeit hängt von der Art des Chlorsilans ab. Bei der Reaktion mit Dichlordiphenylsilan entsteht in hoher Ausbeute ungelöstes, wasserfreies Magnesiumchlorid, das als Trägermaterial für die Herstellung eines Titan-Katalysators verwendet wurde. Dieser zeigt mit Et3Al und Ph2Si(OMe), als Cokatalysatoren eine hohe Aktivität für die Propylenpolymerisation.
    Notes: Reaction of chlorosilanes (Me3SiCl, R2SiCl2, SiCl4; R=Me, Ph) with MgCl2 · 6 H2O were investigated for the efficiency of removal of water. The nature of chlorosilane is found to govern the rate of dehydration. The treatment of hydrated magnesium chloride with dichlorodiphenylsilane gives unsolvated anhydrous magnesium chloride in high yields. Anhydrous MgCl2 is used as support for the preparation of titanium catalyst. The catalyst in conjunction with Et3Al and Ph2Si(OMe)2 as cocatalyst system shows high activity for propylene polymerization.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1993.052070106
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    Syntheses and reactions of photopolymers, I. New photosensitive azo monomers, photolysis, interfacial polycondensation, viscosity measurements, photodegradation (1993)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 207 (1993), S. 65-79 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wird die Synthese verschiedener, mindestens bifunktioneller Azoverbindungen und deren Einbau in eine Polymerhauptkette mittels Grenzflächenpolykondensation beschrieben. Die thermischen und photochemischen Eigenschaften von Modellverbindungen sowie der Polymeren wurden durch UV-Spektroskopie und DSC-Messungen untersucht. Mit Hilfe von Viskositätsmessungen wurde der Kettenabbau eines Azopolymeren nachgewiesen.
    Notes: The synthesis of new, unsymmetrically functionalized azo compounds and their incorporation into polymers is described. Their photochemical decomposition and thermal stability was studied by UV spectroscopy and differential scanning calorimetry (DSC), respectively. Chemical degradation was followed by viscosity measurements.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1993.052070107
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    Rôle des pigments dans une réaction de polymérisation sous lumière UV-visible (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 218 (1994), S. 81-109 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Das Verhalten eines neuartigen photoinitiierenden Systems, das die Polymerisation von pigmenthaltigen Schichten großer Dicke in einem Reaktionsschritt gestattet, wird dargestellt. Die verschiedenen Wechselwirkungen, die in einem pigmenthaltigen System auftreten, werden qualitativ beschrieben, und der Anteil der von einem Photoinitiator absorbierten Lichtintensität wird berechnet. Neben dem Absorptions- und Reflexionsverhalten von verschiedenen Pigmentklassen werden die optischen Eigenschaften verschiedener Strahlungsquellen untersucht, um die Strahlungsbereiche zu finden, die am besten mit den optischen Parametern der Pigmente korrespondieren. Weiterhin wird die Beschleunigung von Polymerisationen durch die photokatalytische Wirkung einiger Pigmente behandelt.
    Notes: Ce travail sur le rôe des pigments définit le comportement d'un nouveau systeme photosensible qui permet de polymériser des milieux épais et pigmentés selon un procédé en une seule étape. Les différentes interactions présentes en milieu pigmenté sont décrites de façon qualitative, et la part de l'intensité lumineuse absorbée par un photo-amorceur dans un systéme pigmenté est evaluée. Les propriétés optiques telles que l'absorption et la réflectance des différentes familles chimiques de pigments sont déterminées, et, en paralléle, les propriétés optiques des différentes sources d'irradiation sont étudiées de manière à répondre au mieux aux fenêtres de transmission des pigments. L'effet photocatalytique de certains pigments est mentionné, ceci afin d'amkliorer la réaction de polymérisation.
    Additional Material: 18 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052180107
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    Molar mass distribution of polybutadiene synthesized with nickel-based Ziegler-Natta catalysts, I (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 218 (1994), S. 153-162 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Herstellung von cis-1,4-Polybutadien erfolgte mittels Polymerisation von 1,3-Butadien mit einem Katalysatorsystem, das in einer zweistufigen Reaktion gebildet wird: (1) BF3 · O(C2H5)2 und Al(C2H5)3, (2) Ni(OOC8H15)2 und Al(C2H5)3, genannt in-situ-Katalysatorsystem.Die Molmassenverteilungen (MMD) der erhaltenen Polymeren sind mit der Größenausschlußchromatographie (SEC) untersucht worden. Sie lassen sich mit Summen aus Schulz-Flory-Funktionen (SFF) beschreiben. Veränderte Katalysatorformierungs- und Polymerisationsbedingungen beeinflussen die Parameter der SFF. Veränderte Peakflächen und Molmassenmittelwerte der Einzelpeaks zeigen, daß die Polymerisation über mehrere Arten aktiver Zentren verläuft.
    Notes: Cis-1,4-polybutadiene was produced by polymerization of 1,3-butadiene using a catalyst system formed by a two-step formation, Namely (1) BF3 . O(C2H5)2 and Al(C2H5)3, (2) Ni(OOC8H15)2 and Al(C2H5)3 named in-situ-catalyst.The molar mass distributions (MMD) of the polybutadienes are investigated by means of size exclusion chromatography (SEC). The MMD's were fitted by a sum of Schulz-Flory-Functions (SFF). Changed catalyst formation and polymerization conditions influenced the parameters of the SFF. Changed areas and changed molar mass averages indicate a polymerization with more than one peak maximum and kind of active species and lead to a better understanding of the polymerization.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052180111
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    Synthesis and characterization of epoxy resins containing chromium acrylate (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 219 (1994), S. 1-10 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Umsetzung von Chromacrylat mit Bisphenol A und einem Überschuß Epichlorhydrin wurden neuartige Epoxid-Harze hergestellt. Epoxy-Äquivalentgewicht, Gehalt an Hydroxygruppen und hydrolysierbarem Chlor sowie die Viskosität wurden bestimmt, und die Harze wurden mittels IR- und 1H-NMR-Spektroskopie charakterisiert. Die thermischen Eigenschaften der bei 30°C für 24 h mit Ciba Geigy HY 850 (aliphatisches Amin) gehärteten Harze wurden gemessen. Die Harze besitzen eine gute thermische und chemische Stabilität und eine gute elektrische Leitfähigkeit. Die Reaktion verläuft nach erster Ordnung; die Aktivierungsenergie beträgt 47 kJ mol-1 bzw. 34 kJ mol-1 mit bzw. ohne Chromacrylat. Aus spektroskopischen Untersuchungen wird geschlossen, daß das Chrom mit Bisphenol A einen Komplex bildet, der die Epoxidierung beschleunigt.
    Notes: Novel epoxy resins containing chromium acrylate have been synthesized by reacting chromium acrylate with bisphenol-A and excess epichlorohydrin. The quantities such as epoxy equivalent weight, hydroxy content, hydrolyzable chlorine content and viscosity have been determined. The resins have been characterized by IR and 1H NMR spectroscopy. The cured resins were evaluated for thermal properties. The curing of resins was carried out with Ciba Geigy HY 850 (aliphatic amine adduct) at 30°C for 24 h. The cured resins have excellent thermal and chemical resistance, in addition to an excellent electrical conductivity. The reaction follows first order kinetics with an activation energy of 47 kJ mol-1 and 34 kJ mol-1 in the presence and absence of chromium acrylate, respectively. The chromium forms a complex with bisphenol-A, as indicated by spectroscopic studies, which increases epoxidation.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052190101
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    Interpenetrating polymer networks based on liquid natural rubber. 1. Synthesis and effect of nco/oh ratio on physical and mechanical properties (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 219 (1994), S. 67-76 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Interpenetrierende Polymernetzwerke (IPNs) aus Polystyrol und Polyurethan auf der Basis von hydroxyterminiertem Naturkautschuk mit unterschiedlichen NCO/OH-Verhältnissen wurden unter verschiedenen Reaktionsbedingungen hergestellt und zu widerstandsfähigen Filmen verarbeitet. Die IPNs wurden durch ihre physikalischen, mechanischen und morphologischen Eigenschaften wie Dichte, Shore-A-Härte, Vernetzungsdichte, Zugfestigkeit und Reißdehnung charakterisiert. Mit steigendem Polystyrolgehalt erhöhen sich auch Dichte, Shore-A-Härte und Zugfestigkeit, während die Reißdehnung abnimmt. Die Untersuchungen der Vernetzungsdichte lassen eine Phasenumkehr vermuten.
    Notes: Interpenetrating polymer networks (IPNs) of polyurethane based on hydroxyterminated natural rubber with varying NCO/OH ratios and polystyrene were synthesized under different experimental conditions. These IPNs were found to make tough films. The IPNs were characterized by their physical, mechanical and morphological properties like density, Shore-A hardness, crosslink density, tensile strength and elongation at break. The IPNs exhibited an increasing trend in density, Shore-A hardness and tensile strength with increasing polystyrene content, while elongation at break decreased with similar variation in polystyrene content. The crosslink density measurements indicated a possible phase inversion process.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052190106
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    Plasma treatment of polyethylene ultrafiltration membranes (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 219 (1994), S. 117-124 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß einer Plasmabehandlung von Ultrafiltrationsmembranen aus Polyethylen auf die Fouling- und Reinigungseigenschaften bei der Filtration von Rinderserumalbumin werden diskutiert. Bei 2,45 GHz erzeugtes Luft-Plasma steigert die Hydrophilie der Membranoberfläche von 0 auf 60%. Der Durchfluß bleibt bei 90 bis 99%. Mit Plasma behandelte Membranen sind leichter zu reinigen als unbehandelte; dennoch sind sie anfälliger für die Ablagerung von Rinderserumalbumin.
    Notes: The effect of plasma treatment of polyethylene ultrafiltration membranes on fouling and cleaning phenomena during filtration of bovine serum albumin solutions is discussed. Air-plasma of 2.45 GHz raises the membrane surface hydrophilicity from 0 up to 60%. The flux is maintained at 90-99%. Plasma-treated membranes are easier to clean than untreated polyethylene membranes. Despite that, the plasma-modified membranes are susceptible to more intensive deposition of albumin.
    Additional Material: 4 Tab.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052190110
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    Preparation and characteristics of immobilized glucose oxidase on membranes of photosensitive polymers (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 219 (1994), S. 101-115 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Immobilisierung von Glucose-Oxidase in einer Poly(vinylalkohol) (PVAL)-Membran in Gegenwart von UV-Photoinitiatoren wurde untersucht. Enzym-Membranen wurden aus PVAL-Diazoharz- und PVAL-Photoinitiator-Systemen durch Vernetzung mit UV-Licht hergestellt. Mit diesen immobilisierten Glucose-Oxidase-Membranen wurde eine wirkungsvolle Enzymelektrode entwickelt, deren Eigenschaften untersucht wurden. Der Einfluß der Photoinitiatorkonzentration in Poly(vinylalkohol) und der UV-Bestrahlungsdauer auf den Grad der Unlöslichkeit sowie die Aktivitätsausbeute der Membran wurden mit Glucose als Substrat untersucht. Temperatur- und pH-Abhängigkeit der relativen Aktivität, Stabilität bei mehrmaligem Gebrauch, Lagerstabilität und Kalibrierungsdiagramme der Enzym-Membranen wurden ermittelt. Eine beim Erstgebrauch auftretende Instabilitätserscheinung der Membranen wurde ebenfalls untersucht.
    Notes: A study of the immobilization of glucose oxidase on a poly(vinyl alcohol) (PVAL) membrane in the presence of UV sensitizers was carried out. Enzyme membranes were prepared from PVAL-diazoresin and PVAL-sensitizer systems, crosslinked by means of UV irradiation. An effective enzyme electrode was developed by using the immobilized glucose oxidase membrane, and its characteristics were investigated. The effects of the concentration of sensitizers in poly(vinyl alcohol) and UV irradiation time on the degree of insolubility as well as the activity yield of the membrane were examined for the immobilized glucose oxidase using glucose as a substrate. Temperature and pH dependences of the relative activity, stability in repeated use, storage stability and calibration plots of the enzyme membranes were evaluated. The unstability phenomenon, found in the initial use of the immobilized glucose oxidase membrane, which was prepared from PVAL-sensitizer system, was also investigated.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052190109
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    Auswirkungen von Sterilisationsverfahren auf biologisch abbaubare Kunststoffe (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 219 (1994), S. 11-26 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Biopol, Biocellat and Mater-Bi, three biologically decomposable plastics have been tested for their use in medical industries. Biopol did not loose its stress and stiffness under sterilisation, and was also resistant against temperature and alcohol. Mater-Bi and Biocellat, the two other materials, did not satisfy the test applications. Water vapor sterilisation, temperature up to 60°C, at higher temperatures this material will embrittle.
    Notes: Für den Einsatz biologisch abbaubarer Kunststoffe in der pharmazeutischen Industrie und Medizintechnik wurden Produkte verschiedener Hersteller, wie Biopol, Biocellat und Mater-Bi untersucht. Dabei zeigte vor allem Biopol das notwendige Anforderungsprofil, d.h. die Anwendbarkeit aller Sterilisationsverfahren ohne Festigkeitsbzw. Steifigkeitsverluste sowie Temperatur- und Alkoholbeständigkeit. Dagegen wiesen die Werkstoffe Mater-Bi und Biocellat einige Schwachstellen auf. Bei Mater-Bi lagen diese bei der Wasserdampfsterilisation sowie bei der geringen thermischen und Medienbeständigkeit. Biocellat versprödet dagegen durch die erhöhte Temperatur bei der Dampfsterilisation, d.h. daß ein Einsatz über 60°C nicht möglich wäre.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052190102
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    Polymers and copolymers based on vinyl tetrazoles, 2Part 1 cf.10.. Alkylation of poly(5-vinyl tetrazole) (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 219 (1994), S. 89-99 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Alkylierung von Poly(5-vinyltetrazol) mit Dimethylsulfat und tert-Butylalkohol sowie Alkylhalogeniden RHal (R=CH3, C2H5, CH2—CH=CH2, n-C4H9 und t-C4H9) und die Kinetik dieser Reaktion wurden untersucht, um eine neue Herstellungsmethode für tetrazolhaltige Polymere mit wertvollen Eigenschaften zu entwickeln. Die vergleichenden Untersuchungen über die isomere Zusammensetzung und die spektroskopischen Daten von Poly(N-alkyl-5-vinyltetrazol)en, die durch die Alkylierung von Poly(5-vinyltetrazol) sowie durch die Copolymerisation der entsprechenden Monomeren hergestellt wurden, wurden mit IR-, 1H-NMR- und 13C-NMR-Spektroskopie durchgeführt. Der Alkylierungsumsatz beträgt bis zu 99,8%; dadurch können polymere Produkte erhalten werden, deren Zusammensetzung, Struktur und Eigenschaften denen der Homo- und Copolymeren sehr ähnlich sind.
    Notes: Alkylation of poly(5-vinyl tetrazole) with dimethyl sulfate and tert-butyl alcohol as well as with alkyl halides RHal (R=CH3, C2H5, CH2—CH=CH2, n-C4H9, t-C4H9) has been studied under various conditions in order to develop a new method of synthesis of tetrazole-containing polymers having a complex of valuable properties. The kinetic study of the process and comparison of isomeric compositions and spectroscopic characteristics (IR, 1H NMR and 13C NMR) of poly(N-alkyl-5-vinyl tetrazole)s synthesized by alkylation of poly(5-vinyl tetrazole) and of those prepared by (co)polymerization of the corresponding vinyl tetrazoles have been carried out. The alkylation is found to proceed to high conversion extents (up to 99.8%) and enables to obtain a wide variety of polymeric products having the composition, structure and properties very similar to those of homo- and copolymers.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052190108
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    Dyes for nonlinear optics prepared from 2-hydroxyethyl methacrylate. Nonlinear properties of the resulting copolymers (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 220 (1994), S. 75-87 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Farbstoffe mit nichtlinearen optischen Eigenschaften wurden in einer zweistufigen Synthese aus 2-Hydroxyethylmethacrylat (HEMA), 4-Carboxybenzaldehyd und verschiedenen Anilinderivaten hergestellt. Die Farbstoffe (aromatische Iminester von HEMA) wurden mit Styrol copolymerisiert, die erhaltenen Copolymere wurden mit DSC sowie IR-, 1H NMR- und UV-VIS-Spektroskopie charakterisiert, und ihre nichtlinearen Eigenschaften wurden untersucht. Es zeigte sich, daß die nichtlinearen Koeffizienten d31 und d33 vom Farbstoffgehalt der Copolymeren und der Art der elektronenspendenden Gruppen abhängig sind.
    Notes: Dyes for nonlinear optics have been synthesized in two steps from 2-hydroxyethyl methacrylate (HEMA), 4-carboxybenzaldehyde and various substituted anilines. The obtained dyes (aromatic imine esters of HEMA) have been copolymerized with styrene, the copolymers characterized by DSC as well as IR, 1H NMR and UV-VIS spectroscopy, and studied for their nonlinear properties. The d31 and d33 nonlinear coefficients proved to be dependent on the dye content of the copolymers and on the nature of electrondonating groups.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052200107
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    Viscosity behaviour of multivalent metal ion-containing carboxymethyl cellulose solutions (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 220 (1994), S. 123-132 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß von Ca2+-bzw. Al3+-Ionen auf das Viskositätsverhalten (Salzverträglichkeit) wäßriger Lösungen von Natriumcarboxymethylcellulose (CMC) sowohl mit unterschiedlichem Polymerisationsgrad (DP) als auch mit unterschiedlichem Substitutionsgrad (DS) und verschiedenartiger Substitutentenverteilung wurde untersucht. Aus Viskositätsmessungen mit einem Rotationsviskosimeter bei einer Scherrate von 500 s-1 geht hervor, daß die relative Abnahme der Viskosität im Ergebnis des Zusatzes der mehrwertigen Metallkationen unabhängig vom DP (im Bereich von 160 bis 900) der CMC ist. Homogen hergestellte CMC-Proben 2 mit einem größeren Gehalt an 2,3,6-Tri-O-carboxymethylglucose-Einheiten in der Polymerkette weisen im Vergleich zu heterogen hergestellten CMCs 1 bei gleichem Gesamt-DS eine höhere Salzverträglichkeit auf.
    Notes: The influence of Ca2+-and Al3+-ions, respectively, upon the viscosity behaviour (so-called salt tolerance) of aqueous solutions of sodium carboxymethyl cellulose (CMC) with different degree of polymerization (DP) and, on the other hand, with both different degree of substitution (DS) and distribution of substituents, was investigated. Viscosimetry by means of a rotational rheometer at a shear rate of 500 s-1 shows that the relative drop in viscosity as a result of addition of the multivalent metal cations is independent of DP (ranging from 160 to 900) of the CMC samples. Homogeneously synthesized CMCs (2) with a higher content of 2,3,6-tri-O-carboxymethyl glucose units in the polymer chain possess a significantly higher salt tolerance than those (1) prepared under heterogeneous reaction conditions at comparable total DS values.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052200111
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    Linear polythioesters, XXIII. Products of interfacial polycondensation of 4,4′-dimercaptobiphenyl with acid dichlorides (1993)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 207 (1993), S. 173-186 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Phasengrenzflächenpolykondensation von 4,4′-Dimercaptobiphenyl mit ausgewählten aliphatischen und isomeren Phthalsäuredichloriden wurden neue Polythioester erhalten. Um die optimalen Bedingungen der Phasengrenzflachenpolykondensation zu bestimmen, wurde der Einfluß folgender Faktoren auf die reduzierte Viskosität und Ausbeute der Polythioester ermittelt: Art der organischen Phase, Konzentration der Reagenzien, Verhältnis der wässrigen zur organischen Phase, Art und Konzentration des HC1-Akzeptors, Reaktionstemperatur und -zeit. Die Polykondensation von Dithiol mit Isophthalsäuredichlorid wurde als Modellsystem speziell untersucht. Die Polythioesterstrukturen wurden mittels Elementaranalyse, IR-Spektroskopie und Riöntgenspektroskopie bestimmt. Aus der thermogravimetrischen Analyse wurden die Anfangszersetzungstemperatur, die Gewichtsabnahme bei dieser Temperatur und das Maximum der Zersetzungsgeschwindigkeit erhalten. Es wurden weiterhin einige physikalisch-chemische, mechanische und dielektrische Eigenschaften ermittelt. Aufgrund der geringen Löjslichkeit der Polythioester konnten die mittleren Molekulargewichte nicht bestimmt werden.
    Notes: New polythioesters were obtained by interfacial polycondensation of 4,4′-dimercaptobiphenyl with selected aliphatic and isomeric phthaloyl dichlorides.To determine the optimum polycondensation conditions, the influence of the following factors on reduced viscosity and yield were studied: type of organic phase, concentration of hydrogen chloride acceptor, type of catalyst, reaction temperature and rate of acid dichloride addition.A thorough examination was carried out only for the polycondensation of dithiol with isophthaloyl dichloride chosen as a model system. The structures of polythioesters were determined by elemental analysis, X-ray and infrared spectra. The temperature of initial decomposition, the percentage of its mass loss, and temperature of the fastest decomposition process were determined from curves of differential and thermogravimetric analysis.Some physicochemical, mechanical and electrical properties were determined. The molecular weights were not measured because of the low solubility of the obtained polythioesters.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1993.052070116
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    Announcements (1993)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 207 (1993), S. 215-216 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1993.052070120
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    Cationic surface modification by polyelectrolytes: Polyelectrolyte complex formation at inorganic particle surfaces (1993)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 207 (1993), S. 203-213 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die negativ geladene Oberfläche von feindispersen anorganischen Materialien wie Kieselgur, Perlit, Kaolin oder Glas kann durch die Adsorption von kationischen Polyelektrolyten umgeladen werden. Bei hohen Mengen an adsorbiertem Polykation besitzen die Oberflächen der unterschiedlichen Materialien dann gleiche elektrokinetische Eigenschaften. An den derart modifizierten Grenzflächen können anionische Farbstoffe adsorbiert werden. Bei Zugabe eines Polyanions, resultierend in der Bildung eines Polyelektrolytkomplexes, kann die Zahl der kationischen Zentren in der Grenzfläche und damit die Adsorptionskapazität für den Farbstoff erhöht werden. Die experimentellen Resultate deuten darauf hin, daß das Zetapotential bestimmt wird durch die außeren Bereiche der PEC-Schicht, wahrend die Farbstoffadsorption auch durch die inneren Regionen der Oberfläche mitbestimmt wird. Unmittelbar nach der Modifizierung mit Poly(diallyldimethylammoniumchlorid) und Poly(maeinsäure-co-α-methylstyrol) besitzen die modifizierten Materialien bei einem hohen Überschuß des Poly-anions ein negatives Zetapotential, aber ein positives nach der Abtrennung der überstehenden Lösung. Dieses Verhalten steht in Übereinstimmung mit der Bildung eines nichtstochiometrischen PEC mit Polykation im Überschuß und einer reversiblen Wechselwirkung mit überschüssigem Polyanion in der Lüsung. Die Ergebnisse deuten an, daß die Oberflache als fest-analoger Polyelektrolyt in Konkurrenz zu dem Polyanion an der Reaktion beteiligt ist.
    Notes: The surface charge of inorganic finely dispersed materials like diatom earth, perlite, glass or clay may be changed from negative to positive by the adsorption of cationic polyelectrolytes. Different materials exhibit equivalent electrokinetic surface properties with high amounts of the polycation adsorbed. Interfaces modified this way are able to adsorb anionic dye stuffs. Their adsorption capability for the dye stuff may be enhanced by addition of polyanions due to the formation of a nonstoichiometric polyelectrolyte complex (PEC) and therefore an increased number of cationic centres in the interface. Experimental results indicate that the zeta potential is correlated to the outer PEC layer whereby dye stuff adsorption measurements are sensitive for the more inner surface regions, too. Immediately after modification, materials modified with poly(diallyldimethylammonium chloride) and poly(maleic acid-co-α-methylstyrene) have negative zeta potentials at high excess of added polyanion and a positive one after separation of the solid. This behaviour is attributed to the formation of a nonstoichiometric PEC with polycation in excess and reversible interaction with polyanion in the surrounding solution. Experimental results indicate that the surface may act as “solid-like” polyelectrolyte in competition to the polyanion.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1993.052070119
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    Sulfobetaine polyurethane ionomers, 2. Dielectric relaxation in polyether-based polymer and related compounds with Co2+ (1993)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 207 (1993), S. 195-202 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die dielektrischen Relaxationsprozesse in Sulfobetain-Polyurethanionomeren mit Polyethersegmenten (Co2+ -komplexierte und H,S-behandelte Formen) wurden mit der TSDC-Methode untersucht und mit denen nichtionischer Polyurethane und verwandter Verbindungen verglichen. Vier mit c, βs, β′ und βh bezeichnete Relaxationsprozesse wurden in Polyurethanionomeren im Temperaturbereich von 110 bis 370 K beobachtet und mit möglichen molekularen Bewegungsprozessen korreliert. Die Einflüsse des Gehalts an Hartsegmenten, der Komplexierung sowie der H2S-Behandlung auf die Relaxationsprozesse wurden unter Berücksichtigung der strukturellen Modifikationen der harten und der weichen Mikrophasen erklärt.
    Notes: Dielectric relaxation processes in sulfobetaine polyurethane ionomers based on polyether, were studied comparatively to nonionic polyurethane and related compounds with Co2+ (complexed and H2S-treated forms) by using thermally stimulated depolarization currents (TSDC).Four relaxation processes denoted as γ, βs, β′ and βh in polyurethane ionomers over the 110-370 K range were observed. Molecular origin of these processes was suggested. The effects of the hard segments content, complexation and H2S treatment on the relaxation processes were explained in terms of the structural modifications of the hard and soft microphases.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1993.052070118
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    Metal ion complexation of poly(acrylamide)-supported amines crosslinked with N,N′-methylene-bis-acrylamideSystematic name: N-(acrylamidomethyl)acrylamide. (1993)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 208 (1993), S. 1-15 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Komplexierung von Co(II), Ni(II), Cu(II), Zn(II) und Hg(II) in Amin-funktionalisierten, mit N-(Acrylamidomethyl)acrylamid (NNMBA) vernetzten Polyacrylamiden wurde untersucht. Die Metallionenaufnahme hängt vom Vernetzungsgrad ab und nimmt in der Reihenfolge Hg(II) ≫ Cu(II) 〉 Zn(II) 〉 Ni(II) 〉 Co(II) ab. Die Kinetik der Komplexierung ist erster Ordnung. Die Metallkomplexe wurden mittels IR- und EPR-Spektroskopie charakterisiert. Die Harze können ohne Kapazitätsverlust nach Dekomplexierung mehrmals verwendet werden; die desorbierten Harze komplexieren bevorzugt das vorher gebundene Metallion. Das Quellvermögen der komplexierten ist geringer als das der nichtkomplexierten Harze und hängt vom Vernetzungsgrad ab.
    Notes: The complexation of amino functions supported on poly(acrylamides) with 2-20 mol-% of N-(acrylamidomethyl)acrylamide (NNMBA) crosslinks towards Co(II), Ni(II), Cu(II), Zn(II), and Hg(II) ions was investigated. The metal ion uptake was found to be dependent on the extent of the NNMBA crosslinking. The observed trend in complexation is Hg(II) ≫ Cu(II) 〉 Zn(II) 〉 Ni(II) 〉 Co(II). The kinetics of complexation was found to be of first order. The derived metal complexes were characterised by IR and EPR. The complexed resins can be recycled several times without capacity loss. The metal-desorbed resins showed specificity to the metal ion which was initially present. The extent of swelling of the complexed resins is lower than that of the uncomplexed resins and it varies with the extent of crosslinking.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1993.052080101
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    Conduction mechanism of polycarbonate doped with different transition metals (1993)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 208 (1993), S. 17-23 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die elektrische Leitung von mit verschiedenen Übergangsmetallen (Fe, Co, Cu, Cr) dotiertem Polycarbonat (PC) wurde im Temperaturbereich von 293 bis 493 K untersucht. Die Leitfähigkeit von PC mit FeCl, war siebenmal höher als jene der anderen Proben. Die effektive Potentialschwelle Φ wurde zu 0,2 eV berechnet. Weiterhin wurde die Dielektrizitätskonstante bei verschiedenen Temperaturen untersucht.
    Notes: The electrical conduction of polycarbonate (PC) doped with different transition metals was studied in the temperature range of 293-493 K. The conductivity of PC doped with FeCl3 is 7 orders higher in comparison with the other samples. The effective potential barrier (Φ) for pure PC was calculated (0.2 eV). Also, the dielectric constant at different temperatures was studied.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1993.052080102
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    Photooxidative ageing of low density polyethylene. Kinetics determined by an electrical method (1993)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 208 (1993), S. 25-38 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Wirkung von Lichtstabilisatoren im ersten Stadium der Alterung von Polyethylen niedriger Dichte (LDPE) wurde mit elektrischen Methoden untersucht. Drei verschiedene UV-Stabilisatoren wurden verwendet: ein Phosphit-Derivat (3,9-Bis[(2,4-di-tert-butyl)phenoxy]-2,4,8,l0-tetraoxa-3,9-diphosphaspiro[5.5]undecane), ein Benzophenon-Derivat (2-Hydroxy-4-octyloxybenzophenon) und ein Chelat [2,2′-Thiobis(4-tert-octylphenolato)(n-butylamino)nickel(II)]. Diese Stabilisatoren, speziell das Chelat, verbesserten die UV-Stabilität von LDPE für elektrische Anwendungen.
    Notes: The efficiency of light stabilizers is investigated by electric methods in the initial stage of photooxidative ageing of low density polyethylene (LDPE). Three types of UV light stabilizers are tried to improve the UV stability of LDPE: a phosphite type (3,9-bis-[(2,4-di-tert-butyl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane) a benzophenone type [2-hydroxy-4-octyloxy-benzophenone] and a stabilizer based on chelate salt [2,2′-thiobis(4-tert-octyl phenolato) (n-butylamine) nickel (II)]. LDPE is very susceptible to ultraviolet light. UV light stabilizers improve the stability of low density polyethylene for electrical applications, especially the UV stabilizer based on chelate salt.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1993.052080103
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    Volume change by solvent and temperature of poly(vinyl alcohol) crosslinked by electron irradiation (1993)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 208 (1993), S. 39-46 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Ein Poly(vinylalkohol)-Film (PVA) wurde nach Erhitzen in siedendem Wasser gequollen und durch Bestrahlen mit Elektronen vernetzt. Das so erhaltene PVA-Hydrogel weist eine höhere Elastizität und bessere mechanische Eigenschaften auf, obwohl es noch quellbar ist. Das Volumen des vernetzten Hydrogels reagiert sehr empfindlich auf einen Wechsel des Quellungsmittels und eine Temperaturänderung. Nach Kontraktion durch Eintauchen in Aceton nimmt die Zugfestigkeit zu. Durch wiederholtes Erhitzen des Hydrogels in siedendem Wasser und anschließendes Abkühlen wurden Kontraktions-Quellungs-Zyklen durchlaufen. Bei Temperaturen oberhalb 40°C nimmt das Quellungsverhältnis stark ab.
    Notes: Responsive poly(vinyl alcohol) PVA hydrogels obtained by electron irradiation after heating of a water-swollen film show higher elasticity and tougher properties even after boiling in water, although some swelling did occur. The volume of the hydrogel after boiling was very sensitive to solvent (acetone) and temperature. The crosslinked hydrogels show higher tensile strength after rapid contraction by immersion in acetone. The crosslinked PVA was boiled and cooled to induce contraction and swelling cycles. The swelling ratio of hydrogel decreased remarkably at temperatures higher than 40°C.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1993.052080104
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    The interfacial polycondensation of tetrabromobisphenol-A polycarbonate. I. Model reaction and mechanism studies (1993)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 208 (1993), S. 65-77 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Umsetzung von 2,2′,6,6′-Tetrabrombisphenol A (TBBPA) mit Phosgen in einer mit Trialkylamin katalysierten Grenzflächenpolykondensation liefert nur Polymere mit niedrigem Molekulargewicht. Die geringe Reaktivität von TBBPA wird auf dessen sterisch anspruchsvolle Struktur und den elektronenziehenden Charakter der o-Bromsubstituenten zurückgeführt. Aus der Bildung von Carbamaten bei der Reaktion einer Modellverbindung (2,4,6-Tribromophenylchlorformat, TBPC) mit Trialkylaminen geht hervor, daß durch Zerfall des Katalysator-TBPC-Komplexes die Polymerisation abgebrochen wird. Das Carbamat wird durch Zersetzung des Acylammoniumsalzes gebildet, wobei eine nucleophile Substitution durch das Chloridion an dem an das positiv geladene Stickstoffatom gebundenen Kohlenstoffatom stattfindet.
    Notes: 2,2′,6,6′-Tetrabromobisphenol-A (TBBPA), a sterically hindered bisphenol, is known to give only low-molecular-weight polymers using the interfacial phosgenation process. The low reactivity is attributed to the bulkiness and electron-withdrawing character of bromine substituents at the ortho positions. From the formation of carbamate products in model compound (2,4,6-tribromophenyl chloroformate, TBPC) reactions with trialkylamines, the trialkylamine catalyst was found to act as a terminator by the degradation of the chloroformate-trialkylamine complex. The generation of carbamate occurs through the decomposition of the acyl ammonium salt proceeding via nucleophilic displacement by Cl- at the carbon attached to the positive nitrogen center. The relative catalytic abilities of trialkylamines and pyridine derivatives were determined in the homogeneous (dichloromethane) and interfacial (dichloromethane/water) systems. From the results of model reactions with TBPC and sodium tribromophenolate, 4-dimethylaminopyridine (DMAP) was found to be the best catalyst.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1993.052080106
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    Change of mechanical properties of crosslinked polyethylene during its thermo-oxidative aging (1993)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 208 (1993), S. 47-64 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die thermische Alterung von extrudierten Proben von mit Elektronenstrahlen vernetztem linearem Polyethylen wurde im Temperaturbereich von 110-170°C untersucht. Kurz- und langfristige Veränderungen der mechanischen (Dehnungs-)Eigenschaften wurden beobachtet; die entsprechenden Alterungsmechanismen werden auf der Basis ergänzender Sol-Gel-, Dichte-, FTIR- sowie gravimetrischer Messungen und Zugversuche an Mikrotomschnitten diskutiert.Zwei Mechanismen führen zu kurzfristigen Eigenschaftsänderungen: eine Nachvernetzung und eine Änderung der Kristallstruktur (bei Proben oberhalb ihrer Schmelztemperatur). Im vorliegenden Fall wurden die Polymeren im festen Zustand vernetzt, so daß die Änderung der Kristallstruktur zu einer erkennbaren Abnahme der Streckspannung (ca. 5 MPa) führte.Die langfristigen Veränderungen treten nach dem Ende der Oxidationsinduktionsperiode auf. Sie können als Übergang vom zähen in den spröden Zustand interpretiert werden, der durch Strukturänderungen sowohl auf molekularer (durch Kettenspaltung) als auch makroskopischer Ebene (durch diffusionskontrollierte Kinetik der Oxidation verursachte Kern-Schale-Struktur) hervorgerufen wird. Durch IR- und DSC-Analysen wurde festgestellt, daß wahrnehmbare Änderungen in der Dehnung erst kurz vor dem Ende der Induktionsperiode auftreten.
    Notes: The thermal aging of extruded samples of electron beam-crosslinked linear polyethylene has been studied in the 110-170°C temperature range. Short and long term changes of mechanical (tensile) properties were observed, and the corresponding mechanisms are discussed on the basis of complementary sol-gel and gravimetric measurements on whole samples, and density, FTIR and tensile testing on microtome sections.Two mechanisms are involved in short term changes: a post-crosslinking and a change of the crystalline morphology (for samples exposed above the melting point). The latter effect is especially important in the case under study where the polymer was crosslinked in the solid state and leads to a noticeable decrease (∼5 MPa) of the yield stress.The long term changes take place after the end of the induction period of oxidation. They can be interpreted in terms of ductile-brittle transition induced by structural changes occurring on the macromolecular level (chain scission) as well as macroscopically (core-shell structure resulting of the diffusion control of oxidation kinetics). It appears that noticeable changes of ultimate elongation occur just before the end of the induction period as detected by IR or DSC method.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1993.052080105
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    Modification of melamine-formaldehyde moulding compounds with ethylene/vinyl acetate copolymers (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 222 (1994), S. 61-87 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Melamin-Formaldehyd-Harz-Formmassen (MF) wurden durch mechanisches Mischen mit Ethylen-Vinylacetat-Copolymeren (EVA) und teilverseiftem EVA modifiziert, wobei Etherbindungen zwischen dem hydrolysierten EVA und dem MF-Harz nachgewiesen werden konnten, die die mechanischen Eigenschaften von spritzgepreßten Formteilen im Vergleich zur Modifizierung mit EVA verbessern. Der Zusatz solcher Modifikatoren erhöht die Duktilität und verringert im Falle von EVA die Nachschwindung der überaus steifen MF-Matrix, solange der Modifikatoranteil gering bleibt. Dagegen werden die Steifigkeit und die Wärmeformbeständigkeit verschlechtert. Die durch solche unvernetzten Polymeren erreichbare Steigerung der Schlagzähigkeit bleibt allerdings unzureichend.
    Notes: Melamine-formaldehyde moulding compounds (MF) were modified by mechanical mixing with ethylene/vinyl acetate copolymers (EVA) and with partially hydrolysed EVA. Ether linkages between the hydrolysed material and the MF resin improve the mechanical properties of the transfer moulded parts containing the hydrolysed material compared to those made with EVA. The use of both modifying polymers improves the ductility and, in case of the partially hydrolysed material, the postshrinkage of the extremely rigid MF matrix, as long as the modification polymer content is kept low. On the contrary, Young's modulus and the heat deflection temperature are deteriorated. The improvement in impact strength by use of those uncrosslinked polymers is still insufficient.
    Additional Material: 17 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052220106
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    Synthesis and properties of biodegradable copolyesteramides: Nylon 6,6/∊-caprolactone copolymers, 1 (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 222 (1994), S. 111-123 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Eine Reihe von Copolyesteramiden mit Molekulargewichten zwischen 1000 und 7000 (GPC, NMR) wurden aus Adipinsäure/1,6-Hexandiamin/∊-Caprolacton bzw. Nylon 6,6-Salz/∊-Caprolacton hergestellt. Die thermischen Eigenschaften der synthetisierten Polymeren (Glasübergangs-, Schmelz-, und Zersetzungstemperaturen, Schmelzenthalpien) wurden durch DSC- und TGA-Messungen bestimmt und in Bezug auf das Comonomerverhältnis in der Ausgangsmischung diskutiert. Die Übereinstimmung der Copolymerzusammensetzung mit dem Ausgangscomonomerverhältnis wurde mit FT-IR- und NMR-Spektroskopie untersucht. Die Bioabbaubarkeit der Copolyesteramide wurde durch enzymatische Hydrolyse geprüft.
    Notes: A series of copolyesteramides based on adipic acid/1,6-hexane diamine/∊-caprolactone and Nylon 6,6 salt/∊-caprolactone were synthesized. Their molecular weights, determined by gel permeation chromatography and NMR spectroscopy, were found to lie within the range from 1000 up to 7000. Their thermal properties (glass transitions, melting points and heats of melting, and decomposition temperatures) were recorded with diferential scanning calorimetry and thermogravimetry, respectively, and correlated to the comonomer feed composition. The FT-IR and NMR spectra were also recorded in order to confirm the composition of the copolyesteramides and to compare them with that of the comonomer feed. The biodegradability of the synthesized copolymers was tested by enzymatic hydrolysis.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052220109
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    Study of the condensation products of abietic acid with formaldehyde at high temperatures (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 222 (1994), S. 165-174 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch sulfonsäurekatalysierte Umsetzung von Abietinsäure und Paraformaldehyd bei hohen Temperaturen wurden neuartige Kondensationsprodukte erhalten. Als Nebenprodukte der Polykondensation werden eine Ketoverbindung sowie Wasser und Kohlendioxid gebildet. Die Carboxygruppen der Abietinsäure sind an der Kondensationsreaktion beteiligt. In Abwesenheit von Paraformaldehyd wurde das Abietinsäure/Sulfonsäurekatalysator-System untersucht, um zusätzliche Informationen über die Reaktion zu erhalten. Der Reaktionsverlauf hängt von der Temperatur und der chemischen Struktur des Katalysators ab. Ein möglicher Reaktionsmechanismus der Kondensation wird diskutiert.
    Notes: New condensation products have been synthesized by heating abietic acid and formaldehyde at high temperatures in the presence of sulfonic-type acid catalysts. The main polycondensation reaction is associated with a secondary one which leads to a ketonic compound, carbon dioxide and water. The carboxylic groups of abietic acid participate in this condensation reaction. The behaviour of the abietic acid-sulfonic acid catalyst system was studied in absence of formaldehyde to acquire additional information about the reaction. The process is defined by the reaction temperature and chemical nature of the catalyst. A possible mechanism of the condensation reaction is discussed on the basis of the obtained results.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052220112
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    Tailored polymers by cationic ring-opening polymerization (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 223 (1994), S. 1-11 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: After a general classification of the cationic ring-opening polymerizations (CROP's) according to their polymerization mechanism, a number of examples of tailored polymers based on CROP are presented. The monomers used for the synthesis of these tailored structures are tetrahydrofuran (THF), N-tert-butyl aziridine (TBA), 2-methyl-1,3-oxazoline (MeOX) and 1,3-dioxolane (DXL).The polymer structures include different block and graft copolymers, macromonomers, star-shaped polymers, polymer networks and interpenetrating polymer networks (IPNs).
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052230101
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    Massgeschneiderte PolymereVortrag anläßlich der Tagung der Fachgruppe “Makromolekulare Chemie” der Gesellschaft Deutscher Chemiker über “Fortschritte in der Polymersynthese” in Bad Nauheim, 21.-22. März 1994. Synthesestrategien für Telechele, Makromonomere, Block- und Pfropfcopolymere (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 223 (1994), S. 29-46 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In diesem Beitrag wird ein überblick über neuere Entwicklungen auf dem Gebiet der Synthese von Telechelen, Makromonomeren, Block- und Pfropfcopolymeren gegeben. Synthesestrategien aus den Bereichen der Polykondensation, der radikalischen, anionischen und kationischen Polymerisation, der Kettenspaltung sowie der Criss-Cross-Cycloaddition werden diskutiert.
    Notes: New developments in the synthesis of telechelics, macromonomers, block- and graftcopolymers are presented. Synthetic strategies for them are demonstrated with examples from different fields such as polycondensation, radical, anionic, and cationic polymerization, chain cleavage and criss-cross-cycloaddition.
    Additional Material: 1 Tab.
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    Alkane als initiatoren zur radikalischen polymerizationHerrn Professor Dr. rer. nat. Dr.-Ing. E.h. Hansjörg Sinn mit den besten Wünschen zum 65. Geburtstag gewidmet (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 223 (1994), S. 69-79 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Alkanes with highly substituted carbon-carbon bonds can be cleaved in free radicals by homolytic dissociation under the influence of thermal energy. The energy of dissociation is mainly determined by the type and size of the respective substituents. For tetraarylbutane dinitriles the temperatures of decomposition are in the range of other technically used initiators. But nevertheless, these compounds are up to now rather seldom used to initiate free radical polymerizations. This is connected with the special mechanism of initiation: the formed highly substituted alkyl radicals are relatively stable and show only a rather low reactivity against the usually used monomers. Therefore, in the beginning of the polymerization the radical concentration is rather high which leads not only to addition to monomers but also to a pronounced primary radical termination. In some cases this termination process is reversible which results in an unusual polymerization kinetics. Depending on the type of monomer and the degree of reversibility of the primary radical termination, either a period of “dead-end” polymerization follows or the cleavage of the oligomers at the chain end results in a re-initiation process with a “normal” polymerization with increased rate. The reaction mechanism, kinetics and some possible applications of such initiating alkanes are reported.
    Additional Material: 3 Ill.
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    Cycloolefin-copolymere: Eine neue klasse transparenter thermoplasteHerrn Prof. Dr. H. Sinn zum 65. Geburtstag gewidmet. (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 223 (1994), S. 121-133 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Untersuchungen wesentlicher Aspekte der Polymerisation und der Eigenschaftsmodifikation auf Metallocen-Katalyse basierender Cycloolefin-Copolymere (COC) zeigen, daß mit dieser Monomer-Katalysator-Kombination eine neue Klasse transparenter Thermoplasten zugänglich gemacht wird. COC können mit Metallocenen in beliebiger zusammensetzung und mit kontrollierter Mikrostruktur hergestellt werden. Die somit erreichte und durch zusätzliche Modifikationen noch erweiterbare Breite des Eigenschaftsspektrums ermöglicht vielfältige Anwendungen dieser neuen Polymerklasse. Die wichtigsten Schlüsselfaktoren im rohstofflich-technologischen Bereich, die diese Struktur- und Eigenschaftsvielfalt ergeben, werden beispielhaft beschrieben.
    Notes: Investigation of the polymerization process and property modification of metallocene-based cycloolefin copolymers (COC) shows that this monomer-catalyst combination enables synthesis of a new class of transparent thermoplastic polymers. Metallocene catalysis offers much opportunity to vary the composition and microstructure of the copolymers. The breadth of the polymer spectrum which can be further widened by polymer modification enables many applications for this new class of thermoplastics. The key parameters that control structure and properties in the COC family are discussed in this paper.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052230109
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    Funktionalisierte Kammpolymere: Synthesen, modifizierung und anwendungen (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 223 (1994), S. 165-175 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The present paper deals with the synthesis and modification of functionalized polymers characterized by a special molecular architecture. The reactivity of a functionalized polymer with comb-like structure can be controlled in a significant manner by the crystalline order of the side chains. In contrast, photocrosslinking of comblike polymers containing cinnamic components in the side chains influences the crystallization process. The air drying process of a modified polybutadiene system with comb-like structure was shown to depend sensitively on the side chain order. Enzymatic synthesis of new monomers and polymers is briefly reviewed. The complexing capability of cyclodextrines were used to synthesize polyrotaxanes. Finally, the synthesis of a chiral polymerizable dendrimer containing eight estergroups in the monomer unit is presented.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052230112
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    Intramolekular vernetzte poly(organosiloxan)partikel (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 223 (1994), S. 203-216 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Intramolecularly crosslinked poly(organosiloxane) particles are prepared by means of emulsion polycondensation or emulsion polymerization of alkoxysilanes or cyclic organic siloxanes. Starting from these intramolecularly crosslinked poly(organosiloxane) particles, graft copolymers are obtained by free-radical emulsion polymerization of unsaturated olefinic monomers (e.g. acrylates, styrene) in the presence of (functionalized) organosiloxanes. Intramolecularly crosslinked poly(siloxane) particles and their graft copolymers are characterized by means of light scattering (in dispersion), electron microscopy and thermal analyses (DSC, DMTA).
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052230115
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    Chemical modification of poly(epichlorohydrin) with unsaturated potassium carboxylates (1993)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 209 (1993), S. 95-109 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Poly(epichlorhydrin) wurde durch nukleophile Substitution mit aliphatischen Kaliumcarboxylaten mit endstandigen Doppelbindungen (10-Undecenoat, 4-Pentenoat und 3-Butenoat) modifiziert. Die Reaktionsbedingungen wurden variiert, um ihren Einfluß auf den erreichten Substitutionsgrad zu untersuchen. Die hergestellten Polyether wurden mittels Elementaranalyse, spektroskopischen und thermischen Methoden sowie Viskositäts- und osmometrischen Messungen charakterisiert. Es wurde sowohl eine geringe Vernetzung als auch die bereits bekannte Hauptkettenspaltung beobachtet. Während der Substitutionsreaktion isomerisierte das Vinylacetat zum Crotonsäureester.
    Notes: Poly(epichlorohydrin) was modified by nucleophilic substitution with some aliphatic potassium carboxylates containing terminal double bonds (10-undecenoate, 4-pentenoate and 3-butenoate). In order to monitor the degree of substitution achieved, different reaction conditions were tested. The polyethers obtained were characterized by spectroscopic techniques, elemental analysis, thermal methods, viscosity determinations and osmometric measurements. A slight crosslinking and the reported main chain cleavage were both detected. Finally, it must be pointed out that, during the substitution reaction with the vinylacetate, isomerization to crotonic ester took place.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1993.052090109
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    Surface modification of a polypropylene film by low-pressure discharge and the adhesion of a vacuum-deposited layer of aluminium (1993)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 210 (1993), S. 21-32 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polypropylen wurde mittels Gasentladung unter niedrigem Druck behandelt. Die Oberflaäachenmodifizierung wurde durch ESCA-Analysen, Messungen der Benetzbarkeit und Adhäasionsunterschungen in Abhäangigkeit von der Behandlungszeit und der Art des verwendeten Gases (Luft oder Argon) charakterisiert. Die Ergebnisse von “advancing”- und “receding” -Kontaktwinkelmessungen mit Wasser (sehr polar) und Diiodmethan (unpoler) in einem automatischen dynamischen Tensiometer ziegen eine Zunahme der Benetzbarkeit nach der Oberfläachenbehandlung. Dier wird auf die entstehung hochenergetisch polarer Stellen auf der Oberfläache zuräuckgefäuhrt. Die ESCA-Analyse belegt, daß die modifizierte Oberfläahe aud niedermolekularem Material besteht; sie ist in Methanol läolich.Die Adhäsion von Aluminium an der Polypropylen-Oberfläche wird bereits durch eine wenige Sekunden dauernde Gasentladungsbehandlung verbessert. Sie hängt von der polaren Komponente der Oberflächenenergie des Polymeren ab.
    Notes: Low-pressure discharge treatments were applied to the surface of polypropylene. ESCA analyses, wettability measurements and adhesion tests were carried out to characterize surface modifications as a function of treatment time and nature of gas (air or argon). Advancing and receding contact angles were measured with an automatic dynamical tensiometer. The liquids used were water (very polar liquid) and methylene iodide (apolar liquid). The results show an increase in wettability by the surface treatment. This is due to the creation of high-energy polar sites. ESCA analysis also shows that the modified surface layer is soluble in methanol and is made up of low-molecular-weight material.Adhesion of polypropylene/aluminium is also increased by the low pressure discharge treatment from the few first seconds of the treatment. This adhesion increase is a function of the polar component of the polymer surface energy.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1993.052100103
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    Poly-ε-caprolactone/poly(Methylmethacrylate) reactive blends: Correlation between synthesis, morphology and physical properties (1993)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 210 (1993), S. 47-59 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Blends aus Poly-ε-caprolacton (PCL) und Polymethylmethacrylat (PMMA) wurden durch Polymerisation von Methylmethacrylat in Gegenwart von PCL hergestellt. Die thermeischen, morphologischen, dynamisch-mechanischen und mechanischen Eigenschaften der Blends wurden ermittelt. Zum Vergleich wurden Blends durch mechanisches Mischen von PCL-und PMMA-Homopolymerschmelzen hergestellt und charakterisiert. Die nach beidenMethoden hergestellten Blends unterscheiden sich wesentlich in der phasenstrukturund den mechanischen eigenschafte, was wahrscheinlich auf die bildung von gepfropften Anteilen bei der erstgenannten Methode zuräuckgefäuhrt werden kann.
    Notes: Blends of poly-ε-caprolactone (PCL) and poly(methylmethacrylate) (PMMA) were prepared by a reactive method and characterized by thermal, morphological, dynamic mechanical and mechanical analyses. For comparison, “mechanical” blends, obtained by melt-mixing of preformed polymers, have been prepared and characterized. The two series of blends are different in phase structure and in mechanical tensile properties, probably due to the formation of grafted species during reactive blending.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1993.052100105
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    Composites of surface-treated wood fiber and recycled polypropylene (1993)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 210 (1993), S. 33-46 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß der Oberfläachenbehandlung von Säagemehl auf die physikalisch mechanischen Eigenschaften von mit Säagemehl gefäulltem Polypropylen wurde untersucht. Wäahrend mit Elastomerem beschichtetes Säagemehl die Festigkeit der Compostie veschlechtert, fäuhrt diein-situ-Addition von Oberfläachenmodifikatoren (mit Maleinsäaureanhydrid oder N-(3-Maleimidophenyl) maleimid modifiziertes Polypropylen) wäahrend des Knetens des Polypropylens mit unbehandeltem odermit Elastomerem vorbehandeltem Säagemehl zu einer Verbesserung der mechanischen Eigenschaften bei nurgeringer Beeinträachtigung der Schlagzäahigkeit. Die chemische Natur des Oberfläachenmodifikators ist dabei von besonderer Bedeutung, d.h. mit Maleinsäaurenhydrid modifiziertes Polypropylen erwies sich als der effektivste der untersuchten Modifikatoren. Halogenierte Elastomere und mit einem Phenolharz modifiziertes Polypropylen verbessern das Brandverhalten der Composite. Außerdem häangen die Eigenschaften von der Größe der Holzfasern ab. Die morphologische Untersuchung von Bruchfläachen der Composite zeigte, daß die Grenzfläachenadhäasion durch das mit Maleinsäaureanhydrid modifizierte Polypropylen verbessert wird.
    Notes: The effect of surface treatment of saw dust on the physico-mechanical properties of saw dust-filled polypropylene composites was studied. Whereas the elastomer-pretreated saw dust decreases the strength of composites, in-situ addition of interface modifiers, such as maleated polypropylene, m-phenylene bismaleimideSystematic name: N-(3-maleimidophenyl)maleimide.-modified polypropylene, during kneading of polypropylene with untreated or elastomer-pretreated saw dust improved the mechanical properties with a marginal sacrifice of impact strength. The chemical nature of interphase modifiers played an important role on the mechanical properties of the composites, e.g., maleated polypropylene was most effective among the modifiers used in this study. Halogenated elastomers and phenolic modified polypropylene improved the flame resistant properties of the composites. More over, properties varied with the particle size of wood fiber. The morphological study of the fracture surfaces of composites revealed that interfacial adhesion is improved by adding maleated polypropylene.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1993.052100104
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    Study on poly(2,6-dimethyl-1,4-phenylene oxide)/SBS triblock copolymer blends (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 214 (1994), S. 153-167 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Zusammenhang zwischen der Mischbarkeit und den physikalischen Eigenschaften von Polymerblends aus Poly(2,6-dimethyl-1,4-phenylenoxid) (PPO), die in unterschiedlichen Zusammensetzungen in einem Doppelschneckenextruder mit Polystyrol, schlagzähem Polystyrol oder Styrol-Butadien-Copolymeren hergestellt wurden, wird diskutiert. Die Verträglichkeit der Komponenten wurde mittels DSC und DMA, die Morphologie der Blends mittels SEM untersucht. Mit abnehmendem Polystyrolanteil wurde eine schlechtere Mischbarkeit bei den Blends beobachtet, deren Kerbschlagempfindlichkeit sich erhöhte. Die Untersuchungsergebnisse werden mit dem Micellmodell interpretiert.
    Notes: The relationship between the miscibility and the physical properties of polymer blends of poly(2,6-dimethyl-1,4-phenylene oxide) and polystyrene (PS), high-impact polystyrene (IPS) and poly(styrene-block-butadiene-block-styrene) (SBS), which are blended in different compositions by a twin-screw extruder is discussed. The three types of SBS that were used are SBS1, SBS2 and SBS3 having different styrene/butadiene ratios. Dynamic mechanical analysis and differential scanning calorimetry were used to study the miscibility. The morphology was examined by SEM. The miscibility of the blends decreases with decreasing PS content. The notch sensitivity is improved by blending. Finally, the micelle model was used to explain the testing phenomena.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052140114
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    Water-soluble polyamides as potential drug carriers, VIIPresented in part at the Symposium on Water-soluble Polymers, 198th National Meeting Am. Chem. Soc., Miami Beach, Florida, 10-16 September 1989. For Part VI, cf1.. Synthesis of polymers containing intrachain- or extrachain-type amine ligands by interfacial polymerization (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 214 (1994), S. 137-152 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Aliphatische Polyamide mit Poly(ethylenoxid)-Kettensegmenten unterschiedlicher Länge wurden durch Grenzflächenpolymerisation aus Succinylchlorid und Jeffamine ED-900 (O,O'-Bis(2-aminopropyl)poly(ethylenglykol) 800) bzw. Jeffamine ED-2001 (O,O'-Bis(2-aminopropyl)poly(ethylenglykol) 1900) zur Verwendung als Trägersubstanzen für Medikamente synthetisiert. Copolyamide mit kurzkettigen Diamin- und Jeffamine-Segmenten sowie Polyamide aus Cystin und Diamineinheiten wurden auf die gleiche Weise hergestellt. Die Polymerisationen wurden im zweiphasigen System Dichlormethan/Wasser bei Temperaturen um 0°C durchgeführt. Die Polymerprodukte wurden durch stufenweise Dialyse in wäßriger Phase bis zu einem Molekulargewicht von 25000 fraktioniert, nach Gefriertrocknung als wasserlösliche Harze oder Feststoffe erhalten und durch Mikroanalyse sowie 1H NMR-Spektroskopie charakterisiert. Die inhärenten Viskositäten liegen im Bereich von 10-20 ml/g. Die Eignung eines repräsentativen Zielmoleküls zur Bindung von Medikamenten wurde durch eine kovalente Verankerung einer als Medikamentmodell fungierenden Ferrocen-Verbindung untersucht. Dabei wurde ein wasserlösliches Polymer-Ferrocen-Konjugat erhalten.
    Notes: Aliphatic polyamides comprising poly(ethylene oxide) chain segments of various lengths, designed for use as drug carriers, are synthesized by interfacial polymerization of succinyl chloride with the two Jeffamine types ED-900 and ED-2001, formally described by the supplier as O,O'-bis(2-aminopropyl)poly(ethylene glycol) 800 and O,O'-bis(2-aminopropyl)poly(ethylene glycol) 1900. Copolyamides comprising both short-chain diamine and Jeffamine segments are similarly prepared, as are polyamides made up of cystine and diamine segments. The polymerizations are performed in a two-phase methylene chloride-water system at temperatures near or below 0°C. The product polymers, crudely fractionated by staged aqueous-phase dialysis at an ultimate molecular-mass cut-off of 25000, are collected after freeze-drying as water-soluble resins or solids and are characterized microanalytically and by 1H NMR spectroscopy. Inherent viscosities are in the range of 10-20 ml g-1. The drug-binding potential of a representative target polymer is probed by the covalent anchoring of a ferrocene compound used as a drug model, giving a water-soluble polymer-ferrocene conjugate.
    Additional Material: 2 Tab.
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    Studies on vinyl ester resin and its urethane derivative as coating materials (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 214 (1994), S. 211-216 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Über die Anwendung von Vinylesterharzen aus dem Diglycidylether von Bisphenol A sowie dessen Urethanderivat als Beschichtungsmaterial wird berichtet. Die mit den Harzen beschichteten Flußstahlplatten wurden auf Oberflächenglanz, Kratzfestigkeit und Chemikalienbeständigkeit untersucht. Harze mit Styrolanteil zeigen deutlich verbesserte Beschichtungseigenschaften.
    Notes: The present paper is concerned with the coating applications of a vinyl ester resin derived from diglycidyl ether of bisphenol-A and its urethane derivative. The mild steel panels coated with the synthesized resins were evaluated for their gloss on the surface, scratch hardness and chemical resistance. The incorporation of styrene in the resin systems improves the properties of coatings remarkably.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052140118
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    Silica gel supported zirconocene dichloride/methylalumoxane catalysts for ethylene polymerization: Effects of heterogenation on activity, polymer microstructure and product morphology (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 215 (1994), S. 47-57 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Das Katalysatorsystem Zirkonocendichlorid/Methylalumoxan wurde auf Siliciumdioxid aufgebracht, um Katalysatoren fur die Suspensions- order Gasphasenpolymerisation von Ethylen herzustellen. Die häochste Aktivitäat wurde für eine sandwichartige, dreilagige Verankerung von Zirkonzentren auf der Träageroberfläache gefunden. Dieneuen Katalysatorsysteme besitzen eine im Vergleich zu den entsprechenden homogenen Katalysatoren geringere Aktivitäat. Die Immobilisierung der aktiven Katalysatorzentren führt zu einer deutlichen Erhäohung der Polymermolmassen. Dabei bleibt die enge Molekulargewichtsverteilung der Polymerprodukte nahezu erhalten. Solche auf Träager aufgebrachte Metallocen-Katalysatoren käonnten für die Herstellung von Polyethylenen mit kontrollierter Rheologie Anwendung finden.
    Notes: The system zirconocene dichloride/methylalumoxane was supported on silica in order to provide ethylene polymerization catalysts for suspension or gas phase processes. Highest activity was found for a sandwich-like, three layer anchoring of the zirconium centers on the support surface. The new catalyst systems show a decrease of activity compared to polymerization experiments in homogeneous phase. However, the molecular weights are increased and the weight distributions remain narrow by immobilization of the active catalyst sites. Those supported metallocene catalysts could find application for the synthesis of polyethylene materials with controlled rheology.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052150105
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    Evaluation of poly(butyl acrylate-co-ethylene glycol dimethacrylate) sorbents for chromatographic separation of biomolecules (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 215 (1994), S. 129-138 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Vernetzte Copolmere aus Butylacrylat (BA) und Ethylenglycol-dimethacrylat (EGDMA) wurden auf ihre Eignung als stationäare Phase für die Chromatographie untersucht. Es wurde festgestellt, daß gering vernetzte Copolymere (〈 30 Gew.-% EGDMA) nicht poräos sind, wäahrend Matrices mit mehr als 40 Gew.-% EGDMA eine konstante Porositäat aufweisen. Eine Erhäohung des Vernetzergehaltes beeinflußt hauptsäachlich die Hydrophobie der Oberfläache. Zwei Meßmethoden für diese Eigenschaft werden diskutiert: Die Absorption von Alkylalkoholen und von Aminosäauren. Für letztere wurde aus der Steigung der Beziehung zwischen der Sälenkapazitäat und dem Hydrophobie-Parameter der Aminosäauren ein Matrix-Hydrophobie-Index berechnet und dieser mit den bekannten Energien der Wechselwirkung von Alkylalkohol—CH2 Gruppen mit der Polymermatrix verglichen. Die Vorteile der Verwendung des Hydrophobie-Indexes bei der Bewertung von polymeren Sorbentien werden aufgezeigt.
    Notes: Copolymers of butyl acrylate (BA) crosslinked with ethylene glycol dimethacrylate (EGDMA) were evaluated as potential chromatographic packings. It was found that slightly crosslinked copolymers (up to 30 wt.-% EGDMA) did not provide porous material, while for matrices which exceeded 40 wt.-% of EGDMA the porous structure remained unchangeable. The increase of crosslinker content mostly affected the surface hydrophobicity. Two methods of measurement of this property were discussed: Sorption of alkyl alcohols and amino acids. Taking the latter for testing, a polymer matrix hydrophobicity index was calculated as the slope of dependence of column capacity vs. amino acid hydrophobicity parameter. The indices were verified against well-established interaction energies of —CH2— groups of alkyl alcohols and polymer surfaces. Some benefits of the use of the hydrophobicity index in evaluation of polymer sorbents were demonstrated.
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    URL: http://dx.doi.org/10.1002/apmc.1994.052150111
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    Epoxysiloxane resins by the condensation of 3-glycidyloxypropyltrimethoxysilane with diphenylsilanediolDedicvated to Prof. Dr. Dr.-Ing. E. h. Hansjörg Sinn on the occasion of his 65th birthday (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 218 (1994), S. 111-126 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Kondensation von 3-Glycidyloxypropyltrimethoxysilan I mit Diphenylsilandiol II wurde untersucht. Abhängig von Lösungsmittel, Temperatur und Katalysator werden unterschiedliche Primärprodukte erhalten. Die Reaktion in Masse bei 120°C mit Titan(IV)-isopropylat als Katalysator liefert ein transparentes Harz A. Das eduktfreie Produkt wurde IR-, 1H- und 13C-NMR-spektroskopisch charakterisiert und chromatographisch mit GPC und HPLC untersucht. Die trimeren und tetrameren Siloxane bestehen aus Diphenylsilan- und 3-Glycidyloxypropylmethoxysilaneinheiten. Das Verhältnis von cyclischen zu linearen Molekülen beträgt 2:1. Höhermolekulare Verbindungen entstehen nur in geringen Mengen. Das Epoxysiloxangemisch löst sich in unterschiedlichen organischen Lösungsmitteln und ist mit kommerziell verfügbaren Epoxiden mischbar. Die Zeitabhs̈ngigkeit von Viskosität und Epoxidwert bei der Lagerung unter Normalbedingungen wurden gemessen und mit HPLC verfolgt . Die Lagerstabilität wurde durch eine zusätzliche thermische Behandlung verbessert.
    Notes: Condensation of 3-glycidyloxypropyltrimethoxysilane I with diphenylsilanediol II was investigated. Depending on solvent, temperature and catalyst, different products were obtained. Bulk reaction at 120°C using titanium(IV)-isopropylate as a catalyst provided the transparent resin A. A was characterised by IR, 1H- and 13C-NMR spectroscopy and contained no reactants. GPC and HPLC studies revealed that A consists of trimer and tetramer siloxanes of pertinent diphenylsilane and 3-glycidyloxypropylmethoxysilane moieties. The proportion of cyclic to linear molecules was evaluated 2:1. Only small amounts of high-molecular-weight compounds were observed. The epoxysiloxane product proved to be miscible with various organic solvents and with commercial epoxy resins. Time dependence of viscosity and epoxy content were recorded during ambient storage and monitored by HPLC. Pot-life was improved by a subsequent thermal procedure.
    Additional Material: 7 Ill.
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    Molar mass distribution of polybutadiene synthesized with nickel-based Ziegler-Natta catalysts, IIPart I cf.14. (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 218 (1994), S. 163-170 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Cis-1,4-Polybutadien wurde durch Polymerisation von 1,3-Butadien mit Katalysatorsystemen hergestellt, die Ni(OOC8H15)2 und Al(C2H5)3 sowie die Lewissäuren BF3 · O(C2H5)2 oder TiCl4 enthalten. Die Molmassenverteilungen (MMD) der erhaltenen Polybutadiene wurden mit der Größenausschlußchromatographie (SEC) untersucht. Sie lassen sich mit Summen aus Schulz-Flory-Funktionen (SFF) beschreiben. Da eine Art aktiver Zentren eine SFF ergibt, die durch Molmassenmittelwerte definiert ist, lassen sich verschiedene Molmassenverteilungen nach Bandentrennung auf gleiche und verschiedene Arten aktiver Zentren untersuchen. In den untersuchten Systemen lassen sich zwei vergleichbare und eine unterscheidbare Art aktiver Zentren zuordnen. Auf diese Weise wurde das Kettenwachstum in Abhängigkeit von den Komponenten und Katalysatorformierungsbedingungen untersucht.
    Notes: Cis-1,4-polybutadiene was produced by polymerization of 1,3-butadiene using a catalyst system containing Ni(OOC8H15)2 and Al(C2H5)3 and the Lewis acids BF3 · O(C2H5)2 or TiCl4. The molar mass distributions (MMD) of the polybutadienes are investigated by means of size exclusion chromatography (SEC). The MMD's were fitted by a sum of Schulz-Flory-Functions (SFF). Taking into account that one kind of active species gives one SFF defined by molar mass averages, one comparable active species in both systems and one different were found. This way it was tried to find a relationship between the grown up of the active species depending on components and reactions conditions.
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    Morphological and structural studies of poly(gly-gly-ala) (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1049-1057 
    Details
    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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    Supporting evidence for an extended helical conformation in Poly(L-glutamic acid) (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1099-1101 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/bip.360100615
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    A statistical mechanical theory of unfolding of globular proteins induced by preferential binding of solvent components in water-organic solvent systems (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1081-1098 
    Details
    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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    The effects of aqueous neutral-salt solutions on the melting temperatures of deoxyribonuclcic acids (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1103-1103 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360100616
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    Representation of a protein molecule as a tree and application to modular computer programs which calculate and modify atomic coordinates (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1121-1138 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    Optical properties of the polyglycine II helix (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1207-1212 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    Quenching of the emission of tryptophan, tyrosine, and serum albumins by cupric ion (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1229-1242 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    Volume and sound velocity changes associated with coil-β transition of poly (S-carboxymethyl L-cysteine) in aqueous solution (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1253-1260 
    Details
    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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    Energy transfer between tryptophans and aromatic ligands in apomyoglobin (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1317-1329 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    URL: http://dx.doi.org/10.1002/bip.360100806
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    Pressure independence of the rotor speed-induced aggregation of DNA (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1365-1369 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    Time dependent model for hemoglobin and allosteric enzymes. II. (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1331-1349 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    Optical activity of dye-apohemoglobin complexes (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1421-1425 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/bip.360100813
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    Announcement (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1427-1428 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/bip.360100902
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    Comparaison entre oligoribonucleotides et oligodesoxyribonucleotides. I. Formation des doubles helices (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1429-1454 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    Physicochemical studies of oligodextran. I. Molecular weight dependence of intrinsic viscosity, partial specific compressibility and hydrated water (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1513-1524 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    Rotatory properties of molecules containing two peptide groups: experimental and theoretical results (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1559-1581 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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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    Conformational energy calculations on alginic acid. II. Conformational statistics of the copolymers (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1617-1623 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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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    URL: http://dx.doi.org/10.1002/bip.360100915
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    Conformation of poly-S-carboxyethyl-L-cysteine in aqueous solutions (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1635-1648 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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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    Calorimetry of rat tail tendon collagen before and after denaturation: the heat of fusion of its absorbed water (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1681-1699 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    Masthead (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971) 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Induced optical activity of acridine orange bound to poly-S-carboxymethyl-L-cysteine (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1743-1757 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    The circular dichroism in the ultraviolet of aminoacridines and ethidium bromide bound to DNA (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1853-1863 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    Density-gradient sedimentation equilibrium of DNA and the effective density gradient of several salts (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1901-1924 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    Theory of friction-limited DNA unwinding (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1949-1972 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    Cooperative nonenzymic base recognition II.For an introduction compare paper I of this series Eigen & Pörschke (1970). thermodynamics of the helix-coil transition of oligoadenylic + oligouridylic acids (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1989-2013 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    Theory of interaction of polymer and small molecules which can aggregate in solution (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 2049-2049 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/bip.360101020
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    Concentration dependence in three-component systems in sedimentation equilibrium in buoyant density gradients (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 2071-2077 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    Specificity in the genetic code: the role of nucleotide base-amino acid interaction (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 2083-2094 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    Statistical thermodynamics of nucleic acid melting transitions with coupled binding equilibria (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 2147-2160 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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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    Thermodynamic parameters of helix-coil transition in polypeptide chains. II. Poly-L-lysine (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 2181-2197 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    Polarization of fluorescence of an oriented solution of rodlike particles bearing a fluorescent label (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 2029-2037 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    Molecular motion in poly(β-benzyl-L-aspartate) (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 2039-2048 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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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    Potentiometric titration of poly-L-lysine: the coil-to-β transition (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 2133-2145 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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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    Temperature dependence of the aminoacylation of tRNA by bacillus stearothermophilus aminoacyl-tRNA synthetases (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 2209-2221 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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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    β-Carbonylamides in peptide chemistry. I. Optical rotatory properties of N-acetoacetyl amino acids (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 2275-2281 
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    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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    Eleclrooptical study of the electric polarizability of rodlike fragments of DNA (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 2345-2358 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    Masthead (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971) 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/bip.360101201
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    Ionic polysaccharides. IV. Free-rotation dimensions for disaccharide polymers. Comparison with experiment for hyaluronic acid (1970)
    New York : Wiley-Blackwell
    Biopolymers 9 (1970), S. 811-824 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The root-mean-square end-to-end distance has been calculated for a model allowing free rotation about glycoside bonds for the general case of polysaccharides having a disaccharide repeating unit. Numerical estimates are given for several naturally occurring structures based on an idealized pyranose unit in the C1 chair conformation. Extrapolation procedures which make use of the intrinsic viscosity [η] in good solvents to obtain unperturbed dimensions do not represent, data for hyaluronic acid very well, especially at low molecular weights. However, order-of-magnitude estimates suggest that this polymer behaves similarly to other polysaccharides, and probably has stiffer local structure than typical non-ionic synthetic polymers. A double logarithmic plot of the product of [η] and M̄w, the weight-average molecular weight, against the degree of polymerization in the range for M̄w of 104 to 2 × 104 permits a straight-line fit of available data for all the glycosaminoglycans, including heparin and the chondroitin sulfates, as well as sodium carboxymethyl cellulose. This result suggests similarity of short-chain hydrodynamic behavior of these polymers.
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    The 4th Jerusalem symposium (1970)
    New York : Wiley-Blackwell
    Biopolymers 9 (1970), S. 875-875 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1970.360090711
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    Masthead (1970)
    New York : Wiley-Blackwell
    Biopolymers 9 (1970) 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1970.360090801
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  • 297
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    Diffusional boundary spreading in the ultracentrifuge (1970)
    New York : Wiley-Blackwell
    Biopolymers 9 (1970), S. 865-874 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A common approximation for deriving solutions to the Lamm equation is to neglect diffusion. This paper presents a singular perturbation technique that allows one to estimate the band spreading due to nonzero diffusion coefficient. We illustrate the general mathematical technique by its application to sedimentation when pressure effects are important. Comparison of the approximate solution with accurate numerical solutions shows that the relative errors are of the order of 1% both for concentration and concentration gradient for parameters of chemical interest.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1970.360090710
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  • 298
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    Role of pH in charging of glycogen (1970)
    New York : Wiley-Blackwell
    Biopolymers 9 (1970), S. 891-896 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Glycogen acquires a negative charge in both alkaline and acidic solutions and can move in an electrical field, its mobility being related to the degree of alkalinity or acidity. There is a slight increase in relative viscosity at both ends of the pH spectrum. These effects and the changes in nuclear magnetic resonance as a function of pH are interpreted.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1970.360090803
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    Studies on the viscosity of solutions of bovine liver glutamate dehydrogenase and on related hydrodynamic models; effect of toluene on enzyme association (1970)
    New York : Wiley-Blackwell
    Biopolymers 9 (1970), S. 877-889 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The viscosity of bovine liver glutamate dehydrogenase solutions was studied at 10 and 20° C in 0.2.M sodium phosphate buffer at pH 7, in the concentration range 0.1-8 mg/ml. A method for the study of the viscosity of very dilute solutions of associating enzymes is described. It was found that the reduced specific viscosity ηsp/c of glutamate dehydrogenase continuously increases with increasing enzyme concentration, from about 4 ml/g at the lowest concentrations to about 16 ml/g at 8 mg/ml. In the presence of 10-3M GTP and 10-3M NADH the viscosity increase is much smaller and the results can be extrapolated to zero enzyme concentration to yield an intrinsic viscosity [η] = 3.2. The values of ηsp/c in phosphate buffer alone apparently extrapolate to the same value of [η], or to a value close to it. We also observe that, in the presence of toluene ηsp/c increases very much more with enzyme concentration: ηsp/c already equals 16 ml/g at a concentration of 0.75 mg/ml. These observations are in good agreement with the hypothesis that the active oligomer of glutamate dehydrogenase (MW = 312,000) associates with increasing enzyme concentration to form linear rodlike polymers of indefinite length. This association is strongly diminished by the addition of 10-3M GTP, 10-3M NADH. Toluene, on the other hand, promotes reversible association to linear polymers of very high molecular weight. The transverse and axial rotary frictional coefficients of macroscopic bodies, similar to a physical model for the structure of glutamate dehydrogenase recently advanced, were determined. Assuming that the viscosity of the model is equal to that of an ellipsoid of rotation with identical frictional coefficients, we calculate [η] = 3.26 ml/g according to Kuhn and 3.20 ml/g according to Simha, for the glutamate dehydrogenase oligomer, in good agreement with the result derived from the study of enzyme solutions.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1970.360090802
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    Surface chemistry of poly(β-beiizyl L-aspartate) (1970)
    New York : Wiley-Blackwell
    Biopolymers 9 (1970), S. 911-922 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular monolaycrs of poly(β-benzyl L-aspartate) spread at. an air-water interface have been studied. The results obtained both by direct observations on the monlayer and from examination of collapsed films with polarized infrared spectroscopy and electron diffraction are consistent with the presence of right handed α-helices in the mono-layer when the molecular weight is high. When 1% (v/v) isopropanol is present in the subphase the right-handed helix prevails, provided that the monolayer is first spread on water. Monolayers of low molecular weight polymer appear to form the crossed-β structure. Orientated collapsed films of high molecular weight polymer can be converted to the left-handed α-helical and to the ω-conformation, and the mechanisms are discussed. The surface chemistry of this polymer is compared with that of related polymers and a consistent pattern of behavior emerges.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1970.360090805
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