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  • 1994  (14,566)
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  • 1929  (2,236)
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  • 2005-2009
  • 1990-1994  (14,566)
  • 1980-1984  (8,849)
  • 1935-1939
  • 1925-1929  (2,236)
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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 214 (1994), S. 57-65 
    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: Positive und negative Photostrukturen wurden in einem Polyimid (PI) aus 4,4′-Biphthalsäureanhydrid (BPA) und 4,4′-Diamino-3,3′-dimethyldiphenylmethan (DADMDPM), PI(BPA/DADMDPM) erzeugt, nachdem dieses mit Michlers Keton (MK) bzw. Benzophenon (BP) dotiert und einer ultravioletten Strahlung von 400 ± 50 nm ausgesetzt und naß entwickelt wurde. Das Prinzip der positiven Abbildung basiert auf dem Photokupplungseffekt von MK mit PI, der die Löslichkeit des Polyimids erhöht und so die Entwicklung eines Positivmusters ermöglicht. Die Erzeugung negativer Muster wird durch intermakromolekulare Wasserstoffbrücken zwischen der Carbonylgruppe des Imid-Rings und der Hydroxygruppe, die bei der photoinduzierten Kupplung von Benzophenon mit dem Polyimid gebildet wird, bewirkt. Die lithographische Auswertung zeigt, daß der mit MK dotierte, positive Polyimidfilm nicht in der Lage ist, brauchbare Muster zu erzeugen, da die UV-Wellenlängen von MK absorbiert werden, wodurch die Photokupplung in den tieferen Schichten des Films verhindert wird. Andererseits können in dem 0,6 μm dicken, mit Benzophenon dotierten Polyimidfilm sogar 2 μm schmale Linien aufgelöst werden.
    Notes: Positive and negative photostructures are formed after the polyimide (PI) of 4,4′-biphthalic anhydride (BPA) and 4,4′-diamino-3,3′-dimethyldiphenylmethane (DADMDPM), PI(BPA/DADMDPM) is doped with Michler′s ketone (MK) and benzophenone (BP), respectively, and is subjected to UV light (400 ± 50 nm) irradiation and solvent development. The principle of positive feature formation is based on the photocoupling of MK with PI, which increases PI solubility and thus enables a positive pattern to be developed. The phenomenon of negative photopatterning results from intermacromolecular H-bonding between the carbonyl group of the imide ring and the hydroxy group which is formed in the photoinduced coupling reaction between BP and PI. Lithographic evaluation shows that the MK-doped positive-acting PI film cannot form useful patterns because UV wavelengths are strongly absorbed by MK, which limits the depth of photocoupling in the film. On the other hand, 2-μm-wide lines can be resolved in the BP-doped negative-acting 0.6-μm-thick PI film.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 214 (1994), S. 101-113 
    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.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 214 (1994), S. 179-196 
    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.-%.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 214 (1994), S. 197-210 
    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.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 215 (1994), S. 11-24 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 215 (1994), S. 107-119 
    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.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 215 (1994), S. 139-145 
    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.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 215 (1994), S. 189-200 
    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.
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  • 9
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    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.
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  • 10
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 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.
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  • 11
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 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.
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  • 12
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The 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
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  • 13
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 217 (1994), S. 43-49 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
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  • 14
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    Angewandte Makromolekulare Chemie 218 (1994), S. 81-109 
    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.
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  • 15
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 218 (1994), S. 153-162 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die 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.
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  • 16
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    Angewandte Makromolekulare Chemie 219 (1994), S. 1-10 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
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  • 17
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    Angewandte Makromolekulare Chemie 219 (1994), S. 67-76 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
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  • 18
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    Angewandte Makromolekulare Chemie 219 (1994), S. 117-124 
    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.
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  • 19
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    Angewandte Makromolekulare Chemie 219 (1994), S. 101-115 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
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  • 20
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    Angewandte Makromolekulare Chemie 219 (1994), S. 11-26 
    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.
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  • 21
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
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  • 22
    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.
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  • 23
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    Angewandte Makromolekulare Chemie 220 (1994), S. 123-132 
    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.
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  • 24
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    Angewandte Makromolekulare Chemie 222 (1994), S. 61-87 
    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.
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  • 25
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    Angewandte Makromolekulare Chemie 222 (1994), S. 111-123 
    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.
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  • 26
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    Angewandte Makromolekulare Chemie 222 (1994), S. 165-174 
    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.
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  • 27
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    Angewandte Makromolekulare Chemie 223 (1994), S. 1-11 
    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).
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  • 28
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
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  • 29
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    Angewandte Makromolekulare Chemie 223 (1994), S. 69-79 
    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.
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  • 30
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    Angewandte Makromolekulare Chemie 223 (1994), S. 121-133 
    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.
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  • 31
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    Angewandte Makromolekulare Chemie 223 (1994), S. 165-175 
    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.
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    Angewandte Makromolekulare Chemie 223 (1994), S. 203-216 
    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).
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  • 33
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    Angewandte Makromolekulare Chemie 214 (1994), S. 153-167 
    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.
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  • 34
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
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  • 35
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    Angewandte Makromolekulare Chemie 214 (1994), S. 211-216 
    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.
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  • 36
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    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.
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  • 37
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    Angewandte Makromolekulare Chemie 215 (1994), S. 129-138 
    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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  • 38
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die 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.
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  • 39
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    Angewandte Makromolekulare Chemie 218 (1994), S. 163-170 
    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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  • 40
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The DNA-ligand interactions of a series of phenanthridinium compounds with various combinations of amino, azido, and hydrogen functions at R3 and R8 were examined to determine the contribution of these particular substituents to ligand binding. Spectrophometric titrations using calf-thymus DNA emphasized the importance of amino substituents in conferring a strong interaction and also stabilizing the interaction against reversal by high ionic strength. Although azido groups were not as effective as amino groups, they were more effective than hydrogen functions in enhancing the interaction. Furthermore, an amino substitution at R8 was consistently, though only slightly, more effective than an amino substituent at R3. The results from superhelical titrations using plasmid pBR322 DNA demonstrated that analogs with amino and/or azido functions at both R3 and R8 produced the greatest unwinding, and compounds with an amino or an azido function at R8 proved more effective than those with the corresponding amino or azido substituent at R3.
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  • 41
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The magnetic shielding constant of the 31P nucleus of the dimethylphosphate anion is calculated by an ab initio method for different values of the torsion angles about the PO ester bond and different orientations of the methyl groups. The results obtained tend to show that both types of conformational parameters contribute to the value of σ31P. The largest shielding is obtained when the methyl groups are staggered with respect to the PO bond; the smallest, for the eclipsed arrangement. Measurements carried out on the 16 deoxyribodinucleoside monophosphates show that in the majority of cases σ31P is shifted toward lower field for the dimers having large values of 3JPH3′ and 3JPH5′(5″). The theoretical results are discussed in relation to experimental data for polynucleotides and nucleic acids.
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  • 42
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    Biopolymers 23 (1984), S. 471-491 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The optical modes of DNA that displace one strand against the other are modeled by the motion of an oscillator in an asymmetric quartic double-well potential whose minima represent the A- and B-conformations. Assuming that the variation of the polarizability during vibration derives mainly from the tilting of the base rings relative to the helix axis, the total polarizability tensor is shown to possess approximately ellipsoidal symmetry and to depend nonlinearly on the instantaneous displacement of the two strands. The Raman spectrum of a collection of randomly oriented molecules is calculated. It consists of one or more peaks with characteristic shape. The depolarization ratio is 3/4, independent of molecular conformation and frequency. The results are discussed in the light of existing experimental and theoretical information.
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  • 43
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    Biopolymers 23 (1984), S. 511-536 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the semiempirical potential functions, conformational energies of the model compounds DMP-, d(pCp), d(pGp), and d(pCpGpCp) are calculated, and the B → Z transition is discussed along the pseudorotational path of the sugar ring. For dimethylmonophosphate anion, DMP-, the energy contour map is presented and the stabilities of the phosphodiester conformations discussed. For the sugar ring without the base attached, the minimum energies for each sugar-puckering form are calculated along the pseudorotational path. The energy barrier of the interconversion between the C(3′)-endo form and the C(2′)-endo form is calculated to be about 2.0 kcal/mol. From the conformational energy calculations of the interconversions of mononucleoside diphosphates, d(pCp) and d(pGp), between the C(2′)-endo conformer and the C(3′)-endo conformer, the purine sugar segment is known to be more convertible than the pyrimidine sugar segment. The results also support the finding that the pseudorotational transition occurred with the O(1′)-endo form more easily than with the O(1′)-exo form. Based on the results of conformational studies of DMP-, d(pCp), and d(pGp), a topological transition of the handedness of the model compound, d(pCpGpCp), is studied. The left-handed Z-form is found to be less stable by about 8.5 kcal/mol than is the right-handed B-form. The energy barrier of the Z → B transition is calculated to be about 17.4 kcal/mol. The contributions of the electrostatic and nonbonded energies to the energy barrier are discussed in connection with the conformation changes of the model compound, d(pCpGpCp).
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  • 44
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    Biopolymers 23 (1984), S. 593-599 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dielectric properties of aqueous solutions of DNA were measured at frequencies ranging from 0.1 to 12 GHz. The results are analyzed using the Maxwell mixture theory and yield a value for the hydration of the DNA of about 0.4 g/g, which is in the range observed in other investigations. No evidence was found for an additional absorption effect at microwave frequencies, which has been predicted to occur in certain DNA analogs due to the vibrational excitation of the double helix by the applied microwave field.
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  • 45
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Self-association of substance P and its C-terminal partial peptide sequences was studied by CD, quasi-electric light scattering, and sedimentation experiments. CD spectra of these peptides are strongly influenced by self-association. They exhibit strong characteristic negative ellipticities, suggesting the formation of a presumably B-type ordered structure. The tendency to form multimers depends on chain length and constitution and has its maximum at the octapeptide (SP 8). The peptide multimers have a broad distribution of sizes in the range of 30- and 800-nm diameter. Subdivision of this distribution into two size classes gives mean diameters of 60-100 nm (predominating)/200-800 nm for substance P and 30-50 nm/200-800 nm for SP 8 multimers.
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  • 46
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    Biopolymers 23 (1984), S. 819-829 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C-nmr chemical shifts of backbone carbonyl and side-chain β-carbons in polypeptides provide structural information. Recent utilization of substituent effects on 13C-nmr chemical shifts (principally γ-effects) has permitted the rationalization of their sequence and conformation dependence when observed in linear, flexible polypeptides. In this report, we apply the γ-effect method to study the 13C-nmr chemical shifts observed in solution and in the solid state for the backbone carbonyl and side-chain β-carbons in conformationally rigid polypeptides, which are usually cyclic. As found previously for flexible, linear polypetides, the relative 13C-nmr chemical shifts observed for the backbone carbonyl and side-chain β-carbons in conformationally rigid polypeptides are predictable from knowledge of their peptide residue sequence (primary structure) and conformation (secondary structure) via the γ-effect method.
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  • 47
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    Biopolymers 23 (1984), S. 847-852 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 48
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The CD spectra of the peptides Boc-X-(Aib-X)n-OMe (n = 1, 2, 3) and Boc-(Aib-X)5-OMe, where X = L-Ala or L-Val have been examined in several solvents. The X = Ala and Val peptides behave similarly in all solvents, suggesting that the Aib residues dominate the folding preferences of these peptides. The decapeptides adopt helical conformations in methanol and trifluoroethanol, with characteristic negative CD bands at 222 and 205 nm. In the heptapeptides, similar spectra with reduced intensities are observed. Comparison with nmr studies suggest that estimates of helical content in oligopeptides by CD methods may lead to erroneous conclusions. The pentapeptides yield solvent-dependent spectra indicative of conformational perturbations. Peptide association in dioxane results in an unusual spectrum with a single negative band at 210 nm for the decapeptides. Disaggregation is induced by the addition of methanol or water to dioxane solutions. Aggregation of the heptapeptides is less pronounced in dioxane, suggesting that a critical helix length may be necessary to promote association stabilized by helix dipole-dipole interactions.
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  • 49
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    Biopolymers 23 (1984), S. 831-841 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of poly-5-bromouridylic acid [poly(BU)] with adenosine and 9-methyladenine was studied by equilibrium dialysis, optical melting, and microcalorimetry. The stacking free energy, ω, was estimated as -17.6 kJ/mol for adenosine·2poly(BU) and -18.8 kJ/mol for 9-methyladenine·2poly(BU) from the binding isotherms constructed from equilibrium dialysis results. The binding isotherms constructed from a series of melting curves also gave ω values for adenosine·2poly(BU). The thermal stability of the complex depends on monomer concentration, and the partial molar enthalpies of the complex formation at the midpoint of the transition were evaluated from the Tm coefficients as a function of free monomer concentration. The values of -92.0 and -90.4 kJ/mol were obtained for adenosine·2poly(BU) and 9-methyladenine·2poly(BU) in 0.4M NaCl-0.02M Na-cacodylate-5 × 10-4M EDTA (pH 7.0), respectively. Microcalorimetric measurements provided lower integral heats of reaction values for these complexes, i.e., -73.2 kJ/mol for adenosine·2poly(BU) and -71.5 kJ/mol for 9-methyladenine·2poly(BU). A comparison with a polyribouridylic acid system provided a quantitative understanding of a stabilization by bromination in terms of thermodynamic parameters.
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    Biopolymers 23 (1984) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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  • 51
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    Biopolymers 23 (1984), S. 191-194 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 52
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    Biopolymers 23 (1984), S. 257-270 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A molecular-dynamics simulation was used to carry out an introductory study of the hydration of a section of a rigid single A- or B-DNA helix with one Na+ counterion per nucleotide. Four Na+ ions and four nucleotides and periodic boundary conditions were used to mimic an infinite helix. The atoms of the helix and the Na+ ions were assumed to be Lennard-Jones spheres that also carried charges. Stillinger four-point charge model water molecules were used. We carried out five calculations, for 26 and 46 water molecules in B-DNA and 20, 32, and 46 in A-DNA fragments. The arrangements of the Na+ ions are found to have some similarities to those obtained by Clementi and Corongiu. In the calculations with 46 water molecules, we found that two Na+ ions can be bridged by about two water molecules and form a hydrated bound pair, which in turn forms a bridge between the guanine N7 and a near phosphate group. These bound pairs may be important in stabilizing the helix structure of DNA molecules.
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    Biopolymers 23 (1984), S. 313-323 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ethylurea was used to weaken hydrophobic interactions during collagen fibrillogenesis in vitro. Intact and enzyme-digested type I collagen was studied. In all preparations, ethylurea decreased the extent and rate of fibril formation, inhibition being greatest in the enzyme-digested collagens. With intact collagen (and probably also with carboxypeptidasedigested collagen), there was no evidence the ethylurea altered the mechanism of fibril growth; in pepsin-digested collagen, however, the growth mechanism was altered by ethylurea, possibly reflecting a conformational change of the “hydrophobic cluster” in the C-terminal peptide. Such a structural change could occur in a hydrophobic environment once the distal portion of the C-terminal peptide (presumed to be essential for its structural stability) is removed by pepsin. The results further emphasize the importance of hydrophobic interactions in collagen fibril nucleation and growth in vitro.
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  • 54
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    Biopolymers 23 (1984) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 55
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report the crystal-structure analysis of a complex involving the drug proflavine and the two dinucleoside monophosphates cytidylyl-3′,5′-adenosine (CpA) and uridylyl-3′,5′-guanosine (UpG). The planar drug molecule is intercalated between C⃛G and U⃛A Watson-Crick base pairs, in a double-helical fragmentlike arrangement. Sugar conformations at the 3′-ends of the two strands are dissimilar. The backbone conformations fall within the ranges of values noted previously for dinucleoside intercalation complexes, and some correlations involving these are noted. The separation of the two strands and the basic twist angle of 16°, compared to other reported complexes, are indicative of sequence-dependent effects of the drug binding.
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  • 56
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    Biopolymers 23 (1984), S. 1057-1066 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Helical hydrophobic moment ratios, 〈h2〉/〈H2〉, have been evaluated for 34 polypeptides under conditions where the helix content is dictated solely by the short-range interactions operative in aqueous media. The mean-square helical hydrophobic moment is denoted by 〈h2〉, and 〈H2〉 is the averaged of the squared hydrophobicites. This ratio would be one in absence of any correlation in the hydrophobicities of amino acid residues in helices. The 〈h2〉/〈H2〉 tend to be substantially larger than values of the analogous ratio formulated for the mean-square dipole moments of typical synthetic polymers. For 24 of the 34 polypeptide chains considered, 〈h2〉/〈H2〉 is found to be greater than one, indicating a tendency to form helices with amphiphilic character. The ratio is exceptionally large in the case of the δ-hemolysins. It is also large for two other surface-active peptides, for two of the four apolipoproteins examined, and for myohemerythrin. A much smaller 〈h2〉/〈H2〉 is found for melittins. If melittins is to form helices with large 〈h2〉/〈H2〉, the configurational statistics must be governed by effects in addition to those short-range interactions that occur when water is the solvent.
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  • 57
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    Biopolymers 23 (1984) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 58
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformational-energy computations have been carried out for the N-acetyl-N′-methylamides of the Pro-Pro, Pro-Gly, and Gly-Pro dipeptides and of the Pro-Pro-Gly-Pro tetrapeptide, serving as models for the conformational analysis of single-stranded poly(Gly-Pro-Pro). The probability of β-bend formation for the Pro-Gly sequence is very high, viz., 0.72 for the terminally blocked Pro-Gly dipeptide, and rises to 0.86 in the tetrapeptide. The β-bend conformations of the Pro-Gly sequence are of low energy in single-chain poly(Gly-Pro-Pro) as well. The β-bend structure had been postulated earlier to be a requirement for post-translational proline hydroxylation during the biosynthesis of collagen. The present results lend strong support to this proposal by demonstrating that the β-bend structure is energetically favorable and hence can be accommodated easily in single-stranded poly(Gly-Pro-Pro).
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  • 59
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The interaction of Cu(II) with the protamine scylliorhinine Z3 was studied by means of CD measurements. At a 1:1 molar ratio, three complexes are formed. (1) In the pH range 5-6.5, the results suggest the formation of a five-membered chelate ring through the coordination of two nitrogen atoms, the N-terminal and the contiguous peptide nitrogen. (2) At pH ≥ 6.4, there is involvement of the lateral NH2 group of Arg; at pH 6.5-8, the formation of a 3N cupric complex is strongly suggested. (3) At pH ≥ 8, results indicate the formation of a 4N complex as a major species in Cu(II)-Z3 solution. The transformation from a 2N to a 3N complex, and from a 3N to a 4N complex was followed with the help of the σ(αNH2) → Cu(II) charge-transfer dichroic band transitions. At Cu(II):Z3 molar ratios ≥ 2 and at pH 〉 8, a new dichroic band appears, indicating the involvement of the tyrosine residue side chain in metal-ion complexation.
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  • 60
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Studies of the optical birefringence of solutions of acid-soluble collagen from rat-tail tendon at 22°C in the pH range 1.0-6.0 show that collagen exhibits an isotropic to mesophase transition only between pH 2.4 and 3.0 at 10% weight concentration. Such liquid crystalline order is probably essential for the orientation of collagen in a magnetic field. When solutions of neutral salt-soluble collagen were precipitated at pH 7.0 by warming to 37°C (“heat gelling”) in a magnetic field of ca. 20 kG, the resulting fibrils wee oriented perpendicular to the direction of the field. Heat gelling is shown to be a useful technique for maintaining the orientation induced in precursor solutions even after the sample is removed from the magnetic field.
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  • 61
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    Biopolymers 23 (1984), S. 1295-1306 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyamines are ubiquitous cellular components that interacts strongly with nucleic acids. Although many of the interactions of oligocations with DNA can be rationalized with polyelectrolyte theories that treat counterions as point charges, some structural effects are evident. We have explored the effects of polyamine structure on one important aspect of DNA behavior, its thermal melting transition, by using a series of spermidine analogs NH3(CH2)3NH2(CH2)nNH33+, where n varies from 2 to 8 [Jorstad et al. (1980) J. Bacteriol. 141, 456-463]. For spermidine itself, n = 4. Tm for calf-thymus DNA in the presence of each of these analogs, and the other naturally occurring polyamines putrescine2+ and spermine4+, was measured over a wide range of NaCl concentrations and polyamine:DNA phosphate ratios. There are modest, but significant structural effects. particularly with the shorter n = 2 and 3 derivatives, whose geometry my not allow full electrostatic interaction with DNA. Longer analogs, on the other hand, are not much different than spermidine in their effects on Tm, though a moderate maximum occurs at n = 5. Since polyamines are important in the cellular condensation and packaging of DNA, we have also delineated the critical polyamine and salt concentrations that are required to cause DNA aggregation. Here again, there are significant structural effects, which are not easily rationalized by any simple considerations.
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    Biopolymers 23 (1984), S. 1315-1323 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The observed difference between the CD spectrum of B-DNA mononucleosomes and that of free DNA has been attributed to the tertiary structure of the core DNA. This conjecture is tested here. The tertiary structure is modeled as an optical system consisting of two identical, planar, linear retarders rotated with respect to each other. The retarders have the same linear birefringence and linear dichroism as oriented B-DNA. Such an optical system is circularly dichroic. The predicted wavelength dependence and magnitude of the CD are in reasonably close agreement with the experimental results.
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    Biopolymers 23 (1984), S. 1367-1377 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absorption and CD spectra of the complexes of poly(L-arginine) (PLA) and azo dyes have been measured in aqueous solution. On complexation, Blue-shifted additional absorption bands were observed. In the wide pH 4-11 range, induced CD was observed at the visible wavelengths corresponding to the blue-shifted absorption bands. The induced CD arose from the dimeric dye molecules bound to PLA in the α-helical structure. When a modified analysis of induced CE is made by the excition chirality method, the origin of the induced CD can be assigned to the dipole coupling. The PLA-dye complexes showed the counterlockwise (negative, S) chirality of the transition dipole moments of dyes.
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    Biopolymers 23 (1984), S. 1347-1365 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ionization properties of the tyrosyl groups of bovine plasma albumin in various conformational states - the native state (N), the two acid states (F and E), and the state (B) stable at slightly alkaline pH - were studied by means of a stopped-flow-pH-jump technique. The technique allows us to obtain the tyrosyl titration curve in a conformational state that is unstable in the pH region of the titration. The pH jumps from the N and B states to various alkaline pH's, where the tyrosines ionize to bring about a time-dependent increase in absorption at 296 nm, indicating that a number of the tyrosines buried initially become susceptible to ionization as a result of the alkaline transition occurring above pH 10.8. Extrapolation of the observed absorption change to zero time gives a spectrophotometric titration curve in the initial conformational state. Only 30-401% of the 19 tyrosines of the protein can ionize both in the N and the B state at pH 12. The pH jumps from the F and E states, on the other hand, give a decrease in absorption between pH 9 and 11.7, indicating that the tyrosyl groups initially exposed are remarked by refolding after the pH jumps, and the zero-time titration curves show that essentially all the tyrosyl groups ionize normally in these acid states. The results are discussed in relation to the known results of the tyrosyl exposure of the protein measured by other techniques, and the consistency among them demonstrates the effectiveness of the pH-jump titration method. Hydrogen bonding between the abnormal tyrosyl and carboxylate groups as a mechanism to stabilize native albumin is suggested from characteristics of the alkaline transition, which also involves the exposure of the tyrosyl groups, and from the tyrosyl titration curves in the native and acid states.
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    Biopolymers 23 (1984), S. 1137-1139 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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  • 66
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    Notes: Two series of peptides with hydrophobic side chains, Nps-(L-Leu-L-Leu-L-Ala)n-OEt and Nps-(L-Met-L-Met-LLeu)n-OEt (n = 1-6), were synthesized by the fragment condensation method using dicyclohexylcarbodiimide in the presence of N-hydroxysuccinimide. The tripeptide fragments were prepared stepwise by dicyclohexylcarbodiimide-mediated reaction of Nps-amino acids, which were synthesized by an improved rapid procedure.
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    Biopolymers 23 (1984), S. 1457-1463 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dielectric properties of sonicated calf-thymus DNA sodium salt in aqueous solutions have been studied in the frequency range from 40 MHz to 2 GHz by time domain spectroscopy (TDS). A dielectric dispersion not previously reported was found, which has a characteristic frequency of about 150 MHz. All of the dielectric parameters are insensitive to the size of DNA fragments and to helix-to-coil transitions. The study of this dispersion as a function of DNA concentration and temperature allows us to conclude that it may be due to counterion fluctuation on short sections, probably in a direction transverse to the macromolecular axis.
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    Biopolymers 23 (1984), S. 1465-1479 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of L-adrenaline (epinephrine) in the presence of [Fe(tetpy)(OH)2]+ ions bound to poly(L-glutamate) or to poly(D-glutamate) has been studied at pH 7 (tetpy = 2,2′:6′,2″:6″,2‴-tetrapyridyl). Electron transfer from the substrate to the central metal ion, which is rate-determining, proceeds stereoselectively only when extensive and possibly specific interactions between adrenaline and the peptidic residues of the ordered polymer in the close environment of the active sites occur. This ensures different steric constraints for the two diastereomeric precursor complexes, which are thought to affect the separation and orientation of the redox centers differently, leading to the observed phenomena. Some data on the catalytic oxidation of L-dopa(3,4-dihydroxyphenylalanine) are also presented, showing stereoselective effects similar to those observed with L-adrenaline, despite the diverse distance of the chiral center from the reacting OH groups. A mechanistic interpretation of the results is discussed in the light of a few general considerations concerning the structural features of the catalytic systems. Possible explanations for the finding that stereoselectivity occurs at the expense of the efficiency of catalysis are also considered.
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    Biopolymers 23 (1984), S. 1917-1930 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solution-phase Raman spectra of diastereomeric alanyl dipeptides, D-Ala-L-Ala and L-Ala-L-Ala, and various mono- and dideuterated isotopomers in H2O and D2O, are reported. Spectral differences between the diastereomeric forms are interpreted, using the Raman analog of the coupled oscillator model, in terms of geometric differences between certain vibrations in the diastereomeric forms. Application of the coupled-oscillator formalism allows the determination of a dihedral angle between the coupling vibrations. The results are compared with vibrational coupling employed by other workers in the determination of the vibrational spectra of peptides.
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    Biopolymers 23 (1984), S. 1951-1960 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational equilibria of five β-cellobiose conformers have been studied theoretically in 10 solvents. The stability of the conformers in dilute solution has been compared by using the method that has already been tested for 2-methoxytetrahydropyran, β-maltose, and D-glucose. The solvation energy consists of electrostatic, dispersion, and cavity terms which have been determined from the properties of the solute calculated by the PCILO quantum-chemical method and physicochemical properties of the solvents. The calculated abundance of conformers depends on the solvent (e.g., in dioxane C1:C2:C3:C4:C5 = 60.0:34.1:2.9:2.0:1.0; in dimethylsulfoxide, 75.5:22.1:1.8:0.5:0.2; and in water, 82.2:16.2:1.3:0.2:0.1). The results obtained indicate that the preponderant conformer in the aqueous solution is similar to the one adopted by β-cellobiose in the crystalline form. The role of individual contributions to the solvation energy have been analyzed. Based on the determined abundance of conformers, averaged residual optical activity and nmr parameters have been calculated and compared with observable properties. The marked differences observed between solvent-induced conformational changes for β-cellobiose and β-maltose have been discussed from the viewpoint of the solubility of the cellulose.
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  • 71
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    Topics: Chemistry and Pharmacology
    Notes: With a view to understanding the role of hydrogen bonds in the recognition of nucleic acids by proteins, hydrogen bonding between the bases and base pairs of nucleic acids and the amino acids (Asn, Gln, Asp and Glu, and charged residues Arg+, Glu-, and Asp-) has been studied by a second-order perturbation theory. Binding energies have been calculated for all possible configurations involving a pair of hydrogen bonds between the base (or base pair) and the amino acid residue. Our results show that the hydrogen bonding in these cases has a large contribution from electrostatic interaction. In general, the charged amino acids, compared to the uncharged ones, form more stable complexes with bases or base pairs. The hydrogen-bond energies are an order of magnitude smaller than the Coulombic interaction energies between basic amino acids (Lys+, Arg+, and His+) and the phosphate groups of nucleic acids. The stabilities of the complexes of amino acids Asn, Gln, Asp, and Glu with bases are in the order: G-X 〉 C-X 〉 A-X U-X or T-X, and G · C-X 〉 A · T(U)-X, where X is one of these amino acid residues. It has been shown that Glu- and Asp- can recognize guanine in single-stranded nucleic acids; Arg+ can recognize G · C base pairs from A · T base pairs in double-stranded structures.
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    Biopolymers 23 (1984) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 23 (1984), S. 2195-2210 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of histone H1 on the conformation and stability of control and acetylated HeLa high-molecular-weight chromatin that had been stripped of H1 and nonhistone proteins was compared by circular dichroism (CD) and thermal denaturation measurements. Two different preparations of H1, originating from rat thymus and chicken erythrocyte, were used in the reconstitution studies. The control and acetylated stripped chromatin had identical CD and thermal denaturation properties, as did their reconstitutes with rat thymus H1. Reconstitutes of the two chromatins with chicken erythrocyte H1 had similar CD properties, but thermal denaturation studies showed that the acetylated reconstitute was destabilized compared to the control reconstitute. Reconstitutes of both chromatins with chicken erythrocyte H1 had a more condensed and stabilized structure than the reconstitutes with rat thymus H1. Thus, acetylation caused a decrease in the stability of chromatin in the presence of erythrocyte H1, but more marked differences were detected in the structure of stripped chromatin after reassociation with different H1 preparations.
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  • 74
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    Topics: Chemistry and Pharmacology
    Notes: Human fibrinogen was treated with thrombin in the presence of fibrinoligase (Factor XIIIa) and calcium ion at pH 8.5, ionic strength 0.45, and the ensuing polymerization was interrupted at various time intervals (t) both before and after the clotting time (tc) by solubilization with a solution of sodium dodecyl sulfate and urea. Aliquots of the solubilized protein were subjected to gel electrophoresis on polyacrylamide gels after disulfide reduction by dithiothreitol and on agarose gels without reduction. The degree of γ-γ ligation was determined from the former. The latter provided the size distribution of ligated end-to-end sequences produced by splitting the ligated staggered overlapped oligomers down the middle, for degrees of polymerization, x, from 1 to 10. Addition of fibrinoligase (in which the activating thrombin had been inhibited by p-nitrophenyl-p′-guanidinobenzoate, NPGB) to Kabi fibrinogen showed the presence of small amounts of ligatable oligomers. Addition of fibrinoligase to a polymerizing mixture in which the action of thrombin had been stopped before clotting by NPGB produced the same distribution of ligated end-to-end sequences that was obtained when fibrinoligase was originally present, at least for reaction times up to 0.7 of the clotting time. The kinetics of γ-γ ligation by fibrinoligase acting on a polymerized mixture stabilized by NPGB were followed. The reaction was first order in the concentration of ligatable γ-γ junctions and the initial velocity was proportional to the enzyme concentration. The time evolution of size distribution of ligated end-to-end sequences agreed with a theory based on random ligation of ligatable junctions.
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    Biopolymers 23 (1984), S. 201-212 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A mean-square helical hydrophobic moment, 〈h2〉, is defined for polypeptides in analogy to the mean-square dipole moment, 〈μ2〉, for polymer chains. For a freely jointed polymer chain, 〈μ2〉 is given by Σmi2, where mi denotes the dipole moment associated with bond i. In the absence of any correlations in the hydrophobic moments of individual amino acid residues in the helix, 〈h2〉 is specified by ΣHi2, where Hi denotes the hydrophobicity of residue i. The tendency for correlations in orientations of residue hydrophobic moments in helices therefore dictates the size of 〈h2〉/〈H2〉, where 〈H2〉 denotes the average value of ΣHi2 for all helices. The value of 〈h2〉/〈H2〉 will be greater than one in amphiphilic helices. A necessary prerequisite for this diagnostic usage of 〈h2〉/〈H2〉 is that the residue hydrophobic moment be oriented prependicular to the principal axis of the helix. Matrix-generation schemes are formulated that permit rapid evaluation of 〈h2〉 and 〈H2〉. The behavior of 〈h2〉/〈H2〉 is illustrated by calculations performed for model sequential copolypeptides.
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    Biopolymers 23 (1984), S. 271-285 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report a calculation of the distribution of small ions around a charged cylinder representing a polyelectrolyte molecule in solution. The Monte Carlo method of Metropolis, Rosenbluth, and Teller was used to avoid the inaccuracies known to be associated with the Poisson-Boltzmann equation. The systems examined contained a long polyelectrolyte cylinder with charge parameter, χ, equal to 4.2, corresponding approximately to a DNA molecule. In one model, the cylinder had charges on its axis and an exclusion radius to the center of the small ions equal to 10 Å, while the small ions had various radii in the range from 1 to 10 Å and one or two protonic charges. Various systems were studied; some had one species of small ion alone, others had mixtures of different types. The results showed good agreement with the solution of the Poisson-Boltzmann equation when only the species with 1-Å radius was present, but considerable discrepancies appeared with larger ions as a result of excluded volume interactions between the latter. Deviations from the Poisson-Boltzmann equation also appeared when both positive and negative small ions were present; the deviations were in the direction of a higher concentration of both counter- and co-ions, but particularly co-ions, close to the polyelectrolyte. In another model, the charges were arranged along two helices on the surface of the cylinder; the resulting radial distribution of small ions was not much different from that found when the charges were situated on the axis. In all cases there was a striking accumulation of counterions in a layer of concentration exceeding 1 mol/L at the surface of the polyion.
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    Biopolymers 23 (1984), S. 337-351 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Brillouin scattering was used to determine the longitudinal acoustic velocity along the axis of collagen fibers as the relative humidity decreased from 95 to 0%. Between 0 and 86%, the velocity decreased linearly at a modest rate. Above 86%, the decrease was steep. The changing mass of the absorbed water accounts for most of the velocity change in the lower humidity range. The remaining deviation is probably due to variation of the elastic coupling between molecules. At low humidity, the adsorbed water is known to be attached to the collagen molecules, whereas the additionally adsorbed water at high humidity has the properties of bulk liquid. The high-humidity sonic velocity variation is ascribed to the presence of free water. It is possible to identify the five water regimes of Pineri et al. [(1978) Biopolymers 17, 2799-2815] with the variations of the sonic velocity with water content.
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    Biopolymers 23 (1984), S. 353-361 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optical rotation, viscosity, and density studies are reported on solutions of α-gelatin in solvent mixtures of water and various monohydric alcohols. Reversion to the collagen fold by the protein is shown to be order in all cases, but changes in magnitude as a function of concentration of the particular alcohol are observed. The structuring effects of the alcohol on water are seen to be reflected in the extent of helix regeneration by the protein. Shorter chain alcohols appear to influence the initial rate of reversion by direct interaction with the protein.
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    Biopolymers 23 (1984) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 80
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have recorded high-resolution 13C-nmr spectra of collagen fibrils in the solid state by the cross-polarization-magic-angle-spinning(CP-MAS)method and analyzed the spectra with reference to those of collagenlike polypeptides. We used two kinds of model polypeptides to obtain reference 13C chemical shifts of major amino acid residues of collagen (Gly, Pro, Ala, and Hyp): the 31-helical polypeptides [(Gly)nII, (Pro)nII, (Hyp)n, and (Ala—Gly—Gly)nII], and the triple-helical polypeptides [(Pro—Gly—Pro)n and (Pro—Ala—Gly)n]. Examination of the 13C chemical shifts of these polypeptides, together with our previous data, showed that the 13C chemical shifts of individual amino acid residues are the same, within experimental error (±0.5 ppm), among different polypeptides with different primary sequences, if the conformations are the same. We found that the 13C chemical shifts of Ala residues of the 31-helical (Ala—Gly—Gly)n and triple-helical (Pro—Ala—Gly)n are significantly displaced, compared with those of the α-helix, β-sheet, and silk I form, and can be utilized as excellent probes to examine conformational features of collagen-like polypeptides. Further, the 13C chemical shifts of Gly and Pro residues in the triple-helical polypeptides are substantially displaced from those found in (Gly)nII and (Pro)nII of the 31-helix, reflecting further conformational change from the 31-helix to the supercoiled triple helix. In particular, the 13C chemical shifts of Gly C = O carbons of the triple-helical polypeptides are substantially displaced upfield (4.1-5.1 ppm), with respect to those of the 31-helical polypeptides. These displacements are interpreted by that Gly C = O of the former is not involved in NH … O = C hydrogen bonds, while this carbon of the latter is linked by these kinds of hydrogen bonds.On the basis of these 13C chemical shifts, as reference data for the collagenlike structure, we were able to assign the 13C-nmr peaks of Gly, Ala, Pro, and Hyp residues of collagen fibrils, which are in good agreement with the values expected from the model polypeptides mentioned above. We also discuss a plausible conformational change of collagen fibrils during denaturation.
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  • 81
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    Biopolymers 23 (1984), S. 2349-2360 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dermorphin (Tyr—D-Ala—Phe—Gly—Tyr—Pro—Ser—NH2), a potent natural peptide opioid, its synthetic L-Ala2 analog, and all the N fragments from the tripeptide (Tyr—D-Ala—Phe—NH2) to the parent hexapeptide amide were characterized for the first time by means of proton nmr spectroscopy at 11.74 T. Assignments of most protons of dermorphin were facilitated by the study of the N-terminal fragments. Comparison of spectroscopic parameters with relative pharmacological activity is proposed as a possible means of studying flexible agonists in solution.
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  • 82
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    Biopolymers 23 (1984), S. 2715-2724 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The magnetic circular dichroism (MCD) of adenine, hypoxanthine, and guanosine 5′-diphosphate reveals that, for each species, the uv-absorption band near 200 nm is composed of at least two electronic transitions. The theory of MCD shows that the dipoles of these transitions are not parallel to one another. The transitions are assigned within the framework of current theories of the electronic structure of the purines. Knowledge of the presence of more than one transition within an absorption envelope is important in interpreting the corresponding natural CD of DNA and RNA.
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  • 83
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    Biopolymers 23 (1984), S. 2963-2966 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 84
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    Biopolymers 23 (1984), S. 719-734 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The aggregation of poly(γ-benzyl-α,L-glutamate) and its enantiomer in toluene has been investigated by following the viscosity as a function of temperature, concentration, molecular weight, molecular-weight distribution, helix chirality, and shear rate. The temperature and concentration data for a 138,000-molecular-weight sample was fitted to an open, reversible end-to-end aggregation model. The aggregation numbers resulting from this fit were consistent with the sudden onset in non-Newtonian flow resulting from only a 0.2-wt% increase in concentration. The association equilibrium constant was then used to predict viscosity for comparison with other data, in particular, the effect of molecular weight and molecular-weight distribution. A mixture of right-and left-handed helices showed the aggregation was not chiral selective. The stiffness of end-to-end aggregated (hydrogen-bonded) molecules differed little from their covalent counterparts, at least below a molecular weight of ∼106. We conclude that polybenzylglutamate aggregation in toluene can be described by an open end-to-end aggregation model.
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  • 85
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    Biopolymers 23 (1984), S. 797-808 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Quasielastic light-scattering (QELS) studies were performed on a monodisperse preparation of dinucleosomal-sized DNA having an average of 375 base pairs. The QELS data were obtained at several time intervals at each angle examined over the range 30° 〈 θ 〈 60° for the ionic strength solvents 500, 50, 10, and 1 mM in KCl. What results from this study is that two relaxation domains persist over the entire ionic strength range where the “splitting” between these two domains increases as the ionic strength is lowered. The ordinate intercept of Dapp vs Cp/2Cs, where Cp is the polyion concentration and Cs is the added salt concentration, is shown to give the “true” hydrodynamic value for the diffusion coefficient. The “splitting phenomenon” is interpreted in terms of two models currently in vogue: small ion-polyion coupled modes and translational-rotational coupled modes for rigid rods in congested solutions. Although neither model is in perfect agreement with the experimental results, the small ion-polyion coupled mode theory appears to provide a better quantitative description of the observations.
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  • 86
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    Biopolymers 23 (1984) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 87
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    Biopolymers 34 (1994), S. 11-20 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: αD-N-acetyl neuraminic acid (Neu5Ac, sialic acid) is a commonly occurring carbohydrate residue in various cell surface glycolipids and glycoproteins. This residue is linked terminally or internally to Gal residues via an α(2 → 3) or α(2 → 6) linkage. In the cell surface receptor, sialyl-LewisX, a terminal α(2 → 3) linkage is present. Previous studies from our laboratory have shown that in solution LewisX adopts a relatively rigid structure. In order to model the Neu5Ac residue, vacuum molecular dynamics of this monosaccharide were compared with simulations that explicitly include solvent water. The dynamical average of the monosaccharide conformation obtained from the two simulations was similar. Vacuum calculations for the disaccharide Neu5Ac α(2 → 3) Gal β-O-methyl show that a number of low energy minima are accessible to this disaccharide. Molecular dynamics simulations starting from the low energy minima show conformational transitions with a time scale of 10-50 ps among several of the minima while large barriers between other minima prevent transitions on the time scale studied. Simulations of this disaccharide in the presence of solvent show fewer conformational transitions, illustrating a dampening effect of the solvent that has been observed in some other studies. Our results are most consistent with an equilibrium among multiple conformations for the Neu5Ac α(2 → 3) Gal β linkage. © 1994 John Wiley & Sons, Inc.
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  • 88
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The properties of collagen are affected by the replacement of Pro by imino acid analogues. The structural effect of the low-level local substitution of L-azetidine-2-carboxylic acid (Aze) has been analyzed by computing the energy of CH3CO-(Gly-Pro-Pro)4-NHCH3 triple helices in which a single residue of one strand has been replaced by Aze. When Aze is in position Y of a (Gly-X-Y) unit, low-energy local deformations are introduced in the triple helix, i.e., it becomes more flexible. On the other hand, the flexibility of the triple helix is not increased with Aze in position X. The energy of the triple helix to coil transition is not changed significantly by this amount of substitution. In an earlier study, we have demonstrated that the regular substitution of Aze in every tripeptide distorts or destabilizes the triple helix to a large extent [A. Zagari, G. Némethy, & H. A. Scheraga (1990) Biopolymers, Vol. 30, pp. 967-974 ]. Thus, it appears that a high level of substitution is required to cause the observed chemical and biological effects of Aze on collagen. © 1994 John Wiley & Sons, Inc.
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  • 89
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    Biopolymers 34 (1994), S. 357-364 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A dielectric relaxation peak due to bound water of globule proteins in aqueous solution was observed at first by the use of a time domain reflectometry. This peak locates around 100 MHz as well as that of the aqueous DNA solution and the moist collagen, and has a relaxation strength in proportion to surface of the globule protein except for trypsin and pepsin of hydrolase. It is suggested that this peak is caused by orientation of bound water molecules on the protein surface. The number of bound water molecules estimated is in good agreement with that obtained by other method such as x-ray analysis. The solution exhibits another peak below 100 MHz, which is caused by the rotation of globule protein supplemented by migration of the counterion. Its relaxation time is completely proportional to the molecular weight of the protein. © 1994 John Wiley & Sons, Inc.
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  • 90
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    Biopolymers 34 (1994), S. 393-401 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The enthalpies of interactions of porcine arterial elastin with alkali metal and alkali earth halides and sulphates were investigated by means of flow microcalorimetry and the stoichiometry measured using radiotracer techniques. In aqueous solutions, all alkali earth halides interacted exothermically at concentrations ranging from 0.01 to 2.5M. All the alkali metal halides, particularly NaCl, exhibited complex concentration-dependent interactions, exothermic at low concentrations and endothermic at high concentrations. Both the anion and cation contributed to the response, although the anion seemed to dominate. SO42- interacted most strongly of the anions tested. All interactions were reversible in the sense that repeat experiments gave identical results, but the enthalpy of “adsorption” was generally different from that of “desorption.” The enthalpy of interaction depended on the conformation of the elastin in a salt-specific manner. For example, CaCl2 and MgCl2 interacted similarly in water but very differently in 1 : 1 water : methanol. © 1994 John Wiley & Sons, Inc.
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  • 91
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    Biopolymers 34 (1994), S. 435-442 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photophysical behavior of protoporphyrin IX (P) and 1-naphthylacetic acid (N), covalently bound to ε-amino groups of poly (L-lysine) (PL), was investigated by steady-state and time-resolved fluorescence as a function of pH. Within the whole range of pH explored, i.e., 7-11, exciplex emission is minor and nearly pH independent. Fluorescence quantum yields, decay time measurements, and transient absorption spectra suggest that quenching of the excited naphthyl chromophore chiefly occurs by interconversion to the triplet state when the sample is randomly coiled and by intramolecular electron transfer (ET) from ground-state porphyrin when the polypeptide is in α-helical conformation. The kinetic law, based on a two-state model for the polymeric matrix, is presented. The specific rate constant of photoinduced ET is 3.1 · 107 s-1 (25°C), in excellent agreement with that obtained by taking simply into account the lifetimes of naphthalene fluorescence in α-helical PNPL and NPL (pH 11). The relaxation time of the helix-coil transition was found to be definitely shorter than 20 ns. © 1994 John Wiley & Sons, Inc.
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  • 92
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aggregation of filipin in aqueous medium and filipin-induced changes in cholesterol micelles have been studied using intensity and dynamic light scattering. The dependencies of filipin aggregate dimensions on concentration, solvent, and temperature were studied, and revealed that the aggregates do not have a well-defined geometry, i.e., a critical micelle concentration cannot be detected and stable structures are not formed. The aggregates are of size Rg ≈ 110 nm and Rh ≈ 63 nm, referring to the radius of gyration and hydrodynamic radius, respectively. In the concentration range studied (1 μM 〈 C 〈 30 μM), a low molecular weight species (monomer/dimer) is always present together with the aggregates. In ethanol/ water mixtures, large (Rg ≈ 500 nm), narrow distribution aggregates are formed in the water volume fraction range 0.45 〈 ΦH2O 〈 0.65. Aggregation also occurs on changing the temperature; In the range 7-37°C, smaller aggregates (10-30 nm) form and the process is only partially reversible.No pronounced effect of filipin on the structure of the cholesterol micelles was observed (a small increase in Rg and Rh is noted). These results rule out any “specificity” for the filipin interactions with cholesterol, which has been considered a key event in the filipin biochemical mode of action. A reevaluatiori Of this question is suggested and some alternatives are advanced. © 1994 John Wiley & Sons, Inc.
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  • 93
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    Biopolymers 34 (1994), S. 489-505 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polypeptide α-carbon backbones were modeled as freely rotating chains made up of spherical monomers. The monomers were assigned an abstract binary “hydrophobicity” property that could be either present or absent. Under the assumption that “hydrophobic” residues tend to cluster together, away from the polar solvent, three-dimensional conformations of random copolymers of “hydrophobic” and “hydrophilic” monomers were calculated by a novel algorithm based on distance geometry techniques. The simulated molecules were globular and compact, in shape, and possessed distinct hydrophobic cores, indicating that our method was capable of reproducing some of the important global features of real polypeptides. © 1994 John Wiley & Sons, Inc.
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  • 94
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    Biopolymers 34 (1994), S. 559-563 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 95
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The linear nonapeptide hormone bradykinin (Arg1-Pro2-Pro3-Gly4-Phe5-Ser6-Pro7-Phe8-Arg9) is involved, either directly or indirectly, in a wide variety of physiological processes, particularly pain and hyperanalgesia. Additional evidence suggests that bradykinin also plays a major role in inflammatory response, asthma, sepsis, and symptoms associated with the rhinoviral infection. It has long been speculated that a β-turn at the C-terminus of bradykinin plays a major role in the biological activity of the neuropeptide. The β-turn forming potential of bradykinin in three vastly different local chemical environments, DMSO, 9 : 1 dioxane/water, and in the presence of 7.4 mM lyso phosphatidylcholine micelles, was investigated using two-dimensional homonuclear nmr experiments coupled with simulated annealing calculations. The results of these investigations show that in all three systems residues 6-9 of the C-terminus adopt very similar β-turn like structures. These results suggest that the β-turn at the C-terminus of bradykinin is an important secondary structural feature for receptor recognition and binding. © 1994 John Wiley & Sons, Inc.
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  • 96
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using dynamic light scattering (DLS), we have measured the diffusion coefficient and internal motions of narrow topoisomer distributions of pUCl8 DNA (2687 base pairs) as a function of linking number. The topoisomer distributions were prepared by C-18 reversed phase high performance liquid chromatography separation of topoisomerase I/ethidium-generated topoisomer families. The measured diffusion coefficients agree well with those predicted by a Monte Carlo model for the generation of equilibrium ensembles of DNA topoisomers of defined linking number. The only parameters used in the model were the bending persistence length, torsional rigidity, and hydrodynamic radius of DNA known independently from other techniques. Two different values for the torsional rigidity, α = 4 · 10-12 and 8.8 · 10-12 dyn cm, were used. Intrachain interactions in the DNA were taken into account by using an “effective DNA radius,” which was varied between rDNA = 1-8 nm. The best agreement between the measured and calculated values was obtained for α = 4 · 10-12 dyn cm, rDNA = 4 nm. The internal motions of the DNA topoisomers were characterized by the amplitude of the fast relaxation of the DLS autocorrelation function. Our earlier result that supercoiling leads to a decrease in the amplitude of internal motion was confirmed. In addition, we see a characteristic maximum of the internal motion amplitude at a superhelix density of σ = -0.03. The maximum occurs in the same range as a structural transition in pUC8 dimers previously described by L. Song et al. (1990 J. Mol. Biol. 214, 307-326). © 1994 John Wiley & Sons, Inc.
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  • 97
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of a series of 2-phenylquinoline derivatives with RNA was investigated by means of viscometric, pKa, spectroscopic, binding, Tm, and kinetic methods. Compounds 1,2, and 3 have a piperazyl substituent at the para, meta, or ortho position, respectively, while 4 has an unsubstituted phenyl ring. The pKa results suggest that 1 has three charges, 2 and 3 have more than two charges, and 4 has two charges at pH 6.2. Spectroscopic and Tm results indicate that 1 binds more strongly to RNA than 2-4. Kinetic and modeling results indicate that 1 is a threading intercalator while 2 and 4 are classical intercalators. All experimental results indicate that 3, which has a large twist between the phenyl and quinoline rings, binds weakly with RNA. © 1994 John Wiley & Sons, Inc.
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  • 98
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Urethane bonds, derived from the hydroxyl group of the tyrosine side chain, have been investigated as a new type of amide bond mimetic in the design of pseudopeptides. The structure of a representative cyclic pseudotetrapeptide that consists of an  -  Ala  -  Tyr(urethane) Ala  -  Tyr (urethane) sequence fused into a rigid ring has been studied in the solid state by x-ray crystallography and in solution by two-dimensional nmr techniques. The cyclic pseudotetrapeptide has an oblong shape. The backbone urethane bonds assume a trans-trans conformation. The carbonyl groups in the ring have an alternating pattern of down, up, down, up with respect to the average ring plane. Solution nmr studies give observed nuclear Overhauser effects and coupling constants largely in agreement with the crystal structure. However, in solution the observed structure is likely to be conformationally averaged, and in the averaged structure, the urethane bond is perpendicular to the plane of the aromatic ring of the tyrosine, while in the crystal it is close to this plane. These differences may be explained by intermolecular hydrogen-bonding interactions. Four aspects of the conformation of the cyclic pseudotetrapeptide were investigated in detail: the tyrosine residue with the attached side-chain urethane bond (the tyrosine-urethane unit), the conformation of the two urethane backbone linkages, the conformation of the two conventional peptide bonds within this unusual ring structure, and the tight turns within the cyclic pseudotetrapeptide. The conformation of the tight turns present in the cyclic pseudotetrapeptide is very similar to that of a β-bend of type II. Intermolecular hydrogen bonding, joining adjacent layers of the cyclic pseudotetrapeptide in the solid state, resemble a parallel β-pleated sheet. The presence of these structural motifs in the cyclic pseudotetrapeptide indicates that the tyrosine urethane unit may find applications in peptide and protein engineering. © 1994 John Wiley & Sons, Inc.
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  • 99
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    Biopolymers 34 (1994), S. 415-433 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have developed a model for the simulation of the structure and dynamics of covalently closed circular DNA. It is based on the generalization of the original Brownian dynamics algorithm [D. L. Ermak & J. A. McCammon (1978) Journal of Chemical Physics, Vol. 69, pp. 1352-1359; M. Fixman (1978) Journal of Chemical Physics, Vol. 69, pp. 1527-1537] developed for bead-chain models of linear DNA to a second order numerical integration [ A. Iniesta & J. Garcia de la Torre (1990) Journal of Chemical Physics.Vol. 92, pp. 2015-2018], which we extended here to accommodate the torsional potential. The topological constraints and torsional-bending coupling in superhelical DNA are explicitly taken into account in this work by adapting a model for torsional-bending motion of linear DNA developed by Allison et al. [S. A. Allison, R. Austin, & M. Hogan (1989) Journal of Chemical Physics, Vol. 90, pp. 3843-3854].The dynamics of closed DNAs of 1124 base pairs (380 nm in length) were simulated up to ≅ 40 μs for linking number differences ΔLk between 0 and -6. Each bead in the model corresponded to 37 base pairs.For -2 ≅ ΔLk -6, the writhing number appears to decay to a limiting negative value with a single exponential law, and the relaxation time of this decay, starting from a planar closed molecule, is 3-6 μs. For the trajectories studied here, the formation of the superhelix proceeds through an initial phase of 1-2 μs where a toroidal-like structure is formed, which then converts into an interwound structure starting from a random nucleation site. For one simulation at ΔLk = -6, a branched structure was observed that did not convert into the linear interwound form for the time course of the simulation (31 μs).A verification of the simulation was performed by computing the diffusion coefficient of the 1124 base pair circle through known hydrodynamic formulas or through the center of mass displacement, and comparing these theoretical values with diffusion coefficients previously measured by dynamic light scattering. © 1994 John Wiley & Sons, Inc.
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    Biopolymers 34 (1994), S. 443-445 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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