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  • Chemistry  (101,922)
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  • 101
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 238 (1996), S. 55-62 
    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: Tetrahydrofuran (THF) wurde mit dem Initiatorsystem 4,4′-Azobis(4-cyanopentanoylchlorid)/SnCI4 kationisch polymerisiert. Das gebildete Poly(THF) mit je einer Azogruppe in der Hauptkette wurde als Initiator für die Polymerisation von Styrol (S) und Methylmethacrylat (MMA) bei 70°C eingesetzt. Die dabei entstandenen PTHF-PS-PTHF- bzw. PTHF-PMMA-Blockcopolymeren wurden mittels Fällungsfraktionierung, spektroskopischen Methoden und Viskositätsmessungen charakterisiert.
    Notes: The cationic polymerization of tetrahydrofuran (THF) initiated by 4,4′-azobis(4-cyanopentanoyl chloride) (ACPC) and SnCI4 is described. Poly(THF) samples possessing azo gorups in the main chain thus obtained were used as initiator in the polymerization of styrene (S) and methyl methacrylate (MMA) at 70°C to yield PTHF-PS-PTHF and PTHF-PMMA block copolymers. Characterization of the block copolymers was carried out by fractional precipitation, spectroscopic methods and viscosity measurements.
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  • 102
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 238 (1996), S. 129-141 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Wirkung von aliphatischem Korrosionsschutzöl auf das Aushärte- und Abbauverhalten eines ölkompatiblen Epoxidharzklebers wurde mittels Differentialkalorimetrie (DSC), Fourier-Transformations-Infrarot-Spektroskopie (FTIR) und Thermogravimetrie (TGA) untersucht. Die Ergebnisse der DSC- und FTIR-Messungen deuten darauf hin, daß die Härtungsgeschwindigkeit des untersuchten Epoxid-Systems durch das Vorhandensein des Öls nur wenig beeinflußt wird. Dennoch bestätigt das Absinken der exothermen Härtungskurve, begleitet von einer Verbreiterung des Glasübergangstemperaturbereichs, daß das Öl den Aushärtemechanismus beeinflussen kann und in der Lage ist, die Struktur des gehärteten Harzes zu verändern. Außerdem geht aus den TGA-Messungen hervor, daß die Temperaturbeständigkeit des Harzes sich in Gegenwart des Öls verschlechtert; dies wird auf Veränderungen in der Struktur und im Abbaumechanismus des Epoxid-Systems zurückgeführt.
    Notes: The effect of aliphatic slushing oil on the curing and degradation behavior of an oil-accommodating epoxy adhesive is studied by using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). The results of FTIR and DSC indicate that the curing rate of the tested epoxy system is little affected in the presence of the oil. However, the decrease of the curing exotherm accompanied with a broadening of the glass transition confirms that the oil can affect the curing mechanisms and may change the structure of the cured resin. Additionally, it is evident from the TGA results that the thermal resistance of the resin deteriorates in the presence of the oil, which is attributed to the changes in the structure and the degradation mechanism of the epoxy system.
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  • 103
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 239 (1996), S. 1-12 
    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 elektrochemische Polymerisation von Pyrrol-2-aldehyd-azin, 2,2′-[1,4-Phenylenbis(nitrilomethylidyn)]dipyrrol und 2,2′-[1,4-Biphenylylenbis(nitrilomethylidyn)]dipyrrol läuft als anodische Fällungspolymerisation ab. Monomere und Polymere wurden voltammetrisch unter Verwendung von Platin- und “Paste-carbon”-Elektroden untersucht. Die Ergebnisse stimmen mit MO-Berechnungen überein, wobei die Reaktivität der Monomeren nach Hückel abgeschätzt wurde.
    Notes: The electrochemical polymerization of some Schiff's base-type monomers like pyrrole-2-aldehyde azine, N,N′-di(2-pyrrolylmethylene)-1,4-diaminobenzeneSystematic name: 2,2′-[1,4-phenylenebis(nitrilomethylidyne)]dipyrrole., and N,N′-di(2-pyrrolylmethylene)-4,4′-diaminobiphenylSystematic name: 2,2′-[4,4′-biphenylylenebis(nitrilomethylidyne)]dipyrrole. proceeds as a precipitating polymerization to the anodic compartment. The voltammetric study of monomers and polymers using Pt electrodes and paste-carbon electrodes were carried out. The results are in agreement with the MO calculations using the Hückel approximation for evaluating of the reactivity of the monomers.
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  • 104
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 239 (1996), S. 33-41 
    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 neuartige dikationische Komplex [dppfNi(MeCN)4][BF4]2 (dppf = 1,1′-Bis(diphenylphosphin)ferrocen) zeigte in Anwesenheit von Diethylaluminiumchlorid (AIEt2CI) hohe Aktivität für die Polymerisation von 1,3-Butadien. Reaktionsdauer, Temperatur und das Aluminium/Nickel-Verhältnis wurden auf maximale Aktivität und Selektivität optimiert. Umsätze über 90% konnten erreicht werden. Im Vergleich zu Polybutadienen, die mit anderen Nickel-Phosphin-Systemen hergestellt wurden, zeigten die synthetisierten Polybutadiene höhere cis-1,4-Anteile (〈80%) und eine geringe Bildung von 1,2-Einheiten (2%). Alle Polymeren hatten niedrige mittlere Molekulargewichte (Mw 〉 11 800).
    Notes: The new dicationic nickel complex [dppfNi(MeCN)4][BF4]2 (dppf = 1,1′-bis(diphenylphosphino)ferrocene) in the presence of diethylaluminium chloride (AIEt2CI) exhibited high activity on the 1,3-butadiene polymerization. Reaction time, temperature and aluminium/nickel molar ratio were optimized in order to achieve maximum activity and selectivity. Conversions higher than 90% were obtained in contrast to other nickel-based systems using phosphine ligands, the resulting polybutadiene showed high cis-1,4 (〈80%) content and only small amount of 1,2-units (2%). All polymers presented low molecular weights (Mw 〉 11 800).
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  • 105
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Bei der Bestrahlung von Polymethylmethacrylat (PMMA) mit Röntgensynchrotronstrahlung ändert sich die chemische Struktur des Polymeren. Die Ergebnisse der analytischen Untersuchungen dieser Arbeit weisen darauf hin, daß neben einem Abbau der Polymerketten auch einzelne Esterseitengruppen abgespalten werden. Durch die Bestrahlung entstehende Langkettenverzweigungen wurden bei PMMA nicht gefunden. Dadurch unterscheiden sich die physikalischen und chemischen Eigenschaften des bestrahlten Polymeren von denen des unbestrahlten.
    Notes: The irradiation of poly(methyl methacrylate) changes the chemical constitution of the polymer. In addition to a decrease in molar mass further radiation-induced radical reactions cause changes in the chemical constitution of the polymer. Analysis of the reaction products shows that formation of long-chain branching can be excluded. Along with degradation of the chain lengths, ester groups in the side chains are attacked. The result is a modified polymer with a physical and chemical behaviour different from that of the starting polymer.
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  • 106
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 239 (1996), S. 133-149 
    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 Zähigkeit von Polyarylaten wurde durch den Einbau von 4,4′-Thiodiphenol und Bisphenol A, die in der wäßrigen Phase einer Grenzflächenpolykondensation vorgelegt wurden, erhöht. Die modifizierten Polyarylate besitzen leicht erniedrigte Zugfestigkeiten und Zugmoduli, aber aufgrund der Flexibilität der eingebauten Segmente stark erhöhte Izod-Schlagzähigkeiten. Darüber hinaus bleiben die guten thermischen Eigenschaften der Polyarylate nach der Modifizierung erhalten, so daß die hergestellten Materialien auch für Anwendungen mit sehr hohen Anforderungen an die thermische Belastbarkeit geeignet sind.
    Notes: The toughness of polyarylates was improved by incorporation of 4,4′-thiodiphenol and bisphenol A, being introduced in the aqueous phase of an interfacial polycondensation reaction. The modified polyarylates possessed slightly lower tensile strength and modulus but much higher Izod impact strength due to the flexibility of the incorporated segments. In addition, the superb thermal properties typical for polyarylates were reserved in the modified polyarylate, thus assuring its broad applicability for those applications where extremely stringent criteria of thermal characteristics are required.
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  • 107
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The photocrosslinking efficiency of a series of commercial photoinitiators and multicomponent photosensitive systems on uncrosslinked acrylic matrices has been estimated. Copolymers used for this study are tricyclo[5.2.1.02,6]dec-4-en-8-yl acrylate/ethyl acrylate copolymers of variable composition (100/0, 40/60, 20/80, 0/100) synthesized in solution by a free-radical process. The irradiations were carried out at large wavelengths (λ ≥ 310 nm). Systems of benzophenone/benzoyl peroxide led to really fast crosslinking kinetics for 10 min of irradiation.
    Notes: L'efficacité de photoréticulation de toute une série de photoamorceurs commerciaux et de systèmes photosensibles multicomposants a été évaluée sur des matrices acryliques non réticulées. Les polymères utilisés pour cette étude sont des homopolymères et des copolymères d'acrylate de dicyclopentadiène/acrylate d'éthyle de composition variable (100/0, 40/60, 20/80, 0/100) synthétisés en solution par voie radicalaire. Les irradiations ont été effectuées à des grandes longueurs d'ondes (λ ≥ 310 nm). Les systèmes benzophénone/peroxyde de benzoyle ont permis d'obtenir des cinétiques de réticulation très rapides pour des temps d'irradation de 10 min.
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  • 108
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 13-21 
    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: Polysulfide wurden mit hoher Ausbeute durch Hochtemperatur-Lösungspolykondensation von 4,4′-Dimercaptobiphenyl mit ausgewählten aliphatischen und aromatisch-aliphatischen Dihalogenkohlenwasserstoffen hergestellt. Um die optimalen Polykondensationsbedingungen zu bestimmen, wurde der Einfluß folgender Faktoren auf die reduzierte Viskosität und die Ausbeute der Polysulfide ermittelt: Art des organischen Lösungsmittels, Art des Halogenwasserstoff-Akzeptors, Konzentration der organischen Reagenzien, Reaktionstemperatur und -zeit. Die Polykondensation des Dithiols mit Bis(4-chlormethylphenyl)methan wurde als Modellsystem eingehender untersucht. Die Polysulfidstrukturen wurden mittels Elementaranalyse, IR-Spektroskopie und Röntgenstrukturanalyse bestätigt. Aus der thermogravimetrischen Analyse wurden die Zersetzungstemperatur, der Gewichtsverlust bei dieser Temperatur und das Maximum der Zersetzungsgeschwindigkeit erhalten. Weiterhin wurden einige physikalisch-chemische, mechanische und dielektrische Eigenschaften ermittelt. Die beste thermische und chemische Bestandigkeit zeigt das aus dem Dithiol und 4,4′-Bis(chlormethyl)biphenyl hergestellte Polysulfid, was auf dessen vorwiegend aromatische Struktur zuriickgefuhrt werden kann.
    Notes: Polysulfides were synthesized with high yield by high-temperature solution polycondensation of 4,4′-biphenyldithiol with selected aliphatic and aromatic-aliphatic hydrocarbon dihalides. To determine the optimum polycondensation conditions, the influence of the following factors on reduced viscosity and yield was studied: type of organic solvent, type of hydrogen halide acceptor, concentration of reagents, reaction temperature, and reaction time. A thorough examination was carried out only for the polycondensation of dithiol with bis(4-chloromethylphenyl)methane chosen as model system. The structures of the polysulfides were confirmed by elemental analysis, X-ray analysis, and infrared spectroscopy. The temperature of initial decomposition, the percentage of mass loss, and the temperature of the fastest decomposition, process were determined from curves of differential thermal and thermogravimetric analysis. Some physicochemical, mechanical and electrical properties were determined. The highest thermal and chemical resistance has been found for the polysulfide obtained from 4,4′-biphenyldithiol and 4,4′-bis(chloromethyl)biphenyl, probably because of the predominantly aromatic structure.
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  • 109
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 61-72 
    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: Drie organisch-anorganische Hybridmaterialien wurden nach dem Sol-Gel-Verfahren durch kovalenten Einbau von Poly(styrol-co-methylmethacrylat)(Poly(St-co-MMA))-, Polymethylmethacrylat(PMMA)- und Polystyrol(PS)-Struktureinheiten in ein SiO2-Netzwerk hergestellt und als Füllstoffe (bis zu 60 Gew.-%) in Dentalharzen verwendet. Der Einfluß der Füllstoffe auf einige mechanische Eigenschaften der Harze wurde untersucht. Die Härte der gefüllten Dentalharze nahm mit steigendem Füllstoffgehalt zu, wogegen die Biegefestigkeit abnahm. Die Druckfestigkeit der gefüllten Harze war besser als die des ungefüllten Harzes, nahm jedoch mit steigendem Füllstoffgehalt ab.
    Notes: By incorporating poly(methyl methacrylate) (PMMA), polystyrene (PS), and poly(styrene-co-methyl methacrylate) (poly(St-co-MMA)) structure units covalently into the SiO2 glass network via a sol-gel approach, three organic-inorganic hybrid materials (PMMA-SiO2, PS - SiO2, and poly(St-co-MMA) - SiO2) have been prepared. The three hybrid sol-gel materials were used as filler (up to 60 wt.-%) for dental composite resins. The effect of the three filler materials on several mechanical properties of the dental composite resins was investigated. The hardness of the filled dental composites increased with increasing filler content, whereas the bending strength decreased. The compressive strength of the composites was improved, compared with the unfilled resin, but decreased with inreasing filler content.
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  • 110
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 107-116 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Adsorption von Benzol, Toluol und p-Xylol (BTX) aus wäßrigen Lösungen mittels hochvernetzter kationischer Stärke mit tertiären Amingruppen wurde untersucht. Der endotherme Adsorptionsvorgang ist vom Anfangs-pH-Wert und der Anfangskonzentration abhängig und kann mit einer Langmuir-Isotherme beschrieben werden.Die Adsorptionswärme (Δ) bei pH 4 beträgt für Benzol, Toluol und Xylol 29,45 kJ mol-1, 34,41 kJ mol-1 bzw. 35,58 kJ mol-1, bei pH 10 30,17 kJ mol-1, 35.56 kJ mol-1 bzw. 39,39 kJ mol-1. Die adsorbierte Menge nimmt in der Reihenfolge Benzol 〉 Toluol 〉 Xylol ab.
    Notes: The removal of benzene, toluene and p-xylene (BTX) compounds from aqueous solutions with highly crosslinked cationic starch containing tertiary amine groups was investigated. The adsorption process has found to be initial pH- and initial concentration-dependent, endothermic, and follows the Langmuir isothermal adsorption.The heats of adsorption (ΔH) at initial pH = 4 of benzene, toluene and p-xylene compounds are 29.45 kJ mol-1, 34.41 kJ mol-1, and 35.58 kJ mol-1, respectively, those at initial pH = 10 are 30.17 kJ mol-1, 35.56 kJ mol-1, and 39.39 kJ mol-1, respectively. The order of the amount of adsorbed BTX compounds on the adsorbent is benzene 〉 toluene 〉 p-xylene.
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  • 111
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    Angewandte Makromolekulare Chemie 251 (1997), S. 157-170 
    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: Bi-Sr-Ca-Cu-Komplexverbindungen von Polymethacrylsäure (PMAA) und Kresolnovolaken, die als Precursoren für Hochtemperatursupraleiter (HTSL) eingesetzt werden, sowie deren Cu-Komplexsalze wurden ESR-spektroskopisch und thermogravimetrisch untersucht. In den PMAA-Proben wurden drei verschiedene Cu2+-Spezies nachgewiesen: i) Cu2+-Paare, ii) isolierte Cu2+-Ionen und iii) Cu2+-Cluster. Bei niedrigem Cu-Gehalt der Proben bilden die Cu2+-Paar-Bindungen den Hauptanteil, bei hohem Cu-Gehalt überwiegen die Clusterbindungen. In den Novolakproben wurden nur isolierte Cu2+-Ionen und Cu2+-Cluster nachgewiesen. Die Einführung der Cu-Ionen erniedrigt die thermische Stabilität der Polymeren, der thermische Abbau erfolgt stufenweise. In den PMAA-Proben wird die erste Abbaustufe bei ≈ 220°C durch die Cu2+-Paar-Komplexe verursacht.
    Notes: Bi-Sr-Ca-Cu complexes of poly(methacrylic acid) (PMAA) and cresol novolac, which are precursors for high-temperature superconductors (HTSC) and Cu complexes of those polymers were investigated by ESR spectroscopy and thermogravimetry. In the PMAA samples three different kinds of Cu2+ species were detected: i) Cu2+ pairs, ii) isolated Cu2+ ions and iii) Cu2+ clusters. While Cu2+ pairs are the main species at low Cu concentrations, clusters become dominant at high Cu contents. In the novolac samples Cu2+ was only detected in isolated sites and clusters. The introduction of Cu ions lowered the thermal stability of the polymers and led to a stepwise decomposition. In the PMAA samples the first decomposition step at ≈ 220°C is caused by the Cu2+ pair complexes.
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  • 112
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 193-205 
    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: Neodymchlorid-2-ethylhexanolate mit der allgemeinen Formel NdCl3 · nL wurden durch eine Liganden-Austauschreaktion zwischen Neodymchloridisopropanolat (I) und 2-Ethylhexanol (EH) hergestellt. Die Hexanolate NdCl3 · 1,5 EH (II) und NdCl3 · 2,5 EH (III) wurden durch Elementaranalyse und Gravimetrie charakterisiert. Die katalytische Aktivität der Hexanolate bei der Homopolymerisation von 1,3-Butadien in Gegenwart von Triethylaluminium wurde untersucht. Die Verbindung III zeigte eine höhere Aktivität als die Verbindung II. Höhere Katalysator- und Cokatalysatorkonzentrationen sowie eine höhere Temperatur steigerten den Umsatz, wogegen die Viskosität der Produkte abnahm. Mit zunehmender Reaktionszeit erhöhten sich sowohl der Umsatz als auch die Viskosität. Die cis-1,4-Konformation wurde durch die Variation von Temperatur und Cokatalysatorkonzentration beeinflußt. Der gesamte Anteil der cis-1,4-Stuktur lag jedoch in allen Fällen über 99%, während die Produkte nur einen sehr geringen Vinyl-Anteil von 〈1% enthielten. Die Zugabe einer elektronenspendenden Verbindung verringerte den cis- 1,4-Gehalt aber auf 87%.
    Notes: Neodymium chloride 2-ethylhexanolates of the general formula NdCl3 · nL were prepared by ligand exchange reaction between neodymium chloride ispropanolate (I) and 2-ethylhexanol (EH). These hexanolates, NdCl3 · 1.5 EH (II) and NdCl3 · 2.5 EH (III), were characterized by elemental analysis and gravimetry. The catalytic activity of these hexanolates in combination with triethyl aluminium in the homopolymerization of 1,3-butadiene was studied, and the activity was found to be higher with III than II. The conversions increased with increasing the catalyst and co-catalyst concentrations and the temperature, whereas the intrinsic viscosity decreased. The conversions and the intrinsic viscosity decreased. The conversions and the intrinsic viscosity increased with reaction time. The cis-1,4 structure was influenced by variation in temperature and co-catalyst concentration, however, the total cis-1,4 structure was always more than 99% with very low vinyl content (〉1%). Addition of an external electron donor decreased the cis-1,4 content to 87%.
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  • 113
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The critical conditions in which the classical Flory-Stockmayer gelation theory (F-S theory) is applicable to monovinyl-divinyl copolymerizations were pursued in detail. The resulting prepolymers or precursors of ideal crosslinked-polymers were characterized as standard polymers for the discussion of network formation in free-radical monovinyl-divinyl copolymerizations. Methyl methacrylate was copolymerized with a small amount of ethylene dimethacrylate, butylene dimethacrylate or nonapropyleneglycol dimethacrylate in the presence of lauryl mercaptan, a chain transfer agent to reduce the occurrence of a thermodynamic excluded volume effect and intramolecular crosslinking as the primary and secondary factors, respectively, for the greatly delayed gelation in the free-radical monovinyl-divinyl copolymerizations and, moreover, to keep the primary chain length constant by inhibiting a gel effect. The ratio of the actual gel point to the theoretical one reached 1.1, supporting the validity of F-S theory. The resulting prepolymers were subjected to SEC-MALLS analysis to determine the molecular weights, the molecular-weight distributions and the radii of gyration; the correlations of molecular weight vs. elution volume and radius of gyration vs. molecular weight were useful for the characterization of the precursors of ideal network-polymers.
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  • 114
    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 Mesylchlorid mit vernetzten Pullulan-Mikropartikeln wurde untersucht, insbesondere der Einfluß der Reaktionsbedingungen auf das Produktverhältnis Chlordeoxy-/O-Mesylpullulan. In N,N-Dimethylformamid wird vorwiegend Chlordeoxypullulan gebildet, während in Pyridin bei niedrigen Temperaturen der Mesylester das Hauptprodukt ist. In N,N-Dimethylacetamide entstehen Chlordeoxy und Mesylgruppen im Verhältnis 2:1. Durch die Einführung der Chlordeoxy- bzw. Mesylgruppen werden die Mikropartikel hydrophob.
    Notes: The reaction of mesyl chloride with crosslinked pullulan microparticles was investigated, in particular the influence of the reaction conditions on the ratio between the two possible products chlorodeoxy or O-mesyl pullulan. It was found that in N,N-dimethylformamide the preponderent reaction product is chlorodeoxy pullulan, while in pyridine at low temperatures the main product is the mesyl ester of pullulan. In N,N-dimethylacetamide, the substituent groups are both chlorodeoxy and mesyl ones, in about 2:1 ratio. By the introduction of either chlorodeoxy or mesyl groups, the pullulan-crosslinked microparticles become hydrophobic.
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  • 115
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    Angewandte Makromolekulare Chemie 241 (1996), S. 41-56 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Poly(4-hydroxybutylacrylat) poly(4-HBA) wurde aus wäßrigem Medium mit Ammoniumpersulfat als Initiator auf Seide (bombyx mori) aufgepfropft. Die Gewichtszunahme stieg proportional mit der Monomerkonzentration im Pfropfsystem. Der Pfropfgrad lag im Bereich von 45 bis 65%. Die Feuchtigkeitsaufnahme nahm bei einer Gewichtszunahme von 〉10% stark ab. Die mechanischen Eigenschaften der Seidenfasern zeigten mit steigender Gewichtszunahme keine wesentliche Änderung. Doppelbrechung und isotroper Brechungsindex nahmen bis zu einer Gewichtszunahme von 35% ab und blieben dann unverändert. Röntgenbeugungsdiagramme zeigten, daß die kristalline Struktur durch die Pfropfbehandlung nicht modifiziert wird. Kalorimetrische (DSC), thermomechanische (TMA) und thermogravimetrische (TG) Analysen ergaben, daß das thermische Verhalten der poly(4-HBA)-gepfropften Seidenfasern nur leicht verändert wird. Die zur Bestimmung des dynamisch-mechanischen Verhaltens der Seidenfasern durchgeführten DMA-Messungen zeigten eine Verschiebung der E′- und E″-Modulspitzen zu niedrigeren Temperaturen mit steigender Gewichtszunahme. Ablagerungen auf der Faseroberfläche der bei einem hohen Monomer/Seide-Verhältnis (〉50%) gepfropften Seide wurden mit Rasterelektronenmikroskopie nachgewiesen.
    Notes: Poly(4-hydroxybutyl acrylate) poly(4-HBA) was graft-copolymerized onto silk fibres (bombyx mori) in aqueous medium with ammonium persulfate as initiator. The weight gain increased with increasing concentration of monomer in the grafting system. The grafting efficiency ranged from 45 to 65%. Equilibrium moisture regain decreased sharply beyond 10% weight gain. The tensile properties of the silk fibres did not change significantly as a function of the increasing weight gain. Birefringence and isotropic refractive index decreased until 35% weight gain and then remained unchanged. The X-ray diffraction patterns showed that the crystalline structure was not affected by grafting. Differential scanning calorimetry (DSC), thermomechanical (TMA), and thermogravimetric (TG) measurements showed that poly(4-HBA)-grafted silk fibres underwent only slight changes in the thermal behaviour. The dynamic mechanical measurements (DMA) exhibited a downward shift of both the storage (E′) and loss modulus peak (E″) with increasing weight gain. Scanning electron microscopy (SEM) observations showed the presence of some deposits adhering to the surface of silk fibres grafted at high monomer/silk ratio (〉50%).
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  • 116
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: MgCl2-Träger für einen Ethylenpolymerisationskatalysator wurden mit Hilfe der Rekristallationsmethode hergestellt, wobei Methanol als Lösungsmittel diente. Der Einfluß verschiedener Lösungsmethoden des rekristallisierten MgCl2-Alkohol-Adduktes auf die morphologischen Charakteristika der Katalysatoren wurde untersucht. Die Lösungsmethode beeinflußt die Eigenschaften der Katalysatoren beträchtlich. Die dargestellten Katalysatoren wiesen unterschiedliche Ti/Mg-Verhältnisse auf, sowohl was die Oberfläche als auch die gesamten Katalysator-Partikel betrifft. Betrachtet man die Ti-Verteilung und Aktivitätsprofile, dann erweisen sich nicht nur die Polymerisationsbedingungen, sondern auch die Ti-Verteilung auf dem Katalysator als wichtige Faktoren, welche die Dichte der Polymeren beeinflussen.
    Notes: The MgCl2 supports for an ethylene polymerization catalyst were prepared by the recrystallization method using methanol as a solvent. The effects of different desolvation methods of the recrystallized MgCl2-alcohol adduct on the morphological characteristics of the catalysts were examined. The desolvation method greatly affects the characteristics of the catalyst. The prepared catalysts had different Ti/Mg ratios with respect to both surface content and entire catalyst particles. Considering Ti distribution and activity profiles, not only the polymerization conditions but also the Ti distribution on the catalyst appear to be an important factor which affects the bulk density of the polymers.
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  • 117
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    Angewandte Makromolekulare Chemie 253 (1997), S. 89-97 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Aromatische Poly(etherketon)e mit Ferrocen-Einheiten in der Hauptkette wurden durch direkte Polykondensation von 1,1′-Ferrocendicarbonsäure mit Diphenylether oder 1,4-Diphenoxybenzol hergestellt. Als Katalysatoren wurden Trifluormethansulfonsäure, Methansulfonsäure/P2O5 (Eatons Reagens) oder Trifluormethansulfonsäure/P2O5 verwendet. Polykondensationen bei Raumtemperatur für 24 h ergaben Poly(arylenetherketon)e mit Grenzviskositäten bis zu 40 mL g-1. Die Monoacylierung von Diphenylether mit Ferrocencarbonsäure wurde im Hinblick auf die Effektivität von Eatons Reagens als Katalysator und Lösungsmittel eingehender untersucht.
    Notes: Aromatic poly(ether ketone)s with ferrocene units in the main chain were prepared by direct polycondensation of 1,1′-ferrocenedicarboxylic acid with diphenyl ether or 1,4-diphenoxybenzene using various catalysts such as trifluoromethanesulfonic acid (triflic acid), a combination of methanesulfonic acid/P2O5 (Eaton's reagent) or a combination of triflic acid/P2O5. Polycondensations at room temperature for 24 h gave poly(arylene ether ketone)s with inherent viscosities up to 40 mL g-1. Monoacylation of diphenyl ether with ferrocenecarboxylic acid was studied in detail in order to show the efficiency of polymer formation employing Eaton's reagent as catalyst and solvent.
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  • 118
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    Angewandte Makromolekulare Chemie 251 (1997), S. 73-80 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die mechanischen und strukturellen Eigenschaften von Blends aus Phenolphthalein-Polyethersulfon und ultrahochmolekularem Polyethylen (UHMWPE) wurden anhand von Zug- und Biegeversuchen, Raster- und Transmissionselektronenmikroskopie untersucht. Die Zugabe einer geringen Menge UHMWPE (2 Gew.-%) führt zu einer Verstärkung der PES-C-Matrix. Höhere UHMWPE-Konzentrationen verschlechtern die mechanischen Eigenschaften. Die Strukturuntersuchungen zeigen, daß die Blends im gesamten Zusammensetzungsbereich mehrphasig sind. Bei geringen UHMWPE-Konzentrationen ist die UHMWPE-Phase gleichmäßig verteilt und entlang der Fließrichtung orientiert, was mit der starken Grenzflächenadhäsion zur Verbesserung des mechanischen Verhaltens beiträgt. Mit steigender UHMWPE-Konzentration nimmt die Domänengröß der UHMWPE-Phase zu.
    Notes: Mechanical and structural properties of blends of phenolphthalein poly(ether sulfone) (PES-C) with ultra-high molecular weight polyethylene (UHMWPE) were investigated using tensile and bending testing, scanning electron microscopy and transition electron microscopy. The incorporation of minor amounts of UHMWPE (2 wt.-%) into PES-C has a reinforcement effect. With higher concentrations of UHMWPE, the mechanical properties decrease gradually. Structural studies demonstrated that the blends are multiphasic in the whole composition range. The minor UHMWPE, dispersed uniformly and oriented along the flow direction, as well as the strong interfacial adhesion contribute to the increase of the mechanical performance of the blends. The domain size of the UHMWPE phase was found to increase with the increase of its concentration.
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  • 119
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    Angewandte Makromolekulare Chemie 251 (1997), S. 117-130 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Ein Redoxcopolymeres, ein makroporöses Poly(Styrol-co-Divinylbenzol) (S/DVB)-Harz mit N-Bromsulfonamidgruppen, wurde angewandt, um Cyanide aus wäßrigen Lösungen zu entfernen. Dieses Harz enthält aktives Brom in den funktionellen Gruppen (1.86 mmol g-1, 3.72 meq g-1) und weist Oxidationseigenschaften auf. Es wurde sowohl in statischen als auch in dynamischen Systemen für die Oxidation von Cyanidionen zu nichttoxischen Verbindungen angewandt. Die Reaktionen wurden in wäßrigen Lösungen mit 26-2600 mg L-1 CN- bei unterschiedlichen pH-Werten durchgeführt. Die Ergebnisse zeigten, daß dieses Harz die Cyanide leicht zu Cyanaten oxidiert, die ca. 1000 mal weniger toxisch sind. Bei Kontakt mit dem Harz fiel die Cyanidkonzentration in den Lösungen unter 0.05 mg L-1 CN-. Die —SO2NBrNa-Gruppen gingen dabei in —SO2NH2-Gruppen über. Diese konnten wiederum mit Natriumhypochlorit- und Natriumbromid-Lösungen reaktiviert werden. Es wurde auch eine Alternative zu der Cyanidionenoxidation mit N-Bromsulfonamid-Harz untersucht, indem ein analoges N-Chlorsulfonamid-Harz in Gengenwart von katalytischen Mengen von Bromiden angewandt wurde.
    Notes: A redox copolymer, macroporous poly(styrene-co-divinylbenzene) (S/DVB) resin having N-bromosulfonamide groups, was used for removal of cyanide ions from aqueous solutions. This resin contains active bromine in functional groups (1.86 mmol g-1, i. e. 3.72 meq g-1) and shows oxidative properties. It was employed in static and flow system for oxidation of cyanide ions to non-toxic compounds. The reactions were carried out in aqueous media containing 26-2600 mg L-1 CN- at different pH values. The data showed that the resin having active bromine easily oxidized cyanides, forming cyanates being 1000-times less toxic than cyanides. In contact with the resin the concentration of cyanides in tested solutions dropped below 0.05 mg L-1 CN-. During the oxidation processes the —SO2NBrNa groups transform to —SO2NH2 groups. They can be reactivated by use of sodium hypochlorite and bromide solutions. As an alternative to oxidation of cyanides by N-bromosulfonamide resin, the oxidation of these ions by N-chlorosulfonamide resin with addition of a small amount of bromides was examined.
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  • 120
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    Angewandte Makromolekulare Chemie 251 (1997), S. 207-208 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No Abstract
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  • 121
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    Angewandte Makromolekulare Chemie 252 (1997), S. 33-43 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Novel Polyester glycols with alkyl side groups were used for the improvement of thermal stability and hydrolytic stability of polyester urethane elastomers. The novel polyester glycols used are poly( β -methyl- δ -valerolactone)glycol (PMVL), poly(3-methyl pentamethylene adipate) glycol (PMPA), poly(nonamethylene-co-2-methyl octamcthylene carbonate) gycol (PNCO). A mixture of PNCO and poly(dimethyl siloxane)gycol (PNCO/PDMS) was also used. Polyurethane network elastomers were prepared from 4,4′-diphenylmethane diisocyanate (or 2,4-tolylene diisocyanate), and a mixture of 1,4-butane diol and trimethylol propane by a prepolymer method. Mechanical properties, Tg, thermal stability, and hydrolytic stability were measured. Morphology were also measured by means of polarizing microscopy, dynamic viscoelastometer, and ESR. The properties of novel polyurethane elastomers have good mechanical properties comparable to those of the general purpose polyester urethanes, and better thermal and hydrolytic stability than PTMG-based polyurethane. These polyurethane elastomers were exposed in out door during 2 year in Nagasaki, JAPAN. The novel polyurethane clastomers held alomost constant values for gel fraction, swelling ratio, relative modulus during 12 months, while poly(oxytetramethylene oxide)-based polyurethane as a control decreased the these values. Relationship of degradation behaviors with chemical structure and morphology were discussed.
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  • 122
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    Angewandte Makromolekulare Chemie 252 (1997), S. 139-151 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the chain oxidation of N-alkylamides with molecular oxygen, propagation is the ratedetermining step under conditions when the oxidation rate is independent of oxygen pressure. The oxidizability of lactams and lactam-based polyamides correlates with the energy of the formation of N-alkylamide radical by abstraction of hydrogen from the methylene group adjacent to nitrogen. While for lactams this energy depends on the number of carbons in the lactam ring, for N-alkylamides and polylactams such dependence is not observed.
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  • 123
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    Angewandte Makromolekulare Chemie 252 (1997), S. 179-193 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An X-band EPR-Imaging apparatus which allowed us to determine the distribution of nitroxyl radicals within solid samples of polymeric materials containing hindered amine stabilizers, is described. It is shown that EPR Imaging represents a powerful tool for investigating the growth and decay of nitroxyls formed in polymers irradiated under air for long periods. Since the variations of the radical concentration can be monitored both in time and in the space, this technique provides valuable information not easily attainable by means of other methods.
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  • 124
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    Angewandte Makromolekulare Chemie 252 (1997), S. 237-256 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A re-examination of the photo-oxidation mechanism of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) at both long and short irradiation wavelengths under accelerated conditions is reported. The formation rate of poly-2,6-dimethylphenoxy (PDMP) radicals, have been observed by esr spectroscopy, while benzylic-type radicals have been detected by spin trapping experiments using nitrosodurene under UV irradiation conditions. The changes of FTIR spectra obtained under accelerated photo-oxidative conditions show the formation of primary oxidation products such as aromatic aldehydes and quinones. The direct formation of radical cations and superoxide anions by a photo-induced electron-transfer reaction is suggested under our conditions. In addition, some results on the of photo-oxidation PPO/PS blends as a function of polystyrene tacticity are also reported. In the case of syndiotactic polystyrene the blend photostability shows some differences in comparison with the blend containing atactic polystyrene. This effect has been ascribed to the absence of excimers in syndiotactic polystyrene which are not revealed by fluorescence measurements. Finally, the chemical modification of PPO with bromine gave a bromomethylated PPO with different amounts of CH2 Br groups, which has been used for further substitution reactions with alkoxy sodium salts of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and 4-hydroxy-1,2,2,6,6-pentamethylpiperidine (PMPP). The accelerated photo-oxidation of a modified copolymer PPO-PMPP containing a 60% PMPP moieties as side groups and its blends with pure PPO has been followed by FTIR and esr spectroscopies. Some comparisons with a commercially available hindered amine light stabilizers (HALS) and a modified copolymer PPO-PMPP are also reported under the same photo-oxidative conditions.
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  • 125
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    Angewandte Makromolekulare Chemie 253 (1997), S. 27-49 
    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: For innovative applications of plastics, which take advantage of special properties of polymeric materials, comprehensive understanding on strengthening and toughening mechanisms is required. The temperature-dependent mechanical behaviour of PMMA, PS and PC under dynamic loading conditions were investigated by means of an instrumented Charpy impact tester. The elastic-plastic fracture mechanics parameters, the energy-determined J-integral, and the deformation-determined crack opening displacement, δ, enable to do structure-related quantification of micromechanical processes. The J-integral values showed a maximum, resulting from an energy-dissipative process. The maximum values for PMMA occurred at 50°C and for PC at 40°C , which is related to the secondary(β) relaxation as evaluated from the frequency dependence of the mechanical loss factor. The 0-relaxation initiated shear deformation mechanisms, which led to a local increase of toughness. In polycarbonate, toughness is strongly increased due to a stress-induced shear flow process at temperatures higher than -25°C. Correlations between morphology and toughness can be derived with the help of optical investigations of stable crack propagation on fracture surfaces.
    Notes: Innovative Kunststoffanwendungen, die die speziellen Eigenschaften polymerer Werkstoffe gezielt ausnutzen, erfordern vertiefte Kenntnisse über festigkeits- und zähigkeitsbestimmende Mechanismen. Das sich in Abhängigkeit von der Temperatur ändernde Werkstoffverhalten von PMMA, PS und PC wurde bei dynamischer Beanspruchung mittels instrumentierter Kerbschlagbiegeprüfung bestimmt. Mit der verformungsbestimmten Rißöffnungsverschiebung δ und dem energiebestimmten J-Integral stehen Kenngrößen der Fließbruchmechanik zur Verfügung, die eine strukturbezogene Quantifizierung der temperaturabhängigen mikromechanischen Prozesse erlauben. Die J-Integralwerte zeigen für PMMA bei 50°C und für PC bei -60°C ein durch einen energiedissipativen Prozeß verursachtes Maximum. Dieses Maximum steht, wie sich aus der Interpretation der Frequenzabhängigkeit des mechanischen Verlustfaktors ergibt, mit der Neben(β)-Relaxation in Beziehung. Dabei initiiert die β-Relaxation Scherdeformationsmechanismen, die ihrerseits die lokale Zähigkeitserhöhung bewirken. Ab -25°C führt für PC ein spannungsinduzierter Scherfließprozeß zu einer erheblichen Zähigkeitssteigerung. Durch die Einbeziehung lichtmikroskopischer Untersuchungen des stabilen Rißfortschritts auf der Bruchfläche können Morphologie-Zähigkeits-Korrelationen abgeleitet werden.
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  • 126
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    Angewandte Makromolekulare Chemie 253 (1997), S. 71-88 
    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 Polyamidimid-Polyimid-Blockcopolymeren (PAI-PI-BCPs) wurde durch Polykondensation von PAI-Blöcken mit Amino-Endgruppen und PI-Blöcken mit Anhydrid-Endgruppen hergestellt. Zur Synthese der Blöcke mit Molekulargewichten im Bereich von ca. 2000 bis 15000 wurden nur technisch leicht zugängliche Monomere, wie Trimellitsäureanhydridchlorid, Benzophenontetracarbonsäuredianhydrid, 4,4′-Diaminodiphenylmethan, 2,4-Toluylendiamin und 4,4′-Diaminodiphenylsulfon eingesetzt. Dabei zeigte sich, daß durch den blockartigen Aufbau die Löslichkeit-und damit die Verarbeitbarkeit-im Vergleich zu den reinen, unlöslichen Polyimiden wesentlich verbessert werden konnte, bei nahezu gleichbleibender Thermostabilität. So wurden BCPs mit guten mechanischen Eigenschaften, Thermostabilitäten bis ca. 480°C (Thermogravimetrie, 5% Gewichtsverlust) und guten Löslichkeiten in Dimethylacetamid und anderen polaren aprotischen Lösungsmitteln erhalten.
    Notes: New poly(amide-imide)-poly(imide) block copolymers (PAI-PI-BCPs) were prepared by polycondensation of amino-terminated PAI-blocks with anhydride-terminated PI-blocks. For the syntheses of the blocks with molecular weights from 2000 to 15000 only commercially available monomers were used, e.g. trimellitic acid anhydride chloride, benzophenone tetracarboxylic acid dianhydride, 4,4′-diaminodiphenylmethane, 2,4-toluenediamine and 4,4′-diaminodiphenylsulfone. The BCPs were shown to have better solubility compared to the pure, insoluble PIs with only minor decrease of the thermostability. Thus, BCPs with good mechanical properties, thermostabilities up to 480°C (thermogravimetric analysis, 5% weight loss) and good solubility in dimethylacetamide and other polar aprotic solvents were obtained.
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  • 127
    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 Polysiloxan/Poly(N-acetyliminoethylen)-(PSiO/PNAI)-Block- und -Pfropfcopolymeren wurde durch Polymerisation von 2-Methyl-2-oxazolin (MeOZO) mit funktionellen Polysiloxan-Prepolymeren als Initiatoren synthetisiert. Die Copolymeren wurden mit IR- und 1H NMR-Spektroskopie sowie Elementaranalyse, Differentialkalorimetrie und Thermogravimetrie charakterisiert. Der Einbau sowohl von hydrophoben als auch von hydrophilen Sequenzen verleiht den Polymeren amphiphile Eigenschaften. Ihre Eigenschaften in Lösung und als Feststoffe lassen die Produkte für Anwendungen als nichtionische Emulgatoren, Oberflächenmodifikatoren, Gele, usw. geeignet erscheinen.
    Notes: A series of polysiloxane/poly(N-acetyliminoethylene) (PSiO/PNAI) block and graft copolymers were synthesized by the initiation of 2-methyl-2-oxazoline (Me-OZO) polymerization with functional polysiloxane prepolymers. The copolymerization products were characterized by IR- and 1H NMR spectroscopy, elemental analysis, DSC and thermogravimetry. The insertion of both hydrophobic and hydrophilic sequences in the macromolecular structure induces a behavior characteristic of amphiphilic compounds. Their solution and solid state behavior evidenced peculiarities which make them able to act as nonionic emulsifiers, surface modifiers, gels, etc.
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  • 128
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Zustand von Wasser in Protonenaustausch-Membranen, hergestellt durch Pfropfen von Styrol auf Polyvinylidenfluorid-Filme (PVDF-g-PS) mittels Elektronenstrahlen und anschließendes Sulfonieren (PVDF-g-PSSA), wurde mittels Differentialkalorimetrie (DSC), Raman-Spektroskopie und Rontgen-Diffraktion (SAXS) ermittelt. Die Raman-Untersuchungen zeigten, daß einzelne Wassermolekule durch hydrophobe Wechselwirkungen an die Polymerketten gebunden sind. Die DSC-Untersuchungen zeigten, daß Wasser in den Membranen in drei verschiedenen Umgebungen vorliegt: nicht gefrierendes ionisch gebundenes Wasser, gefrierendes freies Wasser und gefrierendes gebundenes Wasser. Die Menge an nicht gefrierendem Wasser betragt unabhangig vom Pfropfungsgrad etwa 10 H2O/SO3H (mol/mol). Die Menge an gefrierendem Wasser ist stark vom Pfropfungsgrad abhangig. Oberhalb eines Pfropfungsgrades von 50% werden Werte von 40 H20/S03H (mol/mol) erreicht. Die Leitfahigkeit von nur nicht gefrierendes Wasser enthaltenden Membranen ist gering, d. h., das ionisch gebundene Wasser kann nicht allein die fur den Transport von Protonen und Wasser notwendigen Kanale bilden. Die SAXS Untersuchungen zeigten, daß Wasser/Sulfonsaure-Cluster in Membranen aus hydratisiertem PVDF-g-PSSA mit einem Bragg-Abstand von 25 Å gebildet werden. Diese Cluster formen die Kanale fur den Ionentransport und die Leitfähigkeit.
    Notes: The state of water in proton exchange membranes prepared by pre-irradiation (electron beam, 100 kGy) grafting of styrene onto poly(vinylidene fluoride) films (PVDF-g-PS), followed by sulfonation (PVDF-g-PSSA), has been studied with thermal analysis, Raman spectroscopy and small angle X-ray diffraction (SAXS). Raman spectra show that, in addition to free liquid water in the membranes, single water molecules are weakly bound to the polymer backbone. Thermal analysis shows that there are three types of water molecules in the membrane; non-freezable water associated with the ionic sites, freezable free water, and freezable bound water. The amount of non-freezable water is around 10 H2O/SO3H (mol/mol), and is independent of the degree of grafting (d.o.g.). The amount of freezable water is strongly dependent on the d.o.g. as long as the grafting has not penetrated the whole of the film, and reaches a value of around 40 H2O/SO3H (mol/mol) above a d.o.g. of 50%. The conductivity of membranes containing only the non-freezable water is low, i. e. the ionically bound water alone does not form the domains necessary for proton and water transport. SAXS measurements show that water/sulfonic acid clusters in hydrated PVDF-g-PSSA membranes with a Bragg distance of 25 Å are formed; these form the ion conducting channels in the membrane.
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    Angewandte Makromolekulare Chemie 253 (1997), S. 211-211 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    Angewandte Makromolekulare Chemie 253 (1997), S. 201-210 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Zug- und Biegemoduli von preßgeformten Polypropen-Probekörpern mit unterschiedlichen Oberflächenkristallinitäten wurden basierend auf der Annahme eines Schicht-Verbund-Modells untersucht. Es zeigte sich, daß die Spannungs-Dehnungs-Kurven der Zugversuche und die Werte der Biegeablenkung im wesentlichen von der Oberfächenkristallinität abhängen, jedoch erwiesen sich die Bruchspannungen als von der Oberflächenkristallinität unabhängig. Es wird angenommen, daß das beobachtete Zug- und Biegeverhalten der Proben auf der Grundlage eines Schicht-Verbund-Modells, bei dem eine massive, starre Platte zwischen zwei weichen Schichten eingebettet ist, charakterisiert werden kann.
    Notes: The tensile and flexural moduli of the compression-molded sheets of polypropene with different surface layer crystallinity were investigated based on a layered composite model. It was found that the tensile stress-strain curve and flexural deflection depended largely on the surface layer crystallinity, but the ultimate strain-at-break values were independent of the surface layer crystallinity. It is suggested that the tensile and flexural behavior can be characterized using a layered composite model in which a bulk plate was sandwiched between two surface layers.
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  • 131
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Poly-L-proline in the molecular weight range 50,000-90,000 has been synthesized from L-proline-N-carboxyanhydride. The molecular weight obtained is dependent on the initiator concentration. The rate constants for the polymerization have been determined by measuring the CO2 evolution. By observation of rotation during the polymerization, it is possible to deduce the conformation of the polymer in the polymerization solution. It is concluded that the immediate product of the polymerization is neither pure form I nor pure form II. The differences between form I and form II of poly-L-proline have been further characterized by measurements of their ultraviolet rotatory dispersion and their ultraviolet spectra.
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  • 132
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    Topics: Chemistry and Pharmacology
    Notes: The base-catalyzed hydrolysis rate of the cationic esters obtained by quaternization of N,N,N′,N′-tetramethylethylenediamine with phenylbromoacetate was studied in buffers and in solutions of partially neutralized polymeric acids. The polyanions were found to be powerful inhibitors of the reaction. This effect was interpreted as due to the association of the ester with the polyanion, from which the catalytically active hydroxyl groups are repelled. It is shown that kinetic data may be interpreted by a procedure similar to the Lineweaver-Burk plot to yield the reactivity of the bound ester and the dissociation constant of the polymer-ester complex.
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  • 133
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: A series of high molecular weight copolypeptides of L-proline and sarcosine have been synthesized. Experimental evidence is presented which indicates that the products are true copolymers rather than mixtures of homopolymers. In contrast to poly-L-proline I, a copolymer of L-proline-sarcosine I containing approximately 50% sarcosine is soluble in water. Two molecular conformations of the copolymers, similar to those found for polyproline, have been characterized by means of infrared spectroscopy and optical rotatory dispersion. The residue rotation of L-proline has been obtained from the copolymers and is -250°.
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  • 134
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    Biopolymers 2 (1964), S. 1-8 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The results of electrophoresis experiments on aqueous solutions of native and thermally denatured DNA are reported. A significant decrease of the electrophoretic mobility has been observed following thermal denaturation, which under suitable conditions gives rise to a resolution into two peaks of 1 : 1 mixtures in the electrophoretic pattern. This result is entirely consistent with the previously reported increase of the activity coefficient of sodium counterions following thermal denaturation. The hypothesis that thermal denaturation of calf thymus DNA induces a large decrease of charge density on the macroion which has been ascribed to the population of more extended conformations of the chains in the disordered region of the molecule is therefore further confirmed.
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  • 135
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the depolymerization of native dextran in dilute hydrochloric acid at different temperatures has been followed by measurements of M̄w, M̄n, [η], 〈ρ2〉1/2, and S. The data allow the correlation of the various parameters of the total hydrolyzate at various degrees of depolymerization. At a first approximation the results conform to a random splitting of a statistical, branched polymer.
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  • 136
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    Topics: Chemistry and Pharmacology
    Notes: The γ-ethyl-L-glutamate NCA polymerization initiated by di-n-butyl and di-isopropyl amine was studied. The experimental kinetic curves show an autocatalytic portion with 25-30% conversion, followed by a pseudo first-order region which extends up to at least 85-90%. In this linear region, the reaction order appears to be 0.5 in initiator with both amines. High degrees of polymerization and high reaction rates were observed. These results are similar to those obtained in the γ-benzyl-L-glutamate NCA polymerization initiated by sodium methoxide.
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  • 137
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    Topics: Chemistry and Pharmacology
    Notes: The dielectric constant and the electric birefringence of poly-γ-benzyl-L-glutamate in ethylene dichloride-dichloroacetic acid mixtures have been measured as functions of the solvent composition. These properties undergo a marked decrease with the addition of a small amount of dichloroacetic acid, as well as an abrupt change accompanying the helix-coil transition in the vicinity of 75 vol.-% dichloroacetic acid. The former is attributed to the apparent diminution of the dipole moment of helical poly-γ-benzyl-L-glutamate molecule, which may be due to the protonation of terminal amide groups.
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  • 138
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    Biopolymers 2 (1964) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 139
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The polymerization of γ-benzyl-L-glutamate NCA initiated by n-hexylamine in DMF proceeds with two successive propagation rates whose ratio is about 1.5. The onset of the increase in rate of propagation occurred at a DPn of 7-14, which was independent of initiator to anhydride ratio and anhydride concentration and not a result of anhydride impurities. The increase in rate is likely a result of a conformational change in the polymer at a DPn of 7-14.
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  • 140
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    Biopolymers 2 (1964), S. 147-161 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The NCAs of the N-benzyl derivatives of β-alanine, β-DL-aminobutyric acid, and β-DL-aminoisobutyric acid (nonplanar six-membered rings) were prepared by reacting the corresponding N-chloroformyl derivatives, obtained on reaction of the N-benzyl amino acids with phosgene, with triethylamine. Contrary to the others, the NCA of N-benzyl-β-alanine polymerized readily on heating in vacuo or in solution, using n-hexylamine or methanolic sodium methoxide as initiators. With n-hexylamine the molecular weights of the polymers obtained in benzene, dioxan, and dimethylsulfoxide, were in accordance with DP = [NCA]/[Initiator], as was found with conventional five-membered ring NCAs of α-amino acids. With sodium methoxide initiation, DPs of the polymers obtained were smaller than the (NCA)/[Initiator] ratio, contrary to what was found previously with α-amino acid NCAs. The possibility that stereochemical factors are responsible for the differences in polymerization activity of various. N-alkyl β as well as α amino acid NCAs is discussed.
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    Biopolymers 2 (1964), S. 231-236 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electrophoretic mobility of DNA in the presence of tetramethylammonium and alkali metal ion chlorides has been studied as a function of ionic strength. Each cation exhibits a characteristic behavior in accord with the idea that the order of inter-action with DNA is Li+ 〉 Na+ 〉 K+ 〉 TMA+. The application of theories of the electrophoresis of polyelectrolytes is discussed, leading to an attempt to calculate the fractional charge per DNA phosphorus from the mobility data. Over the range 0.05-0.4M a constant and unique value of the DNA charge is obtained in the presence of each cation. Values of the zeta potential and of the friction factor per monomer unit are also calculated.
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    Biopolymers 2 (1964), S. 135-146 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simple quantitative theory of inactivation of transforming DNA has been formulated. It is based on the idea that genetic recombination of the molecule of transforming DNA with the bacterial genome is possible only, from the point mutation of the gene up to the nearest hit or point of damage on the corresponding DNA molecule. Our data and the data of other authors on the kinetics of inactivation by HNO2 or U.V. light or both are consistent with these theoretical predictions. Theoretical predictions were made concerning the extent of reactivation by fusion mid annealing of damaged DNA with a diluting genetically inactive DNA. These estimates have been reasonably confirmed by our experimental results.
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  • 144
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    Angewandte Makromolekulare Chemie 252 (1997), S. 45-54 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Addition of HALS-stabilisers, the cut-off wavelength of the light source, the temperature and the oxygen pressure have an influence on the UV-degradation mechanism of polyolefins. All these parameters influences the conversion of oxygen into polymeric carbonyls. The results are explained assuming that the initiation of the UV-degradation of pololefins is due to substrate-oxygen charge transfer complexes (CTCs).
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  • 145
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    Angewandte Makromolekulare Chemie 252 (1997), S. 69-88 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The applicability of fracture mechanics was studied on UV-exposed HDPE Charpy specimens. The failure distribution of the stress at failure measured in three-points bending tests showed a bifurcation in failure processes. At high stresses yielding occurs, resulting in large strain at failures. At lower stresses crack propagation causes low strain at failures. Due to the bifurcation in failure processes the ductile-brittle transition temperature of exposed specimens is hard to determine.Specimens notched after exposure showed a decrease in the critical stress intensity values. The effective notch depth of exposed specimens was found to be larger than the thickness of the oxidized layer measured by FT-IR and density measurements.
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  • 146
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    Angewandte Makromolekulare Chemie 252 (1997), S. 119-138 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the 2-hydroxyphenyl-1,3,5-triazines, the intramolecular hydrogen bond is stronger than in the corresponding 2-hydroxyphenylbenzotriazoles. Compounds with only one aryl group in the 2-hydroxyphenyl-1,3,5-triazine series show proton-transferred fluorescence with large Stokes shift and high quantum yield. No such fluorescence is observed, in contrast, for compunds with three aryi groups bearing no electrondonating groups on the aryl moieties. When the hydrogen atom of the intramolecular hydrogen bond is replaced by CH3, the respective derivative shows fluorescence with a normal Stokes shift.Various copolymers of MA-TIN 1 (2-[2-hydroxy-3-tert.-butyl-5-(O-[2-hydroxy-3-(2-methylpropenoyloxy)propyl]-2-carbonyloxyethyl)phenyl]benzotriazole), and MA-TZ 1 (2,4-Bis(2,4-dimethyl-phenyl)-6-[2-hydroxy-4-(2-hydroxy-3-[2-methylpropenoyloxy])propoxyphenyl]-1,3,5-triazine) with styrene, methyl methacrylate, and methacrylic acid have been synthesized by radical polymerization. The absorption spectra in the longwavelength UV region appear unchanged compared to those of the monomeric UV absorbers indicating that the stabilizer chromophores are conserved intact in the polymer. Both the monomeric and the polymeric stabilizers exhibit a strongly Stokesshifted, temperature-dependent, low-quantum-yield, proton-transferred fluorescence. This may be taken as evidence that the intramolecular hydrogen bond, which is essential for the photostability of this type of UV absorber, remains intact also in the copolymers. Activation energies of the radiationless deactivation process can be evaluated from the temperature dependence of this fluorescence. These energies lie between 4 and 5 kJ/mol for most of the benzotriazole and triazine stabilizers investigated.Fluorescence-decay measurements with crystalline MA-TIN 1 at different temperatures reveal a close correspondence of the temperature dependence between decay times and relative quantum yields. The radiationless process is thence concluded to originate from the proton-transferred level S1'. The decay time at room temperature is estimated at 70 ps, close to the value for crystalline TIN P (2-(2-hydroxy-5-methylphenyl)benzotriazole). The proton-transferred fluorescence of MA-TIN 1 exhibits a biexponential decay profile whereas solid TIN P, in contrast, displays only one single lifetime.
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    Biopolymers 2 (1964), S. 15-25 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to study the effect of glucose substitution on the sedimentation velocities of the T-even phage DNA's, T2 and T2*, and T6 and T6* bacteriophages were grown with H3and P32 labeling. Zone sedimentation of the DNA's isolated from these phagea showed that the glucosylated DNA's from both T2 and T6 sediment faster than the nonglucosylated molecules. Nonglucosylated DNA from TG and T2 phages sedimented with the same velocity, suggesting that the molecules of these phages are of the same length.
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  • 148
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    Biopolymers 2 (1964), S. 43-49 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report a simple method for measuring partial specific volumes, of polymers in dilute solutions with an accuracy of 3 parts per thousand. This method has been applied to 7 polypeptides in 4 organic solvents. The residue volumes deduced from these data are compared to those calculated by a differential method. The discrepancy is generally of the order of 1.5%.
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    Biopolymers 2 (1964), S. 283-286 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 150
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    Biopolymers 2 (1964) 
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  • 151
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    Topics: Chemistry and Pharmacology
    Notes: It is shown that the formation of the three-strand poly (A + 2U) complex is accompanied by a decrease in optical absorbance at 280 mμ, while the format ion of poly (A + U) is not. This difference makes it possible to demonstrate that in dilute solutions (∼10-4 monomolar), a 1 : 1 mixture of poly A and poly U always forms poly (A + U) at room temperature. At higher temperatures in solutions containing more than about 0.2M sodium ion, poly (A + U) is converted to poly (A + 2U) and free poly A. These results are consistent with the observations reported by Miles and Frazier, using infrared absorption spectra, at much higher polymer concentrations. It is concluded that most of the physicochemical studies of 1 : 1 mixtures of poly A and poly U in dilute aqueous solution refer to the two-stranded species.A simple thermodynamic analysis is developed to explain the two- to three-strand conversion, and with the use of a “phase diagram” showing conditions of stability of the various poly A-poly U structures as a function of salt and temperature, it is possible to estimate the value of the enthalpy of formation of poly (A + 2U).
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  • 152
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    Biopolymers 2 (1964), S. 337-347 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a chromatographic technique, the adsorption of the polyribonucleotides s-RNA and poly-A provided with tri-n-butylammonium ions from an aqueous solution on to the surface of polymeric hydrocarbon granules has been demonstrated. The aqueous solution from which adsorption takes place is the aqueous phase which results on agitating together n-butanol (100), water (130), tri-n-butylamine (10), n-butyl ether (10), and glacial acetic acid (2.5) (parts by volume). Microporous polyethylene granules, microporous fluorinated polyethylene granules, and solid grains of polyethylene powder have been employed as adsorbents. The adsorbed polyribonucleotides could be eluted by aqueous solutions of sodium chloride, urea, or triethylammonium acetate. s-RXA with tri-n-butylammonium counterions could also be adsorbed on polymethacrylic acid in tri-n-butylammonium form and eluted therefrom with aqueous urea solutions. It is considered that the adsorption from aqueous solution of polyribonucleotides with tri-n-butylammonium counterions on polymeric hydrocarbon surfaces is mediated by hydrophobic bond formation. Van der Waals forces may also contribute to the bonding. It is suggested that studies on the adsorption of polynucleotides provided with counterions: possessing nonpolar groups at an aqueous solution-polymeric hydrocarbon interlace may permit the elaboration of experimental systems to serve as models for the evaluation of the role of hydrophobic and van der Waals bonding forces in the interaction of polynucleotides with cell membrane surfaces.
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    Biopolymers 2 (1964), S. 395-398 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Biopolymers 2 (1964), S. 361-380 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Deoxyribonucleic acids (DNA's) extracted from several biological sources have been studied by means of the flow dichroism method, using the transparent coaxial cylinder apparatus. This study has two purposes: (1) to make clear the hydrodynamic behavior of the DNA chain, and the regularity in the orientation of purine and phrimidine bases about the molecular axis; and (2) to develop this particular flow dichroism method as an established device for the study of chain regularity of DNA and other chain polymers. The velocity gradient dependence of dichroism agrees well, to a first approximation, with the behavior of a model of a hydrodynamically equivalent ellipsoid in revolution. Differences between theoretical and empirical curves have been tentatively ascribed to the flexibility of the chain under consideration. Two kinds of data, 1 lie rotary diffusion coefficient and internal dichroism, have been evaluated by a graphical device in which the double logarithmic plots of reduced dichroism and velocity gradient of flow are compared with the theoretical curve. The data obtained have shown good reproducibility for DNA samples prepared by the same method from the same biological source. However, a remarkable difference in internal dichroism and rotary diffusion constant has been observed between DNA groups of different biological origin. The difference may be caused by fragmentation of DNA during the deproteinization procedure, bill the possibility that some of these differences originate in the biological source of the DNA cannot be denied. Orientation of purine and phrimidine bases in aqueous solution is found to be quite regular in direction, as predicted by the Watson-Crick model. Dichroic spectra have shown that the direction of the oscillator dipole corresponding to the 260 mμ absorption band has a different angular relationship to the helical axis than the oscillator dipole for the 220 mμ band.
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    Biopolymers 2 (1964), S. 381-393 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of the super helical structure of synthetic polypeptides, such as poly-γ-benzyl-D (or L)-glutamate (PBDG or PBLG) was carried out. The PEG was dissolved in dimethylformamide (DMF). The solution was either allowed to remain at room temperature for a long time or poured into some fatty acid, such as formic acid, acetic acid, propionic acid, or caprylic acid. Whether the polymer precipitated slowly or rapidly depended upon the aging of the solution or the nature of the acid used. The precipitated gels revealed the coiled coil fibrils, but the feature and degree of coiling varied, depending upon the length of aging or the nature of the acid used for precipitation. After a short aging of the solution, there was no helical structure in the gels. After long aging, very fine-coiled coil macrofibrils or small spindle-like fibrils were obtained. The macrofibrils consisted of the spindle-like fibrils which in turn consisted of microfibrils (diam. 60-70A.). When using the fatty acid precipitation very fine to medium fine super helices were obtained. Extremely fine super helices were obtained in propionic acid. In these gels the PBG chains have an α-helical conformation. When PMLG-DCA solution was stored for a long time, another type of precipitation was obtained, one giving evidence of so-called cross-β crystallization and no coiled coil fibrils. The precipitation of cross-β fibrils was obtained when the concentration of the solution was above 8%.
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    Biopolymers 2 (1964) 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 2 (1964), S. 399-413 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Titration studies of the 1 : 1 helical polynucleotide complex of polyinosinic acid and polycytidylic acid reveal that these two polymers form a complex when the polycytidylic acid is protonated near pH 3. Sedimentation studies show that the protonated complex also has a 1 : 1 stoichiometry. However, the protonated complex is more stable than the unprotonated neutral complex as judged by its thermal stability. The molecular structure of the protonated complex is not the same as the neutral form. Study of the kinetics of the reaction of the protonated complex with formaldehyde suggests that the amino group of cytosine is involved in hydrogen bonds which hold the polynucleotide strands together.
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    Biopolymers 2 (1964), S. 415-444 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The protein sequences now known have been reconstructed as a kind of intriguing logical-mathematical puzzle using information about fragments of the molecules. We wish to show that the reconstruction can be done systematically by repeating a series of elementary operations on these same data governed by a set of well-defined rules. The completely automatic reconstruction of polymer sequences by a high speed digital computer using these operations and rules is demonstrated.
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  • 159
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    Topics: Chemistry and Pharmacology
    Notes: The mechanism of the renaturation of DNA molecules is examined on the basis of the bimolecular interaction of Gaussian chain polymers. In the nucleus formation by hydrogen bonding in segment-segment interaction, two types of interchain interaction, that is, one between complementary chains and one between noncomplementary chains, and one noncomplementary intrachain interaction are considered to be, in competition. Several previously observed characteristics of the renaturation process are displayed by this simple model. In particular it accounts for the dependence of the extent of renaturation on the heterogeneity, molecular weight, and radius of gyration of DNA, and of the ratios of the reaction rates between complementary and noncomplementary segments. Among these variables the ratio of reaction rates has shown to have a quite specific value, as high as the order of 104, which favors the complementary-strand interaction. This very great bias in favor of complementary strand interaction emphasizes that the renaturation phenomena displays the same character of biological specificity that is associated with enzyme-substrate interaction or antigen-antibody interaction. Moreover, since DNA is a good example of a one-dimensional system, it seems to provide a suitable clue for pursuing the analysis of pattern recognition at the macromolecular level.
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    Biopolymers 2 (1964), S. 463-481 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of DL-β-Phenylalanine N-carboxy anhydride adsorbed on polysarcosine dimethylamide has been studied further. This unusual reaction, which is analogous kinetically to reactions catalyzed by enzymes, was called the “chain-effect.” For polymerization of N-carboxy anhydrides by this mechanism it is necessary that the initiating polymer should possess an adsorption site and a terminal base group. The effect is shown to occur with simple compounds such as amino acid dimethylamides but not with poly-L-proline due to the inability of this polymer to adsorb the anhydride. From a study of the reaction of block copolymers of L-proline and sarcosine with DL-β-phenylalanine it is concluded that the relative positions of the adsorption site and terminal base group do not greatly influence the reaction rate, but the accessibility of the adsorption sites is an important factor determining the reactivity of polysarcosine dimethylamides of various degrees of polymerization (n). At high values of n the polymer exists in a coiled form and only those sites close to the terminal base group participate in the reaction. Initial rate studies give a detailed description of the early stage of the chain-effect polymerization. With these data and by use of analog computer techniques the complete reaction has been studied. It is concluded that the poly-DL-β-phenylalanine block produced is not permanently attached to the polysarcosine chain by hydrogen bonds during its formation but that an equilibrium exists between the polysarcosine and the poly-DL-phenylalanine blocks.
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  • 161
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Del Re's method for the study of saturated compounds has been adapted so as to deal with the σ-framework of conjugated molecules. This modified procedure is used in evaluating the σ-contribution to the dipole moments of the nucleic bases and of the A-T and G-C base pairs and also to the free energy change in the tautomeric, equilibria of the bases. Associated with an appropriate Hückel method for evaluating the π-contribution, the results obtained predict a small resultant moment for A-T versus a large moment for G-C. The energy calculations predict the keto and amino forms of the bases to be the most stable forms and cytosine to be the most easily involved in tautomeric shift to the rare form.
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  • 162
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    Biopolymers 2 (1964) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 163
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Temperature jump measurements employing optical rotation to follow transients show an upper limit of 10μsec. on the half time of the helix-random coil relaxation in poly-α, L-glutamic acid. No relaxations are observed under conditions where the polymer exists in completely helical or completely random coil form. Assuming that the helix-coil transition can be described kinetically as a pure growth process, expressions for the relaxation time are derived for three special cases. A comparison is made between the rate of the helix-coil transition and the rate of imide proton exchange.
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  • 164
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    Biopolymers 2 (1964), S. 501-501 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 165
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    Biopolymers 2 (1964), S. 561-574 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Numerical calculations have been done on the exciton spectrum of a schematic model of a linear polymer. The model consists of a random sequence of two kinds of subunit whose energy levels and transition moments are almost, but not quite, the same. The orders of magnitude of parameters are taken from DNA, but the full helical geometry has not been considered. Results are given for the density of energy levels, the dipole transition strength per unit energy, and the distribution of excitation energy along the polymer in individual states. A number of localized exciton states were found.
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  • 166
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    Biopolymers 19 (1980), S. 823-831 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of the DNA-binding oligopeptide distamycin A on the B to A transition of DNA in ethanol/water solutions has been studied by means of CD. (The overbars indicate that it does not matter which particular form of the corresponding families is considered.) The results show that increasing the concentration of distamycin A reverses the A conformation (in 82% ethanol) to the B conformation due to its strong binding and stabilization of the latter. In accordance with previous data for pure aqueous solutions, a site size of 3.5 base pairs is obtained from the studies in water/ethanolic solutions. From the data on the B to A transition in the presence of distamycin A, we estimated the length of the cooperativity ν0 = 10 base pairs.The results demonstrate that the oligopeptide systems of distamycin, as well as those of netropsin, are effective stabilizers of the DNA B-conformation.
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  • 167
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Tetrapeptides with proline in position 2, asparagine or leucine in position 3, and glycine in positions 1 and 4, with end groups free or blocked on the N-terminal side, were studied in their various ionic states in 2H2O and in Me2SO-d6 by 1H- and 13C-nmr. In order to clarify or refine some details, successive substitutions of the residues in these peptides with amino acids enriched to 85% in 13C, or to 85% 13C plus 97% 2H were carried out. The 1H and 13C chemical shifts as well as the 1H-1H, 13C-13C, and 13C-1H coupling constants and the signal intensities show strong similarity of behavior between the tetrapeptides of asparagine and leucine. The main conformational characteristics are (1) the almost total stabilization of the trans conformer in the type I β-turn structure when the peptide is in the zwitterion state dissolved in Me2SO. This is deduced from the 3JC3αH-N3H and the 3JC2′-H3α coupling constants, which both furnish a dihedral angle of φ3 = -90°, and from the positive value of the temperature coefficient of the glycine-4 amide protons, which suggests a type 4 → 1 hydrogen bond; (2) the evolution of cis and trans isomer fractions which change with the ionic state of the peptides in Me2SO, whereas they remain constant in aqueous solution; and (3) the conformation of the pyrrolidine ring as it follows the variations in cis:trans isomer populations together with the side-chain rotamer fractions of the residue in position 3. In the β-turn conformation the isomer cis is less abundant and the pyrrolidine ring is more flexible; this explains the perfect accommodation of the proline residue in position 2 of a bend. The interdependence of these phenomena where interactive forces play a predominant role underlines the importance of cooperative effects in the molecule. The results also suggest that the cis isomer of proline can adapt itself just as well as the trans isomer to position 2 of a type I β-turn.
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  • 168
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    Topics: Chemistry and Pharmacology
    Notes: An algorithm is presented for the Monte Carlo simulation of the decay of fluorescence polarization from segmentally flexible molecules. Based on the random walk model of Brownian motion, the treatment explicitly follows the stochastic changes in the diffusion coefficients as the molecule bends. It includes the effects of a linear restoring force opposing the bending and the effects of hydrodynamic coupling between the translational, rotational, and bending motions. One application is presented: the simulation of anisotropy decay curves for hinged rods. A variety of decay curves are obtained, including single- and multiexponential behavior, and the following conclusions are reached: (1) increasing the flexibility is usually, but not always, accompanied by a more rapid rate of depolarization; (2) reducing the size of the fluorescent subunit will usually, but not always, increase the rate of depolarization; and (3) the complex interplay between the effects of molecular shape, relative sizes of the subunits, restoring force, and orientation of the transition dipoles renders it unlikely that any simple method can be used to interpret anisotrophy data without simulation. In particular, it is not possible to determine the extent of bending by fitting the data with the two-exponential approximation used by some investigators in the past.
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  • 169
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    Biopolymers 19 (1980), S. 977-990 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C-nmr spectra of red seaweed galactans, belonging to the agar and carrageenan groups or having the “intermediate” type of structure, were interpreted on the basis of 13C-nmr spectra of model compounds. Signal assignments have been made for most of the known extreme structures of such galactans. 13C-nmr spectroscopy was shown to be a rapid and convenient method of structural analysis, which permits one to determine the type of galactan structure, the absolute configurations of its constituents (galactose and 3,6-anhydrogalactose), and the positions of the sulfate and O-methyl groups in a polysaccharide molecule.
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  • 170
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    Topics: Chemistry and Pharmacology
    Notes: The dielectric response of human umbilical cord hyaluronic acid in various environments has been studied at microwave frquencies using a resonant microwave cavity as a probe. Both the real and imaginary parts of complex dielectric constant and the loss tangent for hyaluronate solutions are obtained by utilizing equations for perturbation of a resonant cavity. Dielectric changes at room temperature have been observed in aqueous solutions of hyaluronic acid as a function of concentration ranging from 0 to 350 mg/ml. The data indicate the existence of ordered phases in hyaluronate solutions at selective concentrations, that is, exhibiting lyotropic-type transitions. Hyaluronate solutions at 1.5 and 3 mg/ml concentrations have been studied at various pH in the range of 6-8 and at constant ionic strength 0.1. A temperature-dependent transition in hyaluronate solution of 120 mg/ml concentration has been observed at physiological temperature. It is shown that this temperature-dependent behavior can be related to the orientational polarizability term in the Debye theory of polar molecules in liquids.
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  • 171
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    Biopolymers 19 (1980), S. 945-964 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In 1974, Zimm described a theory which predicts that the sedimentation coefficient of high-molecular-weight DNA will decrease as the rotor speed of measurement increases. In 1979, this theory was revised, and the new formula predicts speed-dependence effects that are substantially smaller than the predictions of the original version. This report describes the results of subjecting both the original and the revised versions of the theory to quantitative tests using a well-defined sucrose-gradient system and a DNA of known molecular weight (T4c DNA). T4c bacteriophage is a mutant, whose DNA contains the unmodified base cytosine, instead of the glucosylated hydroxymethylcytosine characteristic of the T-even bacteriophages, and has a molecular weight of 115 ± 3 × 106. The DNA of the wild-type phage (T4D+) was also used in some experiments.In addition to the quantitative tests, the experiments test for an effect first observed by Rubenstein and Leighton, which showed that the sedimentation coefficient measured for T2 DNA depended on the composition of the centrifuge tube used for the measurement (tube composition effect). It can be inferred from this observation that an interaction occurs between particle and tube wall during sedimentation, and this leads to a reduction in sedimentation velocity independent of the reduction in S described by Zimm's theory.The results show that in the range of 25,000-50,000 rpm, the original but theoretically incorrect form of the theory quite accurately describes the sedimentation behavior of both T4c and T4D+ DNA, although T4D+ was a special case in some respects. The revised (corrected) form of the theory predicts much less of a speed-dependence effect than that actually observed. The discrepancy between corrected theory and observation suggests that other factors (perhaps arising from the use of the swinging bucket rotor geometry) are causing the additional observed reduction in S20,w. However, the experiments show that the tube composition effect does not seem to be one of these.
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  • 172
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    Topics: Chemistry and Pharmacology
    Notes: The fixation of cis (NH3)2Cl2Pt(II) to poly(I)·poly(C) leads to the formation of two complexed species. One involves coordination to a single base (accounting for about 70% of the total platinum bound over the rb range 0.07-0.25) and the other to two bases which are not adjacent to each other but may be on the same strand and separated by a loop. Reaction of the platinum compound with poly(I) gives in addition to the above two species a minor one (about 15%, independent of rb over the range 0.05-0.30) in which the platinum is bound to two adjacent bases. The availability of such coordination reduces the dominance of the 1:1 species, which, however, remains the major one (ca. 55%).
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  • 173
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    Biopolymers 19 (1980), S. 1329-1344 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complex of CH3Hg(II) with the accessible cysteines of glyceraldehyde-3-phosphate dehydrogenase (GAPD, EC 1.2.1.12) from rabbit muscle has been studied by phosphorescence and optically detected magnetic resonance (ODMR) spectroscopy. The wavelength dependence of the phosphorescence decay kinetics has also been measured. Comparison of CH3Hg(II)-GAPD with GAPD by these methods shows that a specific optically resolved tryptophan site of GAPD is perturbed by the interaction with a nearby mercury atom. The perturbation on the luminescence and ODMR properties is typical of an external heavy-atom effect. Based on the x-ray diffraction structure of the lobster enzyme, it is proposed that the heavy-atom effect results from the interaction of tryptophan-310 with CH3Hg(II) bound to cysteine-281 in the rabbit muscle enzyme.
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  • 174
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    Biopolymers 19 (1980), S. 1415-1434 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The energy of interaction of a spermine molecule with the A- and B-forms of DNA has been calculated, assuming that the molecule of spermine is fixed in the narrow groove of the DNA helix with the formation of hydrogen bonds between the amino groups of spermine and the phosphate groups of DNA. The atom-atom potentials method was used. Optimal structures for the A-DNA-spermine and B-DNA-spermine complexes are suggested. It is shown that, in agreement with the experimental data, the interaction of the spermine molecule with the A-DNA is energetically more favorable than that with the B-DNA. Two main factors are responsible for this: (1) the distance between neighboring phosphates of the chain in A-DNA (which is about 1 Å less than that in B-DNA) corresponds better to the distance between the amino groups of the propyl part of spermine; and (2) the orientation of phosphate groups in A-DNA inside the groove is preferable for complex formation with spermine to the outside groove arrangement of the phosphates in B-DNA. These conclusions are further confirmed by the calculations for DNA-propane diamine complexes.
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  • 175
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    Topics: Chemistry and Pharmacology
    Notes: The crystal structure of a synthetic analog of valinomycin, cyclo[-(D-Ile-Lac-Ile-D-Hyi)3-] (C60H102N6O18), has been determined by x-ray diffraction procedures. The crystals are orthorhombic, space group P212121, with cell parameters a = 11.516, b = 15.705, c = 39.310 Å, and Z = 4. The atomic coordinates for the C, N, O atoms were refined in the anisotropic thermal motion approximation and for the H atoms in the isotropic approximation. Values of standard (R) and weighted (Rw) reliability factors after refinement are 0.073 and 0.056, respectively. The structure is completely asymmetric. The cyclic molecular backbone is stabilized by six intramolecular hydrogen bonds N—H…O=C, five bonds being of the 4→1 type and one being of the 5→1 type. The side chains are located on the molecular periphery. The conformational state of isoleucinomycin in the crystal is intermediate between the corresponding crystalline states of valinomycin and meso-valinomycin. The observed conformation suggests that complexation could proceed via entry of the ion at the face possessing the L-Lac residues, the less crowded face.
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  • 176
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    Biopolymers 19 (1980), S. 1555-1566 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Possible conformations of lacto-N-tetraose, lacto-N-neotetraose, related disaccharides, and other milk oligosaccharides have been studied by an energy-minimization procedure using empirical potential functions. Lacto-N-tetraose favors a “curved” conformation, while lacto-N-neotetraose favors an approximately “straight” conformation. These two conformations differ mainly in the position of the terminal galactose residue with respect to the rest of the molecule. This difference explains the greater strength of lacto-N-neotetraose compared with lacto-N-tetraose in its ability to inhibit the cross-reaction of blood group P1 fractions with Type XIV pneumococcal antipolysaccharide. Although the favored conformation of lacto-N-tetraose (inactive) agrees with the model proposed by the earlier workers, that for lacto-N-neotetraose (active) differs. The favored conformations for the disaccharides galactose-β(1-4)-N-acetylglucosamine, galactose-β(1-3)-N-acetylglucosamine, and lactose are similar in overall shape, differing only in the nature and orientation of the side groups. This explains their nearly equal inhibitory activity. These theoretical models also explain the increased activity of lacto-N-fucopentaose I over that of lacto-N-tetraose and the relative activities of the substituted lactoses. The present studies suggest that it is the overall shape of the molecule which is important for activity, rather than the terminal β(1-4)-linked galactose residue alone.
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    Biopolymers 19 (1980), S. 1571-1585 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C spin-lattice relaxation times of poly(L-lysine) have been obtained at 67.9 MHz in aqueous solution and in a mixed solvent (40% methanol/60% water). A concomitant determination of the conformation by CD permits the correlation of conformation and rotational diffusion of the polymer. The dependence on pH of the spin-lattice relaxation times of the 13Cα and the side-chain carbon resonances reflects the diffusional motion in the random-coil conformation, in the helix-coil transition, and in the conformation of the α-helix. In the mixed solvent the reorientational correlation time of the Cα-Hα vector increases from τ = 0.37 nsec (random coil) to τ = 12.0 nsec (α-helix). In aqueous solution the correlation time of this vector increases from τ = 0.33 nsec (random coil) to τ ≫ 11 nsec. The reorientation rates of the side-chain methylene groups in the two solvents are markedly different. The reorientation of all methylene groups is reduced in the mixed solvent.
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  • 178
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solid-state conformation of copolymers of β-benzyl-L-aspartate [L-Asp(OBzl)] with L-leucine (L-Leu), L-alanine (L-Ala), L-valine (L-Val), γ-benzyl-L-glutamate [L-Glu(OBzl)], or ∊-carbobenzoxy-L-lysine (Cbz-L-Lys) has been studied by ir spectroscopy and circular dichroism (CD). The ir spectra in the region of the amide I and II bands and in the region of 700-250 cm-1 have been determined. The results from the ir studies are in good agreement with data obtained by CD experiments. Incorporation of the amino acid residues mentioned above into poly[L-Asp(OBzl)] induces a change from the left-handed into the right-handed α-helix. This conformational change for the poly[L-Asp(OBzl)] copolymers was observed in the following composition ranges: L-Leu, 0-15 mol %; L-Ala, 0-32 mol %; L-Val, 0-8 mol %; L-Glu(OBzl), 3-10 mol %; and Cbz-L-Lys, 0-9 mol %.
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    Biopolymers 19 (1980), S. 1667-1673 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dry purified ligamentum nuchae elastin has been investigated for physical aging. The samples were quenched from a temperature (197°C) close to the softening point to a number of measuring temperatures ranging from -20 to +180°C. At each temperature, the small-strain torsional creep properties were determined at a number of elapsed intervals after the quench. Aging effects were found over the whole temperature range, and the creep and aging behavior of elastin turned out to be very similar to that of synthetic polymers.
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  • 180
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    Topics: Chemistry and Pharmacology
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  • 181
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    Biopolymers 19 (1980), S. 1705-1713 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Covalently closed circular DNA can exist in different configurations known as circular, toroidal, and interwound. Changes among these forms can be made in several ways, including the insertion of dye molecules between adjacent base pairs, which tends to untwist the double-helical structure. The aim of this paper is to discuss these configurations, and the changes among them, in the context of classical elastomechanics. The concepts of twisting, linkage and writhing are explained. Simple experiments on a twisted linear-elastic rod are described, and it is shown that although the circular and interwound forms may be modeled in this way, the toroidal form does not occur, being mechanically unstable. Theoretical energy calculations by Levitt on bent and twisted DNA show that DNA exhibits a particular kind of nonlinear elasticity in which there is an unusual coupling between bending and twisting. The aim of the paper is to show qualitatively that this special kind of elasticity can stabilize the toroidal form of closed circular DNA.
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    Biopolymers 19 (1980), S. 1357-1374 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Light-scattering, viscosity, and sedimentation experiments on aqueous solutions of k-carrageenan show that this sulfated polygalactose is an expanded flexible random coil. This expansion is due to long-range interactions that are predominantly electrostatic. Extrapolation of viscosity data to infinite ionic strength provided values for the intrinsic viscosity which were subjected to the Stockmayer-Fixman analysis, giving a value for the Mark-Houwink coefficient under theta-conditions, Kθ, of 0.27. The characteristic ratio, C∞, under these conditions is 7.8, and the conformation factor σ is 2. In a solution of 0.118 ionic strength, where a Mark-Houwink exponent aη of 0.86 is found, the radii of gyration calculated from viscosity data are lower than those found from the angular dependence of scattered light. On the other hand, the radius of gyration found from the sedimentation rate agrees well with the light-scattering radius. The relations between molecular parameters are corrected for the poly-dispersity of the sample.
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    Biopolymers 19 (1980), S. 1407-1414 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 19 (1980) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 185
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    Biopolymers 19 (1980), S. 1475-1489 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An approximate analytic expression for the translational friction coefficient of a toroid modeled as a continuous shell of frictional elements is derived using the Kirkwood approximation. The accuracy of this expression was determined by comparing the friction coefficients predicted by it to those predicted by extrapolated shell-model calculations using the modified Oseen tensor. To show that these calculations do indeed yield the correct friction coefficients, actual translational friction coefficients were determined by observing settling rates of macroscopic model rings or toroids in a high-viscosity silicone fluid. Our conclusion is that the approximate expression yields friction coefficients that are about 1.5-3% low for finite rings. For thin rings, a comparison is also made with the exact result of Yamakawa and Yamaki [J. Chem. Phys. 57, 1572 (1972); 58, 2049 (1973)] for the translational friction of plane polygonal rings. This comparison shows that the approximate expression yields results which are low by 2-3% unless the rings are extremely thin, in which case the error is larger. In the limit of an infinitely thin ring the approximate expression reduces to the Kirkwood result [J. Polym. Sci. 12, 1 (1954)], which is low by 8.3%. We discuss briefly how this work may be useful in determining the structure of DNA compacted by various solvent-electrolyte systems and polyamines.
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    Biopolymers 19 (1980), S. 1451-1474 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Internal Brownian motions of clean φ29 and λ-DNAs have been studied using photon-correlation techniques at both visible (λ0 = 632.8 nm) and uv (λ0 = 363.8 nm) wavelengths. The present dynamic light scattering data, which extend to K2 = 19 × 1010 cm-2, can in every case be satisfactorily simulated by a Rouse-Zimm model polymer with an appropriate choice of the three model parameters. The effects of pH, salt concentration, single-strand breaks, and molecular weight on those model parameters have also been investigated. Intact clean DNAs exhibit surprisingly little variation with pH from 7.85 to 10.25, with salt concentration from 0.01 NaCl to 5.4M NH4Cl, or with molecular weight or GC content. The single-strand breaks have no effect at pH 9.46, but produce dramatic changes in the model parameters at pH 10.0 and 10.25, indicating the introduction of titratable joints at those pHs. The failure of either single-strand breaks or a large change in GC content to alter the model parameters in the neutral pH range is a strong indication that local denaturation is not required for those flexions and torsions that dominate the relaxation of fluctuations in the scattered light. The Langevin relaxation time for the slowest internal mode of a particular Rouse-Zimm model derived from the dynamic light scattering data is compared with pertinent literature data extrapolated to the same molecular weight. The present algorithm for determining model parameters from the light-scattering Dapp vs K2 curve actually yields a Langevin time in fairly good agreement with the literature value. For unknown reasons the light-scattering D0 values generally exceed those obtained from the molecular weight and sedimentation coefficient by about 20%.
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  • 187
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    Biopolymers 19 (1980), S. 1507-1515 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Raman spectra of polyribouridylic acid excited in the uv region, from 363 to 290 nm, are reported. The conformational changes of the polymer from random coil to ordered structure with stacked bases at high and low temperature, respectively, are reflected by important changes in the Raman line intensities; this Raman hypochromism is itself a function of the excitation wavelength - its profile has been determined and shows negative values in the region of 290 nm (near resonance), i.e., hypochromism becomes hyperchromism. Thus the knowledge of the hypochromism excitation profile is important in following order-disorder transition of a polymer using resonance Raman spectroscopy. Theoretical attempts are proposed for explanation, involving not only the relative variations of the molar extinction coefficient on the order-disorder transition of the polymer, but also the damping factors of the vibronic levels. The theoretical curve is found to fit adequately the experimental data over the excitation range, using only the frequency of the O-O transition of uracil and a vibronic linewidth of 2200 cm-1.
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  • 188
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    Biopolymers 19 (1980), S. 2177-2190 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preferential interaction of sodium poly(α-L-glutamate) and poly(α-L-glutamic acid) with the solvent components in water/2-chloroethanol mixtures has been determined using density-increment measurements. The degree of preferential interaction was deduced from the density increments at constant molality of 2-chloroethanol and at constant chemical potential of 2-chloroethanol. Sodium poly(α-L-glutamate) and poly(α-L-glutamic acid) are both preferentially hydrated in the whole range of solvent composition. A dehydration process occurs during the 2-chloroethanol-induced coil-to-helix transition of sodium poly(α-L-glutamate). This dehydration process was attributed to the release of some moles of water from the neighborhood of the peptide bond during the nucleation of the helix. After the conformational transition, sodium poly(α-L-glutamate) is solvated by one 2-chloroethanol molecule. The location of water and 2-chloroethanol molecules in the different parts of the residue (more polar and less polar portions) is also discussed.
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  • 189
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    Biopolymers 19 (1980), S. 2223-2245 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complex formation between tryptamine and mononucleotides and dinucleoside phosphates containing adenine and/or cytosine has been studied at five pD's ranging from 1.1 to 7.4 by proton magnetic resonance spectroscopy. Chemical shifts of base ring protons and the ribose anomeric proton in the nucleotides and indole ring protons in tryptamine were monitored and their changes with pD and intermolecular interactions interpreted qualitatively. Stacked complexes were found to exist at all pD's in the range studied. Complex geometries differ depending on pD. An electrostatic interaction between the tryptamine amino group and the nucleotide phosphate group contributes to complex formation above pD 4 but is not strong enough to shift the dinucleoside phosphate equilibrium towards the unstacked conformer.
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  • 190
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    Biopolymers 20 (1981), S. 169-185 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The IR data for the R1 CO-O-CHR2-CO-NHR3 derivatives are interpreted in terms of a H…π interaction involving the N—H bond and the π orbitals of the ester function and giving rise to a high ν(C=O) frequency and a low ν frequency. The resulting molecular conformation corresponds to the angular values φ # -90°, ψ # 0°. The H…π interaction in MeCO-L-Lac-NHMe is highly destabilized by water and aprotic solvents but is retained in methanol. Considering the high ν(C=O) ester or amide frequency of the middle function in β-folded depsipeptide or peptide sequences, it may be supposed that the residue indexed i + 2 in β turns experiences a H…π interaction which has a stabilizing effect on β turns. Some examples concerning valinomycin and some model compounds are discussed.
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  • 191
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    Biopolymers 20 (1981) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 192
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    Biopolymers 20 (1981), S. 251-268 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The difference between the theories of Manning, on the one hand, and of Odijk and Skolnick and Fixman, on the other, for the polyelectrolyte contribution to the persistence length of DNA is shown to arise entirely from a subtle geometrical error in the theory of Manning. The corrected theory of Manning predicts a negligible polyelectrolyte contribution in 1.0M NaCl and only 33 Å in 0.01M NaCl, thus giving a change in total persistence length by a factor of only 1.07 over that range, in agreement with Odijk. Pertinent data in the literature indicate that the persistence length must change by a factor of ≤ 1.6 between 1.0 and 0.01M NaCl, and very likely by less than a factor of 1.4. Evidently, the intrinsic rigidity of the uncharged double-strand filament dominates the bending rigidity at NaCl concentrations above 0.01M.
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  • 193
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structures of L-3,4-dehydroproline, t-butoxycarbonyl-L-3,4-dehydroproline amide, and acetyl-L-3,4-dehydroproline amide have been determined. L-3,4-Dehydroproline is orthorhombic with a = 16.756, b = 5.870, c = 5.275 Å, and Z = 4; t-butoxycarbonyl-L-3,4-dehydroproline amide is orthorhombic with a = 6.448, b = 8.602, c = 21.710 Å, and Z = 4; acetyl-L-3,4-dehydroproline amide is monoclinic with a = 4.788, b = 10.880, c = 7.785 Å, β = 105.25°, and Z = 2. The final R value for the L-3,4-dehydroproline is 0.046 based on 529 reflections; for t-butoxycarbonyl-L-3,4-dehydroproline amide, 0.050 based on 792 reflections; and for acetyl-L-3,4-dehydroproline amide, 0.058 based on 632 reflections. The structures clearly establish that the free amino acid exists in the zwitterionic form in the crystalline state. The molecular conformations of the t-Boc and acetyl derivatives consist of two planes: one involving the primary amide and the other the remaining atoms of the molecule. The acetyl-L-3,4-dehydroproline amide contains a tertiary amide bond in the cis conformation. To the best of our knowledge, this is the first example of a cis bond in an acetyl derivative of an amino acid or peptide. At variance with the previously reported proline amides, which present φ and ψ values corresponding to those of a right-handed α-helical conformation (conformation A), the t-Boc and acetyl derivatives both have φ and ψ values corresponding to a collagenlike conformation (conformation F).
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  • 194
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    Biopolymers 20 (1981), S. 359-371 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure of thermally denatured Type I collagen has been studied using laser light scattering. The results indicate that the diffusion coefficients of α-chains and β- and γ-components are 1.550 ± 0.08 × 10-7, 1.000 ± 0.05 × 10-7, and 0.835 ± 0.04 × 10-7 cm2/sec, respectively, at temperatures between 20 and 40°C. It is concluded from diffusion data that these species have hydrodynamic radii of about 13.8 nm (α-chain), 21.5 nm (β-component), and 25.7 nm (γ-component), consistent with previous studies of thermal denaturation by light scattering. It is also concluded, based on volume calculations, that a large volume increase occurs when the triple helix unfolds. Homodyne correlation functions for two component mixtures of α-chains and β-and γ-components appeared to decay exponentially. In all but one case discussed the correlation function could be fitted with a single component having a translational diffusion coefficient which was an intensity weighted average of the diffusion coefficient of each component present.
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  • 195
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    Biopolymers 20 (1981), S. 387-397 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Circular dichroic spectra and oscillator strengths of the π-π transition near 190 nm are calculated for helical (Gly)6 and (Ala)6 at 30° intervals of the backbone torsion angles (φ,ψ) over the range -180° ≤ φ ≤ -60°, -60° ≤ ψ ≤ 180°, using the partially dispersive normal mode treatment of the dipole interaction model. Polarizabilities of atoms and the NC′O group are those determined semiempirically in previous studies. Calculations for (Ala)6 at (φ,ψ) angles corresponding to the α-helix, the poly(Pro) II helix, a collagen single helix, a poly-(MeAla) helix, and single β-helices are found to agree well with most of the available experimental data.
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  • 196
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of the fluorinated antimalarial drug fluoroquine [7-fluoro-4-(diethyl-amino-1-methylbutylamino)quinoline] with DNA, tRNA, and poly(A) has been investigated by optical absorption, fluorescence, and 19F-nmr chemical-shift and relaxation methods. Optical absorption and fluorescence experiments indicate that fluoroquine binds to nucleic acids in a similar manner to that of its well-known analog chloroquine. At low drug-to-base pair ratios, binding of both drugs appears to be random. Fluoroquine and chloroquine also elevate the melting temperature (Tm) of DNA to a comparable extent. Binding of fluoroquine to DNA, tRNA, or poly(A) results in a downfield shift of about 1.5 ppm for the 19F-nmr resonance. The chemical shift of free fluoroquine depends on the isotopic composition of the solvent (D2O vs H2O). The solvent isotope shift is virtually eliminated by fluoroquine binding to any one of the nucleic acids. 19F-nmr relaxation experiments were carried out to measure the spin-lattice relaxation time (T1), 19F{1H} nuclear Overhauser effect (NOE), off-resonance intensity ratio (R), off-resonance rotating-frame spin-lattice relaxation time (T1ρoff), and linewidth for fluoroquine in the nucleic acid complexes. By accounting for intramolecular proton-fluorine dipolar and chemical-shift anisotropy contributions to the fluorine relaxation, all of the relaxation parameters for the fluoroquine-DNA complex can be well described by a motional model incorporating long-range DNA bending on the order of a microsecond and an internal motion of the drug on the order of a nanosecond. Selective NOE experiments indicate that the fluorine in the drug is near the ribose protons in the RNA complexes, but not in the DNA complex. Details of the binding evidently differ for the two types of nucleic acids. This study provides the foundation for an investigation of fluoroquine in intact cells.
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  • 197
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Empirical conformational energy calculations have been carried out for N-methyl derivatives of alanine and phenylalanine dipeptide models and N-methyl-substituted active analogs of three biologically active peptides, namely thyrotropin-releasing hormone (TRH), enkephalin (ENK), and luteinizing hormone-releasing hormone (LHRH). The isoenergetic contour maps and the local dipeptide minima obtained, when the peptide bond (ω) preceding the N-methylated residue is in the trans configuration show that (1) N-methylation constricts the conformational freedom of both the ith and (i + 1)th residues; (2), the lowest energy position for both residues occurs around φ = -135° ± 5° and ψ = 75° ± 5°, and (3) the αL conformational state is the second lowest energy state for the (i + 1)th residue, whereas for the ith residue the C5 (extended) conformation is second lowest in energy. When the peptide bond (ωi) is in the cis configuration the ith residue is energetically forbidden in the range φ = 0° to 180° and ψ = -180° to +180°. Conformations of low energy for ωi = 0° are found to be similar to those obtained for the trans peptide bond. In all the model systems (irrespective of cis or trans), the αR conformational state is energetically very high. Significant deviations from planarity are found for the peptide bond when the amide hydrogen is replaced by a methyl group. Two low-energy conformers are found for [(N-Me)His2]TRH. These conformers differ only in the φ and ψ values at the (N-Me)His2 residue. Among the different low-energy conformers found for each of the ENK analogs [D-Ala2,(N-Me)Phe4, Met5]ENK amide and [D-Ala2,(N-Me)Met5]ENK amide, one low-energy conformer was found to be common for both analogs with respect to the side-chain orientations. The stability of the low-energy structures is discussed in the light of the activity of other analogs. Two low-energy conformers were found for [(N-Me)Leu7]LHRH. These conformations differ in the types of bend around the positions 6 and 7 of LHRH. One bend type is eliminated when the active analog [D-Ala6,(M-Me)Leu7]LHRH is considered.
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  • 198
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Based on steric and electrostatic considerations, the prerequisites for binding to DNA via the intercalation mechanism are proposed. Steric contour energy curves are presented to demonstrate the region inaccessible to an intercalant. They are calculated with a 6-n (n = 14) potential. This method is a soft potential analog of an excluded-volume approach. Electrostatic contours on the steric surface illustrate the relatively positive and negative regions of the binding site. The principal intercalation sites, predicted to fit into B-DNA via a tetramer-duplex unit, and the unconstrained dimer-duplex units, obtained in crystal structures, are examined. These contours illustrate the requirements of size, conformation, and net atomic charges necessary for intercalation and optimum binding. Based on the limited space available for intercalation by the presence of the backbone and the maximum base-pair separation of 8.25 Å, an Essential Metabolite Exclusion Hypothesis is presented.
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  • 199
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    Biopolymers 20 (1981), S. 345-357 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In carbonate buffer at pH 10.5, a transparent solution of poly(L-lysine HBr) was obtained up to fairly high concentration of 3 g/dl at room temperature. The hydrodynamic behavior of the solution has been studied by sedimentation analyses and viscosity measurements. A dimer form for high concentrations and a monomer form for low concentrations were inferred. The dimer and monomer forms were assigned to a β-structure and α-helix, respectively, based on the CD and optical rotary dispersion spectra. Using CD spectroscopy, a reversible transition between α-helix and β-structure was observed as a function of either poly(L-lysine HBr) concentration or temperature. An aggregated form which was assigned to the antiparallel pleated sheet appeared at 50°C on the basis of its ir spectrum.
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  • 200
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    Biopolymers 20 (1981), S. 707-718 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Observations of induced circular dichroism (CD) bands in chloroform solution demonstrate the formation of specific, asymmetric complexes of the aromatic ligands 2-pyridone and 2,6-dichlorobenzoic acid with cyclic dipeptides of the general formula cyclo(L-Pro-X). The induced CD changes sign with the configuration of X due to subtle influences of the side chain on the geometry of the complex. Computations of interaction energies suggest that a plausible model for the complex of an aromatic ligand with the -CONH- of the cis secondary amide is a nearly planar arrangement of six heavy atoms in a ring containing two hydrogen bonds. The observed CD is matched by that computed for a tilt of the aromatic ligand toward the side chain of X. Binding constants were determined from the induced CD as a function of ligand concentration. For dichlorobenzoic acid these are about 450m-1 for the secondary amide and 50m-1 for the tertiary amide. For pyridone the binding constant is about 45m-1 for either the secondary or tertiary amide. For comparison self-dimerization constants determined by vapor-pressure osmometry in chloroform solution at 25°C are 870, 350, 50, and 20m-1 for pyridone, benzoic acid, dichlorobenzoic acid, and cyclo(L-Pro-Gly), respectively.
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