ALBERT

All Library Books, journals and Electronic Records Telegrafenberg

Your email was sent successfully. Check your inbox.

An error occurred while sending the email. Please try again.

Proceed reservation?

Export
Filter
  • Wiley-Blackwell  (32,307)
  • 1995-1999  (21,397)
  • 1980-1984  (8,929)
  • 1950-1954  (1,981)
  • 1999  (1,566)
  • 1998  (7,078)
  • 1996  (12,753)
  • 1982  (8,929)
  • 1950  (1,981)
Collection
Years
  • 1995-1999  (21,397)
  • 1980-1984  (8,929)
  • 1950-1954  (1,981)
Year
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 236 (1996), S. 111-127 
    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: Neuartige Fluoropolyether-Polyol-Harze, die mit konventionellen Härtern wie Polyisocyanaten oder Melaminen aushärtbar sind, wurden hergestellt. Zunächst wurden oligomere NCO-terminierte Prepolymere durch Addition von Fluorpolyether-Makrodiolen unterschiedlicher Molekulargewichte an Isophorondiisocyanate erhalten. Durch die Reaktion dieser Prepolymeren mit Trimethylolpropan wurden endständige Hydroxygruppen eingeführt. Die Viskosität von Lösungen dieser Harze wurde bei unterschiedlichen Konzentrationen (Massenbruch 0,4-0,8) und Temperaturen (25°C-65°C) gemessen. Die erhaltenen Werte wurden auf der Basis der Erickson-Gleichung (Konzentrationsabhängigkeit von η) und unter Berücksichtigung des WLF-und des Arrhenius-Modells (Temperaturabhängigkeit von η) diskutiert. Das thermische Verhalten der Harze und von ausgehärteten Filmen wurde mit DSC bestimmt. Dabei wurden zwei Glasübergange beobachtet, die den separierten fluorhaltigen und nicht-fluorhaltigen Phasen zugeordnet werden können. Die Analyse des Zugverhaltens der Filme zeigte besonders bei den mit Isocyanat gehärteten Proben ein ausgeprägtes hart-plastisches Verhalten. Diese Werkstoffe erscheinen für die Anwendung als hoch-wertige, dauerfeste und klare Beschichtungen geeignet.
    Notes: New fluoropolyether polyolic resins are presented suitable to be cured with conventional hardeners as polyisocyanates or melamines. These resins are prepared by addition of fluoropolyether macrodiols (Fomblin® ZDOLTX) of various molecular weights to isophorone diisocyanate (IPDI) to give oligomeric NCO-terminated prepolymers. The final hydroxy functionality is obtained by the reaction of those prepolymers with trimethylolpropane (TMP). The viscosity of the resins is measured at various concentrations (weight fraction 0.8 - 0.4) and temperatures (T = 25-65°C). The results are discussed in terms of the Erickson equation (η vs. concentration) and using the WLF and Arrhenius models (η vs. T). The thermal behavior is studied by DSC for both the resins and cured films indicating the presence of two Tgs, corresponding to the segregated fluorinated and hydrogenated phases, the former particularly evident with the highest molecular weights of the fluorinated macromer. Tensile curves of selfsupported films are then analyzed showing an evident tough-plastic behavior especially for the isocyanate-cured films. The application of such materials as high-durability clear coats is finally proposed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 237 (1996), S. 1-44 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Zur Verbesserung der Maßhaltigkeit und der Zähigkeit von gehärteten Melamin-Formaldehyd-Harz-Formmassen (MF) wurden teilverträgliche, methylolgruppenhaltige Epoxidharze (EP) auf Bisphenol A-Basis hergestellt und charakterisiert. Die Vernetzung solcher Epoxyresolharze durch 2-Ethyl-4-methylimidazol in Gegenwart von MF-Harz wurde untersucht. Spritzgepreßte Probekörper zeigen eine Zweiphasenstruktur; die EP-Phase kann als Wirt für carboxy-funktionalisierte, oligomere NBR-Kautschuke (CTBNX) dienen, die für sich allein in MF-Harzen nicht wirksam sind. Unter der Voraussetzung von kovalenten Bindungen in der Phasengrenzfläche kann durch den Zusatz von 0,5 bis 4 Gew.-% CTBNX zur MF-Formmasse bei EP-Anteilen bis 20 Gew.-% eine 50 bis 100proz. Steigerung von Bruchdehnung und Schlagzähigkeit erreicht werden, ohne daß Steifigkeit und Wärmeformbeständigkeit wesentlich abfallen. Bei moderaten EP/CTBNX-Gehalten wird zusätzlich die Nachschwindung von MF-Formteilen vermindert.
    Notes: In order to improve dimension stability and toughness of melamine formaldehyde moulding materials (MF), compatible bisphenol A epoxy resins (EP) with additional methylol groups were synthesized and characterized. Crosslinking of those epoxyresol resins with 2-ethyl-4-methylimidazole in the presence of MF resin was investigated. Transfer-moulded specimens revealed a two-phase morphology in which the EP phase is used as a host for modification with carboxylic functionalized oligomeric NBR rubber (CTBNX), which is not effective in MF moulding materials alone. The addition of 0.5 - 4 wt.-% CTBNX to the MF moulding materials at an epoxy content of maximum 20 wt.-% results in 50-100 % increase of elasticity and toughness without serious decrease in stiffness and heat deflection temperature, provided that covalent interfacial bonds exist. In addition, the post-shrinkage of MF parts decreases if a moderate EP/CTBNX content is introduced.
    Additional Material: 26 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 238 (1996), S. 11-30 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der gleichzeitige Einfluß des Verhältnisses von Fließhilfsmittel (Paraloid K 120N), Rußart und Schlagzähmodifikator (CPE 3615 und Kane Ace B56 A) auf die wichtigsten physiko-mechanischen Eigenschaften unplastifizierter PVC-Mischungen wurde studiert.Die erhaltenen Resultate wurden mathematisch verarbeitet und graphisch als Funktionsflächen dargestellt. Bemerkenswert ist, daß die Einführung von 2,5 und 5 Teilen Ruß eine Verbesserung der physico-mechanischen Eigenschaften ermöglicht. Dieses Resultat ist durch die Anwesenheit der Schlagzäh- und Fließmodifikatoren zu erklären.
    Notes: The concurrent influence of the processing aid (Paraloid K 120N) and the carbon black ratio, as well as the nature and the ratio of the impact modifier (CPE 3615 and Kane Ace B56 A) on the main physico-mechanical characteristics of the poly(vinyl chloride)-based unplasticized mixtures have been studied. The results obtained, processed mathematically and plotted graphically in the form of response surfaces, evidenced that the improvement of certain physico-mechanical properties becomes possible by the introduction of 2.5 parts and 5.0 parts carbon black into these compounds. This is due to the introduction of impact modifiers and processing aids into the mixtures.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 238 (1996), S. 63-71 
    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 neuartiger Polyhydrazide mit endständigen Phenoxygruppen wurde aus äquimolaren Anteilen von Dicarbonsäuredichloriden und Phenoxyterephthalsäuredihydrazid durch Lösungspolykondensation in N-Methyl-2-pyrrolidinon (NMP) bei niedriger Temperatur hergestellt. Durch thermische Cyclisierung der Polyhydrazide wurden die entsprehchenden Poly(1,3,4-oxadiazol)e mit endständigen Phenoxygruppen erhalten. Die Polymeren wurden durch Viskosimetrie, Löslichkeitsuntersuchungen, IR-Spektroskopie, Differentialkalorimetrie und Thermogravimetrie charakterisiert.
    Notes: A series of new polyhydrazides containing pendent phenoxy groups has been synthesized by low-temperature solution polycondensation of equimolar amounts of diacid dichlorides and 2-phenoxyterephthalic dihydrazide in N-methyl-2-pyrrolidi-none (NMP). The thermal cyclization of the polyhydrazides gave the corresponding poly(1,3,4-oxadiazole)s containing pendent phenoxy groups. The polymers were characterized by viscometry, solubility measurements, IR spectroscopy, differential scanning calorimetry (DSC) and thermogravimetric analysis.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 238 (1996), S. 105-117 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Ein Ethylen-Vinylacetat-Copolymeres (EVA) mit 12% Vinylacetat-Gehalt wurde mit Trimethylolpropantrimethacrylat (TMPTMA) als Sensibilisator mit Elektronen bestrahlt. Die mechanischen und elektrischen Eigenschaften der bestrahlten Copolymerproben wurden untersucht. Die Resultate zeigen, daß sich Zugfestigkeit und Bruchdehnung zunächst mit zunehmender Strahlungsdosis verbessern und bei Überschreiten einer optimalen Strahlungsdosis und Sensibilisatorkonzentration wieder verschlechtern. Durch die Bestrahlung wird eine Vernetzung des Polymeren ausgelöst, die auf den sich mit der Strahlungsdosis erhöhenden Gelanteil zurückgeführt wird. Im Vergleich mit den Originalproben nehmen sowohl die Dielektrizitätskonstante als auch der dielektrische Verlustfaktor durch die Elektronenbestrahlung ab.
    Notes: Ethylene-vinyl acetate (EVA) copolymer (12% vinyl acetate content) is subjected to electron beam irradiation using trimethylolpropane trimethacrylate (TMPTMA) as a radiation sensitizer. Mechanical and electrical studies of these irradiated samples show that the strength properties (tensile strength, elongation at break) are increased with radiation dosage up to an optimum radiation dose and sensitizer level above which the properties begin to deteriorate. Crosslinking of the polymer takes place on irradiation which is attributed to an increased gel content with increasing radiation dose. Compared to the original samples both dielectric constant and dielectric loss factor decrease for samples subjected to irradiation.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 238 (1996), S. 143-163 
    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: Cellulose-p-toluolsulfonsäureester (Cellulosetosylate) lassen sich durch homogene Umsetzung von Cellulose in einer Lösung aus N,N-Dimethylacetamid und LiCl mit Tosylchlorid (Tos-Cl) und Triethylamin in 24 h bei 8°C in hoher Ausbeute und mit minimalem Einbau von Chlordesoxy-Gruppen herstellen. Die unterschiedlichen Celluloseausgangsmaterialien hatten durchschnittliche Polymerisationsgrade von 280 bis 5100. Die Produkte wurden mit Elementaranalyse, 13C-NMR- und FTIR-Spektroskopie und durch Bestimmung der Grenzviskositäten charakterisiert. Die Erhöhung des Molverhältnisses Tos-Cl/Anhydroglucose-Einheit (AGU) von 0.6 auf 9.0 führte zu einem Anstieg des Substitutionsgrades (DS) von 0.4 bis auf einen Maximalwert von 2.3. Die Cellulosetosylate sind in herkömmlichen organischen Lösungsmitteln wie Dimethylsulfoxid (im gesamten DS Bereich) und in N,N-Dimethylacetamid, N,N-Dimethylformamid, Aceton, Tetrahydrofuran und Trichlormethan (in Abhängigkeit von DS) löslich. Durch 13C-NMR-Spektroskopie wurde nachgewiesen, daß die Tosylierung am O-6 Atom der AGU schneller als an den O-2/3 Atomen erfolgt. Die Analyse der korrespondierenden Ioddesoxycellulosen, die durch Umsetzung mit NaI in Acetylaceton synthetisiert wurden, bestätigte dies zusätzlich. Darüber hinaus wurden wichtige Eigenschaften der Cellulosetosylate wie die Stabilität gegenüber Alkali und thermischer Beanspruchung untersucht.
    Notes: Pure cellulose p-toluenesulfonates (tosylates) with an insignificant formation of chlorodeoxy groups were prepared by reacting cellulose dissolved in a solution of N,N-dimethylacetamide and LiCI with tosylchloride (Tos-CI) in the presence of triethylamine within 24 h at 8°C. Various cellulosic starting materials with a degree of polymerization from 280 to 5 100 were used. The samples obtained were characterized by means of elemental analysis, FTIR and 13C NMR spectroscopy, and their intrinsic viscosities. The rise of the molar ratio of Tos-CI/anhydroglucose unit (AGU) from 0.6 to 9.0 leads to an increase in the degree of substitution (DS) from 0.4 up to a maximum value of 2.3. The cellulose tosylates are readily soluble in common organic solvents like dimethyl sulfoxide (within the whole DS range) and in N,N-dimethylacetamide, N,N-dimethylformamide, acetone, tetrahydrofuran and trichloromethane depending on DS. As revealed by 13C NMR spectroscopy a faster tosylation takes place at the O-6 atom of AGU compared with the O-2/3 atoms. This was additionally confirmed by analysis of the corresponding iododeoxy celluloses synthesized with NaI in acetylacetone. Furthermore, some important properties as stability against alkaline and heat were studied as well.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 239 (1996), S. 27-32 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Herstellung einer SiC-Oberfläche auf Kohlefasern unter Verwendung einer Sol-Gel-Mischung von Tetraethylorthosilikat (TEOS) und Phenolharz wurde untersucht. FTIR- und SEM-Untersuchungen zeigten, daß die SiC-Oberfläche durch carbothermische Reduktion der Sol-Gel-Mischung bei 1 420°C innerhalb von 15-20 min in einer Argon-Atmosphäre gebildet werden kann. Mittels TGA konnte gezeigt werden, daß die SiC-Beschichtung die thermo-oxidative Stabilität der Kohlefasern erhöht. Bei der erreichten SiC-Schichtdicke von 0,47 μm, bei einem C/Si-Verhältnis von 4, zeigt sich keine Beeinflussung der mechanischen Stabilität der Kohlefasern.
    Notes: The preparation of a SiC coating on a carbon fiber surface using a sol-gel mixture of tetraethyl orthosilicat (TEOS) and phenolic resin was studied. FTIR and SEM investigations indicated that the SiC coating can be formed by carbothermal reduction of the sol-gel mixture at 1420°C for 15-20 min in an argon atmosphere. TGA of the coated fiber was also performed, showing that the SiC coating improves the thermooxidative stability of the carbon fiber. With the thickness of the obtained coating of 0.47 μm using a C/Si ratio of 4, this treatment does not affect the carbon fiber strength.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 239 (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: Diese Mitteilung behandelt den Einfluß von oligomeren Polypropylen- und Polybutylenölen mit unterschiedlichem Molekulargewicht auf die adhäsiven Eigenschaften von ataktischem Polypropylen (aPP) und dessen Mischungen mit einem Styrol-Ethylhexylacrylat-Copolymeren. Die mechanische Adhäsionsarbeit Am von Mischungen, die ataktisches Polypropylen und das Oligomere enthalten, steigt mit dem Molekulargewicht des Oligomeren, was im Fall des Propylenöls signifikanter ist. Im Fall der ternären Mischungen des ataktischen Polypropylens mit dem Styrol-Ethylhexylacrylat-Copolymeren und Oligomeren wird ein Adhäsions-Maximum beobachtet, wenn der Gehalt an Styrol-Ethylhexylacrylat-Copolymeren in der Mischung ungefähr 30 Gew.-% erreicht. Wenn kein Oligomeres in der Mischung vorhanden ist, kann man bei dieser Zusammensetzung ein Adhäsions-Minimum beobachten, was auf die Unverträglichkeit der übrigen Komponenten zurückzuführen ist.
    Notes: This paper deals with the influence of oligomers, namely propylene oil and butylene oil, of different molecular weight on the adhesive properties of atactic polypropylene (aPP) and its mixtures with styrene-2-ethylhexyl acrylate (S-EHA) copolymer. The mechanical work of adhesion Am of the mixture containing atactic polypropylene and oligomer increases with the molecular weight of the oligomer, which was more significant in the case of propylene oil. For ternary mixtures aPP-S-EHA copolymer/oligomer a maximum of adhesion can be observed if the content of the S-EHA copolymer in the mixture reaches about 30 mass-%. In the absence of oligomers in the mixture a minimum of adhesion can be observed for this composition, which can be attributed to the incompatibility of the remaining components.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 9
    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: After comparison of three catalyst systems, i.e. [Nd(Oct)3/Al2Cl3ET3/Al(i-But)3, Ni(Oct)2/BF3OEt2/AlEt3 and Al(i-But)3/I2/TiCl4] the titanium catalyst system was used for the copolymerization of 1,3-butadiene with propylene oxide. The effects of monomer ratio on copolymer composition, conversion, microstructure, molar mass and molar mass distribution as well as of time of polymerization and of the aluminium/titanium ratio were evaluted. The copolymerization parameters were determined according to Kelen-Tüdős as rbutadiene = 0,9 and rpropylene oxide = 3,9. Copolymerization was confirmed by 13C NMR spectroscopy and extract evaluation combined with 1H NMR spectroscopy.
    Notes: Für die Copolymerisation von 1,3-Butadien mit Propylenoxid wurde nach dem Vergleich der drei Katalysatorsysteme Nd(Oct)3/Al2Cl3ET3/Al(i-But)3, Ni(Oct)2/ BF3OEt2/AlEt3 und Al(i-But)3/I2/TiCl4 das Titankatalysatorsystem eingesetzt. Neben dem Einfluß der Monomerzusammensetzung auf den Umsatz, die Microstruktur, die Copolymerzusammensetzung, die Molmassen sowie die Molmassenverteilungen wurden auch die Polymerisationszeit und das Aluminium/Titan-Verhältnis untersucht. Die Copolymerisationsparameter wurden nach Kelen-Tüdős zu rButadien = 0,9 und rPropylenoxid = 3,9 bestimmt. Der Copolymernachweis erfolgte über 13C-NMR-Spektroskopie und Extraktionsuntersuchungen in Verbindung mit 1H-NMR-Spektroskopie.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 239 (1996), S. 191-199 
    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: Phosphorhaltige Polyurethane (PU-P) auf der Basis von Bisphenol A wurden durch N-Alkylierung hergestellt und mittels IR- und 1H NMR-Spektroskopie charakterisiert. Physikalische und thermische Eigenschaften dieser Polyurethane wurden mittels Differentialkalorimetrie, Thermogravimetrie, Röntgenbeugung und Untersuchungen der Löslichkeit, der Feuerbeständigkeit (Sauerstoffindex, LOI) und der reduzierten Viskosität bestimmt. Die Glastemperaturen der N-alkylierten Polymeren sanken von 120°C für das Ausgangspolymere bis auf 29°C für das N-alkylierte Polyurethan mit 2 Gew.-% Phosphor. Die Viskosität der N-alkylierten Polyurethane nahm von 0,36 dL g-1 auf 0,24 dL g-1 ab. Die phosphorhaltigen Polyurethane besitzen eine geringere thermische Stabilität und bessere Löslichkeit sowie höhere Feuerbeständlgkeit als das Ausgangspolymere. Die Röntgenstreuexperimente ergaben, daß ein erhöhter Phosphorgehalt der Polyurethane die Kristallinität herabsetzt.
    Notes: Phosporus-containing polyurethanes (PU-P) based on bisphenol A were prepared by N-alkylation. The structures of N-alkylated polyurethanes were characterized by IR and 1H NMR spectra. Physical and thermal properties of the phosphorus-containing polyurethanes were investigated with differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction, tests of solubility, limiting oxygen index (LOI) and reduced viscosity. Tg of the N-alkylated polymers decreased from 120°C for the starting polymer to 29°C of the 2.0 wt.-% phosphorus-containing polyurethanes. The viscosity of N-alkylated polyurethanes also decreased from 0.36 dL g-1 to 0.24 dL g-1. The thermal stability of polyurethanes decreased on the introduction of phosphorus groups. The LOI values of polyurethanes showed that fire resistance of phosphorus-containing polyurethanes was enhanced. X-ray diffraction measurements showed that the increased phosphorus content was accompanied by decreased crystallinity of the polyurethanes. The solubility of PU-P was improved.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 11
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This question was addressed using various methods to monitor the process of curing and state of the final network. Attention was particularly focused on the possible inhomogeneous network formation as a consequence of the crosslinking process. An analysis of experimental data has revealed that some cured resins can be considered as homogeneous as the corresponding uncrosslinked materials. Resins cured by simple stepwise alternating chemistries, with good compatibility of components, usually fulfill the criterion of homogeneity. A family of epoxy resins cured with polyamines belongs to this category. Nodular structures seen by electron microscopy are a result of interaction of the electron beam or etching. Such structures are also observed for uncrosslinked polymers investigated under the same conditions. Formation of inhomogeneities in a number of thermoset systems is due to (a) chainwise mechanism of network formation with fast propagation inducing cyclization and steric volume exclusion and (b) poor compatibility of components of the system made stronger by increasing molecular weights and crosslinking during curing. Networks formed by freeradical polymerization and copolymerization of polyvinyl monomers can serve as an example of crosslinking-driven formation of inhomogeneities.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 12
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The base and transition metal catalyzed isomerization of allyl and crotyl ethers affords a facile, high yield route to the preparation of a variety of mono-, di-, and multifunctional 1-propenyl and 1-butenyl ethers. Employing this novel method, monomers containing epoxide, ester, ether carbonate and urethane groups can be prepared from their readily available allyl and crotyl precursors. In general, these monomers display very high reactivity in cationic polymerizations. In our work, we have focused on photoinduced cationic polymerizations of these monomers using diaryliodonium and triarylsulfonium salt photoinitiators. To study these very fast photopolymerizations, extensive use of real-time infrared spectroscopy was made. Employing this technique, the effects of monomer and photoinitiator structure on the rates of polymerization were studied.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 240 (1996), S. 137-149 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rubber elasticity is associated with changes in configurational entropy of a long chain. Because the chain cannot change its configuration instantaneously, there is a time delay in deformation to an applied force. This delayed response is the source of viscoelasticity and hysteresis energy loss of elastomer networks. Many tire performance properties are related to the viscoelasticity of tire components. Wet and dry traction of tire is related to the energy loss of the tread material at very high frequencies. On the other hand, rolling resistance of tire is characterized by the energy loss of tread material at relatively low frequencies. The dynamic viscoelastic properties of elastomer network shows characteristic zones on a frequency scale. At very high frequencies the energy loss is controlled by the segmental motions of the polymer chain. At lower frequencies the energy loss is related to the longer range motions of the chain. A series of polymers was synthesized to study the effect of micro- and macro-structure of the polymer on the viscoelastic properties of tread compounds and their tire performance properties. As expected from the theory, the wet traction of the tire was highly correlated to the segmental motions of the chains; namely, the glass transition temperature of the polymer. The energy loss of the compounds at a higher temperature, however, was related to the macrostructure of the polymer chain. Those examples illustrate that the fundamental understanding of the theory of elastomer network allows a tire engineer to obtain the best balance of tire performance characteristics.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 14
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 240 (1996), S. 171-180 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cationic, anionic, and radical ring-opening polymerization of spiro and bicyclic monomers, and their application to network polymers have been developed. Bicyclo orthoesters (BOEs), spiro orthoesters (SOEs), and spiro orthocarbonates (SOCs) were polymerized by cationic double ring-opening. Bicyclobis(γ-butyrolactone)s and spirobis(γ-butyrolactone)s were copolymerized with epoxides by anionic alternating ring-opening. Polymers from SOCs bearing exomethylene groups consisted of ring-opened and vinyl polymerized units. The degree of ring-opening of SOCs depended upon the number of rings and steric hindrance. The radical polymerization of vinylcyclopropanone cyclic acetals depended on the ring-size. With the monomers bearing 5- and 6-membered acetal rings, single ring-opened polymers were obtained. With the monomer bearing 7-membered acetal ring, the polymer mainly consisted of double ring-opened unit. These monomers could be crosslinked by bifunctionalization. Poly(cyclic orthoester)s linked by covalent bonds with dithiols to bifunctional SOEs were crosslinked by acid catalysts, and the reversible crosslinking-depolymerization system could be controlled by temperature.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 15
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 240 (1996), S. 205-211 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyester urethane network elastomers with incorporated hard segment oligomers have been prepared by poly(ethylene adipate)glycol (PEA), 2,4-tolylene diisocyanate (TDI), and 1,4-butanediol (BD). These hard segment oligomers were hydroxy-terminated oligomers ([BD-TDI]n-BD; n=1,3), obtained by reacting BD with TDI. Concentrations of allophanate as a cross-linking site were determined by the amine degradation method. Hard segment moieties were obtained by a novel selective hydrolysis of soft segments in the elastomers. Molecular weight distributions of hard segment were measured by means of GPC. Mechanical and thermal properties were measured. Dependence of rubber elasticity on physical cross-linking between normal elastomers and the elastomers with incorporated hard segment oligomers were discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 16
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly (vinyl alcohol) with pendent styrylpyridinium groups (SbQ) is insolubilized by photoirradiation. An association takes place in SbQ groups. The association of polymer chains becomes marked with increasing the number of SbQ groups. Mainly intermolecular crosslinks were formed. Transparent and homogeneous macrogels consisting of several intermolecular crosslinks are obtained.The proportion of the free water to the bound water in PVA-SbQ gels was 3.3-2.9 despite of the large change in conversion of photodimerization of SbQ groups, x=0.27-0.58. The water uptake after swelling of the gels in water increased 6-27 times compared to the original weight at pH=7. The higher the degree of photocrosslinking, the lower was the degree of swelling. The water diffusion coefficients, D, were (2.2-5.8) × 10-5 cm2 S-1 for a 88% saponified PVA with 1 . 3 mol% SbQ groups. The volume of the gel increased discontinuously about 10-fold for the 99% saponified PVA with 0 . 096 mol% SbQ and 51% water (49% acetone). The acetone concentration at the transition decreased with increasing the degree of saponification of the PVA.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 17
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 239 (1996), S. 151-160 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch anionische Copolymerisation von Allylmethacrylat und Methylmethacrylat wurden Makromonomere unterschiedlicher Kettenlänge mit durchschnittlich drei Allyl-Doppelbindungen pro Kette hergestellt́ und mit NMR-Spektroskopie und Gelpermeationschromatographie charakterisiert. Durch Copolymerisation der Makromonomeren mit 1-Vinyl-2-pyrrolidon wurden dreidimensionale Strukturen erhalten. Die optischen und mechanischen Eigenschaften der Produkte wurden untersucht, und die Quellungseigenschaften und Vernetzungsgrade wurden bestimmt. Die Copolymereigenschaften wurden durch Makromonomere mit Kettenlängen bis 40 Einheiten nur wenig beeinflußt. Bei Kettenlängen über 50 Einheiten wurde eine leichte Abnahme der Wasseraufnahmefähigkeit und eine deutliche Erhähung des Elastizitätsmoduls beobachtet. Die Vernetzungsgrade hängen von der Makromonomer-Kettenlange ab; eine merkliche Erhöhung aufgrund der groößeren Zahl an Methyl-Methyl-Wechselwirkungen wurde bei Kettenlangen über 50 Einheiten festgestellt. Die Copolymeren zeigen günstige Festigkeits-Dehnungs-Eigenschaften und einen geringen Gehalt an wasserlöslichen Extrakten, in denen durch IR-Spektroskopie 1-Vinyl-2-pyrrolidon-Homopolymere identifiziert wurden. Obwohl mit allen untersuchten Makromonomeren gute Resultate erzielt wurden, scheint für die Copolymerisation mit 1-Vinyl-2-pyrrolidon das Makromonomere mit 50 Einheiten am besten geeignet.
    Notes: Macromonomers of various chain lengths with an average of three allyl double bonds per chain were prepared by anionic copolymerization of allyl methacrylate with methyl methacrylate. The macromonomers were characterized by gel permeation chromatography and nuclear magnetic resonance. The macromonomers were then copolymerized with 1-vinyl-2-pyrrolidone to form three-dimensional structures. Their optical, swelling and mechanical properties were studied and the crosslinking efficiency was determined. The copolymer properties are not greatly affected by macromonomer chain lengths up to 40-mers; above 50-mers there is a slight decrease in the equilibrium water content and a significant increase in the modulus of elasticity. The crosslinking efficiency depends on the macromonomer chain length; a marked increase was observed for the 50-mer because of a greater number of methyl-methyl interactions. Copolymers have favourable strength-strain properties and a low content of water-soluble extracts, in which the IR analysis demonstrated the presence of 1-vinyl-2-pyrrolidone homopolymers. In spite of the good results obtained for all the macromonomers described in this work, the 50-mer seems to be optimal for copolymerization with 1-vinyl-2-pyrrolidone.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 18
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 239 (1996), S. 201-213 
    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 curing of diglycidyl ether of bisphenol A (DGEBA) with 2,6-dimethylol-p-cresol modified by hexahydrophthalic acid anhydride was investigated and compared with the analogous in situ curing of DGEBA, hexahydrophthalic acid anhydride and 2,6-dimethylol-p-cresol. The chemical reactions were investigated by means of titration and different spectroscopic and chromatographic methods. It was examined whether the less complicated and therefore cheaper in situ reaction delivers postcured products with equal or better properties. Furthermore, it was investigated whether the results are similar using technical phenolic hardeners.
    Notes: Die Härtung von Diandiglycidylether (DDGE) mit hexahydrophthalsäureanhydridmodifiziertem 2,6-Dimethylol-p-kresol (HHPSA-DMPK) wurde untersucht und mit der in situ durchgeführten Vernetzung von DDGE mit Hexahydrophthalsäureanhydrid (HHPSA) und 2,6-Dimethylol-p-kresol (DMPK) verglichen. Die chemischen Reaktionen wurden durch Titration der Epoxidgruppen und mit verschiedenen spektroskopischen und chromatographischen Methoden untersucht. Es wurde geprüft, ob die weniger aufwendige und daher preiswertere in situ-Härtung zu Produkten mit gleichen oder besseren Endeigenschaften führt. Weiterhin wurde die Übertragbarkeit der Ergebnisse auf den Einsatz technischer Phenolharzhärter getestet.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 19
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Zur Entwicklung neuartiger ökologisch verträglicher makromolekularer Schlichtemittel wurden in früheren Arbeiten Copolymerisationsreaktionen zwischen Polyvinylalkohol (PVA) und Stärke unter Verwendung von chemisch reaktiven bifunktionellen Verbindungen wie N-Methylolacrylamid beschrieben. Im Rahmen dieser Arbeit werden die physikochemischen Eigenschaften des resultierenden Copolymeren untersucht. Von Bedeutung sind hierbei insbesondere Merkmale wie Molekulargewichtsverteilung, Klebekraft, Stabilität, Löslichkeit sowie rheologische Eigenschaften. Derartige Kenntnisse über die physikochemische Beschaffenheit der PVA-Ausgangsverbindung sowie des makromolekularen Endproduktes sind eine wesentliche Voraussetzung für die Entwicklung von neuen Produkten, die als wasserlösliche, recycelbare Schlichtemittel zur Anwendung in der Textilindustrie kommen können.
    Notes: A macromolecular sizing agent based on the copolymerization of poly(vinyl alcohol) (PVA) with hydrolysed starch was prepared using the chemically reactive bifunctional compound N-methylolacrylamide. Detailed characteristics of the resultant PVA/N-methylolcarbamoylethylated starch copolymer were studied where emphasis has been placed on solubility, rheological properties, molecular weight distribution, adhesive power and stability. Elucidation of the nature of the macromolecular segments of both N-methylolcarbamoylethylated PVA as well as PVA/N-methylolcarbamoylethylated starch copolymer fulfilled the prerequisite to tailor PVA/starch copolymer which is appropriate for application as a water-soluble recyclable sizing agent by ultrafiltration.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 20
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Seismic isolation was reconfirmed to be extremely efficient for the protection of buildings, and hence human life, on the occasion of the Great Hanshin Earthquake. Rubber bearings are placed under the buildings for isolation, and thus the type of rubber bearings is a dominant factor for efficient isolation. In this report, the performance of peripherally restraining type rubber bearing (PRB) was examined where its contracted model was found to simulate the performance of full scale PRB precisely. Damping ratio and vertical spring constant of PRB are as good as the existing ones. PRB showed lower critical shear strain, but it was concluded that no problems were found for the actual use of PRB.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 21
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The network formation of phenol-formaldehyde resin was investigated by the Monte Carlo (MC) simulation technique. The observed value of the gel point, pc, was exactly determined as a critical extent of reaction, where the Mw/Mn in soluble parts is maximum. The MC simulation with the cubic percolation theory was applied to the gelation of phenolic resins and gave an exact gel point, which was in excellent agreement with the observed value of pc. The simulation showed that the intramolecular reaction occurred frequently with increasing the gel fraction beyond the gel point. The structural analysis of the maximum cluster with the computer strongly supported the contribution of the intramolecular reaction to the network formation of the gel.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 22
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure of the hydrogel of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) was investigated by small angle X-ray scattering (SAXS) of synchrotron radiation. A physically crosslinked blend gel, which was prepared by repetitive freezing and thawing of an aqueous solution of PVA and PAA, could be chemically crosslinked by esterfication of PVA with PAA even in the hydrogel state. The chemical crosslinking induced the destruction of physical crosslinks into a folded structure, indicating that the chemical crosslinking proceeds at the sites around the physical crosslinks that contain PVA and PAA in much higher concentration than other portion of the gel. The pH-induced structure changes of the PVA hydrogels, chemically crosslinked with poly(acrylic acid) (PAA) were investigated by SAXS on the samples of various chemical crosslinking time. The gels were shrunk at pH4, and swollen at pH8. The results of SAXS showed, that the Porod slope changed with chemical crosslinking time from -3.5 to -2.9 at pH4, and from -2.9 to -2.4 at pH8. The results suggest that a folded structure as a structural domain, which is characterized by fractally rough interface, tends to change into the structure that corresponds to percolation cluster, particularly at pH8. The gels immersed in pH8 showed a remarkable structure change accompanying swelling. The results revealed that a conformational change of PAA chains, induced by the pH change, can be explained by the presence of a structural domain in the gel network, where both PVA chains and PAA chains get entangled and partially form a interpenetrating polymer network(IPN).
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 23
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyurethane elastomers were investigated as electrically active materials for actuators. Components in hard segment and soft segment in the elastomers were varied. The elastomers with excellent electrostrictive properties were limited to those which had soft segments of polyesters and polylactones. It turned out, that the elastomers, whose soft segments are polyethers are electrically inert under the experimental conditions. The chemical structure of the hard segment seems not to influence to the electrostrictive property. The charging and discharging process was investigated. The charging process was found to proceed simultaneously with the contracting process caused by the electric field, suggesting that the orientation of the soft segment in the elastomer plays critical rolls in the electrostrictive action. In the elastomer, which has a soft polyether segment and was inactive to the electric field, could be actuated very efficiently when the elastomer was swollen with dimethyl sulfoxide. We conclude that the polyurethane elastomer, whose soft segment has chemical bonds with a relatively large dipole moment, can be actuated by the electric field application, and that even the elastomer, whose soft segment is inactive, could be actuated in the presence of a solvent with a large dipole moment. Thus, the concept found with the gel, could be applied to an elastomer, the soft segment of which plays partly the roll of the solvent in the gel.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 24
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 240 (1996), S. 263-273 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Chitosan and 6-O-glycolchitosan, a water-soluble chitosan derivative, were oxidized by periodate. In the case of chitosan, only degradation products were obtained. With 6-O-glycolchitosan, however, water-soluble amphoteric polyelectrolyte derivatives of chitosan having higher molecular weight were obtained. The oxidized 6-O-glycolchitosan (OX-GC) showed a pH sensitive change of viscosity in aqueous solution. Moreover, the OX-GC hydrogel, cross-linked with glutaraldehyde, showed a pH sensitive swelling behavior. The OX-GC showed biodegradation behavior by lysozyme after acetylation.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 25
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 241 (1996), S. 11-29 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Das Fließ- und Bruchverhalten eines durch das gleichzeitige Härten eines ungesättigten Polyesters (UP) und eines wärmehärtbaren Bismaleimidharzes (BMI) erhaltenen quervernetzten Polymernetzwerkes wurde über einen weiten Temperatur- und Beanspruchungsbereich untersucht. Die Fließspannung σy und der Youngsche Elastizitätsmodul E steigen bei Zunahme der Spannungsbeanspruchung bzw. bei Absinken der Temperatur. Zudem steigen bei ansonsten gleichen Testbedingungen σy und E mit zunehmendem BMI-Gehalt im Blend. Andererseits wurde eine Beeinflussung des Bruch-Parameters Kc durch die Gegenwart des BMI nicht beobachtet. Der Fließprozess wurde sowohl mit Hilfe der Theorie von Argon als auch mit der von Bowden untersucht; die daraus abgeleiteten Molekül-Parameter wurden mit der bei der Härtung gebildeten Molekularstruktur in Beziehung gesetzt.
    Notes: The yielding and the fracture behaviour of an intercrosslinked polymer network obtained by the simultaneous curing of an unsaturated polyester (UP) and a thermosetting bismaleimide resin (BMI) was investigated in a wide range of temperatures and testing rates. The yield stress σy and the Young's modulus E increase by increasing the testing rate and decreasing temperature. Moreover, under the same testing conditions, σy and E increased as the BMI content in the blend was enhanced. On the other hand, it was found that the fracture parameter Kc was not affected by the presence of BMI. The yielding process was analyzed using the theories both of Argon and Bowden and the molecular parameters derived there were related to the molecular structure of the network developed upon curing.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 26
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 242 (1996), S. 159-169 
    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: Dicarbonsäuredichloride mit sowohl Hexafluorisopropyliden-Brücken und Imidringen im Molekül wurden mit p-Aminobenzhydrazid oder Mischungen aus aromatischen Diaminen und p-Aminobenzhydrazid oder Terephthaldihydrazid zu Poly(hydrazidimid-amid)en umgesetzt, die anschließend zu neuen fluorhaltigen Poly(1,3,4-oxadiazol-imid-amid)en mit verschiedenem Amid/Oxadiazol-Verhältnis cyclodehydriert wurden. Diese sind in polaren amidischen Lösungsmitteln löslich; aus solchen Lösungen lassen sich flexible Filme herstellen. Die Glasübergangstemperaturen liegen zwischen 254°C und 325°C. Sie sind bis zu 415-450°C thermisch stabil.
    Notes: A series of new fluorinated poly(1,3,4-oxadiazole-imide-amide)s containing various ratios of amide/oxadiazole groups in the repeating unit have been prepared by cyclodehydration of the corresponding poly(hydrazide-imide-amide)s resulting from the reaction of diacid dichlorides incorporating both hexafluoroisopropylidene bridges and imide rings with p-aminobenzhydrazide or with mixtures of certain aromatic diamines and p-aminobenzhydrazide or terephthalic dihydrazide. The new polymers are soluble in polar amidic solvents and can be processed into flexible films by casting from solution. Their glass transition temperatures are in the range 254-325°C and they are thermally stable up to 415-450°C.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 27
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Blockcopoly(ester-ether) mit verschiedenen ionischen Einheiten wie Sulfobetain (S-Betain), Carbobetain (C-Betain) und Ammoniumtosylat wurden hergestellt und hinsichtlich ihrer Eignung als antistatische Modifikatoren für Polyethylenterephthalat (PET)-Fasern untersucht. Die ionischen Segmente wurden aus N,N-Bis(2-hydroxyethyl)methylamin generiert und statistisch mit den Polyester- und Polyoxyethylen(PEO)-Einheiten cokondensiert. Aus den Copolymeren mit S-Betain-Einheiten wurden im Schmelzspinnverfahren dicke Filamente hergestellt und deren elektrischer Widerstand bestimmt. Abhängig von der Zusammensetzung (25-75 Gew.-% PEO, 1-2 mol-% S-Betain) wurden Widerstände zwischen 108 und 1010 Ω cm-1 gemessen. Die drei copolymerartigen Modifikatoren wurden mit PET durch Blendspinnen gemischt. Die so erhaltenen PET-Fasem zeigen nicht nur gute mechanische sondern auch verbesserte antistatische Eigenschaften. Die Fasern aus dem S-Betain enthaltenden Copolymeren weisen dabei die kürzeste Halbwertszeit des Abbaus der elektrostatischen Ladung auf, obwohl der Oberflächenwiderstand dieses Materials in der Größenordnung 1013 Ω cm-2 dem Wert der mit C-Betain und Ammoniumtosylat hergestellten Fasem ähnlich ist. Die PET-Fasern bewahren ihre guten antistatischen Eigenschften auch nach dem Fäben und wiederholtem Waschen, da sowohl die hydrophilen als auch die ionischen Gruppen an den Polyesterketten fixiert sind.
    Notes: Block copoly(ester-ether)s containing different ionic units, i.e., sulfobetaine (S-betaine), carbobetaine (C-betaine), and ammonium tosylate, were prepared and evaluated as antistatic modifiers of PET fiber. The ionic units were readily derived from N,N-bis(2-hydroxyethyl)methylamine and co-condensed randomly with the polyester and poly(oxyethylene) (PEO) units. For the copolymers containing S-betaine units, a thick filament was melt-spun to evaluate their apparent electric resistivity. Depending on the unit compositions (25-75 wt.-% of PEO and 1-2 mol-% of S-betaine), resistivities ranging from 108 to 1010 Ω cm-1 were obtained. Then, the three copolymer-type modifiers were blended with poly(ethylene terephthalate) (PET) by the ordinary blend-spinning technique. The blend PET fibers obtained showed not only good mechanical properties, but also improved antistatic properties. Particularly, the fiber blended with the copolymer containing S-betaine units had the shortest half-life time of leakage of static charge, although the surface area resistivity, being in the order of 1013 Ω cm-2, was similar to that of the fibers blended with the copolymers containing C-betaine and ammonium tosylate units. These blend PET fibers were found to retain good antistatic properties even after dyeing and repeated washings, because both the hydrophilic and ionic groups are immobilized with the polyester chains.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 28
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: For radical copolymerizations of α-methylstyrene (MS) with methacrylonitrile (MAN) and of MS with acrylonitrile (AN) studies were carried out to examine postulations of kinetic models known from literature, in particular the terminal model with chain-length-independent and chain-length-dependent depolymerization steps. The results of investigations were based on measurements of the sequence length distributions from 13C-NMR spectra. Analyses of MS/MAN copolymers with various compositions were carried out. Reaction parameters and depolymerization constants depending on temperature were calculated. The values of enthalpy and entropy of polymerization and the ceiling temperature were computed for MS to ΔH = 26,5 ± 0,5 kJ mol-1, ΔS = 95 ± 5 J mol-1 K-1, Tceiling = 65 ± 1°C. The terminal model with depolymerization steps turned out to be wrong for the accurate description of the polymerization behaviour in case of the tested systems. Results clearly show important penultimate effects. At the point of knowledge, the description of the polymerization behaviour in terms of a penultimate model with depolymerization steps are suggested.
    Notes: Für die radikalischen Copolymerisationen von α-Methylstyrol (MS) mit Methacrylnitril (MAN) sowie MS mit Acrylnitril (AN) wurden Untersuchungen zur Prüfung der in der Literatur postulierten kinetischen Modelle des „sequenzlängenunabhängigen“ bzw. „sequenzlängenabhängigen“ Terminalmodells mit Depolymerisationsschritten durchgeführt. Sie basieren auf Analysen der Sequenzverteilungen aus 13C-NMR-Spektren. Resultate von 13C-NMR-Untersuchungen an MS/MAN-Polymeren variabler Zusammensetzung werden vorgestellt. Reaktionsparameter und Gleichgewichtskonstanten wurden direkt aus den Informationen der 13C-NMR-Spektren für das Terminalmodell mit Depolymerisationsschritten in Abhängigkeit von der Reaktionstemperatur der Polymeren bestimmt. Hieraus konnten die Polymerisationsenthalpie ΔH = 26,5 ± 0,5 kJ mol-1, die Polymerisationsentropie ΔS = 95 ± 5 J mol-1 K-1 sowie die Ceilingtemperatur Tceiling = 65 ± 1°C für MS bestimmt werden. Es wurde nachgewiesen, daß im Rahmen der Terminalnäherung auch mit Berücksichtigung von Depolymerisationseinflüssen keine adäquate Beschreibung des Copolymerisationsverhaltens im Falle der untersuchten Systeme möglich ist. Vielmehr konnten als Ergebnis der Untersuchungen sowohl in Copolymeren von MS mit AN als auch mit MAN signifikante Penultimate-Effekte nachgewiesen werden. Aufbauend auf diesen Ergebnissen wird die Anwendung eines auf einer Penultimate-Näherung basierenden Modells, welches auch das Gleichgewicht in den Wachstumsreaktionen von MS berücksichtigt, zur theoretischen Vorhersage des Copolymerisationsverhaltens vorgeschlagen.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 29
    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 auf Magnesiumoxid aufgebrachter Polytitazan-Cobalt (III)-Komplex diente als effektiver Katalysator für die Epoxidierung von cis-Cycloocten mit molekularem Sauerstoff bei Normaldruck in Gegenwart von Isobutyraldehyd als Reduktionsmittel. Nach XPS-Untersuchungen wird Cobalt (III) durch den mehrzähnigen Stickstoffliganden des Polytitazans stabilisiert. Bei 25°C beträgt der cis-Cycloocten-Umsatz nach fünf Stunden 95,2%, mit einer Selektivität von 100% für das cis-Cyclohexylenoxid. Der Katalysator Kann mindestens neun Mal ohne Aktivitätsverlust verwendet werden.
    Notes: Magnesium oxide supported polytitazane cobalt (III) complex is demonstrated as an effective catalyst for the epoxidation of cis-cyclooctene with molecular oxygen at atmospheric pressure in the presence of isobutyraldehyde as the sacrificial reductant. XPS data show that the high-valent cobalt (III) is stabilized by the multidentate nitrogen ligand of polytitazane. The conversion of cis-cyclooctene is as high as 95.2% with 100% selectivity to the cis-cyclooctene oxide at 25°C within 5 h. The catalyst can be used at least nine times without loss of its activity.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 30
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 243 (1996), S. 177-187 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wird über die Gleichgewichts-Schmelzpunktsdepression von Polycarbonat aus Bisphenol A (PC) in Mischungen mit Poly-∊-caprolacton (PCL) berichtet. Hierzu wird ein Modell entwickelt, das den gekrümmten Verlauf der gemessenen Hoffman-Weeks-Plots zu erklären vermag. Es berücksichtigt die Konzentrationsinhomogenitäten, die mit fortschreitender Kristallisation an der Kristallwachstumsfront entstehen. Die gelegentlich beobachtete Schmelzpunktsdepression der PCL-Komponente wird diskutiert. Der Flory-Hugginssche Wechselwirkungsparameter wird zu -0,09 berechnet; aus diesem kleinen Wert muß geschlossen werden, daß die Mischungspartner enthalpisch nur schwach wechselwirken. Der merkliche Abfall der Glastemperatur des PC nach Einmischen von PCL bewirkt eine beträchtliche Kristallisation aus der Schmelze; es können PC-Kristallinitätsgrade bis zu 25% erreicht werden.
    Notes: It is reported on the equilibrium melting point depression of polycarbonate from bisphenol A (PC) in its blend with poly-∊-caprolactone (PCL). To this end, a model which explains the bended course of the measured Hoffman-Weeks plots is developed which takes into account the composition changes at the crystal growth front upon progressive crystallization. The occasional melting point depression of the PCL component is discussed. The calculated Flory-Huggins parameter of χ12 ≍ -0.09 indicates only weak enthalpic interactions. The remarkable drop in the glass transition temperature of PC with blending allows PC degrees of crystallinity up to 25% upon crystallization from the melt.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 31
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 243 (1996), S. 151-159 
    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: Leicht vernetzte Hydrogele auf der Basis von Acrylamid, N-(1,1-Dimethyl-3-oxobutyl)acrylamid, N,N-Dimethylacrylamid, Methacrylamid, N-(2-Hydroxypropyl)-methacrylamid und N-[Tris(hydroxymethyl)methyl]methacrylamid wurden in Form von pulverigen Substanzen synthetisiert, die aus Aggregaten sehr kleiner Partikel (∼10-1 μm) bestehen. Die pulverartigen Hydrogele wurden durch Fällungspolymerisation in Aceton und Diethylether unter Verwendung von N,N′-Methylenbisacrylamid und Ethylendimethacrylat als Vernetzungsmittel synthetisiert. Es wurden die Abhängigkeiten des Quellungsgrades in Wasser, der Größe, des Aggregationsgrades und der spezifischen Oberfläche von Partikeln, und des Inhalts von wasserlöslichen Substanzen in den Hydrogelen von den Bedingungen ihrer Synthese verfolgt. Die Eignung einzelner der synthetisierten Hydrogele für die Herstellung von Silikon-kautschuk-Hydrogel-Kompositen wird diskutiert.
    Notes: Lightly crosslinked hydrogels based on acrylamide, N-(1,1-dimethyl-3-oxobutyl)-acrylamide, N,N-dimethylacrylamide, methacrylamide, N-(2-hydroxypropyl)methacrylamide and N-[tris(hydroxymethyl)methyl]methacrylamide were synthesized in form of fine powders, consisting of aggregates of very small (∼10-1 μm) particles. The powdery hydrogels were obtained by precipitation polymerization in acetone and diethyl ether, using N,N′-methylenebisacrylamide and ethylene dimethacrylate as crosslinking agents. Dependences of water-swellability, particle size, aggregation, specific surface and content of the uncrosslinked water-soluble polymers and low-molecular-weight substances in the hydrogels on the conditions of their synthesis were studied. Suitability of particular powdery hydrogels synthesized for the preparation of silicone rubber-hydrogel composites is discussed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 32
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurde der Einfluß der Polymerisationsbedingungen auf die Eigenschaften von Poly(∊-Caprolactam)-Polybutadien-Blockcopolymeren untersucht, die durch Reaktionsformgießen bei der anionischen ∊-Caprolactam-Polymerisation, initiiert durch das ∊-Caprolactam-Kaliumsalz, in Anwesenheit von α,ω-Dihydroxypolybutadien und Isocyanaten oder deren blockierter Derivate als Funktionalisierungsmittel hergestellt wurden.Es wurde der Einfluß des Polybutadiengehalts, dessen Molekulargewichts, des Isocyanat-Typs und der Polymerisationstemperatur auf die mechanischen Grundeigenschaften und auf die Polymerisationsgeschwindigkeit bestimmt.
    Notes: The effect of the polymerization conditions on the properties of poly(∊-caprolactam)-polybutadiene block copolymers prepared by polymerization casting through anionic polymerization of ∊-caprolactam initiated with potassium salt of ∊-caprolactam in the presence of α,ω-dihydroxy-polybutadiene and isocyanates or their blocked derivatives as functionalizing agents was investigated.The influence of the content of telechelic polybutadiene, its molecular weight, type of diisocyanate, and polymerization temperature on the fundamental mechanical properties of the prepared materials and on the polymerization rate was evaluated.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 33
    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.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 34
    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.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 35
    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.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 36
    Electronic Resource
    Electronic Resource
    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).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 37
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 38
    Electronic Resource
    Electronic Resource
    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.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 39
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The 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.
    Additional Material: 12 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 40
    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.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 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: 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.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 42
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    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%).
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 43
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 17-24 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Computer simulation shows that the time required to attain near sedimentation equilbrium is dramatically reduced by a two-step initial loading in which a macromolecular solution at low or zero concentration is layered above one at a higher concentration. To achieve the minimum time requires a good estimate of the molecular weight, but at least a 50% reduction in time can be achieved if the molecular weight of the macromolecule is known only within a factor of 2. Numerical solutions to the differential equation of the ultracentrifuge are calculated using the finite element method. An efficient Gaussian elimination algorithm can be used to minimize calculation time and computer storage requirements.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 44
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 79-88 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The aldehydes present in acid-soluble type I collagen react with pyrenebutyrylhydrazine to form various types of complexes under different reaction conditions. These complexes exhibit one or more of three different pyrene fluorescence bands: monomer, excimer, and aggregate fluorescence. Collagen, whose aldehydes have been reduced with NaBH4, does not react with this fluorescent hydrazine, confirming that the hydrazine reacts specifically with aldehyde groups to form hydrazones. The absence of a reaction with pepsin-treated collagen also shows that the fluorescent labels are primarily in the nonhelical terminal telopeptides. Upon dialysis, the pyrene label bound to a saturated aldehyde in an α-chain is lost; whereas that bound to an unsaturated aldehyde remains on the protein. The pyrene monomer fluorescence in the β-chain of old collagen is stronger than that of young collagen. The formation of the pyrene excimer fluorescence implies the proximity of two pyrene molecules, probably attached to two adjacent aldehydes. Upon changing from acidic to neutral pH, both excimer and aggregate fluorescence bands disappear within a few seconds, revealing a very rapid alteration at the telopeptides.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 45
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 147-157 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We describe conditions which lead to complete helix formation of poly(I) in the presence of NH4+. Binding of NH4+ is shown to be specific in the presence of Li+, which does not by itself support helix formation under these conditions. The NH4+-poly(I) complex is characterized by uv, CD, and ir spectroscopy. The CD spectrum is strikingly different from those of the Na+ or K+ complexes, the first extremum being changed from negative for the metal ions to positive for NH4+. A stereospecific model is proposed for the NH4+-poly(I) helix in which the N of NH4+ is located on the axis of the four-stranded helix, midway between planar tetramers formed by the bases. The model is consistent with the tetrahedral symmetry of NH4+, the requirement for four acceptable hydrogen bonds, the observed stability of the helix, and the accepted geometry of the backbone.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 46
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 159-167 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It has recently been proven that the counterion condensate around an isolated line charge in an electrolyte, as characterized by nonlinear Poisson-Boltzmann theory, is an encapsulating δ-function. Here the identical result is shown to hold in the framework of the polyelectrolyte theory of Fuoss, Katchalsky, and Lifson. The proof fully exploits analytic solutions to the differential equation which are not available for the nonlinear, cylindrical Poisson-Boltzmann equation.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 47
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 203-218 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The extent and modes of binding of the divalent metal ions Mn2+ and Co2+ to DNA and the effects of salt on the binding have been studied by measurements of the effects of these paramagnetic metal ions on the longitudinal and transverse relaxation rates of the protons of the solvent water molecules, a technique that is sensitive to overall binding. The number of water molecules coordinated to the DNA-bound Mn2+ and Co2+ is found to be between five and six, and the electron spin relaxation times and the electron-nuclear hyperfine constants associated with Mn2+ and Co2+ are little or not affected by the binding. These observations indicate little disturbance of the hydration sphere of Mn2+ and Co2+ upon binding to DNA. An average 2-3-fold reduction in the exchange rate of the water of hydration of the bound metal ions and an order-of-magnitude increase in their rotational correlation time are attributed to hydrogen-bond formation with the DNA. The binding constants of Mn2+ to DNA, at metal concentrations approaching zero, are found to be inversely proportional to the second power of the salt concentration, in agreement with the predictions of Manning's polyelectrolyte theory. A remarkable quantitative agreement with the polyelectrolyte theory is also obtained for the anticooperativity in the binding of Mn2+ to DNA, although the experimental results can be well accounted for by another simple electrostatic model. The various modes of binding of divalent metal ions to DNA are discussed.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 48
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 265-275 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dc electrical conductivity of films of the polyelectrolyte complexes of glycol chitosan (GlChi) with the sodium salts of dextran sulfate (DS), carboxymethyl cellulose (CMC), polygalacturonic acid (GalUA)n, and alginic acid (AlgA) was measured at temperatures above and below room temperature. The maximum field strength in the thinnest film used amounted to 3 × 104 V/cm. A plot of normalized current against the reciprocal of the absolute temperature revealed two regions with different slopes, and activation energies in these two regions have been obtained for all the complexes. The activation energies in the high-temperature region vary from 0.85 to 1.18 eV and in the low-temperature region from 0 to 0.22 eV. Reasons are given to show that the conductivity is probably ionic. Near room temperature, the current-voltage relation is almost linear in the GlChi-DS complex, while in the other three complexes the current varies as a power n of the voltage with the value of n ranging from 1.7 to 2.5. A rise in temperatures causes an increase in the slope of the log I vs log V plot in GlChi-DS and GlChi-CMC complexes. The nonlinear current-voltage relation is ascribed to a space-charge-limited conductivity.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 49
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 301-319 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Five different glucomannan samples were recrystallized from dilute solution. Depending on the experimental conditions, the crystals obtained could be identified as corresponding to the mannan I (anhydrous precipitate of more or less regular lozenge-shaped crystals) or mannan II (hydrated gel-forming pseudo-fibrillar precipitate). High-molecular-weight material, low temperature of crystallization, or a polar crystallization medium favored the mannan II polymorph, whereas a low-molecular weight, a high temperature of crystallization, and a crystallization medium of low polarity yielded the mannan I polymorph. Since the base-plane unit-cell dimensions are fairly constant with respect to variation of glucose, it is likely that isomorphous replacement of mannose by glucose occurs in glucomannan crystallization; the data also indicate that perfection of the glucomannan crystals was reduced in specimens having a high glucose:mannose ratio. The oriented crystallization of glucomannan on cellulose microfibrils was also studied under conditions where the mannan I polymorph was obtained. This gave shish-kebab structures that were characterized.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 50
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The primary hydration process of native biopolymers is analyzed in a brief review of the literature, pertaining to various aspects of biopolymer-water systems. Based on this analysis, a hydration model is proposed that implies that the solution conformation of native biopolymers is stable at and above a critical degree of hydration (hp′ = 0.06-0.1 g H2O/g polymer). This water content corresponds to the fraction of strongly bound water, and amounts to ∼20% of the primary hydration sphere. In order to test this model, detailed sorption-desorption scanning experiments were performed on a globular protein (α-chymotrypsin). The results obtained are consistent with the proposed hydration model. They show that under certain experimental conditions, sorption isotherms can be obtained that do not exhibit hysteresis. These data represent equilibrium conditions and are thus accessible to thermodynamic treatment. Valid thermodynamic functions, pertinent to the interaction of water with biopolymers in their solution state, can be obtained from these sorption experiments.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 51
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 451-458 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The light scattering of bovine serum albumin (BSA) has been measured at protein concentration up to 90 g/L and at pH values between 4.4 and 7.6. The dependence of scattering on both protein concentration and pH may be quantitatively accounted for by a simple extension of the hard-sphere model for protein solutions [Ross, P. D. & Minton, A. P. (1977) J. Mol. Biol. 112, 437-452] allowing for electrostatic repulsions between molecules. According to the extended model, the radius of the effective hard spherical particle representing BSA varies with the net electrical charge of the BSA molecule in a manner which may be calculated from electrostatic theory.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 52
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 475-497 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A complete analysis of all possible conformations with correct hydrogen bonds of the collagen II type was performed on the basis of developed simultaneous equations. Using a unimodal search (by varying Ψ3), the energetically favorable structure was obtained. No other energetically satisfactory structural solutions are possible. The next aim was to obtain a precise model of the molecule. The program used includes a subroutine for continual deformation of the pyrrolidine rings. The set of parameters determining the structure consists of 14 independent variables (8 dihedral and 6 bond angles). As starting points for the energy optimization, conformations produced by scanning and some structures from previous work were used. The final structures (practically the same for both polymers) have helix parameters h = 0.285 nm and t = 52°, which are in excellent agreement with the 7/2 symmetry of diffraction data. The conformations of the pyrrolidine rings are of the B type, i.e., C2-Cβ-exo-Cγ-endo. For both polypeptides, the conformations of imino acids in position 3 of the triplet are the same; in position 2, however, they are slightly different. The difference in diffraction patterns for the 7/2 and 10/3 helices is discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 53
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 547-563 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The CD spectrum of the enzyme adenylate kinase has been investigated. Theoretical calculations, based on the x-ray crystal structure, have been carried out by means of an origin independent matrix formalism. The entire molecule was included in the calculations in the sense that essentially all electronic transitions that occur at wavelengths longer than 185 nm were included in the basis set. A linear dielectric function was utilized to evaluate the intertransition coupling potentials. The results of the theoretical calculations were in reasonable agreement with experimental CD spectra of the molecule.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 54
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 633-652 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mode of action of many antitumor agents entails the inhibition of nucleic acid synthesis. Because many of the drugs can intercalate, it is assumed that intercalation is an important step in the mechanism of biological activity. As intercalants contain a planar chromophore as an ingredient essential for intercalation, chromophores that should fit into DNA are desired. This is the main theme of this investigation. Binding to DNA of fundamental moieties, protonated pyridine, aniline, phenol, quinone, and 4H-thiopyran-4-one, is studied to determine their optimum placement in DNA. The optimum orientations for each moiety are superimposed to form polyaromatic systems that can intercalate in a manner in which functional groups on these chromophores are oriented as in the moieties themselves. Ideal intercalants proposed contain three and four fused ring system, have protonated ring nitrogen atoms located to maximize the electrostatic interactions with DNA, hydroxy and amino groups that can hydrogen bond to the OII and O5′ phosphate backbone atoms, and carbonyl and sulfur groups in the central position of the ring system to provide variations in the chromophore and to interact with the relatively positive region in the intercalation site. The optimum orientation occurs when the chromophore and the base pairs overlap to the maximum extent. The ideal intercalants are fundamentally of the type:
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 55
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 665-677 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: DNA reassociation kinetics using the phenol emulsion reassociation technique (PERT) [Kohne, D. E., Levison, S. A. & Byers, M. J. (1977) Biochemistry 16, 5329-5341] has been investigated at high DNA concentrations using an endonuclease S1 assay of reaction progress. Apparent second-order rate constants fall on two intersecting straight lines when presented as a function of DNA concentrations on a log-log plot. In the low DNA concentration range, the rate constants drop about 10-fold when concentration increases 1000-fold. In the high DNA concentration range, the rate constants drop more than 10-fold when concentration increases 10-fold. The slopes of these lines are the same in different solvents and at different temperatures. The intersection between the lines occurs when the available catalytic surface is saturated. At high DNA concentrations, high-complexity heterologous denatured DNA apparently competes 2-4 times better for the surface than homologous DNA because it does not participate in a reassociation reaction. Native and partially native DNA molecules cannot compete with single-stranded DNA for a saturated surface. At high DNA concentrations, reactions using PERT become dependent on the single-strand DNA length. Increasing length lowers reassociation rates.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 56
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 57
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 859-872 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Classical potential functions (CPF) calculations on 3′-mononucleotides, the building blocks of nucleic acids, predict a correlation between the sugar ring pucker and the torsion angle Φ′ around the C3′—O3′ bond. In ribonucleotides, the value of Φ′ depends on the sugar pucker, viz. the C2′-endo sugar pucker is associated with Φ′ = 210° and 270°, while the C3′-endo sugar pucker favors only Φ′ = 210°. On the other hand, in deoxyribonucleotides, both sugar puckers show a preference for Φ′ = 180°. These theoretical predictions are fully corroborated by the results obtained from x-ray and nmr studies on mono-, di-, and polynucleotides.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 58
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of several surfactants on the secondary structure of bovine β-lactoglobulin B was determined from the circular dichroism spectra. The spectra were measured at several concentrations of surfactant ranging from 1 mg/mL to the critical micelle concentration. The surfactants studied were sodium dodecyl, decyl, and octyl sulfate, sodium dodecyl sarcosinate, dodecyltrimethylammonium bromide. The data were analyzed using the method of Chen et al. [Biochemistry (1974) 13, 3350-3359] to determine the percentage of α-helix, β-sheet, and unordered form at each surfactant concentration. In every case, an increase in structured form and a 20-25% decrease in the amount of unordered form was noted when the surfactant concentration reached the critical micelle concentration. However, the relative amounts of the two structured forms present depend on the surfactant used. The profile of the secondary structure of the protein also varied from surfactant to surfactant as the protein was titrated, probably reflecting the delicate balance between ionic and nonionic forces that governs the secondary structure of β-lactoglobulin and most other globular proteins in aqueous solution.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 59
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Amino acids are known to differ in their individual preferences for each of the four positions of the β-turn conformation formed by tetrapeptide segments. Proline and glycine show relatively high preferences for positions 2 and 3, respectively, of the β-turn. Using tripeptides of the type N-acetyl-Pro-Gly-X-OH, where X = Gly, Ala, Leu, Ile, and Phe, we have sought to study the influence of the 4th residue X on the stability of the β-turn conformation in these tripeptides. Our nmr and CD results show that the β-turn stability is quite significantly governed by the nature of the amino acid residue at this position in the following order: Leu 〉 Ala 〉 Ile, Gly 〉 Phe.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 60
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 1153-1166 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermodynamic studies of the binding of adamantanecarboxylate to cyclodextrins have been made as a function of temperature and added organic cosolvent (methanol) using flow microcalorimetry. The negative heat capacity change associated with the adamantanecar-boxylate/β-cyclodextrin interaction and the fact that the interaction is weakened by the addition of methanol implicate the binding process as being a hydrophobically driven one. The negative enthalpy change (ΔH0 = -5.5 kcal/mol) and near-zero entropy change (ΔS0 = 1.5 cal/mol deg) are quite different from the values normally expected for a hydrophobic bond, indicating that other bonding forces are important in addition to the hydrophobic effect. The relative contribution of the hydrophobic effect and other bonding forces (most likely van der Waals forces) to the overall binding was judged from an analysis of the dependence of the thermodynamics of the association process on the surface tension of the water-methanol mixtures following a model for “solvophobic” bonding described by Sinanoglu [Molecular Associations in Biology (1968) Academic Press, New York, pp. 427-445]. From this analysis, adamantane-carboxylate/cyclodextrin complex formation is found to be driven to the extent of -1.9 kcal/mol by the hydrophobic effect. Furthermore, the hydrophobic driving force is found to be characterized by a positive ΔS0 of 10 cal/mol deg. The remaining free energy of binding (and the ΔH0 of binding of ∼-6 kcal/mol) is then due to the intrinsic (surface-tension-independent) van der Waals interaction between the ligand and cyclodextrin cavity.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 61
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 62
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pivaloyl-L-Pro-Aib-N-methylamide has been shown to possess one intramolecular hydrogen bond in (CD3)2SO solution, by 1H-nmr methods, suggesting the existence of β-turns, with Pro-Aib as the corner residues. Theoretical conformational analysis suggests that Type II β-turn conformations are about 2 kcal mol-1 more stable than Type III structures. A crystallographic study has established the Type II β-turn in the solid state. The molecule crystallizes in the space group P21 with a = 5.865 Å, b = 11.421 Å, c = 12.966 Å, β = 97.55°, and Z = 2. The structure has been refined to a final R value of 0.061. The Type II β-turn conformation is stabilized by an intramolecular 4 → 1 hydrogen bond between the methylamide NH and the pivaloyl CO group. The conformational angles are φPro = -57.8°, ψPro = 139.3°, φAib = 61.4°, and ψAib = 25.1°. The Type II β-turn conformation for Pro-Aib in this peptide is compared with the Type III structures observed for the same segment in larger peptides.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 63
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 1333-1363 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The folding-unfolding process of reduced bovine pancreatic trypsin inhibitor was investigated with an idealized model employing approximate free energies. The protein is regarded to consist of only Cα and Cβ atoms. The backbone dihedral angles are the only conformational variables and are permitted to take discrete values at every 10°. Intraresidue energies consist of two terms: an empirical part taken from the observed frequency distributions of (φ,ψ) and an additional favorable energy assigned to the native conformation of each residue. Interresidue interactions are simplified by assuming that there is an attractive energy operative only between residue pairs in close contact in the native structure. A total of 230,000 molecular conformations, with no atomic overlaps, ranging from the native state to the denatured state, are randomly generated by changing the sampling bias. Each conformation is classified according to its conformational energy, F; a conformational entropy, S(F) is estimated for each value of F from the number of samples. The dependence of S(F) on energy reveals that the folding-unfolding transition for this idealized model is an “all-or-none” type; this is attributable to the specific long-range interactions. Interresidue contact probabilities, averaged over samples representing various stages of folding, serve to characterize folding intermediates. Most probable equilibrium pathways for the folding-unfolding transition are constructed by connecting conformationally similar intermediates. The specific details obtained for bovine pancreatic trypsin inhibitor are as follows: (1) Folding begins with the appearance of nativelike medium-range contacts at a β-turn and at the α-helix. (2) These grow to include the native pair of interacting β-strands. This state includes intact regular secondary conformations, as well as the interstrand sheet contacts, and corresponds to an activated state with the highest free energy on the pathway. (3) Additional native long-range contacts are completely formed either toward the amino terminus or toward the carboxyl terminus. (4) In a final step, the missing contacts appear. Although these folding pathways for this model are not consistent with experimental reports, it does indicate multiple folding pathways. The method is general and can be applied to any set of calculated conformational energies and furthermore permits investigation of gross folding features.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 64
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Peptide NH chemical shifts and their temperature dependences have been monitored as a function of concentration for the decapeptide, Boc-Aib-Pro-Val-Aib-Val-Ala-Aib-Ala-Aib-Aib-OMe in CDCl3 (0.001-0.06M) and (CD3)2SO (0.001-0.03M). The chemical shifts and temperature coefficients for all nine NH groups show no significant concentration dependence in (CD3)2SO. Seven NH groups yield low values of temperature coefficients over the entire range, while one yields an intermediate value. In CDCl3, the Aib(1) NH group shows a large concentration dependence of both chemical shift and temperature coefficient, in contrast to the other eight NH groups. The data suggest that in (CD3)2SO, the peptide adopts a 310 helical conformation and is monomeric over the entire concentration range. In CDCl3, the 310 helical peptide associates at a concentration of 0.01M, with the Aib(1) NH involved in an intermolecular hydrogen bond. Association does not disrupt the intramolecular hydrogen-bonding pattern in the decapeptide.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 65
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 1469-1472 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 66
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 1479-1487 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A formalism for extracting the conformations of a proline ring based on the bistable jump model of R. E. London [(1978) J. Am. Chem. Soc. 100, 2678-2685] from 13C spin-lattice relaxation times (T1) is given. The method is such that the relaxation data are only partially used to generate the conformations; these conformations are constrained to satisfy the rest of the relaxation data and to yield acceptable ring geometry. An alternate equation for T1 of 13C nuclei to that of London is given. The formalism is illustrated through an example.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 67
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 1521-1534 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have used broadline proton magnetic resonance to study molecular motion in cellulose, a sodium pectate solution, a calcium pectate gel, and isolated bean cell walls. All samples were prepared in D2O to minimize the contribution of water to the observed signals. For each sample, a free induction decay was obtained, and the second moment, spin-lattice relaxation, and dipolar relaxation were measured. Our results show that the large majority of protons in cellulose are immobile. Rigid and mobile domains were also observed in the pectate samples. We have shown that gelation induces large-scale changes in the free induction decay, the second moment, and the relaxation behavior of the pectate. As with the other samples, rigid and more mobile domains were found in bean cell walls. The fraction in the rigid domains is much larger than the fraction of cellulose in the sample, suggesting that the noncellulosic wall components are also organized into rigid and mobile domains.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 68
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformational energy computations were carried out on collagenlike triple-stranded conformations of several poly(tripeptide)s with the general structure CH3CO—(Gly—X—Y)3—NHCH3. The sequences considered had various amino acid residues in position X or Y of the central tripeptide, with either Pro or Ala as a neighbor, i.e., Gly-X-Pro, Gly-X-Ala, Gly-Pro-Y, and Gly-Ala-Y. Minimum-energy conformations were computed for the side chains, and their distributions were compared for the four sequences. The residues used were Abu (= α-aminobutyric acid), Leu, Phe, Ser, Asp, Asn, Val, Ile, and Thr. The conformational energy of a —Ch2—CH3 side chain in Abu was mapped as a function of the dihedral angle χ1. Intrastrand interactions with neighboring residues do not affect the conformations of a side chain in position Y, and they have a minor effect on it in the X-Ala sequence, but they strongly restrict the conformational freedom of the side chain in the X-Pro sequence. Conversely, interstrand interactions do not affect side chains in position X, but they strongly restrict the conformational freedom of a side chain in position Y if there is a nearby Pro residue in a neighboring strand. Hydrogen bonds with the backbone can be formed in some conformations of long polar side chains, such as Asp, Asn, or Gln. All amino acid residues can be accommodated in collagen. Because of the interactions mentioned above, steric and energetic constraints can be correlated with observed preferences of certain amino acids for positions X or Y in collagen. Hence, these preferences may be explained, in part, in terms of differences in the conformational freedom of the side chains in the triple-stranded structure.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 69
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 1657-1666 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ionization constants of the tyrosyl groups of chymotrypsinogen and of nitrated-chymotrypsinogen (two tyrosyl residues nitrated) have been determined by difference spectrophotometry. In chymotrypsinogen, two of the four tyrosyl groups ionize without any time dependence. Above pH greater than ca. 12.5, time-dependent spectral changes are seen for 0.7 group equivalent. The data can be fitted to the values of pK′1 9.75 ± 0.07, pK′2 11.55 ± 0.05, pK′3 13.30 ± 0.05. In nitrated-chymotrypsinogen, the two nitrated tyrosyl residues have pK′1 6.44 and pK′2 8.30. For both proteins, these pK′ values are in agreement with those evaluated from potentiometric titration and calorimetric data using computer-assisted curve-fitting analysis.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 70
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 2195-2203 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformation of several samples of poly(α,β-L-Asp) with a molar fraction of β-bonds ranging from 0.1 to 0.55 was investigated by means of ir and CD spectroscopy and potentiometric titration and compared with the results obtained previously with poly(α-L-Asp). All samples investigated underwent a conformational change induced by changes in their degree of ionization: unpronounced ir absorption of amide V at 650 cm-1 was shifted to 620 cm-1 and substantially increased on deionization; CD spectra changed with the degree of ionization, passing through an isosbestic point; and the pattern of the titration curves was more complex than that of a simple polyelectrolyte. The conformation developing with the decreasing degree of ionization may be considered to be α-helix, as deduced according to the analogous behavior of other polypeptides. The extent of the conformational change in the individual samples depends on the molar fraction of β-bonds: the higher it is, the lower is the helix-forming ability of the sample.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 71
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 2225-2239 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The use of 1H-nmr spectroscopy is demonstrated to be a useful analytical method to characterize the structure of synthetic peptides attached to soluble, macromolecular polyoxyethylene (POE) supports in the liquid-phase method (LPM) of peptide synthesis. We report an extensive 360-MHz 1H-nmr study of POE-bound homo-oligo-L-methionine peptides. A combination of high field and selective saturation or Redfield pulse methods allows resolution of individual backbone NH and α-CH resonances of dilute peptides in the presence of strong resonances from macromolecular POE and/or protonated solvents. The nmr spectra for the POE-bound peptides in CDCl3 are qualitatively similar to those of the low-molecular-weight Boc-L-Metn-OMe peptide esters. This corroborates other observations that POE has little effect on peptide stucture. The backbone α-CH region of peptides is overlapped by signals from the terminal oxyethylene group of POE, but the peptide side-chain and low-field backbone NH resonances are well resolved. In trifluoroethanol the Boc-(L-Met)n-NH-POE heptamer and octamer adopt the right-handed α-helical structure, and the present nmr studies provide evidence for two strong intramolecular hydrogen bonds to stabilize the helices. In water, the N-deblocked derivatives, (L-Met)n-NH-POE oligomers adopt β-sheet structure and manifest well-resolved nonequivalent NH resonances with 6-7 Hz 3JNH-CH coupling constants.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 72
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 2241-2252 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The concerted model of Monod, Wyman, and Changeux is generalized so that all effects of interactions for an enzyme operating at a nonequilibrium stationary state are considered. In contrast to the original model, which is based on an analogy to equilibrium ligand binding, the generalization may show both “positive” and “negative cooperativity” in both catalytic binding and conformational processes. Furthermore, in contrast to any equilibrium binding model, the Hill coefficients may be greater than the number of sites n. For catalysis, the maximum value is 2n, and for conformational changes, n + 1. These points are illustrated by two cases that yield simpler analytic expressions. The first obtains when catalysis occurs on a much faster time scale than the conformational changes, and the second, when this situation is reversed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 73
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 2315-2316 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 74
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 1473-1477 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 75
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 76
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 1503-1520 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By combining gel permeation chromatography (GPC) and light-scattering spectroscopy, including photon correlation and angular distribution of absolute scattered intensity, we were able to characterize immunologically active Haemophilus influenzae type b polysaccharide (HIB Ps) bovine serum albumin (BSA) conjugates in terms of equivalent hydrodynamic radius rh ∼ (6.2 ± 0.6) × 102 Å, apparent radius of gyration rg ∼ (5.4 ± 0.3) × 102 Å, apparent molecular weight Mw ∼ (3.5 ± 0.4) × 106 g/mol, and a second virial coefficient A2 ∼ (1.9 ± 0.3) × 10-4 cm3 mol/g2. We could study the effects of each of the processes in the conjugate formation according to the following procedure: BSA (dialysis, modification, fractionation) + HIB Ps → HIB Ps/BSA conjugate (conjugate formation, fractionation). Narrow distributions of HIB Ps BSA conjugate formation can be achieved using fractionated BSA.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 77
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 1569-1586 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have measured the ir absorption of 5′CMP, 5′IMP, and poly(I)·poly(C) from ∼25 to ∼500 cm-1. From a comparison of the data with the previously measured absorption of the corresponding nucleosides and bases we can identify several “lines” associated with the deformation of the ribose ring. Out-of-plane deformation of the bases contributes strongly to vibrations near 200 cm-1. The same ribose vibrations observed in the nucleotides are found in poly(I)·poly(C). They sharpen with increasing water absorption. A study of the spectra of poly(I)·poly(C) as a function of the adsorbed water indicates that water does not contribute in a purely additive fashion to the polynucleotide spectrum but depends on the conformation of the helix. However, the only spectral feature that shifts drastically with conformation is near 45 cm-1. Measurements at cryogenic temperatures indicate some sharpening of the spectrum of poly(I)·poly(C). Instead, no sharpening is observed in the spectrum of the nucleotides. Shear degradation of poly(I)·poly(C) produces significant spectral changes in the 200-cm-1 region and sharpening of the features assigned to the low-frequency ribose-ring vibrations.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 78
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 1735-1747 
    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 oxygen replacement reaction of carbon monoxide-saturated hemoglobin (HbA0) was carried out using spectroscopic, calorimetric, and pH titration methods. Under fully saturated conditions the replacement reaction can be defined by a single partition constant over all ratios of bound oxygen to carbon monoxide. This indicates that under saturating conditions Haldane's first law for the ligand binding of gas mixtures holds for any CO/O2 ratio. It further shows that there is no appreciable difference in relative CO-O2 affinity between the α- and β-chains. The same partition coefficient was found to hold for different pH, buffer, and allosteric effector conditions. The lack of any pH dependence of the partition coefficient was confirmed by the absence of proton changes for the replacement reaction. The temperature dependence of the partition coefficient and calorimetric results yield a value for the enthalpy of the reaction of -3.65 ± 0.29 kcal/mol/heme.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 79
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 1763-1780 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We demonstrate that the isotropic absorption and linear dichroism in an unknown flow field can be used to determine base tilt in polynucleotides if three transitions are measured and the directions of the corresponding dipoles are known. The method is applied here to reach conclusions about the base tilt in poly(rA), poly(rA)+·poly(rA), and poly(rC). The respective values are: 28° tilt about the axis + 50° toward C8 from the C1′ → N9, and 25° tilt about the axis + 118° toward C5 from C1′ → N1. The results for poly(rA)+·poly(rA) are consistent with the accepted model. Spectra were measured for poly(rC)+·poly(rC), but definite conclusions must await reliable directions for transition dipoles. The dipole direction for the 218-nm transition in rC is found to be +13° or +43° toward C5 from C1′ → N1. The CD spectra to about 168 nm are presented and discussed.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 80
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 1811-1832 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Measurements of stress relaxation in uniaxial extension and associated time-dependent birefringence have been made on bovine fibrin film, prepared by gentle compaction of coarse fibrin clots, containing 13-22% fibrin plasticized with either aqueous buffer or glycerol. Both unligated and ligated (i.e., with α-α and γ-γ ligation by fibrinoligase, factor XIIIa) films were studied. Both types showed two stages of stress relaxation, with time scales of approximately 10 and 103-104 s, respectively, with a plateau region between. In the plateau, the nominal (engineering) stress for ligated glycerol-plasticized film is proportional to In λ, where λ is the stretch ratio, up to λ ≅ 2, and it decreases with increasing temperature. For unligated glycerol-plasticized film, the stresses are smaller by a factor of one-half to one-third. For ligated film, the second stage of relaxation is relatively slight, and recovery after release of stress is often nearly complete. For unligated film, the second stage involves a substantial drop in stress, and after recovery there is a significant permanent set. A second relaxation for ligated film reproduces the first, but for unligated film it reproduces the first only if the initial relaxation is terminated before the second stage; otherwise, the second relaxation shows a weaker structure. The behavior of water-plasticized film is similar to that of glycerol-plasticized except that the second stage of relaxation occurs at shorter times. During the first stage of stress relaxation, up to about 100 s, the birefringence and the stress-optical coefficient increase; during the plateau zone of stress relaxation, the birefringence of ligated films is approximately constant and is proportional to 2λ2/(λ2 + 1) - 1, where λ is the stretch ratio. This dependence is predicted by a two-dimensional model in which rodlike elements in the plane of the film are oriented with independent alignment. During the final stage of stress relaxation, the birefringence of ligated films decreases slightly; that of unligated films decreases substantially, but less rapidly than the stress, corresponding to a further increase in the stress-optical coefficient. With additional information from small-angle x-ray scattering reported in an accompanying paper, the first stage of relaxation is attributed to partial release of bending forces in the fibers by orientation, accompanied by increased birefringence. The second stage is attributed, for ligated films, to an internal transition in the fibrin units accompanied by elongation of some of the fibers; and in the unligated films, to a combination of the latter transition with slippage of protofibrils lengthwise within the fiber bundles that causes some loss of orientation, which diminishes the birefringence.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 81
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 1899-1908 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A microscope capable of measuring the CD of intact single eukaryotic cells, DNA microcrystals, and other microscopic structures has been constructed and tested. It can measure the CD spectra in the 200- and 800-nm wavelength range and consists of a modification to a standard Cary 60 CD machine in combination with a Zeiss uv microspectrometer. Preliminary CD spectra of red blood cells and lymphocytes are presented.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 82
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 1909-1926 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The distribution of fibers in agarose gels has been studied by electron-microscopic examination of replicas formed from freeze-fracture surfaces. For gels set in water, the results obtained support the model proposed for the gel structure by Arnott et al. (1974) of a random array of long, straight, connected fibers, with each fiber having a diameter equivalent to that of an aggregate of approximately 10-30 agarose helixes, depending on the initial agarose concentration. The density of these fibers, their water content, and the total length of fibers per unit volume have been derived from the measured distribution of intersections per unit area of freeze-fracture surfaces. For gels set in the presence of salt, the distribution of fibers becomes distinctly non-Poissonian, leading to larger interfiber spaces and a gel of greater effective pore size. The larger pore size of gels set in the presence of salt also has been revealed by electrophoretic measurements in which the relative migration rates of plasmid DNA molecules of varying conformations have been determined.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 83
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 1933-1943 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Energy embedding has been shown recently to be a useful extension of the distance geometry approach to conformational calculations in the case of very small molecules and simple energy functions. This paper tests the ability of energy embedding to locate low energy conformations satisfying both weak and strong geometric constraints when the molecule is the small protein, bovine pancreatic trypsin inhibitor, and the energy function is the complicated Oobatake-Crippen residue-residue potential. Using the potential function alone, the algorithm reaches a structure with energy lower than that of the native conformation, but with little resemblance to it. Aided by numerous geometric constraints, such as preformed secondary structure segments, the algorithm again finds a local minimum with energy better than that of the native, and with only 3.3 Å rms deviation from it. This is significantly closer to the native value than can be obtained using standard distance geometry and the geometric constraints alone. Thus, energy embedding using the Oobatake-Crippen potential function is a significant help in finding native conformations of proteins. However, additional trials on a hairpin bend fragment of trypsin inhibitor demonstrate the potential's shortcomings in encouraging proper secondary structure.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 84
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular-mechanics calculations have been carried out on the base-paired deoxy dodecanucleoside undecaphosphates d(CGCGAATTCGCG)2 and d(A12)·d(T12). These refinements were carried out using the model-built Arnott B-DNA geometry as initial coordinates (with a helix repaeat of 10.0 residues/turn), as well as helix repeats ranging from 9 to 12 residues/turn. There was some variation in the optimum calculated helix repeat, depending on the dielectric model, the presence or absence of counterions, and the method used for inclusion for nonbonded interactions; the most interesting general result of these calculations was the coupling between furanose sugar puckering and twist. This coupling was observed for all models. With a helix repeat of 9.0 residues/turn, all sugars remain C(2′)endo after refinement; as the helix repear increases to 12.0 residues/turn, the number of sugars repuckering to O(1′)endo and C(3′)endo increases also. With our most rigorous model (i.e., a model with no cutoff distance for nonbonded interactions) and a helix repeat of 10.0 residues/turn, we find a greater tendency for pyrimidine than purine repuckering in d(CGCGAATTCGCG)2, in agreement with the x-ray structural data of Drew et al. [(1981) Proc. Natl. Acad. Sci. USA 78, 2179-2185].We also carried out a number of calculations in which we “forced” one of two deoxy sugars to repucker or one of the C3′-O3′-P-O5′ (ω) torsion angles to change from gauche- to trans using dihedral angle constraints. After the constraints were removed, some of these structures “reverted” to the sugar pucker of the initial structures, while others remained repuckered. In all cases, the energies for repuckered structures after refinement were very similar to energies of the initial structure. Experiments and theory suggest that local conformational fluctuations play an essential role in nmr relaxation of 31P and 13C atoms in double-helical DNA. The results of our previous calculations on hexanucleoside phosphates and the calculations presented there are consistent with an important contribution to nmr relaxation processes of conformational changes in the torsion angle ω′ from gauche- to trans and deoxy sugar repuckering from C(2′)endo to C(3′)endo. Specifically, the calculations presented here indicate a very flexible phosphate backbone in helixes having an intermediate helix repeat of 10 to 11 residues/turn. These helixes may accommodate sugars of variable pucker without significantly disrupting base-base hydrogen-bonding and stacking interactions. All of the variant structures are similar in energy, suggesting that conversion between them can occur on a nanosecond time scale, as observed in nmr relaxation experiments.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 85
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The microwave absorption of aqueous solutions of DNA extracted from E. coli has been studied between 8 and 12 GHz by the use of an optical heterodyne technique. By measuring optically the temperature rise produced in an absorbing sample by pulsed microwave radiation, unambiguous, direct measurement of the microwave absorption is possible. Our results show that E. coli DNA absorbs microwaves in the 8-12-GHz region substantially more efficiently than water, which is itself an extremely efficient absorber. The observed absorption is featureless and decreases slightly with increasing frequency. These observations are consistent with an explanation involving direct absorption by longitudinal acoustic modes of the double helix.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 86
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 251-263 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The formation of polyelectrolyte complexes of glycol chitosan (GlChi) with sodium salts of dextran sulfate (DS), carboxymethyl cellulose (CMC), polygalacturonic acid (GalUA)n, and alginic acid (AlgA) has been studied. The number of ionizable groups per pyranose ring and the degree of dissociation as a function of pH in the polycation and polyanions have been determined using conductometric and potentiometric titrations. The formation of the complexes at different pH values has been followed by turbidity measurements. It is found that stoichiometric complexes of the polycation with CMC, (GalUA)n, and AlgA are formed at a mixing ratio of 0.5, indicating that the conformation may correspond to chains of equal lengths. In the case of the complex of GlChi with DS, the stoichiometric composition corresponds to a mixing ratio of 0.62. Thin transparent films of the complexes have been obtained by dehydration under reduced pressure on a layer of mercury. The dielectric constant ε′ and loss ε″ of thin films of these complexes have been measured in the range of frequencies of 1-100 kHz at different temperatures above and below room temperature. The GlChi-DS complex shows very little change in the values of ε′ and ε″ with frequency or temperature. On the other hand, films of GlChi-CMC and GlChi-(GalUA)n complexes show a significant increase in ε′ and ε″ as the temperature is increased above room temperature. The increase is more prominent at low frequencies. This behavior is attributed to the Maxwell-Wagner interfacial polarization. In the case of GlChi-AlgA film, the values of ε′ and ε″ increase enormously as the temperature increases. This behavior is similar to the increase in ε′ and ε″ observed by Michels et al. [(1965) J. Phys. Chem. 69, 1456-1465] as the salt concentration increases in another polyelectrolyte complex studied by them. The electric double-layer mechanism proposed by Schwarz [(1962) J. Phys. Chem. 66, 2636-2642] to account for the dielectric properties of biocolloids is shown to account quantitatively for the observations on the GlChi-AlgA film.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 87
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 38 (1996), S. 401-422 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bacteriorhodopsin (bR) continues to be a proven testing ground for the study of integral membrane proteins (IMPs). It is important to study the stability of the individual helices of bR, as they are postulated to exist as independently stable transmembrane helices (TMHs) and also for their utility as templates for modeling other IMPs with the postulated seven-helix bundle topology. Toward this purpose, the seven helices of bR have been studied by molecular dynamics simulation in this study. The suitability of using the backbone-dependent rotamer library of side-chain conformations arrived at from the data base of globular protein structures in the case TMHs has been tested by another set of 7 helix simulations with the side-chain orientations taken from this library. The influence of the residue's net charge on the helix stability was examined by simulating the helices III, IV, and VI (from both of the above sets of helices) with zero net charge on the side chains. The results of these 20 simulations demonstrate in general the stability of the isolated helices of bR in conformity with the two-stage hypothesis of IMP folding. However, the helices I, II, V, and VII are more stable than the other three helices. The helical nature of certain regions of III, IV, and VI are influenced by factors such as the net charge and orientation of several residues. It is seen that the residues Arg, Lys, Asp, and Glu (charged residues), and Ser, Thr, Gly, and Pro, play a crucial role in the stability of the helices of bR. The backbone-dependent rotamer library for the side chains is found to be suitable for the study of TMHs in IMP. © 1996 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 88
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of amino acids with contrasting conformational tendencies on the stereochemistry of oligopeptides has been investigated using an octapeptide Boc-Leu-Aib-Val-Gly-Gly-Leu-Aib-Val-OMe, which contains two helix-promoting Aib residues and a central helix-destabilizing Gly-Gly segment. Single crystal x-ray diffraction studies reveal that a 3 10-helix is formed up to the penultimate Aib residue, at which point there is a helix reversal in the backbone, reminiscent of a C-terminal 6 → I hydrogen bond. The curious feature in the crystal is the solvation of the possible 6 → 1 bond by a CH3OH molecule, where the OH is inserted between O(3) and N(8) and participates in hydrogen bonds with both. The cell parameters are as follows: space group P212121, a = 10.649(4) Å, b = 15.694(5) Å, c = 30.181(8) Å, R = 6.7% for 3427 data (| F0| 〉 3σF) observed to 0.9 Å. Nuclear magnetic resonance studies in CDCl3 using NH group solvent accessibility and nuclear Overhauser effects as probes are consistent with a 3 10-helical conformation. In contrast, in (CD3)2SO, unfolding of the central segment results in a multiple β-turn structure, with β-turn conformations populated at residues 1-2, 3-4, and 6-7. CD studies in methanol-2,2,2-trifluoroethanol (TFE) mixtures also provide evidence for a solvent-dependent structural transition. Helical conformations are populated in TFE, while type II β-turn structures are favored in methanol. © 1996 John Wiley & Sons, Inc.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 89
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 38 (1996), S. 557-566 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The molecular and crystal structure of curdlan triacetate, acetylated (1 → 3)β-D-glucan, was analyzed by means of an x-ray diffraction technique with the help of the linked-atom least-squares method. Unit cell dimensions are a = b = 11.00(1), c(fiber axis) = 22.91 (9) Å, and γ = 120°. The space group is P61. The unit cell contains six chemical repeating units related by 6/I-helical symmetry, which is essentially the same as the backbone conformation of one of the modifications (form I) of curdlan. During the refinement calculation, the terminal methyl in every acetyl moiety was elastically restrained to the trans conformation commonly observed in related oligosaccharide structures. The difference Fourier map, the observed and calculated densities, and the thermogravimetric measurement indicated one water molecule per glucose residue. The water oxygen is linked to two carbonyl oxygens in adjacent molecules by hydrogen bonds. The conformation of the primary acetyl moiety is a (skew, -gauche, trans). So far, no skew conformation was observed for the primary acetyl and hydroxyl moieties except in α, β-panose. In both cases, the unusual eclipsed orientation of the primary group is attributed to the hydrogen bond and this conformation is quite different from that of pachyman triacetate. © 1996 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 90
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nuclear magnetic resonance spectroscopists are increasingly utilizing chemical shifts to characterize the secondary structure of proteins. The present study addresses the effects that the positively charged amino group at the N-terminus of a peptide has on 1HN and 1HCα chemical shifts along the chain. This information is necessary for interpreting chemical shift data for proteins and/or for peptides that are used as models for protein structure. The chemical shifts for the 1H resonances of four peptides that differ only in the location of their N-terminii are assigned using two-dimensional nmr spectroscopy. The peptides have sequences derived from the β subunit of the glycoprotein hormone human chorionic gonadotropin (hCG-β). Comparison of the 1HN and the 1HCα chemical shifts for residues common to all four peptides reveals downfield shifts for 1HN and the 1HCα resonances within three residues of the N-terminus compared with chemical shifts in the interior of the peptide. The magnitude of the downfield shift is larger for resonances nearer the N-terminus. Quantum mechanical calculations of the 1HN and 1HCα chemical shifts in peptides constructed with six alanine units also predict a significant terminus effect. The calculations agree both qualitatively and quantitatively with the experimental data. The inductive nature of the end effect is confirmed in the calculations by Mulliken population analysis. End effects should be taken into account in determining protein secondary structures from chemical shifts. © 1996 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 91
    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 immunogenic peptide of human hepatitis B virus (HBV) preS(120-145), including B and T epitopes, with phospholipid vesicles has been studied by fluorescence techniques and CD. In addition, interaction of three lipopeptides derived from preS(120-145) containing stearoyl, cholanoyl, and tripalmitoyl-S-glyceryl-cysteine (Pam3C) SS moieties with dipalmitoylphosphatidylcholine (DPPC) has been investigated by polarization fluorescence spectroscopy. Fluorescence experiments showed an increase in fluorescence intensity and a blue shift of the maximum emission wavelength upon interaction of preS(120-145) with DPPC vesicles below the transition temperature (Tc), indicating that the tryptophan moiety enters a more hydrophobic environment. Moreover, fluorescence polarization experiments showed that the peptide decreased the membrane fluidity at the hydrophobic core, increasing the Tc of the lipid and decreasing the amplitude of the change of fluorescence polarization associated with the cooperative melting of 1,6-diphenyl-1,3,5-hexatriene labeled vesicles. The absence of leakage of vesicle-entrapped carboxyfluorescein indicates that the peptide did not promote vesicle lysis. Besides, the three lipopeptides derived from preS(120-145) showed a more pronounced rigidifying effect at the hydrophobic core of the bilayer, with a significative increase in the Tc. Stearoyl- and cholanoyl-preS(120-145) restricted the motion of lipids also at the polar surface, whereas Pam3CSS-preS(120-145) did not alter the polar head group order. Finally, CD studies in 2,2,2-triflouroethanol or in presence of vesicles suggested that the bound peptide adopted amphiphilic α-helical and β-sheet structures, with an important contribution of the β-turn. It is concluded that preS(120-145) can interact with the lipid membrane through the formation of an amphipathic structure combination of β-sheet and α-helix aligned parallel to the membrane surface, involving the N-terminal residues, and penetrating only a short distance into the hydrophobic core. The C-terminal part, with a combination of β-turn and β-sheet structure, remains at the outer part of the bilayer, being potentially accessible to immunocompetent cells. Furthermore, coupling of an hydrophobic moiety to the N-terminal part of the peptide favors anchoring to the membrane, probably facilitating interaction of the peptide with the immunoglobulin receptor. These results are in agreement with the induction of immune response by preS(120-145) and with the enhanced immunogenicity found in general for lipid-conjugated immunopeptides. © 1996 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 92
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 38 (1996) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 93
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Inclusion of Arg or Pro residues in proteins and peptides has been proved to play an essential role in biochemical functions through ionic interactions, conformational transitions, and formation of turns as well. In this study we present the conformational properties of the Ac-Arg-Ala-Pro (1), Ac-Arg-Ala-Pro-NH2 (2), Ac-Arg-Pro-Asp-NH2 (3), and Ac-Arg-Pro-Asp (4) tripeptides, using 1H-nmr spectroscopy and molecular dynamics. These peptides were modeled with the aim of studying the role of the Arg-guanidinium to carboxylate ionic interactions on the Xaa-Pro peptide bond isomerization. It was found with 1 and 4 that arginine preferentially interacts with the C-terminal carboxylate group, even though the β-carboxylate is also accessible. This tendency of the Arg moiety was found to induce the cis disposition of the Ala-Pro peptide bond in 1. It was also confirmed that the Arg…Asp side chain-side chain ionic interaction in 3 plays a key role in backbone folding and structural stabilization through a type I β-turn. The nmr pattern for 3 showed a remarkable similarity with that for various Arg-Tyr-Asp containing peptides, a sequence that is crucial for the adhesion properties of the Leishmania gp63 glycoprotein. © 1996 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 94
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 38 (1996), S. 723-732 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In 1968 C. Venkatachalam (Biopolymers, Vol. 6, pp. 1425-1436) predicted the ideal forms of β-turns (type I, type II, etc.) based entirely on theoretical calculations. Subsequently, over a thousand x-ray structures of different globular proteins have been analyzed, with results suggesting that the most important form among the hairpin conformers is the type I β-turn. For the latter type of hairpin conformation, the original computations had predicted φi+1 = -60°, ψi+1 = -30°, φi+2 = -90°, and ψi+2 = 0° as backbone torsion angle values, and these have been used from that time as reference values for the identification of the type I β-turn. However, it has never been clarified whether these “ideal” backbone torsion angle values exist in real structures, or whether these torsion angles are only “theoretical values.” Using the most recent release of the Protein Data Bank (1994), a survey has been made to assign amino acid pairs that approach the ideal form of the type I β-turn. The analysis resulted in four sequences where the deviation from ideal values for any main-chain torsion angles was less than 2°. In order to determine whether such a backbone fold is possible only in proteins owing to fortuitous cooperation of different folding effects, or whether it occurs even in short peptides, various attempts have been made to design the optimal amino acid sequence. Such a peptide model compound adopting precisely the predicted torsion angle values [φi+1 = -60°, ψi+1 = -30°, φi+2 = -90°, and ψi+2 = 0°] could provide valuable information. The solid state conformation of cyclo[(δ) Ava-Gly-Pro-Thr (O1Bu)-Gly] reported herein, incorporating the -Pro-Thr- subunit, yields values suggesting that the “ideal” type I β-turn is even possible for a peptide where there are no major environmental effects present. © 1996 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 95
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 38 (1996), S. 759-768 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stereochemical requirements for δ-opioid receptor binding of a series of linear peptide antagonists with a novel conformationally restricted Phe analogue (Tic) as a second residue were examined by using a variety of computational chemistry methods. The δ-opioid receptor analogues with significant affinity, Tyr-Tic-NH2 (TI-NH2), Tyr-Tic-Phe-OH (TIP), Tyr-Tic-Phe-NH2(TIP-NH2), Tyr-Tic-Phe-Phe-OH (TIPP), Tyr-Tic-Phe-Phe-NH2) (TIPP-NH2), and the low affinity δ-opioid peptides Tyr-Pro-Phe-Pro-NH2 (morphiceptin) and Tyr-Phe-Phe-Phe-NH2 (TPPP-NH2), were included in this study. The conformational profiles of these peptides were obtained by consecutive cycles of high and low temperature molecular dynamic simulations, coupled to molecular mechanical energy minimization carried out until no new conformational minima were obtained. Comparing the results for TPPP-NH2 and TIPP-NH2, the presence of the conformationally restricted Tic residue did not greatly reduce the number of unique low energy conformations, but did allow low energy conformers involving cis bonds between the first two residues. The conformational libraries of these peptides were examined for their ability to satisfy the three key ligand components for receptor recognition already identified by previous studies of high affinity cyclic (Tyr1-D-Pen2-Gly3-Phe4-D -Pen5) enkephalin (DPDPE) type agonists: a protonated amine group, an aromatic ring, and a lipophilic moiety in a specific geometric arrangement. Two types of conformations common to the five high δ-opioid affinity L-Tic analogues were found that satisfied these requirements, one with a cis and the other with a trans peptide bond between the Tyr1 and Tic2 residues. Moreover, both the Tic2 and Phe3 residues could mimic the hydrophobic interactions with the receptor of the Phe4 moiety in the cyclic DPDPE type agonists, consistent with the appreciable affinity of both di-and tripeptides. The low δ-opioid receptor affinity of morphiceptin can be understood as the result of conformational preferences that prevent the fulfillment of this pharmacophore for recognition. © 1996 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 96
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 38 (1996) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 97
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 39 (1996), S. 13-22 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present two experiments that probe the temperature dependence of the flexibility of the filamentous virus fd by examining aspects of the liquid crystalline nature of fd suspensions. The first measurement is of the temperature variation of the coexisting fd concentrations at the isotropic-cholesteric phase transition. The second measurement is of the magnetic field induced birefringence or Cotton-Mouton constant in the isotropic phase as a function of temperature. We compare these measurements with the theoretical treatment of Onsager, Khokhlov-Semenov, and Chen and conclude that the flexibility of fd varies nonmonotonically with temperature and has a minimum in persistence length at 35°C. © 1996 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 98
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 39 (1996), S. 43-50 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The titration of an aqueous solution of a de novo designed peptide with trifluoroethanol (TFE) shows complete helix formation with the addition of only 30% TFE. A molecular simulation of the peptide, in which a single shell of TFE molecules initially surrounds the peptide, reveals preferred sites of solvent interaction. The TFE molecules show greater preference for the hydrophobic compared with hydrophilic side chains. The helix-enhancing ability of TFE in aqueous solution may be rationalized in terms of stabilizing the hydrophobic collapse of apolar side chains of the formed helix. © 1996 John Wiley & Sons, Inc.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 99
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 39 (1996), S. 51-66 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Primary plant cell walls contain highly hydrated biopolymer networks, whose major chemistry is known but whose relationship to architectural and mechanical properties is poorly understood. Nuclear magnetic resonance spectroscopy has been used to characterize segmental mobilities via relaxation and anisotropy effects in order to add a dynamic element to emerging models for cell wall architecture.For hydrated onion cell wall material, single pulse excitation revealed galactan (pectin side chains), provided that dipolar decoupling was used, and some of the pectin backbone in the additional presence of magic angle spinning. Cross-polarization excitation revealed the remaining pectin backbones, which exhibited greater mobility (contact time dependence, dipolar dephasing) than the cellulose component, whose noncrystalline and crystalline fractions showed no mobility discrimination. 1HT2 behavior could be quantitatively interpreted in terms of high resolution observabilities. Mobility-resolved spectroscopy of cell walls from tomato fruit, pea stem, and tobacco leaf showed similar general effects.Nuclear magnetic resonance study of the sequential chemical extraction of onion cell wall material suggests that galactans fill many of the network pores, that extractability of pectins is not dependent on segmental mobility, and that some pectic backbone (and not side chain) is strongly associated with cellulose.Analysis of the state of cellulose in four hydrated cell walls suggests a noncrystalline content of 60-80% and comparable amounts of Iα and Iβ polymorphs in the crystalline fraction. Comparison with micrographs for onion cell walls shows that noncrystalline cellulose does not equate to chains on fibril surfaces, and chemical shifts show that fully solvated cellulose is not a significant component in cell walls. © 1996 John Wiley & Sons, Inc.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 100
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 39 (1996), S. 103-114 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An optimization protocol is proposed that combines a mean field simulation approach with Boltzmann-weighted sampling. This is done by including Boltzmann probabilities of multiple conformations in the optimization procedure. The method is demonstrated on a simple model system and on the side-chain conformations of phenylalanines in a small hexapeptide. For comparison, calculations were performed using classical stochastic dynamics simulations [M. Saunders, K. N. Houk, Y. Wu, C. Still, M. Lipton, G. Chang, and W. C. Guida (1990), Journal of the American Chemical Society, Vol. 12, pp. 1419], iterative optimization of probabilities on a fixed set of basis conformations [P. Koehl and M. Delaure (1994), Journal of Molecular Biology, Vol. 239, pp. 249-275], and simulations with locally enhanced sampling [A. Roitberg and R. Elber (1991), Journal of Chemical Physics, Vol. 95, pp. 9277-9287]. Although approximations are used in our method, the results may be more physically meaningful than those of the other procedures discussed. Furthermore, the approximate Boltzmann distribution allows generalization of the results. © 1996 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
Close ⊗
This website uses cookies and the analysis tool Matomo. More information can be found here...