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  • Wiley-Blackwell  (29,050)
  • 1995-1999
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  • 1989  (11,969)
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  • 1995-1999
  • 1985-1989  (21,977)
  • 1980-1984
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  • 1
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In this part properties and efficiency of the developed model1,2 are discussed. A variation of the parameters shows that vigorous effects are caused by the effective aggregation. All calculations show that at low conversion there are little temporal steps between the sequential aggregation steps. In the range of 5% to 20% conversion the velocity of aggregation decreases and the aggregative stability agrees with experiences given in the literature. It is shown that the calculated results are in agreement with the experimental results and therefore the presented model is a suitable possibility to describe the formation of some PVC-morphology properties.
    Notes: In der vorliegenden Arbeit werden die Eigenschaften des früher1,2 entwickelten Modells untersucht und diskutiert. Die Variation der Modellparameter zeigt einen großen Einfluß der Aggregationsprozesse auf die Subkornmorphologie. Bei niedrigen Monomerumsätzen ist das Zeitintervall zwischen zwei aufeinanderfolgenden Aggregationsschritten sehr klein, so daß für das Teilchenwachstum die Geschwindigkeit der Aggregation der Unterstrukturen entscheidend ist. Im Bereich zwischen 5% und 20% Monomerumsatz sinkt die Aggregationsgeschwindigkeit sehr stark, so daß für das Teilchenwachstum zunehmend die Polymerisationsreaktion an Bedeutung gewinnt. Aggregative Stabilität wird nach dem Modell für einen Teilchengrößenbereich erhalten, der sich in Übereinstimmung mit experimentellen Daten aus der Fachliteratur befindet. Die berechneten Teilchengrößen entsprechen ebenfalls den in der Literatur publizierten experimentellen Werten, so daß das Modell eine gute Grundlage für die Beschreibung einiger morphologisch bestimmter Polymereigenschaften bildet.
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  • 2
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 165 (1989), S. 21-34 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurden unidirektionale Verbundwerkstoffe aus Novolakharz mit Kohlenstoff-Fasern gemäß der Prepreg-Methode verarbeitet. Das Novolakharz wurde durch Polymerisation von Phenol mit Formaldehyd (Mol-Verhältnis 1 : 0,82) und Oxalsäure als Katalysator (1,5 Gew.-% von Phenol) hergestellt. Die Härtung des Novolakharzes wurde mit Hexamethylentetramin (Hexa) durchgeführt, während das geeignete Verhältnis durch die IR-Spektroskopie bestimmt wurde.Es wurden Proben aus Novolak/Hexa (Gew.-Verhältnis 14: 1), verstärkt mit kommerziellen Kohlenstoff-Fasern, unter verschiedenen Bedingungen (z. B. verschiedene thermische Programme und verschiedene Verhältnisse von Novolakharz : Kohlenstoff-Fasern) hergestellt. Die mechanischen Eigenschaften der hergestellten Proben (wie Biegefestigkeit, Zugfestigkeit, usw.) wurden bestimmt, und ihre Struktur wurde mit Hilfe der Elektronenmikroskopie untersucht.Mit zunehmendem Volumenverhältnis der Kohlenstoff-Fasern werden nicht nur alle mechanischen Eigenschaften des verstärkten Materials verbessert, sondern auch sein Nutzungsgrad nimmt zu, und die Herstellungsbedingungen üben einen größeren Einfluß aus. Die mit dem gleichen Verhältnis von Kohlenstoff-Fasern (z. B. 15 Vol.-%) hergestellten Proben weisen mit zunehmendem Härtungsgrad des Novolaks verbesserte mechanische Eigenschaften auf. Der Häirtungsgrad des Novolaks während der Anfangsphase (Gel-Zeit) als auch während der Endphase (Nachhärtung) kann mit Hilfe der IR-Spektren des härtenden Novolaks verfolgt werden, während der Härtungsgrad der Zwischenphase nur indirekt aus den Werten der mechanischen Eigenschaften der entsprechenden Proben bestimmt werden kann.Aus der Korrelation zwischen den Herstellungsparametern und den mechanischen Eigenschaften der Proben ergeben sich optimale Bedingungen für die Verarbeitung in der Wärmepresse zur Herstellung von mit Kohlenstoff-Fasern verstärkten Novolakharzen (1. Phase: T1 = 125-145°C, t1 = 20 min - 1 h, ohne Druck; 2. Phase: T2 = 180-195°C, t2 = 40 min, P2 ≃ 1,5 kN /cm2).
    Notes: Unidirectional composite materials of novolac resin with carbon fibers were fabricated according to the prepreg method. Novolac resin was prepared by polymerization of phenol with formaldehyde (mole ratio 1 : 0.82) in the presence of oxalic acid as catalyst (1.5 wt.-% to phenol). The curing of novolac resin was performed with hexamethylenetetramine (hexa), while the appropriate proportion was determined by using the IR-spectroscopy.Specimens of novolac/hexa (weight ratio 14:1) reinforced with carbon fibers commercially available were fabricated under different conditions (e.g. different thermal programs and different proportions of novolac/carbon fibers). The mechanical properties of the fabricated specimens (like flexural strength, tensile strength, etc.) were determined and their structure was examined by scanning electron microscopy.By increasing the volume proportion of carbon fibers, not only all mechanical properties of the composite material were increased, but also their degree of utilization was increased and also the production conditions had greater influence. Concerning the specimens produced by the same proportion of carbon fibers (e.g. 15 vol.-%) their mechanical properties were improved by increasing the curing of novolac. The degree of curing of novolac during the initial phase (gel time) and during the ultimate phase (post-curing) can be followed with the aid of IR-spectra of the cured resin, while the degree of curing for the intermediate phase can be obtained only indirectly from the values of the mechanical properties of the corresponding specimens.From the correlation between the production parameters and the mechanical properties of the samples the optimal conditions for processing of the thermopress for the manufacture of carbon fiber reinforced novolac were concluded (1. phase: T1 = 125-145°C, t1 = 20 min - 1 h, without pressure; 2. phase: T2 = 180-195°C, t2 = 40 min, P2 ≃ 1,5 kN/cm2).
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  • 3
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 165 (1989), S. 69-78 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In dieser Arbeit interessieren wir uns für den Einfluß von Konzentration und Temperatur auf den elektrischen Widerstand eines Butyl-Kautschuks (IIR), der mit zwei Typen von Ruß (Hoch-Abrasion-Schmelzofen-Ruß (HAF) und Schnell-Extrusion-Hochofen-Ruß (FEF)) versetzt ist. Ergebnis war, daß die Leitfähigkeit bei niedrigem Rußgehalt hauptsächlich durch thermische Aktivierung der Ladungsträger erreicht wird. Bei mittleren Konzentrationen überwiegt der Tunnel-Mechanismus bei niedriger Temperatur, gefolgt von der thermischen Aktivierung bei relativ hoher Temperatur. Dies gilt für beide Rußarten. Das metallartige Verhalten bei Gemischen mit hoher Rußkonzentration kann sowohl der thermischen Ausdehnung der Tunnelwege zwischen Kohlenstoff-Agglomeraten als auch dem Zusammenbruch der Kohlenstoff-Agglomerate bei steigender Temperatur zugeschrieben werden.
    Notes: In this study we are interested in the effect of concentration and temperature on the electrical resistivity of butyl rubber (IIR) loaded with two types of carbon black, (namely, high abrasion furnace black (HAF), and fast extrusion furnace black (FEF)). It was found that the conductivity at low carbon black concentrations is mainly achieved by thermal activation of carriers. Tunneling mechanism at low termperature followed by thermal activation at relatively high temperature is found to be predominant for moderate concentrations for both carbon blacks. The metal-like behaviour which was observed in highly loaded compounds was attributed to both, the thermal expansion of the tunneling paths between carbon-carbon agglomerates and the breakdown of carbon agglomerates with temperature.
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  • 4
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 165 (1989), S. 79-87 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Arbeit beschreibt die Synthese von Halogenderivaten des Phenylglycidylethers und die Möglichkeiten der Verwendung von diesen Komponenten als Flammverzögerer und reaktive Verdünnungsmittel für Epoxidharze.Mit Hilfe der Nelder-Mead-Simplexmethode wurden die besten Reaktionsbedingungen gefunden. Die so hergestellten Produkte zeichnen sich durch eine hohe Qualität aus und wurden mit einem niedermolekularen Epoxidharz gemischt und mit Diaminodiphenylmethan gehärtet.Die Viskosität von Harzgemischen und die Brennbarkeit der gehärteten Systeme wurden untersucht. Mit dem erhöhten Gehalt an Halogen (Chlor oder Brom) steigt die Viskosität, und die Brennbarkeit der Epoxide wird reduziert.
    Notes: This study deals with the synthesis of halogenated derivatives of phenyl glycidyl ether and with possibilities of their use as flame retardants and reactive diluents of epoxy resin.The best reaction conditions optimized by Nelder-Mead simplex method were found. The products of very high quality were prepared. They were mixed with a lowmolecular epoxy resin and cured by diamino diphenyl methane.The viscosity of the resin mixtures and limiting oxygen index of cured systems were determined. It was found that a higher content of halogen, both chlorine and bromine, causes increasing viscosity and reduced flammability of the epoxides.
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  • 5
    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 Messungen von Tg, Tm und Tc (Trübungspunkt) wurden Phasendiagramme der vier verträglichen Polymermischungen von chlorierten isotaktischen Polypropylenen (Chlorgehalt 39,2 (CPP-40) und 49,8 Gew.-% (CPP-50)) mit Poly(ethylen-co-vinylacetat)en (Vinylacetatgehalt 40 (EVA-40) und 45 Gew.-% (EVA-45)) untersucht. Von den vier Mischungspaaren war die Mischung von CPP-50 mit EVA-40 am besten verträglich.
    Notes: By measuring Tg, Tm and Tc (cloud point) phase diagrams for the four miscible blends of chlorinated isotactic polypropylenes (chlorine content 39.2 (CPP-40) and 49.8 wt.-% (CP-50)) with Poly(ethylene-co-vinyl acetate)s (vinyl acetate contents 40 (EVA-40) and 45 wt.-% (EVA-45)) were investigated. The blend of CPP-50 with EVA-40 was the most compatible of the four blend pairs.
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  • 6
    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 Synthese und Charakterisierung von Kationenaustauschmembranen aus PE-PS-DVB-Interpolymeren für die Elektrolyse von Borax-Lösung zur Erzeugung von Borsäure und Natronlauge wurden durchgeführt und mit den Eigenschaften von im Handel erhältlichen Membranen („Nafion 324“ und „Permaplex C-20“) verglichen.
    Notes: The synthesis and the characterization of the PE-PS-DVB interpolymer cationexchange membranes in the electrolysis of borax solutions to produce boric acid and sodium hydroxide simultaneously was carried out. The characterization of the teflon based “Nafion 324” and polystyrene-DVB based “Permaplex C-20” membranes was also performed in the same system for comparison.The DVB contents were varied between 3 - 12% (by wt. in total monomers) and the increase of the cross-links resulted in the decrease of the water contents and ionexchange capacities of the membranes. The PE present in the membrane acted as a barrier for electroosmotic water transport. The membranes with high DVB contents showed better electrolysis performance due to their low water contents and low electroosmotic water transport properties. The use of the interpolymer membrane containing 11.6% DVB resulted in high current efficiency and high sodium cation dynamic transport number and worked satisfactorily at the process conditions of borax electrolysis.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 165 (1989), S. 125-131 
    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: Aus Rizinusöl und difunktionellen Säuren, wie Oxal-, Malon-, Bernstein-, Glutar-, Adipin-, Suberin- und Sebacinsäure, wurden Prepolyester hergestellt. Diese Prepolyester (PPE) wurden anschließend mit Methylmethacrylat und 1% Ethylenglykoldimethacrylat als Vernetzer interpenetriert. Die Polymerisation wurde radikalisch mit Benzoylperoxid gestartet. Die neuen PPE/Polymethylmethacrylat (PMMA)-interpenetrierenden Netzwerke wurden als Pulver erhalten. Sie wurden durch ihr Löseverhalten, IR-Spektroskopie und ihr thermisches Verhalten charakterisiert.
    Notes: Prepolyesters were obtained from castor oil and dibasic acids, viz oxalic, malonic, succinic, glutaric, adipic, suberic and sebacic acid. These prepolyesters (PPE) were subsequently interpenetrated with methyl methacrylate containing 1% ethylene glycol dimethacrylate as crosslinker by radical polymerization initiated with benzoyl peroxide. The novel PPE poly(methyl methacrylate) PPE/PMMA interpenetrating polymer networks (IPNs) were obtained as powder. They were characterized by solubility behaviour, IR spectral study and thermal behaviour.
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  • 8
    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: 2,4-Ionen, ein polymeres quartäres Ammoniumsalz, wurde auf einem makroporösen chlormethylierten Poly(Styrol-co-Divinylbenzol)-Harz (XAD-2) immobilisiert. Der Ionen-Gehalt des Harzes, der durch CHN-Elementaranalyse bestimmt wurde, betrug 50,2 g/kg Harz. Der wichtigste Nebeneffekt des modifizierten Harzes, das Ausbluten des Katalysators 2,4-Ionen, kann durch eine spektrophotometrische Methode, die extrem geringe Konzentraionen an freiem Ionen an der Oberfläche des Harzes messen kann, ermittelt werden.Die Aktivität der immobilisierten 2,4-Ionen/Kobalt(II)-phthalocyanin-tetranatriumsulfonat-Komplexe in bezug auf die oxidative Kupplung von Thiolen ist viel niedriger als im homogenen Fall, aber noch beträchtlich höher als im polymerfreien System. Die beobachtete Abnahme der Reaktionsgeschwindigkeit resultiert nicht aus Behinderungen des Massentransports, sondern vorzugsweise aus den Katalysatoreigenschaften wie z. B. einem sehr niedrigen N+/Co-VerhtUtnis. Die aktiven Zentren scheinen nur in der äußeren Hiille der Harzpartikel vorhanden zu sein.
    Notes: A poly(quaternary ammonium) salt, 2,4-ionene, has been immobilized on a macroporous chloromethylated poly(styrene-divinylbenzene) resin (XAD-2). The ionene content of the resin, determined by CHN elemental analysis, was 50.2 g/kg resin. The most important side effect of the modified resin, catalyst (2,4-ionene) bleeding, can be detected by a spectrophotometric method capable of determining extremely low concentrations of free ionene in the supernatant of the resin.The activity of these immobilized 2,4-ionene/cobalt(II)phthalocyanine-tetrasodiumsulfonate (CoTSPc) complexes towards the oxidative coupling of thiols is much lower than in the homogeneous case, but still considerably higher than for the polymer free system. The observed decrease in reaction rate does not originate from the considerable mass transfer resistances but predominantly from catalyst properties like a very low local N+/Co ratio. The active sites appear to be present in the outer shell of the resin particles only.
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  • 9
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Röntgendiffraktometrische Untersuchungen und DSC-Messungen an Blend-Filmen, die aus Lösungen von PEEK und PES hergestellt wurden, zeigen eine Phasenseparation bei den Filmen, die bei 340°C hergestellt wurden. Das Kristallisationsverhalten von Filmen, die bei 340°C hergestellt, anschließend abgeschreckt und bei 180°C getempert wurden, ist identisch mit dem von PEEK. Filme, die bei 300°C hergestellt wurden, kristallisierten erst durch Tempern bei 250°C. Blockcopolymere, die aus Oligomeren von PEEK und PES erhalten wurden, unterscheiden sich in dieser Hinsicht von Blends der gleichen Zusammensetzung. Die Glastemperatur von Copolymeren mit einem PEEK-Gehalt von mehr als 50% liegt höher als die von PEEK selbst, während der Schmelzpunkt dieser Copolymeren niedriger als der von PEEK ist.
    Notes: Polymer blends of PEEK with PES were prepared by the solution blending method. Copolymers composed of PEEK and PES components were synthesized from these oligomers. The formation conditions exerted an influence over the molecular aggregation and the crystallization behaviors of the blend films and block copolymers which were examined by X-ray diffractometry and DSC analysis. As a result, phase-separation in the blend films was found when the formation temperature was high. The blend films formed at 340°C, quenched and annealed at 180°C, exhibited the same crystallization behavior as those of PEEK. In the case of the blend films formed at 300°C, the annealing of the films at 250°C was required to crystallize the blend films. The Tg of a copolymer with a PEEK component content of more than 50% tends to shift toward a higher temperature than the Tg of PEEK itself, and the Tm of the copolymer toward a lower temperature than that of PEEK ist.
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  • 10
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 168 (1989), S. 129-134 
    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 Reaktionsprodukt eines Cyclohexanon-Formaldehyd-Harzes mit dem Säurechlorid des Radikalinitiators 4,4′-Azo-bis(4-cyanopentansäure) wurde als Initiator für die Styrolpolymerisation eingesetzt, um ein Cyclohexanon-Formaldehyd-Harz/Polystyrol-Copolymeres zu bilden. Das Copolymere zeigte ähnliche Löslichkeit wie Polystyrol.
    Notes: The reaction product of cyclohexanone-formaldehyde resin with an acid chloride of a radical initiator, 4,4′-azo-bis(4-cyano pentanoic acid) was used as initiator for styrene polymerization to form a cyclohexanone-formaldehyde resin/polystyrene copolymer. The copolymer showed similar solubility as polystyrene.
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  • 11
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 168 (1989), S. 145-155 
    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: Entgegengesetzte Ladungen wurden durch tertiäre Amin- und Carboxylgruppen in Polyurethan (PU) und Polystyrol (PS) eingeführt, um durch gemeinsame Massepolymerisation ein interpenetrierendes PU/PS Polymernetzwerk (IPN) zu erhalten. Vier IPNs wurden hergestellt: ein Voll-IPN, zwei Semi-IPNs und ein lineares Blend. Die Wirkung der geladenen Gruppen auf die mechanischen Eigenschaften und die Morphologie der vier Polymermischungen wurde untersucht.Es wurde gefunden, daß PU/PS IPNs mit geladenen Gruppen keine Phasenseparation und somit homogene Verteilung aufweisen, was durch elektronenmikroskopische (SEM) Aufnahmen nachgewiesen wurde. Dynamisch-mechanische Messungen zeigen, daß die Übergangspeaks des Verlust-Moduls E″ in die Mitte zwischen den beiden Übergangspeaks der beiden Komponenten ohne geladene Gruppen liegen. Dies ist von der Zunahme des Gehaltes an geladenen Gruppen abhängig. Gleichzeitig nimmt der Speichermodul E′ in einer Stufe ab, was im Gegensatz zu der zweistufigen Abnahme bei Proben ohne Ladungsträger steht.Die Zugfestigkeit nimmt in allen vier Polymermischungen mit der Zunahme an Acrylsäure (AA) in Poly(Styrol-Acrylsäue) PSAA zu, was in dem PU/PSAA Voll-IPN besonders deutlich wird.
    Notes: Opposite charges, namely tertiary amine and carboxyl groups, were introduced into polyurethane (PU) and polystyrene (PS), respectively, to prepare PU/PS interpenetrating polymer networks (IPNs) by means of simultaneous bulk polymerization. Four IPNs were synthesized: a full-IPN, two semi-IPNs and a linear blend. The effect of charge groups on the mechanical properties and morphology of the four polymer alloys was investigated.It is found that the PU/PS IPN which was incorporated with charge groups is free of any phase-separation, and sufficiently uniformly distributed, as can be seen from the corresponding scanning electron microscopy (SEM) photographs. Dynamic mechanical analysis indicates that the transition peak of the loss modulus E″ will move towards the centre between the two transition peaks of both components in the absence of charge groups, as a function of an increase in the contents of the opposite charge groups. Meanwhile the storage modulus E′ will decrease in a single-stage way from the previous two-stage mode.The tensile strength in all the four polymer alloys increased markedly along with an increase in the contents of acrylic acid (AA) in the poly(styrene-acrylic acid) (PSAA), which clearly can be seen for the PU/PSAA full-IPN.
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  • 12
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 168 (1989), S. 157-168 
    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: Pyrolysis behaviour and coke characteristics of different precursors for carbon processing: thermosetting resins (resol, novolak), hydrolytic lignin, pitch, tar as well as their blends were studied using differential thermal analysis (DTA) and X-ray diffraction techniques. The blends novolak-pitch, resol-tar and resol-hydrolytic lignin show a higher coke yield after carbonisation up to 1000°C compared to the corresponding individual substances. A good correlation between the integral procedural decomposition temperature T*A of the investigated precursors and their coke yield is found.
    Notes: Mittels Thermo- und Röntgenstrukturanalyse wird eine vergleichende Untersuchung des Pyrolysevorganges und der Mikrostruktur des aus zwei Gruppen organischer Bindemittel und deren Mischungen gewonnenen Koksrückstandes durchgeführt. Gruppe I umfaßt reine und mit Hydrolyselignin gefüllte Resol- und Novolak-Phenol-Formaldehydharze und Gruppe II Steinkohlenpech und -teer. Es wird festgestellt, daß sich die Mischungen Novolakharz-Pech, Resolharz-Teer und Resolharz-Hydrolyselignin beim Erhitzen nicht wie mechanische Gemische verhalten und eine erhöhte Ausbeute an Koksrückstand liefern. Weiterhin wird gefunden, daß die integrale Endtemperatur der Pyrolyse (T*A) dieser Substanzen als quantitatives Maß für die Ausbeute an Koksrückstand im Anschluß an die Carbonisierung der Proben dienen kann.
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  • 13
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 168 (1989), S. 217-223 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The paper describes the successful synthesis of silicon containing bismaleimide resin 4,4′-carbo(4,4′-bismaleimido phenoxy)diphenyl silane. The char yield of the bismaleimide resin in N2 atmosphere was found to be 55% at 800°C. Chain extension of bismaleimide with 4,4′-diamino diphenyl sulfone reduced the char yield and thermal stability.
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  • 14
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: As hard blocks in polyether block amides, polyamides are used whose length is intensively regulated by dicarboxylic acids. Since, with regard to melting and crystallization behaviour, this acid constitutes an interfering structural unit in the chain, and in the case of a completely converted product each chain contains one acid molecule, it is essential to know where in the chain incorporation will occur. As opposed to monofunctional chain regulators which always form a chain end, a bifunctional chain regulator can a priori also be randomly incorporated into the inner part of the chain. This leads to a far greater interference than occurs if the chain regulator molecule and the chain end, which acts as an interfering unit in any case, coincide with each other.By means of adipic acid-regulated oligoamides based on lauryl lactam, the incorporation of the chain regulator was examined by NMR spectroscopy and compared with model calculations. This resulted in a close match only if it was presupposed that the incorporation was carried out randomly with the same degree of probability at any point whatsoever between two lauryl lactam structural units or at the chain end.Further calculations illustrate the effects of the incorporation of the chain regulator on the size of the amorphous portion.
    Notes: Als Hartblöcke in Polyetherblockamiden werden durch Dicarbonsäuren stark geregelte Polyamide eingesetzt. Da die Säure in Hinblick auf das Schmelz- und Kristallisationsverhalten einen Störbaustein in der Kette darstellt und bei einem ausgeregelten Produkt jede Kette ein Säuremolekül enthält, ist es von Bedeutung zu wissen, wo in der Kette der Einbau erfolgt. Anders als bei monofunktionellen Reglern, wo der Regler stets ein Kettenende bildet, kann ein bifunktioneller Regler a priori auch statistisch im Inneren der Kette eingebaut werden. Dies führt zu einer viel stärkeren Störung, als wenn das Reglermolekül und das sowieso als Störstelle wirkende Kettenende zusammenfallen. Anhand adipinsäuregeregelter Oligoamide auf Basis von Laurinlactam wird kernresonanzspektroskopisch der Einbau des Reglers untersucht und mit Rechnungen verglichen. Es ergibt sich nur dann gute Übereinstimmung, wenn vorausgesetzt wird, daß der Einbau statistisch erfolgt und dabei mit gleicher Wahrscheinlichkeit für jede beliebige Stelle zwischen zwei Laurinlactambausteinen oder am Kettenende abläuft. Weitere Rechnungen verdeutlichen den Einfluß des Reglereinbaus auf die Größe des amorphen Anteils.
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  • 15
    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: Auf Grund von mikroskopischen Beobachtungen wurde festgestellt, daß unter dem Einfluß von UV-Strahlung die Oberfläche von PVC-Filmen einer Formveränderung unterliegt. Auf der Oberfläche erscheinen Bläschen und Löcher. Die sich absondernden Gasprodukte der Polymerfotodestruktion verursachen die Bildung dieser Bläschen und Löcher. Größere Oberflächenänderungen wurden in Filmen mit einem Zusatz von 1-5% eines MMA/MA-Copolymeren beobachtet. Das weist auf eine in diesem Modifikator stattfindende Photoabbaureaktion hin, deren Ergiebigkeit größer ist als in reinem PVC. Dieser Modifikator wird in PVC eingeführt, um die Filmoberfläche zu verbessern, beschleunigt allerdings ihre Zerstörung unter dem Einfluß von UV-Strahlung. Es wurde festgestellt, daß Cyclohexanonspuren in den Proben den Photoabbau von MMA/MA retardieren, diesen Prozeß in PVC aber beschleunigen.
    Notes: By means of microscopic observation, the deformation of the surface of PVC films caused by 253.7 nm UV radiation was investigated. Numerous blisters and holes were formed by the gaseous photodecomposition products of the polymer.More apparent deformation of the films containing MMA/MA suggests that the photodecomposition of this modifier occurs with higher efficiency than that of PVC.MMA/MA copolymer is introduced into PVC films to improve the smoothness of their surface, but this modifier accelerates the deformation of this surface under UV irradiation. It was also found that traces of cyclohexanone in samples retard the photodecomposition of MMA/MA and accelerate this process in PVC.
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  • 16
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 170 (1989), S. 29-41 
    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: Eine Anzahl von Harzen wurde durch gemeinsame Kondensation von p-Aminoacetophenon (p-AAph), substituierten Benzoesäuren wie m-Tolylsäure (m-TA), o-Tolylsäure (o-TA), Phthalsäure (PhA), p-Nitrobenzoesäure (p-NBA), p-Chlorbenzoesäure (p-CIBA) und Formaldehyd (F) in Gegenwart von verschiedenen Säuren und Basen als Katalysatoren hergestellt. Die Harze wurden IR-spektroskopisch charakterisiert. Die Löslichkeitsparameter wurden gemäß Small's Gruppenbeteiligung berechnet; sie stimmen gut mit den experimentellen Werten überein. Das thermische Verhalten und die bakteriologischen Eigenschaften der Harze wurden auch untersucht.
    Notes: A number of resins has been prepared by condensing p-amino-acetophenone (p-AAph) with substituted benzoic acid such as m-toluic acid (m-TA), o-toluic acid (o-TA), phthalic acid (PhA), p-nitrobenzoic acid (p-NBA), p-chlorobenzoic acid (p-CIBA) and formaldehyde (F) in presence of some acids and bases as catalysts. The resins were characterized by infrared spectra of the characteristic groups. The solubility parameters were calculated from Small's group contribution which agreed well with the experimental values. The thermal behaviour and the bacteriological properties of the resins have also been investigated.
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  • 17
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Notwithstanding their more common beginnings, liquid crystals and molecular biology developed mainly parallel and independently during the last one hundred years.Molecule-phase relationships on the one and complex static-dynamic treatments on the other hand seem to forward mutually integrative views in our days.Biomesogen approaches will deepen our insights into the spatio-temporal coherences of biological systems. They might contribute significantly to the understanding of life processes.
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  • 18
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Recent studies on ionic distribution in solutions and in suspensions were reviewed. Suspensions of latex particles, which were large enough to be seen under an ultramicroscope, were investigated by the 2-D Fourier transformation. The micrograph showing ordered structures gave discrete scattering spots, whereas those of disordered arrangements displayed no spots or halos. The two-state structure gave a limited number of halo, confirming our previous conclusion that the very frequently observed single, broad scattering peak was reminiscent of some kind of ordering of solute species. By using an image data analyser, the crystallization process was shown to follow the Ostwald ripening mechanism. The concurrent study by the quasi elastic light scattering method and by the Fourier analysis gave consistent scattering profiles, which indicated that the ordering phenomena took place in the entire volume of suspensions. The scattering intensity (correctly the lattice factor) was calculated for cubic systems with paracrystalline distortion. The peak intensity was lowered by enhanced distortion, while the peak position itself was not affected. This justifies our previous treatment of the single, broad peak in terms of the Bragg equation. The experimentally found scattering curve was compared with this theoretical calculation; the degree of distortion was evaluated.
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  • 19
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Lyotropic liquid crystalline phases of cellulose derivatives were explored as an analytical tool. Molar mass dependent measurements of the helicoidal cholesteric pitch of a cellulose tricarbanilate/solvent system may be used to determine the molar mass of this derivative by optical means. The compatibility of a ternary liquid crystalline system can be adequately investigated by a study of the supermolecular structure with spectroscopic measurements.
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  • 20
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The application of carotenoids as natural additives in various water-based or water-compatible formulations for the pigmentation of foods and feeds is seriously hampered by their insolubility in aqueous systems.Therefore, in order to develop the full potential of colour strength and to achieve a high degree of bioavailability during gastro intestinal passage, the coarse crystalline material has to be transformed into a microdisperse state.Exemplified with β-carotene, a novel non-mechanical process is described that transforms the carotenoids into a colloidal hydrosol characterized by an average particle size of about 0.1 μm.The process is based on the preparation of a transient high temperature solute state of the carotenoid in a water-miscible solvent, coupled with succeeding rapid aqueous precipitation in the presence of a stabilizing polymer colloid. The obtained hydrosols are characterized by photon-correlation-spectroscopy(size), and microelectrophoresis(colloidal stabilization).The bioavailability was tested by monitoring plasma levels of β-carotene in veal calves.
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  • 21
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymer science is mature enough to allow one to think about tailor-making macromolecular compounds aimed at interacting purposely with living systems. Reasons for developing bioresorbable polymers for temporary therapeutic applications are discussed with respect to property adjustments and economical factors. The field of the applications is first described and guidelines for tailor-making multimeric macromolecules with desired properties are presented. The approach led to focuss investigations on poly(α-hydroxy acids) and functional poly(β-hydroxy acids) derived from natural hydroxy acids, namely lactic, glycolic and malic acids. Physical, mechanical and biological properties of some corresponding polymers and copolymers are presented. Last but not least, examples of applications currently investigated are recalled.
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  • 22
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When blood comes into contact with an artificial surface, a number of events occur which include protein adsorption, platelet activation and the activation of the intrinsic pathway of blood coagulation. With the increased application of blood containing artificial devices, there is a great demand to develop new biomaterials which retard thrombus formation. Our new approach to solving this problem is to mimic the non-thrombogenic surface of natural biological membranes at least in a simple form. We have developed a polymerisable phospholipid and polyesters based on the major phospholipid polar head group present on the erythrocyte outer membrane surface. The coagulation of blood exposed to these polymers was examined by the technique of Material Thrombelastography, a relatively simple test for the in vitro screening of polymer thrombogenicity. We present results which indicate that the polymerised phospholipid and polyesters show reduced thrombogenicity, and may therefore have potential for future biomaterials.
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  • 23
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: After implantation a stable bond between the implant and the surrounding tissue is required. Therefore a high cell adhesion of the polymer surface of the implant must be achieved. Depending on the treatment time of a polydimethylsiloxane foil with oxygen plasma, the cell adhesion can be improved. FT-IR spectroscopy and ESCA analysis were used to characterize the surface modification. The cell spreading and cell adhesion increase with increasing hydrophilic character of the polymer surface after plasma treatment. A pronounced correlation was found between the efficiency of DNA and protein content, characterizing cell growth, and the spreading of the cells.Polydimethylsiloxane, Glow-Discharge, Surface Modification, Cell Adhesion, Cell Proliferation.
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  • 24
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have used synthetic polymers as tools to probe endocytosis and lysosome function. Their particular value lies in their well-defined chemical constitution and in the possibility to custom-synthesize molecules with desired characteristics. Polyvinylpyrrolidone, Percoll and polystyrene beads have been 125I-labelled and used to explore the borderland of pinocytosis and phagocytosis. Derivatized poly(aspartamide), poly(hydroxypropylmethacrylamide) and a polylysine-poly(ethylene oxide) block copolymer have been used to investigate the effects of hydrophobic moieties and sugar residues on substrate-selection in pinocytosis. The effect of cationic moieties has been studied using vinylpyrrolidone-vinylamine copolymers.Poly(hydroxypropylmethacrylamide) with certain oligopeptide side---chains have been shown to be susceptible to lysosomal peptidases. Ethylene glycol oligomers are being used to study the basal permeability of the lysosome membrane.Soluble macromolecules have considerable potential in targeted drug-delivery. Drugs attached to appropriate polymers by covalent links that are susceptible to lysosomal enzymes can deliver drug to target cells and avoid unwanted sideeffects. Synthetic macromolecules have several advantages over their natural counterparts: they are chemically more robust, less immunogenic, and easier and cheaper to prepare in bulk.
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  • 25
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Diagnostics are e. g. reagents or combinations of reagents or measure bloodcomponents down to concentrations of 10-15 mol/1 in reproducable form. To achieve this target diagnostics have to fullfill special requirements in purity, uniformity, producibility and reproducibility. These requirements are also valid for integrated polymers and plastics. Examples of the application of polymers and plastics in diagnostics are e. g. materials for the blood-plasma-separation, the stabilization of proteins, solid phases in immunoassays as reagent tubes, microtiterplates and latexparticles.Reciprocal actions between polymers, plastics, polymer additives, blood and bloodsubstances like proteins in diagnostic tests can be seen as indications to similar effects by the intracorporeal applications of plastics in surgery and in general for contacts of natural materials with plastics, as usual in the foodpacking.
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  • 26
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using Eupergit, a synthetic resin, as an example, the necessary characteristics of a support for high performance affinity chromatography (HPAC) are demonstrated. To such a support different ligands can be immobilized and used for the separation of biopolymers.From the range of possible applications a few examples are chosen. Immunoglobulins are isolated in one step by protein A-HPAC, the purified antibodies are immobilized and applied to immunoaffinity-HPLC for the isolation of corresponding antigens. Concanavalin A-HPAC of membrane proteins was chosen to represent chromatography with immobilized lectins. Antithrombin could be isolated from human plasma by the use of immobilized heparin. HPAC has the advantage of affinity chromatography, which is above all highly specific. As the support is resistant to high pressure and has well defined microparticles with a particular pore size, it provides a much higher yield at considerable flow rates. The handling of materials like this is simpler, the separation of the sample is quicker and can be reproduced more easily.
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  • 27
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 166 (1989), S. 257-272 
    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: Controlled polyelectrolyte adsorption can be used to render phospholipid bilayer membranes sensitive to physical and chemical signals. We describe in this paper the design and construction of macromolecular switches for bilayer membranes, which can be used to create lipid vesicles that release their contents rapidly and quantitatively in response to changes in pH, temperature, light intensity or glucose concentration. The kinetics and mechanisms of the molecular switching processes observed in such systems are also discussed.
    Notes: Kontrollierte Adsorption von Polyelektrolyten kann ein wirksames Werkzeug im Design von dünnen molekularen Filmen sein. Man kann erwarten, daß die Adsorption von Polyelektrolytketten das empfindliche Kräftegleichgewicht erheblich beeinflußt, das die strukturellen und funktionellen Eigenschaften von geordneten Strukturen wie Einzel-, Doppel- und Mehrfachschichten bestimmt. Andererseits ist die Adsorption von Polyelektrolyten außerordentlich sensitiv auf Umgebungsparameter, z.B. pH, Temperatur oder lonenstärke. Kontrollierte Adsorption kann daher zu Sensitivität auf bestimmte chemische oder physikalische Stimuli führen, sodaß auf diese Weise ein molekularer Schaltmechanismus entworfen werden kann. Durch Umsetzen dieser ldee in reale Systeme gelang es uns, molekulares Schalten in Mischungen von Poly(2-ethylacrylsäre) mit natürlichen oder synthetischen Phosphatidylcholinen zu bewirken. Insbesondere haben wir Phosphatidylcholinvesikel hergestellt, die ihren lnhalt nach einer Änderung von pH, Temperatur, Glukosekonzentration oder nach Bestrahlung mit Licht schnell und quantitativ freisetzen. Die Entwicklung und die Herstellung von Doppelschichtmembranen, die auf solche Änderungen reagieren, sowie die Kinetik und der Mechanismus des damit verbundenen molekularen Schaltprozesses werden im vorliegenden Artikel diskutiert.
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  • 28
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Enzymes can be immobilized by gel entrapment, by microencapsulation, by physical or ionic adsorption, by covalent binding to inorganic or organic carriers, or by whole cell immobilization. Of particular interest is the large number of chemical reactions developed for the covalent binding of enzymes via their nonessential functional groups to inorganic carriers such as glass, ceramics and iron, to natural polymers such as cellulose and Sepharose, and to synthetic polymers such as nylon, polyacrylamide, and other vinyl polymers and copolymers possessing reactive chemical groups. The stability of certain enzymes is markedly increased on their immobilization. It was thus possible to transform the biologically active polymer derivatives into active enzyme beads, enzyme capsules, enzyme columns and enzyme membranes and these enabled the construction of enzyme reactors such as the batch-stirred tank reactors, the continuous packed bed reactors, and fluidized bed reactors. So far mainly immobilized hydralases and isomerases are being used in industry on a large scale. It seems likely, however, that once adequate techniques become available for cofactor recycling, the use of immobilized enzymes will be extended to other organic reactions, particularly those involving stereospecific synthesis of simple or complex organic molecules. Among the industrial processes in which immobilized enzymes are being used, it is worth mentioning the industrial-scale continuous production of fructose enriched syrup from glucose by immobilized glucose-isomerase, the batch process for the production of 6-aminopenicillanic acid (6-APA) from penicillin G with the aid of immobilized penicillin amidase; the production of aspartame from aspartic acid and phenylalanine by immobilized thermoase; the large scale production of optically active amino acids with immobilized amino acid acylase; and the large scale production and application of immobilized lactase for the hydrolysis of lactose. The recently developed process for acrylamide production using immobilized nitrilase containing microbial cells should also be referred to. The successful use of an NAD-polyethylene glycol conjugate (NAD-PEG) as a nondialyzable water-soluble coenzyme derivative in the enzymic synthesis of leucine from α-ketoisocaproic acid and ammonia, in a membrane-enclosed reactor containing L-leucine dehydrogenase, NAD-PEG, formate and formate dehydrogenase, illustrates the new possibilities opened up by making use of cofactor-polymer conjugates. The use of enzyme-polymer conjugates in analytical and clinical is also illustrated.
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  • 29
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The genetic make-up of living systems especially of isolated cells can be altered by a variety of methods including chemical or light-induced mutation. More modern procedures are the in vitro recombination of nucleic acids and the cell-cell fusion.The new methods are especially useful to reprogram microorganisms to produce valuable proteins or other natural products in excess quantties. In the following we will elucidate the importance of the new techniques by describing the bacterial production of glucose dehydrogenase, of the proteinase inhibitor stefin A and by outlining the methods and promisses of substractive cloning. Although the economic value of genetic engineering techniques still awaits justification, the importance of the methodology for basic biological research is well documented.
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  • 30
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Immobilization of whole cells has become an efficient tool for biosynthesis, biotransformation and analysis. High cell density, high operational stability, easy handling, propably in continuous systems, and multiple reuse are important advantages of immobilized cells. In comparison to other methods like adsorption, crosslinking and encapsulation, the entrapment within a polymeric network is the most widely applied technique in heterogeneous biocatalysis. For immobilizing mammalian cells nearly exclusively the adsorption onto micorcarriers is used. Requirements for the polymers to be used in such immobilized cell systems are discussed in detail.
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  • 31
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 168 (1989), S. 1-8 
    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: Vier Pyridazinderivate wurden synthetisiert und als Beschleuniger für Naturkautschukmischungen entwickelt. Die rheologischen Eigenschaften wurden mit Hilfe eines Monsanto Rheometers 100 bestimmt. Die rheometrischen Daten wurden für die Berechnung der kinetischen Konstanten der Vulkanisationsreaktion in Anwesenheit der synthetisierten Verbindungen benutzt. Verglichen mit Mercaptobenzthiazol (MBT), einem Beschleuniger der häufig in der Kautschukindustrie eingesetzt wird, zeigten diese Verbindungen eine gute Beschleunigerwirksamkeit.
    Notes: Four pyridazine derivatives were synthesized and evaluated as accelerators in natural rubber (NR) mixes. The rheological characteristics were determined by a Monsanto Rheometer 100. The kinetic constants for the vulcanization reaction in the presence of the synthetic compounds were calculated using the rheometric data. The compounds showed a good accelerating efficiency compared with mercaptobenzothiazole (MBT), which is widely used in rubber industry.
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  • 32
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 170 (1989), S. 173-182 
    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 Ansammlung von als inaktiv angenommenen „Dimeren“ und „Trimeren“ sowie der Verbrauch von aktiven Spezies mit der Reaktionszeit im säurekatalysierten Furfurylalkohol (FA)/Formaldehyd (F) System wurde durch GPC-Technik unter Anwendung eines Doppeldetektors bewiesen.Ein Reaktionsmechanismus wurde für den Kondensationsprozeß vorgeschlagen, der einige Widersprüche der bisherigen Untersuchungen erklären kann.
    Notes: Accumulation of “dimers” and “trimers” considered to be inactive and consumption of active ones with reaction time in furfuryl-alcohol (FA)/formaldehyde (F) acid catalyzed condensation system was proved by GPC technique using double detector.A reaction mechanism was proposed for the condensation process explaining some contradictions of investigations collected so far.
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  • 33
    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: Dieser Artikel befaßt sich mit silylierten bzw. maleinisierten Polybutadienölen und ihren Effekten in Kieselsäure und Silicate bzw. Kreide enthaltenden Kautschukmischungen. Sie erweisen sich als wirksame Hilfsstoffe für die Substitution von Ruß durch mineralische Füllstoffe.
    Notes: This paper deals with silylated and maleated polybutadiene oils and their effects in rubber compounds containing silica(tes) resp. chalk as fillers. They are shown to be efficient aids in the substitution of oil-dependent carbon black by mineral fillers.
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  • 34
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 171 (1989), S. 79-89 
    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 isotherme und nichtisotherme Kristallisation von isotaktischem Polypropylen, das mit ausgewählten organischen Pigmenten gefärbt war, wurde mittels DSC untersucht. Es wurde gefunden, daß die Nukleierungsfähigkeit der Pigmente mit deren chemischem Aufbau und mit der Erniedrigung der freien Energie für den Keimbildungsprozeß verbunden ist. Die experimentellen Daten wurden mit Hilfe der bekannten Avrami-Gleichung analysiert.Blau-Pigment und Rot-Lack beschleunigen die Kristallisation von isotaktischem Polypropylen, während Orange-Pigment die Kristallisationsgeschwindigkeit etwas herabsetzt.
    Notes: The isothermal and non-isothermal crystallization of isotactic polypropylene coloured with selected organic pigments was examined by differential scanning calorimetry. It was found that the nucleating ability of pigments is connected with their chemical nature and with the reduction of the free energy for critical nucleus formation. The experimental data were analysed in terms of the well known Avrami equation.Blue pigment and Red lake are substances which accelerate the crystallization of isotactic polypropylene, while Orange pigment decreases the crystallization rate slightly.
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  • 35
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Um bei Kationen-Austauschmembranen eine dauerhafte Selektivität für die Durchlässigkeit von einwertigen Kationen zu erzielen, wurde eine Polyethylenimin-Schicht auf der Membranoberfläche durch Säureamidbindung zwischen Polyethylenimin und den —SO2Cl-Gruppen einer Styrol-co-Divinylbenzol-Membran erzeugt. Nach der Reaktion wurden die im Inneren der Membran verbleibenden —SO2Cl-Gruppen durch Tauchen in wäßrige Natronlauge hydrolysiert.Die so gewonnenen Kationen-Austauschmembranen wurden mittels Elektrodialyse von Seewasser hinsichtlich ihrer Selektivität für die Durchlässigkeit von einwertigen Kationen, ihres elektrischen Widerstandes, ihrer Stromleistung und ihrer überfüh-rungszahlen für Natrium-Ionen untersucht. ATR-IR-Messungen auf der Membran-oberfläche belegen, daß die Shäureamidbindung gegenüber starker Hydrolyseeinwirkung stabil war.
    Notes: In order to give the monovalent cation permselectivity to the cation exchange membrane permanently, polyethyleneimine layer was formed on the membrane surface by acid-amide bond between polyethyleneimine and the —SO2Cl groups of a styrene-divinylbenzene copolymer membrane. After the reaction, the —SO2Cl groups remaining in the inner part of the membrane were hydrolyzed by immersing the membrane into an aqueous sodium hydroxide solution.The resultant cation exchange membranes were evaluated by electrodialysis of sea water from the point of view of the monovalent cation permselectivity, electric resistance of the membrane, current efficiency, and transport number of sodium ions calculated by membrane potential in connection with reduced viscosity of the various commercial polyethyleneimines, ATR-IR measurements on the membrane surface suggested that the acid-amide bond was stable for severe hydrolysis reaction.
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  • 36
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    Angewandte Makromolekulare Chemie 171 (1989), S. 141-152 
    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 Epoxidgruppen eines Copolymeren, das man durch Pfropfung von 2,3-Epoxypropylmethacrylat auf isotaktisches Polypropylen erhält, wurden mit niedermolekularen Carbonsäuren umgesetzt. Die Reaktion verläuft in Gegenwart von organischen Lösungsmitteln heterogen und kann durch tertiäre Amine beschleunigt werden. Die Geschwindigkeitskonstanten der Reaktion werden mit der Dissoziationskonstanten der gebundenen Säure und mit der Art des verwendeten Beschleunigers korreliert. Die Reaktivität der polymergebundenen Epoxidgruppen ändert sich im Vergleich mit Reaktionen unter homogenen Bedingungen nicht.
    Notes: Epoxy groups on isotactic polypropylene, to which 2,3-epoxypropylmethacrylate was grafted, were reacted with low molecular carboxylic acids. The reaction proceeds under heterogeneous conditions in the presence of organic solvents and it may be catalysed by tertiary amines. The rate constants of this reaction are correlated with the dissociation constant of the bonded acid and with the character of the used catalyst. The reactivity of polymer-bonded epoxy groups is not changed when comparing with reactions performed under homogeneous conditions.
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  • 37
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wird eine neue Methode zur Einführung von hydrophilen Polyetherseitenketten in segmentierte Polyurethane unter Verwendung eines Polypropylenoxid-Macromeren mit 1,3-Diol-Gruppen an einem Kettenende, die als Kettenverlängerer fungieren, beschrieben. In diesem Prozeß wird eine Seitenkette quantitativ und direkt in medizinische Polyurethanelastomere eingebaut. Diese Entwicklung ist auch für Biowerkstoffe in künstlichen Organen von Interesse.
    Notes: A new method of introducing a hydrophilic polyether side chain into segmented polyurethane using a polypropylene oxide macromer with 1,3-diol at one chain-end, which behaves as chain extender, is described. In this procedure, a molecular-designed side-chain is incorporated quantitatively and directly into polyurethane biomedical elastomer. The design is also of interest to biomaterials in artificial organs.
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  • 38
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    Angewandte Makromolekulare Chemie 172 (1989), S. 233-233 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 39
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    Angewandte Makromolekulare Chemie 173 (1989), S. 85-100 
    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 Orientierungsmechanismus von kaltverstrecktem, teilkristallinem Polyoxymethylen wurde durch Messung der Intensität der Weitwinkel-Röntgenstreuung (WAXS) untersucht. Die Anisotropie der Proben wurde im einachsigen Zugversuch bei etwa 130°C im Temperaturbereich zwischen Glasübergangstemperatur und Schmelzpunkt erzeugt. Der Prozess der plastischen Deformation wurde für verschiedene Stadien der Verstreckung diskutiert. Die Orientierungsverteilung der Kristalllamellen wurde qualitativ charakterisiert durch die Berechnung von Polfiguren aus den WAXS Streuintensitätsdaten. Der Grad der Orientierung wurde durch die Berechnung des Orientierungsfaktors für den [100] Flächennormalenvektor der Einheitszelle beschrieben. Die Textur der eingeschnürten Proben mit hoher Orientierung wurde als Mischung von axialer und uniplanar-axialer Textur erkannt. Als mögliche Erklärung für diesen Orientierungstyp wird ein Einfluß der Probengeometrie angenommen.
    Notes: The orientation mechanism of cold-drawn, partially crystalline polyoxymethylene (ULTRAFORM) samples was studied by performing wide angle X-ray scattering (WAXS) measurements. The anisotropic samples were prepared in uniaxial tensile tests around 130°C, in a temperature range between the glass transition and the melting point. The process of the plastic deformation is discussed for different degrees of anisotropy. The orientation distribution of the crystalline lamellae was qualitatively characterized by performing pole figure intensity calculations from the measured WAXS intensities. The degree of orientation was quantitatively described by calculating the orientation factors for the [100] normal vector of the unit cell. The texture of the necked samples with high orientation degrees was a mixture of axial and uniplanar-axial textures. An explanation for the formation of this kind of orientation is proposed assuming an influence of the sample geometry on the orientation process.
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  • 40
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    Angewandte Makromolekulare Chemie 173 (1989), S. 205-212 
    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: Herkömmliches Vernetzen von Polyethylen niedriger Dichte (LDPE) wurde mit Dicumylperoxid (DCP) als Vernetzer durchgeführt. DCP wurde in verschiedenen Konzentrationen mit LDPE-Schnitzeln in einem Extruder bei 135 - 145°C gemischt. Monofilamentfäden wurden bei 110°C auf einer Laborziehmaschine gezogen. Die Zugdehnungseigenschaften, der prozentuale Schrumpf und die Dichte wurden mit Zunahme der DCP-Konzentration und der Heizdauer verbessert, während jedoch die prozentuale Quellung abnahm.
    Notes: Conventional crosslinking of low density polyethylene (LDPE) was carried out using dicumyl peroxide (DCP) as crosslinking agent. DCP in various concentrations was mixed with LDPE chips in an extruder at 135 - 145°C. Monofilaments were drawn on a laboratory drawing machine at 110°C. It was found that tensile properties, percent shrinkage and density were improved with the increase in the concentration of DCP and in the heating period, whereas, however, the percent swelling decreased.
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  • 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 Resultate von Untersuchungen über die chemische Wechselwirkung zwischen einigen monofunktionellen Modellverbindungen, die die Struktur und Reaktivität von wärmehärtbaren Phenol- und Harnstoff-Formaldehyd-Harzen simulieren, mit Holzkomponenten (Hemicellulosen, Cellulose und Lignin) werden dargelegt. Während Hemicellulosen deutlich dazu neigen, Kondensationsprodukte mit diesen Modellverbindungen zu ergeben, reagieren Lignine in manchen Fällen weniger leicht und abhängig davon, durch welchen Prozeß sie gewonnen worden sind, und abhängig von der Art der Modellverbindung. Cellulose reagierte wegen ihrer Kristallinität nicht unter den gegebenen Bedingungen.
    Notes: Results are presented on the chemical interactions occurring when some monofunctional model compounds simulating the structure and reactivity of thermosetting phenol- and urea-formaldehyde resins are mixed with wood components (hemicelluloses, cellulose, and lignins). Whereas hemicelluloses clearly show a propensity to give condensation products with these model compounds, lignins can react less readily in some instances depending on the delignification procedure used to isolate them and on the type of model compound. Cellulose did not react under the conditions chosen, mostly because of its crystalline character.
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  • 42
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    Angewandte Makromolekulare Chemie 173 (1989), S. 183-193 
    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: XPS-, SSIMS- und Wasserkontaktwinkelmessungen wurden verwendet, um den chemischen Einfluß von CF4/O2-Entladungen auf Polycarbonat (PC) aus Bisphenol A zu charakterisieren. Die durch Plasmabehandlung erzeugte Oberflächenmodifizierung kann auf der Basis der im Plasma vorhandenen aktiven Spezies, deren Konzentration durch Actinometrie bestimmt worden ist, erklärt werden.Bei kleinen Gehalten an O2 im Gas (1%) tritt eine umfassende Fluorierung der Oberfläche bedingt durch die Pfropfung von Fluorkohlenstoff-Radikalen ein. Es werden perfluorierte Inseln gebildet, wie der hohe Wert des zunehmenden Kontaktwinkels zeigt. Bei 20-80% O2 reagieren Fluoratome mit der Oberfläche und ätzen sie teilweise. Kleine Gehalte an Fluor, aber keine perfluorierten Inseln werden beobachtet. Sauerstoff trägt zum Ätzen bei und oxidiert die PC-Oberfläche. Die Sauerstoffkonzentration auf der Oberfläche nimmt mit Zunahme des O2-Gehalts im Gas zu, ebenso die Bildung von stark oxidierten Inselchen auf der Probenoberfläche, wie die dramatische Abnahme der Kontaktwinkel zeigt. Eine Verminderung der Aromatizität der Oberfläche, die mit Hilfe von XPS und SSIMS beobachtet wird, ist die Folge dieser Reaktionen.
    Notes: XPS, SSIMS and water contact angle measurements have been used to characterize the chemical effect of CF4/O2 discharges on polycarbonate (PC) made from bisphenol A. We found that the surface modification induced by plasma treatment can be clearly explained on the basis of the acitve species present in the plasma, whose concentration has been studied by actinometry.With very low amounts of O2 in the gas feed (1%) extensive fluorination of the surface occurs, due to grafting of the fluorocarbon radicals. Perfluorinated islands are formed, as shown by the high value of advancing contact angles. In the 20-80% O2 range, fluorine atoms react with the surface, partially inducing etching. Low amounts of fluorine are observed on the sample and no perfluorinated islands. Oxygen participates in etching and oxidizes the PC surface. We observed an increase of the surface concentration of oxygen with increasing the O2 amount in the gas feed and also the formation of strongly oxidized islets on the sample surface, as shown by the dramatic reduction of receding contact angles. A reduction of surface aromaticity, observed by XPS and SSIMS, is the consequence of these reactions.
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  • 43
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    Angewandte Makromolekulare Chemie 173 (1989), S. 213-218 
    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: An attempt was made to obtain cationic cellulose derivatives of highest possible degrees of substitution by treating dissolving grade pulps under homogeneous conditions with glycidyltrimethylammonium chloride in the solvent system dimethylacetamide/lithiumchloride. The influence of temperature, reaction time and molar ratio of the reagents was examined. A reaction time of 8 h and a temperature of 70°C have been found to be optimal. The cellulose content in solution and the molar ratio of the reagents have to be adapted to the used pulp.
    Notes: Es wurde der Versuch unternommen, durch Umsetzung von Zellstoffen mit Glycidyltrimethylammoniumchlorid im Lösungsmittelsystem Dimethylacetamid/Lithiumchlorid kationische Cellulosederivate mit möglichst hohen Substitutionsgraden zu erhalten. Hierzu wurden Temperaturabhängigkeit, Reaktionsdauer und Molverhältnis der Reaktanden untersucht. Als optimal erwies sich eine Reaktionsdauer von 8 h bei einer Reaktionstemperatur von 70°C. Der Cellulosegehalt in Lösung und das Molverhältnis der Reaktanden müssen dem verwendeten Zellstoff angepaßt werden.
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  • 44
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence on the excess scattering function P(μ) of flutuations in the electron density ρ within a macromolecule is treated, to the approximation that the solvent is a structureless medium of constant electron density ρ0. The results for P(μ) and the apparent value of the mean square radius Rapp2, can be expressed as functions of the excess electron density Δρ: P(μ) = X(μ) + (Δρ)-1Y(μ) + (Δρ)-2Z(μ) and Rapp2 = Rx2 + (Δρ)-1Ry2 + (Δρ)-2Rz2, where X(μ) and Rx2 depend only on the shape of the macromolecule, while Y(μ) and Ry2 as well as Z(μ) and Rz2 depend on the shape and the fluctuations in ρ. By varying the electron density of the solvent, the contributions of the shape and the internal structure of the macromolecule can be resolved. The quantities Rx2, Ry2, and Rz2 are evaluated for seven models to illustrate the relative importance of these contributions for representative structures.
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  • 45
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    Biopolymers 16 (1977), S. 121-142 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chiroptical properties of the cyclic dipeptides cyclo (L-alanyl-L-tyrosine) and cyclo(L-tyrosyl-L-tyrosine) have been investigated as a function of molecular conformation. Theoretical optical calculations and conformational energy calculations have been carried out as a function of the side-chain dihedral angles χ1 and χ2, and as a function of the angle of fold of the cyclic dipeptide backbone. The results of these theoretical calculations have been compared with experimental circular dichroism (CD) data. Theoretical predictions are in very good agreement with experiment for c(L-Tyr-L-Tyr). Agreement was not quite as good for c(L-Ala-L-Tyr), although the signs of all of the Cotton effects were apparently predicted correctly except for that associated with the lowest energy tyrosine absorption band.
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  • 46
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    Biopolymers 16 (1977), S. 289-298 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The slow kinetics of annealing processes in multistranded nucleic acids is spectrophotometrically investigated using poly(A)·2poly(U) as a model system. The absorbance changes at specific wavelengths show that double-helical (A·U) base pairs appear as transient intermediates. The annealing process is identified by the enlargement of triple-helical sequences at the cost of (A·U) base pairs and unpaired (U) residues. A large time range in the reorganization of mismatched chain configurations is characterized by a logarithmic dependence on time. This observation is quantitatively described by a kinetic model developed by Jackson. In Jackson's model the rate-limiting process in the slow annealing phase of maximizing triple-helical sequences, is the removal of strand entanglements, knots, and hairpin loops by complete unwinding of those helical stretches which stabilize the mismatched configurations. The results of the present study are briefly discussed in terms of optimum conditions for hybridization experiments and for the preparation of polynucleotide complexes commonly used to produce interferons.
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  • 47
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    Biopolymers 16 (1977), S. 341-368 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of anions of neutral salts on the fluorescence emission of six proteins as well as on tryptophan and tyrosine were studied in relation to the structure of proteins. Most anions are good quenchers of tryptophyl and tyrosyl fluorescence, free or in proteins. The results with tryptophan and tyrosine indicate involvement of a collisional quenching mechanism due to agreement with Stern-Volmer law. The deactivation of fluorescence probably occurs because of the transition from singlet state to triplet state. Lehrer's modification of Stern-Volmer law was applied to proteins. The effective quenching constants ([KQ]eff) and the fraction of fluorescence available ([fa]eff) to the quencher are also calculated.In contrast to its effect on tryptophan, CH3COO- quenches tyrosyl fluorescence and ClO4- does not. The effects on fluorescence of ribonuclease and free tyrosine are similar and without any changes in emission maximum. The anions are divided into three groups based on the effect they have on tryptophan-containing proteins. (1) NO3-, NO2-, Br-, and I- have high [KQ]eff values and readily quench tryptophyl fluorescence of proteins causing a shift of emission maximum to a shorter wavelength. This change is due to the specific quenching of “exposed” tryptophan residues which are accessible to quenchers and the observed residual fluorescence is from the “buried” tryptophyls. (2) ClO4- and SCN- also quench fluorescence of tryptophan in proteins and have lower ([KQ]eff) values. In their presence the fluorescence maximum is shifted to a longer wavelength, which indicates the unfolding of a protein with [(fa)eff] = 1. (3) Cl-, CH3COO-, and SO4— do not have a direct effect on the fluorescence of tryptophan. Besides the “direct” effects, “indirect” effects on fluorophors in protein are also seen, pointing out that the neutral salts can interact in more than one manner with proteins. The effectiveness of anions in quenching fluorescence of proteins follows similar sequences which almost resemble the Hofmeister series, viz., SO4=, CH3COO- ≃ Cl- 〈 ClO4- 〈 SCN- 〈 Br- 〈 I- 〈 NO3- 〈 NO2-.
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  • 48
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of pH upon CD spectra of H-Trp-Trp-OH, H-Trp-Trp-Gly-OH, and H-Gly-Trp-Trp-OH is investigated and data are compared with those obtained for peptides containing only one tryptophyl residue. A negative Cotton effect at around 225 nm, which in previous work has been related to an increase of the conformational rigidity in compounds having the sequence -CO-Trp-Trp, is also observed in the case of H-Trp-Trp-OH and H-Trp-Trp-Gly-OH upon deprotonation of the terminal α-amino group. These data, together with observations arising from solvent and temperature effects, give evidence that H-Trp-Trp-OH undergoes a conformational change upon going from acid to alkaline conditions, where the two aromatic side chains become conformationally more rigid relative to each other. This rigidity generates an exciton coupling between the Bb transitions of the two indoles. Hydrophobic forces, including stacking interactions, do not appear important in stabilizing this conformationally rigid structure. Rather, intramolecular electrostatic interactions (e.g., hydrogen bondings or polar interactions between the aromatic side chain and the peptide backbone) as well as interactions with the OH group(s) of the solvent, are suggested to be the salient forces. Possible structures which obey these requisites are discussed.
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  • 49
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    Biopolymers 16 (1977), S. 427-435 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The fine structure of the thermal denaturation of viral DNA's was analyzed with the spectral method established by Felsenfeld and Hirschman, and Fresco et al. A fully automated system measuring melting curves at four wavelengths at the same time was developed for this purpose. With this device, (G + C)-contents of melting components of λ DNA's were determined. The correlation between the (G + C)-content and the melting temperature of each melting component is found to be well described by the linear relationship given by Marmur and Doty. The denaturation of each component is regarded as cooperative. The Marmur-Doty relation also stands for the local denaturation of T2 DNA, which has a narrow melting range.
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  • 50
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    Biopolymers 16 (1977), S. 461-464 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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  • 51
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have constructed an apparatus for the simultaneous measurement of electrophoretic mobility, μ, and diffusion coefficient, D, of macromolecules and cells. It combines band electrophoresis in a vertical, sucrose-gradient stabilized column, with quasielastic laser light-scattering determination of the diffusion coefficient of the species within the band. The entire electrophoresis cell is scanned through the laser beam of the quasielastic laser light-scattering apparatus by a vertical translation stage. Total intensity light-scattering measurement at each point in the cell gives the macromolecular concentration at that point. Solvent viscosity and electrical potential are measured at each point in the cell. Application of this apparatus to resealed red blood cell ghosts and to bovine hemoglobin indicates that measurements of field, viscosity, and migration distance are reliable, and that electroosmosis is insignificant. Application to T4D bacteriophage gives μ20,w = (-1.05 ± 0.05) × 10-4 cm2/V sec and D20,w = (3.35 ± 0.10) × 10-8 cm2/sec for fiberless particles, and μ20,w = -(0.59 ± 0.03) × 10-4 cm2/V sec and D20,w = (2.86 ± 0.09) × 10-8 cm2/sec for whole phage with 6 fibers. Approximate analysis of these results with the Henry electrophoresis theory for spheres in dicates that each fiber contributes about 193 positive charges to the phage particle, compared with 327 from amino-acid analysis. The advantages and disadvantages of this apparatus, relative to conventional electrophoresis and to electrophoretic light scattering, are discussed.
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  • 52
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(His-Ala-Glu) and poly(Lys-Ala-Glu) were examined by viscosity and potentiometric titration. These measurements were interpreted in terms of the hydrodynamic size of the above sequential polypeptides. Effects of polymer, size and concentration, and solution-salt concentration were demonstrated. Although the sequential polypeptides generally behave like polyampholytes, they do demonstrate some differences. These differences my be attributed to the ability of ionized side chains three residues apart to repel themselves, in the order His 〈 Glu 〈 Lys.
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  • 53
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Proton magnetic resonance spectra of model dipeptide molecules R1-C′1O1-N2H2-C2αH2αR2-C′2O2-N3H3-R3 in CCl4 solutions exhibit splited signals when investigating on mixtures of L and D enantiomers differing from the racemic composition. The major effect is observed on amide proton signals which are the ones most sensitive to the ratio of aggregation. The stereoselective dimerization of enantiomeric molecules in the so-called C5 conformational state is shown to be responsible for such a phenomenon, the intensity of which depends on the bulkiness of the side chain R2. A theoretical approach is proposed which gives predictions in close agreement with our own experimental findings.
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  • 54
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    Biopolymers 16 (1977), S. 1725-1733 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The depolarization thermal current method is applied to the study of the polarization phenomena in the keratin-water system. Three depolarization thermal current peaks have been evidenced in hair keratin. This paper deals with the detailed study of peak II. For the first time, the mechanism responsible for this peak is ascribed to molecular reorientation. The effect of water upon the characteristics of peak II is also described, and an activation energy of 8.4 kcal/mol is computed. These results, in connection with other studies, lead us to interpret peak II as due to the reorientation in the bound or intermediate water molecules. The effect of copper confirms that the carboxyl groups are hydration sites.
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  • 55
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    Biopolymers 16 (1977), S. 1735-1745 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Infrared spectroscopy was used for the determination of the base-pairing content of four specific tRNAs in deuterium oxide solution. Infrared spectra were obtained in the 1750-1550 cm-1 region at various temperatures ranging from about 15 to 90°C. Melting curves were constructed by plotting the molar extinction coefficient at ν = 1657 cm-1 versus temperature. These transition curves enabled us to determine the ranges of temperature which correspond to the ordered (partially double-stranded) or randomly coiled structure of the tRNA. For a set of wavenumbers the extinction coefficients at these temperatures were used for the calculation of the base-pairing content. The procedure employed here is based on a method described earlier by Thomas [(1969) Biopolymers 7, 325-334]. For the conditions selected for this investigation (Mg2+-free D2O-buffer; 0.01M tris-DCl, 0.015M NaCl, pD 7.5) the results of this determination agree within the limits of errors with the number of base pairs predicted by the cloverleaf model.
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  • 56
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    Biopolymers 16 (1977), S. 1779-1793 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have calculated the translational and rotational frictional coefficients of structures related to T2 and T4 bacteriophage, using the theoretical framework developed in the preceding two papers. The structures considered were models for tail-fiberless phage, and for whole phage with fibers in the extended and retracted portions. We also computed and compared with the experiment the changes in translational frictional coefficient produced by successive addition of 1-6 fibers to the fiberless particle. Agreement with experimental results is markedly improved over previous theoretical efforts, especially with respect to the effect of tail-fiber extension. Some significant discrepancies remain, however, in the comparison of fiber-retracted and fiberless phage.
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  • 57
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    Biopolymers 16 (1977), S. 1765-1778 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have used the modified Oseen hydrodynamic interaction tensor along with iterative numerical solution of the coupled hydrodynamic interaction equations to calculate the rotational diffusion coefficients of macromolecular complexes composed of nonidentical spherical subunits. For the one structure, a prolate ellipsoid of revolution, for which exact solutions are available, a subunit model with the same length and volume gives asymptotic agreement with the Perrin equations. Other structures considered include plane polygonal rings, lollipops, and dumbbells.
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    Biopolymers 16 (1977) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 59
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have studied the effects of temperature, EDTA, and ionic strength on C-polysaccharides in solution by examining the details of the time-correlation function using a 96-channel single-clipped photon correlation spectrometer. Our linewidth results have shown that the C-polysaccharides in buffer solution form aggregates of very broad distributions. Thus, fractionation by gel-filtration chromatography is only mildly effective. Although the aggregate sizes seem to remain relatively constant from 4 to 25°C, a fraction of those aggregates break up to form smaller fragments or monomers at higher temperatures. However, the dissolution-association process is quite slow and takes days even at room temperatures before the equilibrium is reached. We have also shown that by adding an excess amoutn of EDTA, the aggregates can be broken up. Again the dramatic changes occur only at short delay times suggesting that a protion of the larger aggregates remains. Finally, the amount and size of aggregates depend upon the ionic strength which exhibit a maximum ΓT/sin2 (θ/2) around 0.1-0.2 M KCl.If the activities of polysaccharides in solution depend upon molecular size, the standard techniques such as gel-permeation chromatography and ultracentrifugation cannot properly characterize the detailed size distribution. Quasielastic laser light scattering can provide us with a qualitative model. The quantitative details must necessarily await more extensive investigations using a combination of the techniques and better fractionation procedures in an appropriate buffer solution.
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  • 60
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    Biopolymers 16 (1977), S. 1033-1052 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The coupling of N-acyl-α-amino-acids with α-hydroxyacid-methyl amides results in depsipeptide molecules containing two chiral centers and one ester function inserted between two amide functions. Their conformational features have been investigated by IR spectroscopy, proton magnetic resonance, X-ray diffraction, and theoretical P.C.I.L.O. calculations.It is shown that most of these molecules are folded by an intramolecular 4 → 1 hydrogen bonding. Two folded conformations, similar to the well known β turn in peptides, are described, the stability of which depends on the configurational sequence in the investigated molecule.LL and LD species are folded in two different ways whereas LG sequences containing an achiral hydroxy-acid residue accommodate both of them. The presence of a N-terminal achiral amino acid noticeably decreases the folding ratio.The above conclusions are then compared with the conformational features of homologous tripeptide molecules.
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  • 61
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    Biopolymers 16 (1977), S. 1153-1158 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 62
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    Biopolymers 16 (1977), S. 2105-2111 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of complex formation between fluorescein mercuric acetate and heat-denatured DNA were studied by measuring the fluorescence quenching of this reagent. This quenching process involved no immeasurably rapid phase and it was shown that this reaction follows simple second-order kinetics. The rate constant at 25°C was estimated to be 2.9 × 104M-1 sec-1 for calf-thymus DNA (42% G + C) and 1.1 × 104M-1 sec-1 for Micrococcus lysodeikticus DNA (72% G + C). Activation parameters for this reaction were calculated from the temperature dependence of the reaction rate, and the activation entropy was found to be highly negative (-27.5 cal/mol deg for calf-thymus DNA and -25.5 cal/mol deg for M. lysodeikticus DNA). The binding of fluorescein mercuric acetate to native DNA, which requires the opening of the double-helical structure, was also followed by measuring the absorbance change of this reagent. There was a lag phase in this binding process, and the enthalpy change for the opening step corresponded roughly to that for the opening of one base pair. These findings are discussed in relation to the results of a similar study with formaldehyde.
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  • 63
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The formation of collagen fibrils from soluble monomers and aggregates by thermal gelation at neutral pH can be divided into two distinct stages: a nucleation phase and a growth phase. Turbidity studies of the kinetics of the precipitation reaction show that the lag-phase time or nucleation reaction time, t′l, is markedly temperature dependent while the growth reaction time is temperature independent. The activation energy of the nucleation reaction is essentially constant over the temperature range studied. In monitoring the nucleation-phase reaction by various physicochemical techniques, including viscosity, sedimentation equilibrium, and light scattering, no evidence for the formation of aggregates was observed. Enrichment of the initial collagen solution with aggregates accelerates nucleation, but de novo nuclei formation is still required even in highly aggregated collagen preparations. Removal of pepsin and pronase susceptible peptides lengthens the nucleation reaction time and increases the sensitivity of the rate of nuclei formation to changes in ionic strength. Electron microscope studies show the fibrils formed from the protease-treated collagen to be less well organized. With pepsin-treated collagen, subfibrils and obliquely striated fibrils are seen, showing that while microfibrils are formed interactions between them are modulated by the enzyme susceptible peptides in the same way that these regions modulate nuclei assembly. It appears that pepsin and pronase susceptible peptide regions of collagen play a more prominent role in the in vitro assembly of collagen molecules to form D-stagger nuclei and fibrils than do ionic interactions between helical molecular regions. A mechanism of nucleation of collagen fibrillogenesis is discussed.
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  • 64
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    Biopolymers 16 (1977), S. 2243-2264 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Circular dichroism spectra of the nucleic acid monomers have been measured in aqueous solution and extended into the vacuum ultraviolet region to about 166 nm. Measurements were made on ribo and deoxyribo derivatives of adenine, guanine, hypoxanthine, cytosine, thymine, and uracil derivatives both with and without the 5′-phosphate (with the exception of ribosyl thymine 5′-phosphate). Absorption spectra of the deoxyribonucleotides measured to about 175 nm are also presented. The results demonstrate that both the circular dichroism and absorption spectra observed below 200 nm are no more complicated than the spectra normally recorded above 200 nm. In most cases, the circular dichroism spectra of the various derivatives of a given base are similar, indicating that the conformations are similar. On the other hand, the differences among the circular dichroism spectra of the various derivatives of a given base are sufficient to identify a particular derivative. The average circular dichroism for the deoxyribonucleotides is compared with the circular dichroism of native E. coli DNA. The comparison reveals that the circular dichroism of DNA below 200 nm is due principally to the interaction between the bases rather than the intrinsic circular dichroism of the monomers. The monomer transitions are discussed in relationship to the absorption and circular dichroism spectra presented.
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  • 65
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    Biopolymers 16 (1977), S. 2281-2298 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A theory for the determination of DNA arrangements in DNA-containing specimens, using planar aromatic dye molecules as probes for plane polarization of fluorescence, has been described. At low dye-to-DNA concentrations, the dye molecules are sandwiched between the stacked bases of DNA; hence, the fluorescence from the dye bound to a local region of DNA helix is plane-polarized with the polarization direction perpendicular to the local axis of DNA. The degree of such polarization from an aligned DNA-specimen complexed with dye is determined both by the DNA orientation and the conformational state (e.g., base tilt) of DNA into that specimen. Analysis has been made of the relationship between the degree of polarization and the orientation of the emitting dipoles of dye. The dye complexes may be aligned in a mechanical shear or electric field. However, any change in the orientation distribution of the emitting dipoles due to force fields should be taken into account. With some assumptions and approximations, the magnitude and the direction of maximum polarization can be related to different orders of DNA coiling and to their various combinations. Since the measured polarization is averaged over all DNA regions of the specimen, if the magnitude of polarization is appreciable and the polarization occurs in the specific direction of the specimen, the theory helps to eliminate several probable arrangements of DNA. The predominant molecular features of the actual DNA arrangement can be determined through this process of elimination, as explained in two subsequent papers with T-even bacteriophage and chromosome systems.
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  • 66
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    Biopolymers 16 (1977) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 67
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    Topics: Chemistry and Pharmacology
    Notes: Fluorescence of 2-p-toluidinylnaphthalene-6-sulfonate (TNS) was enhanced in the presence of maltooligosaccharides, amylose, and other α-glucans. The dependence of relative TNS fluorescence intensity per glucose unit on chain length of oligosaccharides was examined. The values of binding constant and thermodynamic parameters, assuming the 1:1 complex for TNS-amylose (number-average degree of polymerization, DPN = 17), were determined by the fluorescence titration. The values of thermodynamic parameters for 1:1 complex formation of TNS-α- and β-cyclodextrins were also determined and compared with those of TNS-amylose (DPN = 17). The fluorescence intensity of TNS in the presence of amylose (DPN = 600) decreased by the action of glucoamylase and taka-amylase A. The fluorescence of TNS-amylose (DPN = 17) system increased with the increased ionic strength. In the presence of pullulan, TNS fluorescence was also enhanced and decreased by the action of pullulanase. Amylopectin enhanced TNS fluorescence rather more strongly than amylose (DPN = 17) at the same concentration. In the presence of dextran, the fluorescence of TNS was scarcely enhanced. The degree of fluorescence enhancement of TNS in the presence of α-glucans seems to reflect the structures of α-glucans in solution, since TNS fluorescence is enhanced in the hydrophobic environment or by the disturbance of free intramolecular rotation.
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  • 68
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    Topics: Chemistry and Pharmacology
    Notes: Water-soluble, random copolymers containing L-methionine and N5-(3-hydroxypropyl)-L-glutamine have been prepared, fractionated, and characterized. The thermally induced helix-coil transitions of these copolymers in water have been investigated, and it has been found that incorporation of L-methionine increases the helix content of the polymers at all temperatures in the range of 0-60°C. The Zimm-Bragg parameters σ and s for the helix-coil transition in poly(L-methionine) in water were deduced from an analysis of the melting curves of the copolymers using the methods described in earlier papers.
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    Biopolymers 16 (1977), S. 2491-2506 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Normal vibrational analysis was carried out for DNA molecules in both A and B conformations as well as for A-RNA. A simplified backbone model was examined and expanded to include the backbone phosphate-group and the ribose ring. We applied the new force-constant refinement procedure discussed in the preceeding paper [Van Zandt, L. L., Lu, K.-C. & Prohofsky, E. W. (1977) Biopolymers, 16, 2481-90] to fit some observed frequencies in the Raman spectra for all three nucleic acids with the same set of force constants. The results indicate that the observed frequency shift can be attributed to the conformational change solely. We ignored the second-order differences in force constants for the different geometries. The agreement between the observed and calculated frequencies derived from the final refined set of force constants is good and apparently justifies this assumption. Two modes previously assigned to the symmetric diester O-P-O stretch and the symmetric dioxy O‥P‥O stretch are actually fitted. They are mainly backbone phosphate-group modes. The refined ribose-ring force-constants were transferred to the calculation of the vibrational spectrum of tetrahydrofuran. The overall agreement is again good. We discuss these calculations and the resulting normal modes. We also discuss the application of the Green-function refinement scheme and several strategies adopted to bias the convergence of the procedure.
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  • 70
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    Topics: Chemistry and Pharmacology
    Notes: A study of the conformational states of the dinucleotide coenzyme NAD+ has been made using semiempirical energy calculations. Taking low-energy mononucleotide structures as starting conformations, energy minimizations have been performed. The lowest energy states are stacked structures, with interactions between the adenine and nicotinamide rings. Some structures show stabilization gained from electrostatic attractions between the positively charged nicotinamide and negatively charged phosphate oxygens. These predictions correlate well with the available experimental data.
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  • 71
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    Notes: Water-soluble block copolymers of the type (A)m-(B)n-(A)p, where (A)m,p was either poly(D,L-lysine-α,β,β,γ,γ,δ,δ-d7) or poly(D,L-lysine) and (B)n was either poly(L-alanine) or poly(L-phenylalanine), were synthesized for conformational studies by proton magnetic resonance spectroscopy. Analytical determination of the amount of the initiator fragment (n-hexylamine) at the C-terminus of the copolymers was used to obtain the number-average degrees of polymerization, DPn, and thereby, together with the amino acid composition, to establish the covalent structures of the polymers. The values of DPn were found to be much lower than those deduced from sedimentation equilibrium or form viscosity measurements. These deviations, which also are thought to have arisen in similar studies reported in the literature, are attributable to intermolecular aggregation; the relation of such aggregation to covalent structure (and its effect on the polymerization reaction) is discussed in terms of the conditions and mechanism of synthesis of block copolymers of amino acids.
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    Biopolymers 16 (1977) 
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    Biopolymers 16 (1977), S. 1879-1894 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(Lys48, His52), a random copolypeptide of L-lysine (48%) and L-histidine (52%), was used as a model protein for investigating the effects of protonation on the imidazole group of histidines on protein binding to DNA. The complexes formed between poly(Lys48, His52) and DNA were examined using absorbance, circular dichroism (CD), and thermal denaturation. Although increasing pH reduces the charges on histidine side chains in the model protein, the protein still binds the DNA with approximately one positive charge per negative charge in protein-bound regions. Nevertheless, CD and melting properties of poly(Lys48, His52)-DNA complexes still depend upon the solution pH which determines the protonation state of imidazole group of histidine side chains. At pH 7.0, the complexes show two characteristic melting bands with a tm (46-51°C) for free base pairs and a t′m (94°C) for protein-bound base pairs. The t′m of the complexes is reduced to 90°C at pH 9.2, although at this pH there is still one lysine per phosphate in protein-bound regions. Presumably, the presence of deprotonated histidine residues destabilizes the native structure of protein-bound DNA. The binding of this model protein to DNA causes a red shift of the crossover point and both a red shift and a reduction of the positive CD band of DNA near 275 nm. This phenomenon is similar to that caused by polylysine binding. These effects, however, are greatly diminished when histidine side chains in the model protein are deprotonated. The structure of already formed poly(Lys48, His52)·DNA complexes can be perturbed by changing the solution pH. However, the results suggest a readjustment of the complex to accommodate charge interactions rather than a full dissociation of the complex followed by reassociation between the model protein and DNA.
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    Biopolymers 16 (1977), S. 1929-1943 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A theoretical analysis of the conformation of the octapeptide hormone Asn1, Val5 angiotensin II has been carried out by semiempirical potential energy calculations. A preliminary study of the Ala6-Pro-Ala molecule, which mimics the angiotensin backbone, provided us with likely backbone structures on which the effect of the full side chains of the hormone could be assessed. For angiotensin II, the calculations show that only a small number of folded, compact conformations have a high probability of existence. This is the consequence of favorable packing and of the presence of proline in position 7. These results are consistent with various experimental data, both structural and biological. This method is readily applicable to the study of analogs of the hormone or to other peptides of comparable size.
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    Biopolymers 16 (1977), S. 1993-2004 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction between DNA and ionen polymers, -[N+(CH3)2(CH2)mN+(CH3)2(CH2)n]l-, with m-n of 3-3, 6-6, and 6-10 were examined in order to know how the binding behavior of cationic polymers with DNA depends on the charge density of polycation. The ionen polymer has no bulky side chain and the binding forces with DNA would be attributed mainly to electrostatic interaction. When 3-3 ionen polymers were added to DNA solution, precipitable complexes with the ratio of cationic residue to DNA phosphate (+/-) of 1/1 and the free DNA molecules were segregated, while 6-6 and 6-10 ionen polymers formed soluble complexes with DNA molecules up to (+/-) = 0.5. This suggests that 3-3 ionen polymers bind cooperatively with DNA while 6-6 and 6-10 ionen polymers bind noncooperatively. The cooperative binding of 3-3 ionen polymer and the noncooperative binding of 6-6 ionen polymer were also supported by the thermal melting and recooling profiles from the midpoint between first and second meltings. It was concluded that the charge density of DNA phosphate is a critical value determining whether the ionen polymers bind to DNA by a cooperative or by a noncooperative binding, since the distance between successive cationic charges of 3-3 ionen polymer is shorter than that between successive phosphate charges on DNA double helix and those of 6-6 and 6-10 ionen polymers are longer.
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    Biopolymers 16 (1977) 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 16 (1977), S. 2091-2104 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Quasielastic light scattering is used to study the effect of ionic strength on the dynamic behaviour of DNA. In a first approach the spectrum of scattered light is analyzed in terms of a single relaxation process. The large difference between the observed behaviour and that expected according to a pure diffusional process reflects the contribution associated with internal modes, which increases with decreasing ionic strength. Such behaviour is better analyzed in terms of a double relaxation process by using two relaxation times, the reciprocals of which are equal to DK2 and DK2 + τi-1 (K), respectively, where τi (K) is an average value describing the set of modes observed at a given K value. Relative intensity and relaxation times, which are the more accurate parameters, were used to interpret the results. The observed increase of the relative contribution of internal modes with decreasing ionic strength is actually a relative decrease of the diffusional contribution induced by a corresponding increase of the radius of gyration RG. On the other hand, the reciprocal τi-1 (K) of the relaxation time is a linear function of K2 in the analyzed KRG range and is insensitive to ionic strength between 10-2M and 1M. These results, when discussed according to Rouse's model, lead to define for each value of τi-1 (K) a corresponding mean-squared equilibrium length 〈μi2〉 which is found to be a linear function of K-2.
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    Biopolymers 16 (1977), S. 2755-2771 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Derivatives and peptides of β-nitrobenzyl-L-aspartates were studied with high-field nmr. Differences were observed between the chemical shifts of protons located near the extremity of the principal chain as a function of the terminal group. These differences are explained by conformational calculations which exclude the existence of an hydrogen bond and demonstrate the influence of the aromatic ring position on the protons of the main chain. Both nmr experiments and conformational analysis indicate that conformations are nearly the same for ortho, meta, and para nitro substitution. These conclusions are in good agreement with Karplus relationship applied to the α and β protons.
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    Biopolymers 16 (1977), S. 81-94 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Excess small angle X-ray scattering in solvents of differing electron density has been calculated from the crystal structures obtained for rubredoxin, trypsin inhibitor, myogen, ferricytochrome c2, ribonuclease S, lysozyme, nuclease, myoglobin, α-chymotrypsin, elastase, subtilisin, carboxypeptidase A, thermolysin, methemoglobin, deoxyhemoglobin, and a single polypeptide chain of M4 lactate dehydrogenase. The scattering curves for each protein can be reproduced by the sum of three curves, with the weighting of the three curves depending on the electron density of the solvent. The radius of gyration obtained from the small angle X-ray scattering by globular proteins in aqueous solution will usually exceed the values defined by the shape of the macromolecule. Deviations for certain of the proteins cited are calculated to be as large as 6%. These deviations arise from the tendency for the amino acid residues with low electron density to be situated closer to the center of the protein than the amino acid residues of high electron density. An upper limit of 19% is obtained for the discrepancy between the radius of gyration defined by the shape of a spherical globular protein of typical amino acid composition and the apparent radius of gyration measured for that protein in water by small angle X-ray scattering.
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    Biopolymers 16 (1977), S. 157-185 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ability of the macrotetrolide nactins to complex selectivity with a wide variety of cations makes these ionophorous antibiotics important model systems for the study of biologic ionic transport. We report a Raman spectroscopic investigation of the Na+, K+, Rb+, Cs+, Tl+, NH4+, NH3OH+, C(NH2)3+, and Ba++ complexes of nonactin, monactin, and dinactin in 4:1 (v/v) CH3OH/CHCl3 and in the solid state. The nactins display characteristic spectral changes upon complexation, some of which are specific for a given cation. In the K+, Rb+, Cs+, NH3OH+, and C(NH2)3+ complexes, which are apparently isosteric, the ester carbonyl stretch frequency is found to be linearly proportional to the cation-carbonyl electrostatic interaction energy, as calculated from a simplified model. Deviations for the Na+, NH4+, Tl+, and Ba++ complexes are interpreted as arising from additional nonelectrostatic interactions. Additional information is obtained from other spectral regions and from measurements of depolarization ratios. Spectra of the nactin complexes differ from each other more in the solid state than in solution, reflecting the effects of crystalline contact forces.
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    Biopolymers 16 (1977), S. 225-230 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 16 (1977), S. 231-246 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of water with collagenous tissue was investigated using dynamic mechanical spectroscopy and cryogenic X-ray techniques. The loss spectrum was found to be very sensitive to water which is highly associated with the macromolecule. Two water-sensitive loss peaks were observed below 0°C: the β2 or “water dispersion” at 150°K and the β1 at 200°K which is attributed to motion of polar side chains. Changes in peak temperature and intensity were not continuous with water content, but exhibited regimes in behavior which were associated with two types of nonfreezable water, structural and bound water. In cryogenic X-ray experiments, specimens which contained some freezable water exhibited reflections identified with the cubic form of ice. These ice crystals underwent an irreversible transition to the more common hexagonal form when warmed above 200°K. On the basis of these experiments, a model for the hydration of native collagenous tissue was proposed.
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    Biopolymers 16 (1977), S. 299-316 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformation behavior of polyethylenimine has been examined by studies of the fluorescence characteristics of derivatives of the polymer containing pyrenyl ligands. Excimer formation within the macromolecular matrix serves as a sensitive probe of group proximities. The experimental observations combined with nearest neighbor analyses lead to quantitative assessments of the extent of interaction between polymer side chains.
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    Biopolymers 16 (1977), S. 387-401 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chiroptical properties of S-proline conformational isomers are examined on a theoretical model in which electronic wave functions are obtained from semiempirical molecular orbital calculations. The CNDO/S molecular orbital model is used to perform SCF-MO calculations on ground state electronic structure and excited states are constructed in the virtual orbital-configuration interaction approximation. Electronic rotatory strengths and dipole strengths are calculated directly from the complete (but approximate) molecular electronic wave functions. Zwitterionic, cationic, and anionic S-proline structures are studied twotypes of conformational variables are represented in the calculations: (1) pyrrolidine ring conformation; and (2) rotation about the Cα-COO- bond. Rotatory strengths are found to be somewhat sensitive to rotational isomerism about the Cα-COO- bond, but are found to be rather insensitive to conformational changes within the pyrrolidine ring. The CD spectrum of zwitterionic S-proline down to ∼160 nm appears to be well accounted for by the theoretically calculated results if conformational preferences with respect to rotation about the Cα-COO- bond can be assumed to exist in solution media. Furthermore, spectra-structure correlations are offered for the anionic and cationic forms of S-proline in solution.
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  • 85
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    Biopolymers 16 (1977), S. 415-426 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of stereoregular α-(1 → 6) linked glucomannans have been prepared by Lewis acid-catalyzed copolymerization of anhydro sugar derivatives followed by debenzylation. The products have been characterized for mole fraction of the individual monomer, and sequence lengths have been calculated from copolymerization data. The viscosity, specific rotation, and 13C nmr spectra have been correlated with the structure of the various copolymers.
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  • 86
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 87
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper presents the results of a stereochemical analysis of local interactions in unfolded protein chains (sterical repulsions, hydrogen, and hydrophobic bonds, etc.) by means of space-filling modeles. On the basis of this analysis, an evaluation is made of thermodynamic parameters controlling the building-in of all the 20 natural amino acid residues in all the physically possible position of local secondary structures (α-helices, including α-helices with short fragments of helices 310 at the C-terminus; β-bends of different types, helices 310, and their combinations) as well as thermodynamic parameters of separate hydrogen bonds of polar side groups with the neighbor peptide groups (“local contacts”). The accuracy of the obtained results is discussed.
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  • 88
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    Biopolymers 16 (1977), S. 545-549 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The translational diffusion coefficient of a pure sample of α-chymotrypsinogen A is measured by laser light scattering to give a value of D20,w0 = (8.40 ± 0.15) × 10-7 cm2/sec.
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  • 89
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The exchange rate of the indole nitrogen proton with solvent water protons was measured as a function of pH and temperature for tryptophan, N-methyl tryptophan, glycyl tryptophan, tryptophanamide, tryptophylglycine, and tryptophylglycyl glycine. The nmr observation was by long-pulse Fourier transform methods, and kinetics were inferred from saturation recovery, H2O transfer of saturation, and linewidth. There are observable differences between the rates of these compounds, but all are describable within a factor of two by specific acid and base-catalyzed rates kH = 100 and kOH = 108 1/mol-sec at 27°C. It is concluded that this behaviour is representative of this proton on the indole side chain in a random-chain peptide exposed to water.
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  • 90
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stoichiometric mixtures of acridine orange with dermatan sulfate at total dye concentrations ≤ 1 × 10-5 M show fluorescence maxima at 540 nm and 660 nm on excitation at 436 nm. By means of membrane filtration, it is directly demonstrated that the species emitting at 540 nm is due only to unbound dye whereas the 660-nm emitting species is due to bound dye. It is, therefore, possible to differentiate unbound acridine orange from its dermatan sulfate complex solely by spectroscopic methods. Thermodynamic binding parameters can be calculated from rapid spectroscopic measurements without disturbing the system.
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  • 91
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    Biopolymers 16 (1977) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 92
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    Biopolymers 16 (1977), S. 731-747 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general kinetic analysis for unimolecular three-species models is presented. Criteria are established for each model in order to allow selection among alternative models on the basis of their amplitude behavior. These criteria are applied to the previously reported kinetic data for the folding transitions of lysozyme and cytochrome c in guanidine hydrochloride. The degree of success in applying these criteria is found to depend on the extent to which the apparent rate constants, λ1 and λ2, approach each other in certain conditions. Ikai and Tanford have presented a similar kinetic analysis, although these authors considered only the case where no intermediate kinetic species was populated initially. For one protein system, namely, ribonuclease A (RNase A), at least one stable intermediate exists after unfolding outside of the equilibrium transition zone. The criteria developed by Ikai and Tanford cannot be applied to RNase A kinetics and, therefore, a more general analysis is presented. Previously published studies of the reversible folding kinetics of lysozyme and cytochrome c are reexamined using the current amplitude analysis, and it is found that both of these folding transitions can be described by the three-species model, \documentclass{article}\pagestyle{empty}\begin{document}$$ U_{1} \rightleftharpoons U \rightleftharpoons N $$\end{document} used previously to describe the folding kinetics of RNase A (U1 and U2 are two forms of unfolded enzyme and N is the native species). These results suggest that this three-species model may provide a fairly general description of the reversible folding kinetics of small proteins. As an outgrowth of the current analysis, several suggestions for experimental design in studying protein folding will be presented and discussed.
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  • 93
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymer which has both ligand sites (4-vinylpyridine) and redox sites (N-(p-vinylbenzyl)-3-carbamoyl-1,4-dihydropyridine) was synthesized by the dithionite reduction of the copoly(4-vinylpyridine-N-(p-vinylbenzyl)-3-carbamoylpyridinium chloride) and the reduction of a central ferric-iron of ferriprotoporphyrin IX by the above-described copolymer was studied spectrophotometrically in dimethyl sulfoxide. The rate of the reduction by the copolymer was much faster than by N-benzyl-3-carbamoyl-1,4-dihydropyridine. This acceleration by the copolymer could be explained by the intramolecular reduction of ferriprotoporphyrin IX which was coordinated by the pyridine residue of the copolymer.
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  • 94
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    Biopolymers 16 (1977), S. 965-982 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have investigated the B to A conformation change of DNA double helices by a new method “soft-mode analysis.” We find theoretically that a mode does soften when the vibration normal modes are perturbed by increasing the electrostatic interaction between the unbalanced charges on atoms in the double helix. The same mode also softens for enhanced van der Waals interactions. The mode softening indicates the onset of conformation change. The enhancing of the electrostatic and van der Waals interaction mimic the effect of decreasing the polar nature of the solvent or water of hydration associated with the B conformation DNA. We discuss qualitatively the concept of soft modes and their relation to conformation change as well as their applicability to macromolecules. We discuss previous work in which the normal vibrational modes have been calculated. We also discuss the displacement which comes from the soft mode and show that it correlates very well with that expected for the B to A conformation charge.
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  • 95
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    Biopolymers 16 (1977), S. 1015-1031 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An electron microscope study of collagen fibrils from fixed tail tendons of rats has revealed that from some time shortly after birth until maturity, the fibril diameters have a bimodal distribution. The “two” types of fibril are indistinguishable in both transverse and longitudinal section. Unfixed specimens of eight-week-old-tail tendon showed a similar bimodal distribution of diameters though the positions of the peak values compared to fixed specimens of an eight-week-old-tail tendon were shifted upwards by about 30%. It has also been shown quantitatively that the polar collagen fibrils are directed randomly “up” and “down” with respect to their neighbors. Whilst it has been suggested by others that anastomosis is a feature of collagen structure, the results presented here do not support this hypothesis. Fibrillar units ∼ 140 Å in diameter have been observed and the possibilities that these are elastic fibers or the breakdown products of collagen fibrils have been considered.
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  • 96
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The addition of a lytic layer to a preformed linear sucrose gradient induces a temporary (up to half a day) initial gradient of considerable steepness which retards the sedimentation of large (〉T4) DNAs. Centrifugation at sufficiently slow angular velocities permits the temporary initial gradient to disappear and therefore the sedimentation distance increases, yielding a rotor speed dependent effect on sedimentation distance. Gradients which are free of this effect are described and shown to permit mouse leukemia cell DNA to sediment independently of rotor speed (5-30 krpm).
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  • 97
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermally induced helix-coil transitions of three A-T DNAs, d(A)n·d(T)n, d(A-T)n·d(A-T)n, and d(A-A-T)n·d(A-T-T)n, were studied. Experimental transition curves of the DNAs were analyzed using the loop entropy model of DNA melting. The calculation of the melting curve of d(A-A-T)n·d(A-T-T)n is presented using the integral equation formalism of Goel and Montroll. The aim of this work was to evaluate thermodynamic parameters which govern DNA stability and to test the theoretical model employed in the analysis. Our results show (1) an excellent over-all agreement between theory and experiment, (2) a loop entropy exponent k = 1.55 ± 0.05 provided the best fit to all the polymer transition curves, (3) the evaluated stacking free energies reflect the relative stability of the DNAs, and (4) the stacking energies of the ApA·TpT dimer evaluated from d(A)n·d(T)n and d(A-A-T)n·d(A-T-T)n differ. The last result is consistent with different conformations for the dimer in these two polymers.
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  • 98
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Concentration and temperature dependences of the 1H nmr spectra of N-acetyl-L-proline N-methylamide were observed in various solvents [CCl4, CDCl3, (CD3)2CO, (CD3)2SO, H2O, and D2O]. The fraction of the cis isomer (with respect to the bond between the acetyl carbonyl carbon and prolyl nitrogen atoms) depends greatly on the solvent used; the fraction of the cis isomer is higher in polar solvents than in nonpolar solvents. It depends also on concentration and temperature in nonpolar solvents but not in polar solvents. In nonpolar solvents the trans isomer mostly exists in the γ-turn structure with an intramolecular hydrogen bond and the cis isomer tends to form molecular aggregates by intermolecular hydrogen bonds. In polar solvents both the cis and trans isomers exist in monomeric forms which interact with solvent molecules. The pH dependences of the N-methyl proton resonances indicate that the γ-turn structure of the trans isomer is present also in aqueous solution, though its population is difficult to determine. Apparent enthalpy and entropy changes for the conversion of the trans isomer to cis isomer are evaluated for various solvents. The results are discussed in terms of the intra- and intermolecular hydrogen bondings.
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  • 99
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    Biopolymers 16 (1977), S. 1357-1361 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 100
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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