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  • Polymer and Materials Science  (8,795)
  • Cell & Developmental Biology  (1,773)
  • 1995-1999
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  • 1989  (4,828)
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  • 1995-1999
  • 1985-1989  (4,828)
  • 1980-1984
  • 1975-1979  (5,740)
  • 1940-1944
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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
    Electronic Resource
    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
    Electronic Resource
    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
    Electronic Resource
    Electronic Resource
    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
    Electronic Resource
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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
    Electronic Resource
    Electronic Resource
    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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    Electronic Resource
    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
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    Biopolymers 15 (1976), S. 1-14 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The template directed synthesis of poly[d(A-T)] from the nucleoside triphosphates in the presence of DNA polymerase I is carried out continuously in a stirred flow reactor for the first time. The initial objective is to test the kinetic stability of the established steady states at various flow rates. Graphical analysis predicts instable steady states for certain high flow rates. As a consequence of instabilities multiple steady states and steady-state hysteresis may occur. Steady-state hysteresis has now been found experimentally. For a different enzyme fraction of low exonuclease activity we found the steady-state absorbance at 260 nm to be almost invariant with flow rate at high enzyme concentrations even if the flow rate was increased by a large factor. We call this phenomenon kinetic buffering. Relaxation of a large flow perturbation approaches the steady state in a sigmoidal fashion. Concentration oscillations at 260 nm occurred in one experiment using an enzyme fraction of low exonuclease activity after perturbing the steady state by monomer (dATP). Advantages of the stirred flow reactor method over serial transfer are discussed.
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  • 45
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The far-ultraviolet circular dichroic spectrum of the 39-residue peptide hormone porcine corticotropin and the biologically active fragment corticotropin 1-24 is negative from 250 nm to 195 nm in water, but in 6M guanidinium chloride a positive band appears at about 225 nm. The temperature and guanidinium chloride dependence of this spectral transition indicates the absence of any stable ordered secondary structure in corticotropin and the spectrum is seen to be in only partial agreement with results using the model peptide chromophore, Ala-Ala-Ala. Using oligopeptides containing aromatic amino acid residues sandwiched between glycyl residues, it is shown that the shape and intensity of the corticotropin 225 nm positive band which appears in 6M guanidinium chloride is in agreement with the far-ultraviolet transitions of the aromatic chromophores in the hormone. Curve resolution of the near-ultraviolet circular dichroic spectrum of corticotropin and comparison of the rotational strengths of the phenylalanyl and tyrosyl bands reveals no evidence for increased rotational freedom in 6M guanidinium hydrochloride. Spectral changes are observed, however, in the transitions arising from the single tryptophan. This study suggests that corticotropin in aqueous solution may serve as a better model for the circular dichroic spectrum of the aperiodic regions in globular proteins than either synthetic homopolypeptides or reference proteins for which spectral and X-ray diffraction data are available.
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  • 46
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    Biopolymers 15 (1976), S. 131-152 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An all-order classical coupled oscillator theory in which monomer band shapes are explicity taken into account is applied to the calculations of polynucleotide circular dichroism. Calculations are shown for ApA and oligoadenylic acid of varying chain lengths, in both RNA and B-DNA geometry, and the advantages of this theory are assessed. By introducing an effective dielectric constant, good agreement with measured spectra is obtained. Variations in monomer parameters are tested in an attempt to eliminate remaining discrepancies between calculated and measured spectra.
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  • 47
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    Biopolymers 15 (1976), S. 203-218 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Raman Spectra of bovine serum albumin have been obtained in the solute state, in alkaline and acidic solutions, and in the gel. The reversible denaturations of bovine serum albumin solutions by heat, acid's, and alkali were studied and a new mechanism for heat denaturation has been proposed based on a continuous unfolding of the α-helices.
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    Biopolymers 15 (1976), S. 219-225 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New techniques in laser Raman spectroscopy are used to obtain spectra of aqueous solutions of lysozylme for frequency shifts as small as 5 cm-1. In addition, Raman measurements are made on two crystalline forms of hen egg white lysozyme. The spectra obtained from the solution and from the crystal are found to be similar for frequencies above 100 cm-1. However, a low-frequency band at 25 cm-1 observed in crystalline lysozyme is not found in the solution, indicating that this band cannot be attributed to an internal molecular vibration.
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  • 49
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    Biopolymers 15 (1976), S. 257-263 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The adsorption of protein films on polystyrene latex spheres was studied by optical mixing spectroscopy. With this technique, we show that both the hydrodynamic thickness of protein films and their optical density can be measured. Thus, we found that films of the glycoproteins isolated from the human erythrocyte membrane were four times as thick as films of either human serum albumin or bovine serum albumin for about the same surface coverage. This result suggests an end-on orientation for the adsorbed glycoprotein molecules, which is consistent with the model proposed by others for the orientation of these molecules at the surface of the red blood cell itself.
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    Biopolymers 15 (1976), S. 293-299 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solvent binding to bovine serum albumin in 2-chloroethanol-water mixed solvents of different composition, measured previously by Inoue and Timasheff (Biopolymers (1972) 11, 737-43) is applied to a hydrodynamic study of the solvated protein.From sedimentation and diffusion data, the apparent molecular weight of the solvated protein particle can be calculated, provided an average partial specific volume, computed from the composition of the particle, is introduced in Svedberg's equation. The unsolvated molecular weight of the protein can than be calculated by subtraction of the bound solvent. Further data on the hydrodynamic particle (f/fmin and axial ratio of the equivalent ellipsoid) are readily calculated from these experiments, and reinforce the supposition that 2-chloroethanol is a strong helix-inducing solvent.
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    Biopolymers 15 (1976) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 52
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    Biopolymers 15 (1976), S. 403-414 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have carried out a detailed study of ligand binding of ferrihemoglobins under various conditions. Our results show that n varies with time and that this variation is paralleled by changes in the spectrum of methemoglobin. This suggests some form of structural perturbation. The time-dependent value of n is discussed in terms of the observed spectral changes accompanying prolonged equilibration.
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  • 53
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    Topics: Chemistry and Pharmacology
    Notes: The nmr titration curves of chemical shifts versus pH were observed for the protons of various histidine-containing di- and tripeptides. With these results, the macroscopic pKa values and the chemical shifts intrinsic to each ionic species were determined by a computer curve-fitting based on a simple acid dissociation sequence. The pKa value of the imidazole ring in N-acetyl-L-histidine methylamide was assumed to represent the intrinsic (or unperturbed) pKa of the imidazole rings of histidine having peptide linkages at both the CO and NH sides. The pKa values of the imidazole rings observed for most di- and tripeptides were reasonably reproduced by simple calculations using the intrinsic value and the perturbations due to the CO2- and NH3+ groups located at various positions. Some other factors affecting the pKa value of the imidazole ring are also discussed.
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  • 54
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    Biopolymers 15 (1976) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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  • 55
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hyperchromic and hypochromic changes in the intensity of the amide-I and amide-III lines of polypeptides and certain ring vibrations of the bases of polynucleotides are shown to be related to similar changes in the lower energy uv absorption bands. The selection rules strictly limit the pairs of excited electronic states that can contribute to the elements of the polarizability matrix. An energy-dependent term in this equation weights the contribution of the pairs of electronic transitions in favor of those involving the lower energy transitions. For both polypeptides and polynucleotides, there is a large hypochromic inensity change in the first π → π* exciton band upon the coil-to-helix transition. Through the selection rules, certain conformationally sensitive Raman lines are shown to derive their intensity predominantly from this band and hence also display hypochromism. Again, through an application of the selection rules, certain Raman lines can be demonstrated to depend predominantly for their intensity upon the n → π* transition, and consequently have the opposite hyperchromic intensity change upon the same conformational transition.
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  • 56
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    Biopolymers 15 (1976), S. 301-315 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transient electric birefringence experiments have been performed on well-characterized highly monodisperse samples of tobacco mosaic virus (TMV). Experiments and calculations are presented that show that the sensitivity and accuracy of the traditional transient electric birefringence technique can be enhanced by several orders of magnitude through the use of a low-powered laser and crystal polarizing optics, signal averaging, and digital data processing. Measurements of the field-free decay of the birefringence yield for the rotational diffusion coefficient, DR = 318 ± 3 sec-1. The length of the rodlike virion, calculated from the Broersma equation with this value of DR and a rod diameter of 15 nm, is 292.5 ± 1.0 nm. Measurements of the growth of the birefringence when an electric field is applied across the sample yield μ2/kT(α∥ - α⊥) = 0.47 ± 0.07, where μ is the permanent dipole moment (assumed parallel to the symmetry axis of the virus) and α∥ - α⊥ is the electrical polarizability anistropy of the virus. Using the value of α∥ - α⊥ measured by O'Konski et al., we then obtain μ = 2.5 × 10-14 esu cm.
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  • 57
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The high-resolution nmr spectrum of baker's yeast tRNACUALeu, a recently sequenced non-denaturable tRNA, has been compared with the spectra of the native and denatured conformers of the closely related species tRNAUUGLeu. Because of the presence of many common base pairs in the different tRNA's, it is possible to assign most of the low-field resonances to specific secondary-structure base pairs. A comparison of the observed positions of the various resonances with those predicted by a semiempirical ring-current shift theory shows a root-mean-square deviation of 0.14, 0.11, and 0.12 ppm for tRNAUUGLeu (native), and tRNAUUGLeu (denatured), respectively. These results support the ring-current shift theory currently used to interpret the low-field nmr spectra of the tRNA molecules. Differences between the predicted and observed positions of some resonances provide new evidence for higher order effects such as shifts from second nearest neighbors, anomalous shifts exerted by G·U base pairs, and tertiary-structure effects. A model that was previously proposed for the denatured conformer of tRNAUUGLeu is also supported.
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  • 58
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    Biopolymers 15 (1976) 
    ISSN: 0006-3525
    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: The molecular theory of the previous paper in this series is extended to determine the effect of divalent metal ions on helix stability relative to coil at fixed ionic strength and nucleotide phosphate concentration. Specification of the state of condensed counterions, as well as their concentration, is essential for the solution of this problem, and it is assumed that they translate freely within a thin cylindrical shell close to the polynucleotide. As a function of divalent counterion concentration mB2+ the relative stability of the helix is highly nonlinear. Although the overall trend is that the helix stability increases with addition of divalent metal ion, there is a narrow concentration range for which it decreases slightly. The behavior of the relative stability as a function of mB2+ is determined by the translational degrees of freedom of the counterions, both univalent and divalent, both condensed and uncondensed. Detailed comparison of the theory with data is not given here, but it is pointed out that the calculated values of the relative stability are consistent with the order of magnitude of the observed effect Mg2+ on the melting temperature.
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    Biopolymers 15 (1976), S. 503-506 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: X-ray diffraction studies have been made on the polytripeptide poly(L-prolyl-L-α-phenylglycyl-L-proline). Its structure has been found to be helical, with a poly(L-proline) II conformation, packed in an orthorhombic lattice, space group P21212, with a = 14.3 Å, b = 13.5 Å, and c = 9.4 Å.
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    Biopolymers 15 (1976), S. 591-594 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 15 (1976) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 64
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    Biopolymers 15 (1976), S. 649-653 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The stability constant of the complex of tRNA with 50S subunits of ribosomes was compared in ordinary and heavy water. A considerable effect (about fourfold) was observed, showing the importance of hydrogen bonds in this interaction. In addition, the isotope effect of complementary polynucleotide interaction was measured for two examples. In the case of the binary complex of heptainosinic acid oligomers with poly(C) in the presence of 10-3 M MgCl2, the transfer from ordinary to heavy water gave an increase of the stability constant of about 5%. But in the case of a ternary complex of hexaadenylic acid with poly(U) under the same conditions, the stability constant in D2O increased threefold. The isotope effect depends strongly on magnesium ion concentration and is possibly due to some specific mechanism of magnesium ion complexing involving water molecules.
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    Biopolymers 15 (1976), S. 999-1000 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 66
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    Biopolymers 15 (1976), S. 1009-1013 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 15 (1976), S. 1061-1080 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Monte-Carlo calculations of geometric and thermodynamic characteristics of the α-helix and the β-structure of polypeptides have been carried out. To describe a hydrogen bond both the Lippincott-Schroeder and Morse potentials were used. The internal rotation angles ϕ and ψ in the α-helix have been shown to fluctuate in the range of ±7°. The distribution functions on angles ϕ and ψ and on hydrogen bond lengths and angles in the α-helix have been computed and compared with those in myoglobin and lysozyme. Thermodynamic characteristics of the α-helix calculated in different approximations with the two forms of the hydrogen bond potentials have also been compared. The data obtained are close to the experimental values for polypeptides in neutral solution.Some geometric and thermodynamic characteristics of the regular parallel and antiparallel and irregular antiparallel β-structure have been found. In the β-structure the internal rotation angles vary within the interval ±15-20°. An increase in the cross and longitudinal dimensions of the β-structure only slightly influence both the geometric and thermodynamic characteristics.
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  • 68
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    Topics: Chemistry and Pharmacology
    Notes: The preparation of the co-oligopeptides of the series H-Gly-Phe-(Gly)n-Trp-Gly-OH (n = 0, 1, 2) and of other free peptides of glycine, L-tryptophan, and L-phenylalanine is reported. The syntheses have been carried out by conventional methods, using N-hydroxysuccinimide esters for the coupling steps. The ultraviolet absorption properties of the free peptides have been investigated in water. No hypo- or hyperchromicity was found for the aromatic chromophores, with the exception of H-Gly-Phe-Trp-OH, which shows a small but significant hypochromicity. The contribution of the peptide bond to the molar absorptivity in the far ultraviolet has been separated from that of the side chain plus the —COO- group by plotting the measured molar absorptivity ∊ of the farthest accessible uv maximum as a function of the number of peptide bonds (nA). The peptide bond contribution proved to be independent of nA in the range nA = 1-5, thus ruling out the onset of helical conformations in the longer chain peptides.
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  • 69
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    Notes: The properties of the electron distribution in amides, peptides, and carboxylic acids, obtained from ab-initio molecular orbital calculations using both minimal and extended basis sets have been studied. These properties are discussed in terms of some of the common assumptions made in empirical conformational calculations of biomolecules. In particular, population analyses of 15 compounds in these families were carried out with both the minimal and extended basis sets, and compared with results of CNDO/2 calculations. It is suggested that population analysis is a useful tool for recognizing patterns of charge distributions, and investigating the transferability of parameters of different functional groups. However, its use for providing partial charges for conformational analysis is a questionable procedure.A more detailed analysis of the charge distribution was carried out by calculating the spatial electron distribution in the four compounds, N-methylacetamide, acetic acid, diketopiperazine, and N-acetyl-N′-methylalanine. Both total electron-density maps and differencedensity maps are presented. The properties of the overall shape of the molecule and the atoms in the molecule, are discussed in terms of the former along with three-dimensional shape plots of the total density. The distortion accompanying molecular formation, resulting in such features as the lone pair orbital and “bonding deensities” is discussed in terms of the difference maps. Semiquantitative estimates of the bonding and orbital densities resulting from the integration of the densities are also presented. Finally, one of the novel features of the study is the presentation of three-dimensional surfaces of constant difference densities from which the shapes of the orbitals and bonding densities emerge.
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    Biopolymers 15 (1976), S. 1233-1242 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The lack of the positive band at around 226 nm in the CD spectra of poly(prolyl-azetidine-2-carbonyl-proline) in trifluoroethanol and of poly(azetidine-2-carbonyl-prolyl-azetidine-2-carboxylic) acid in F3EtOH and water, the hyperchromism of the absorption maximum at about 202 nm, and the extremely small intensity of the Cβ-Pro, Cγ-Pro, and Cβ-Aze signals for the cis peptide bonds in the 13C nmr spectrum of poly(Pro-Aze-Pro) in F3EtOH indicate that both polyproline analogs exist as disordered chains in this solvent, the trans peptide group being maintained. The disordering of the chains is attributed to an increase in the accessible range of ψ due to the reduced dimensions of the square ring of L-azetidine-2-carboxylic acid residue relative to the pyrrolidine ring of proline and to strong interactions of the haloalcohol with the peptide groups of the chains.
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    Biopolymers 15 (1976), S. 1283-1299 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Two methods for the characterization of protein molecular weights from their diffusion coefficients are discussed. These measurements can be made quickly and reliably at low concentrations using quasielastic light-scattering techniques. First, an empirical calibration of the diffusion coefficient at infinite dilution of denatured random coils against molecular weight is reported. The second method combines the measurement of D0 with the intrinsic viscosity [η]. This D0-[η] relationship proves to be very insensitive to polymers structure or solvent type. The data indicate that the ratio of the hydrodynamic radius measured by viscosity to the hydrodynamic radius measured by diffusion is about 15% smaller than that predicted by theoretical models. The nature of the molecular-weight average obtained for polydisperse systems is defined for a Schulz distribution. These hydrodynamic methods have also been used to demonstrate the presence of chain branching in the glycoprotein ovomucoid. In addition, a method is proposed by which the effective segment length and an excluded volume parameter for random coils may be evaluated for diffusion measurements.
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    Biopolymers 15 (1976), S. 1425-1430 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 15 (1976), S. 1431-1435 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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  • 74
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    Notes: The influence of one DNA region on the stability of an adjoining region (telestability) was examined. Melting curves of three block DNA's, d(C15A15)·d(T15G15), d(C20A15)·d(T15G20), and d(C20A10)·d(T10G20) were analyzed in terms of the nearest neighbor Ising model. Comparisons of predicted and experimental curves were made in 0.01 M and 0.1 M sodium ion solutions. The nearest neighbor formalism was also employed to analyze block DNA transition in the presence of actinomycin, a G·C specific molecule. The results show that nearest neighbor base-pair interaction cannot predict the melting curves of the block DNA's. Adjustments in theoretical parameters to account for phosphate repulsion assuming a B conformation throughout the DNA's do not alter this conclusion. Changes in the theoretical parameters, which provide good overall agreement, are consistent with a substantial stabilization of the A·T region nearest the G·C block. The melting temperature T A·T for the average A·T pari in d(C20A10)·d(T10G20), with 10 A·T pairs, appears to be 4°C greater than TA·T for d(C15A15)·d(T15G15) and d(C20A15)·d(T15G20), both with 15 A·T pairs. Actinomycin bound to the G·C end effectively stabilizes the A·T end by 9°C. These results indicate a long-range contribution to the interactions governing DNA stability. A possible mechanism for these interactions will be discussed.
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  • 75
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    Topics: Chemistry and Pharmacology
    Notes: Dielectric relaxation studies in the frequency range 100 Hz to 2 MHz of poly(γ-benzyl-L-glutamate) in dioxane have been carried out over a range of concentration 10-4-10-2g/g. The structure of aggregates is analyzed in terms of dipole moment and relaxation time. A critical concentration (≃ 10-3 g/g for the studied molecular weights) has been determined below which the aggregates are found to have linear head to tail type structure. Above the critical concentration a different structure of aggregates is apparent which could not be fully analyzed by these measurements alone. Possible forms of aggregation above the critical concentration are discussed. Formation of long range order which would lead to nematic liquid crystalline phase at higher concentrations has been discussed as one of the possible explanations for the observed behavior above the critical concentration.Maximum length of linear head to tail type aggregates for poly(γ-benzyl-L-glutamate) in dioxane as determined from these results correspond to an α-helix of molecular weight 210,000. A slight difference in the purity of dioxane has been shown to have an influence on the reproducibility of the state of aggregation as well as on the rate of disaggregation on dilution.
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    Biopolymers 15 (1976), S. 1585-1590 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Racemization in the synthesis of peptide intermediates and their polymers was investigated, using L-amino acid oxidase. The formation of N-hydroxysuccinimide esters from N-protected peptide acids yielded optically pure products in contrast to p-nitrophenyl and pentachlorophenyl active esters. The racemization in the polymerization step was found to be base sensitive. Partially racemized polymer can result from optically homogeneous monomer. Thus, the optical integrity of active monomer species carries no guarantee for that of the polymer.
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    Biopolymers 15 (1976), S. 1623-1635 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Conformations containing all trans peptide bonds have previously been proposed for N-methylleucine gramicidin-S and (di-N-methylleucine) gramicidin-S based on an evaluation of proton nuclear magnetic resonance parameters in a series of solvents. These gramicidin-S derivatives exhibit full biological activity despite the fact that the proposed solution conformations differ in backbone topology and relative orientation of the Phe and Orn side chains compared to gramicidin-S. The present authors discuss conformations for N-methylleucine gramicidin-S and (di-N-methylleucine) gramicidin-S which incorporate cis peptide bonds at L-Orn-L-N-MeLeu, where the gramicidin-S backbone is essentially retained, and the relative orientation of the Pro, Orn, Val, and Phe side chains correspond to those observed for gramicidin-S. A novel hydrogen-bond arrangement involving one carbonyl group interacting with two peptide protons (1 ←4 and 1 ←5 types) is proposed to stabilize the backbone conformation in the gramicidin-S derivatives. A recent report on the cyclic heptapeptide antibiotic, Ilamycin B1, shows the presence of cis peptide bonds at N-CH3 amino acids, as well as the novel hydrogen-bond arrangement presented above.
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  • 78
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    Topics: Chemistry and Pharmacology
    Notes: The morphology of fibrin strongly depends on solvent medium, as shown by clotting experiments carried out in the presence of different salts. The clots were characterized by electron microscopy and spectrophotometric methods; the kinetics of gelation were determined.In the presence of electrolytes which strongly delay clotting, the strands are thin and few branching points are observed; opposite morphological changes are induced by salts which act as accelerating agents. On the basis of this correlation, and of previous data on the structure of fibrin, a kinetic model of the self-assembly process is outlined. It accounts well for the observed solvent effects on the morphology of the network.An important result emerging from our experiments is that the fibers undergo branching prior to gelation. Branching points arise from the defective growth of the fibers; a simple explanation of the occurrence of branching may be obtained by our self-assembly model.
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    Biopolymers 15 (1976), S. 2025-2041 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The equilibrium between the cis and trans forms of X-Pro peptide bonds can readily be measured in the 13C nmr spectra. In the present paper we investigate how observation of this equilibrium could be used as an nmr probe for conformational studies of flexible polypeptide chains. The experiments include studies by 13C nmr of a series of linear oligopeptides containing different X-L-Pro peptide bonds, with X = Gly, L-Ala, L-Leu, L-Phe, D-Ala, D-Leu, and D-Phe. Overall the study confirms that X-Pro peptide bonds can generally be useful as 13C nmr probes reporting the formation of nonrandom conformation in flexible polypeptide chains. It was found that the cis-trans equilibrium of X-Pro is greatly affected by the side chain of X and the configuration of the α-carbon atom of X. On the basis of these observations some general rules are suggested for a practical applications of the X-Pro nmr probes in conformational studies of polypeptide chains.
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    Topics: Chemistry and Pharmacology
    Notes: Random copolymers of L-glutamic acid and ortho-nitrobenzyl-L-glutamate were synthesized with different percentages of nitrobenzyl-L-glutamate, from 3 to 22%. These copolymers were studied by circular dichroism (CD) and potentiometric titrations in aqueous solutions in order to determine the variation of the stability of the secondary structure when the concentration of nitrobenzylglutamate varies in the copolymer. We observed that the stability increases with the concentration of glutamate. Such a stabilization could be due to either side-chain interactions or interactions between the aromatic side chain with the backbone. An intermolecular aggregation was observed when the percentage of nitrobenzylglutamate was sufficently important, but such an aggregation may be avoided if a dioxane/water mixture is used as a solvent.
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    Biopolymers 15 (1976), S. 2185-2199 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The kinetics of γ-benzyl-L-glutamate NCA's polymerizations in dioxane as solvent are discussed. The partial orders respective to [A], the NCA concentration and [I0], the initial initiator concentration are given; the rate constants are deduced and a mechanism is proposed to justify a rate of polymerization Vp = k[A][I0]2.The dependence of the rate constants on the conformation of the growing chains is demonstrated; the acceleration is attributed to the ordered structures favorable to hydrogen bonding. The kinetics of aging have also been examined and discussed; it is shown that they cannot modify the kinetics of polymerization.The DPn were obtained on the same samples before and after debenzylation; it is proved that at any concentration, DPn ≃ [A0]/[I0].The molecular-weight distributions were obtained by chromatography and a polydispersity lower than 1.3 was deduced for each sample. The trimodal distribution, appearing as soon as [A0]/[I0] is larger than 3, is attributed to the existence of the three structures σ, β, and α. The weight fraction of each of the structures was correlated to the kinetics of polymerization.
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    Biopolymers 15 (1976), S. 1903-1915 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structure of native cellulose (Valonia) has been analyzed by electron diffraction. Possible models for the structure were refined by rigid-body least squares methods, which incorporated parameters defining the preferred orientation of the fibrils around their long axes in the cell wall lamellae. The structure was found to consist of an array of chains having the same sense (i.e., parallel), with packing parameters similar to those recently determined by X-ray diffraction. The eight-chain unit cell could be approximated adequately by a two-chain monoclinic unit cell with dimensions a = 8.18 Å, b = 7.84 Å, c = 10.38 Å (fiber axis), and γ = 97.04°; the space group is P21.
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    Biopolymers 15 (1976), S. 1939-1950 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The coil-to-helix transition temperatures of hydrogen bearing and deuterated poly(γ-benzyl-L-glutamate) in 1,3-dichlorotetrafluoroacetone/H2O and/D2O mixtures, respectively, have been determined. Together with previously obtained data for the conformational transition of this polypeptide in normal and deuterated dichloroacetic acid, these results have been used in an analysis of the effect of deuterium substitution on the intrinsic stability of the α-helical form of poly(γ-benzyl-L-glutamate). The findings, consistent for both solvent systems, showed that the deuterated polypeptide is some 5% more stable than the normal protonated poly(γ-benzyl-L-glutamate), while the polypeptide-active solvent interaction enthalpy is also slightly increased by deuterium substitution in the respective molecules. A consideration of available data for poly(β-benzyl-L-aspartate) reveals an anomaly with respect to the present analysis.
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    Biopolymers 15 (1976), S. 1669-1676 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transient electric birefringence measurements on poly(L-lysine hydrobromide) in methanol-water mixtures have been carried out at various solvent compositions in the vicinity of the helix-coil transition region (from 87 to 98 vol % methanol). Anomalous birefringence transients were observed between 90 and 95 vol % methanol above a threshold field strength. A distinct difference between the responses to weak and strong electric fields was noticed over a narrow range of the solvent composition. The effects of polymer concentration and temperature on the field-strength dependence of the birefringence were studied at a solvent composition of 90 vol % methanol where the anomalous transients appeared most clearly. The double logarithmic plots of the steady-state specific birefringence versus the square of field strength for different concentrations and temperatures could be superimposed by shifting them horizontally along the abscissa. The threshold field strength which was determined from the shift factor decreased with decreasing concentration. The results provide further evidence that strong electric fields can cause a helix-coil transition in this system under favorable conditions.
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    Biopolymers 15 (1976), S. 1701-1715 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Derivatives of tetrapeptide sequences considered likely to form β-turns were investigated by the study of their proton magnetic resonances in methanol and in water. Differential broadening of N - H resonances by an added nitroxyl was used to indicate the presence of the sequestered N - H proton expected in β-turn conformations. Transfer of magnetic saturation from solvent water protons to N - H protons was also examined. The evidence is consistent with significant contributions by β-turn-like backbones to the conformational averages in methanol of the sequences Gly-L-Pro-D-Val-Gly, D(or L)-Val-L-Pro-Gly-Gly, and Gly-L-Pro-L-Asn-Gly, but not the sequence Gly-D-Ala-L-Val-Gly. It is suggested that a Type I turn, Likely in Gly-L-Pro-L-Asn-Gly derivatives, is characterized by sequestered N - H protons of both the third and fourth residues. For all of the peptide derivatives, save possibly Ac-L-Val-L-Pro-Gly-Gly-NHNH2, contributions from folded structures in water are not detectable by line-broadening experiments. However, the transfer of saturation experiments may be interpreted as indicating some degree of chain folding in water.
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    Biopolymers 15 (1976), S. 1717-1739 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this paper we use probabilistic arguments to derive and discuss the spatial distribution of molecules which are undergoing electrophoresis or centrifugation while at the same time they are switching back and forth between two configurational states. An exact solution is obtained for arbitrary values of the diffusion coefficients of the two isomerizing states. The traditional analytic method of solving this problem, namely, by use of “master equations,” is not completely satisfactory because one can find only the Fourier transform of the solution rather than the solution itself. Our treatment yields the answer one would get if it were feasible to perform the inversion of the Fourier transform.
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    Biopolymers 15 (1976), S. 1815-1824 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of sequential oligopeptides having simple nonpolar side chains, Nps-(L-Ala-L-Leu-Gly)n- OEt has been prepared by a stepwise fragment-condensation method using Nps-L-alanyl-L-leucylglycine N-hydroxysuccinimide ester, which was prepared by the Nps-N-carboxy α-amino-acid-anhydride method. The success of the synthesis of the peptide having a high-molecular weight, such as octadecapeptide, results from the highest solubility of the tripeptide unit, L-alanyl-L-leucylglycine. The sequential polypeptide having the same tripeptide sequence was also prepared by polycondensation of the tripeptide N-hydroxy-succinimide ester.
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    Biopolymers 15 (1976), S. 1841-1844 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 15 (1976), S. 1873-1875 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 15 (1976), S. 1879-1902 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal transitions of single-stranded polynucleotides are noncooperative. In contrast, Cu(II) cooperatively disorders the single-stranded helical structures of poly(A) and poly(C), as demonstrated by ORD and UV spectral changes as a function of the Cu2+ activity, and by a dramatic chain-length dependence of the spectral changes. Equilibrium dialysis binding studies indicate that the cooperative disordering is paralleled by a somewhat less cooperative binding process.The difference between the thermal- and Cu(II)-induced transition is explained by the following mechanism. (1) Cu(II) initially binds in a noncooperative fashion to phosphate. (2) The Cu(II) so bound forms a second bond to a nonadjacent base site on the same polymer strand or another strand. These intramolecular and intermolecular crosslinks to the bases are responsible for the disordering. (3) The initial crosslinks formed provide nuclei for the cooperative formation of additional crosslinks, producing cooperative spectral changes paralleled by cooperative binding.A comparison of the spectral and binding transitions indicates that there is appreciable noncooperative binding of copper to phosphate, which produces no spectral changes in the presence of added electrolyte. This comparison also indicates that each copper crosslink disorders several bases. The formation of intermolecular crosslinks is demonstrated by a polymer concentration dependence of the disordering. The formation of intramolecular crosslinks can be deduced from the fact that the “cooperative unit” required to explain the differences between the hexamer, which does not readily form intramolecular crosslinks, and the polymer is considerably larger than the cooperative unit determined from the polymer results.The poly(A) disordering transition is less symmetrical than that of poly(C), particularly at low polymer concentrations. These results, together with other phenomena, are explained by a greater flexibility of poly(A), which favors the formation of small intramolecular loops.
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  • 91
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    Biopolymers 15 (1976), S. 1951-1964 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Potential energy calculations were employed to examine the effect of ribose 2′-O-methylation on the conformation of GpC. Minimum energy conformations and allowed conformational regions were calculated for 2′MeGpC and Gp2′MeC. The two lowest energy conformations of 2′MeGpC and Gp2′MeC are similar to those of GpC itself. The helical RNA conformation (sugar pucker-C(3′)-endo, ω′ and ω,g-g-, bases-anti) is the global minimum, and a helix-reversing conformation with ω′, ω in the vicinity of 20°, 80° is next in energy. However, subtle differences between the three molecules are noted. When the substitution is on the 5′ ribose (Gp2′MeC), the energy of the helical conformation is less than that of GpC, due to favorable interactions of the added methyl group. When the substitution is at the 3′ ribose (2′MeGpC) these stabilizing interactions are outweighed by steric restrictions, and the helical conformation is of higher energy than for GpC. Furthermore, the statistical weight of the 2′MeGpC g- g- helical region is substantially less than the corresponding weight for Gp2′MeC. In addition, 2′MeGpC′s methoxy group is conformationally restricted to a narrow range centered at 76°. This group has a broadly allowed region between 50 and 175° in Gp2′MeC. These differences occur because the appended methyl group in 2′MeGpC is located in the interior of the helix cylinder, as it would be in polynucleotide, while it hangs unimpeded in Gp2′MeC. These findings suggest that 2′-O-methylation has both stabilizing and destabilizing influences on the helical conformation of RNA. For 2′MeGpC the destabilizing steric hindrance imposed by the nature of the guanine base dominates.
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  • 92
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    Biopolymers 15 (1976), S. 2043-2057 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The molecular conformations of the linear oligopeptides H-(L-Ala)n-L-Pro-OH, with n = 1,2 and 3, have been investigated. 13C nmr observation of the equilibrium between the cis and trans forms of the Ala-Pro peptide bond indicated the occurrence of nonrandom conformations in solutions of these flexible peptides. The formation of the nonrandom species containing the cis form of the Ala-Pro bond was found to depend on the deprotonation of the carboxylic acid group of proline, the solvent, and the ionic strength in aqueous solution. The influence of intramolecular hydrogen bonding on the relative conformational energies of the species containing the cis and trans Ala-Pro peptide bond was studied by comparison of the peptides H-(Ala)n-Pro-OH with analogous molecules where hydrogen bond formation was excluded by the covalent structure. In earlier work a hydrogen bond between the protonated terminal carboxylic acid group and the carbonyl oxygen of the penultimate amino acid residue had been suggested to stabilize conformations including trans proline. For the systems described here this hypothesis can be ruled out, since the cis:trans ratio is identical for molecules with methyl ester protected and free protonated terminal carboxylic acid groups of proline. Direct evidence for hydrogen bond formation between the deprotonated terminal carboxylic acid group and the amide proton of the penultimate amino acid residue in the molecular species containing cis proline was obtained from 1H nmr studies. However, the cis:trans ratio of the Ala-Pro bond was not affected by N-methylation of the penultimate amino acid residue, which prevents formation of this hydrogen bond. Overall the experimental observations lead to the conclusion that the relative energies of the peptide conformations including cis or trans proline are mainly determined by intramolecular electrostatic interactions, whereas in the molecules considered, intramolecular hydrogen bonding is a consequence of specific peptide backbone conformations rather than a cause for the occurrence of energetically favored species. Independent support for this conclusion was obtained from model consideration which indicated that electrostatic interactions between the terminal carboxylic acid group and the carbonyl oxygen of the penultimate amino acid residue could indeed account for the observed relative conformational energies of the species containing cis and trans proline, respectively.
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  • 93
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    Biopolymers 15 (1976) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 94
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is described for predicting and solving crystal structures of linear homopolysaccharides. The method is based on the refinement of the structure with respect to either stereochemical constraints or x-ray diffraction intensities. In the refinement process, all conformational and packing features of the molecule, such as bond lengths, bond angles, conformational angles, nonbonded contacts, hydrogen bonds, etc., can be allowed to vary until the structure reaches both a conformation and crystalline packing that are in minimum disagreement with the stereochemical restraints and the diffraction data. In this fashion, both packing and conformational features of the structure can be simultaneously refined, and not separately as has been the custom in the past. The refinement procedure is based on a method of constrained optimization which possesses improved characteristics of reaching a solution and avoiding false minima, in comparison with least squares methods. The procedure is, in addition, capable of easily finding molecules of solvent of crystallization. The method was applied to further refining the previously solved crystal structure of V-amylose. The results indicated that contrary to the previously found six-fold molecular symmetry in the P212121 space group, the V-amylose molecule exhibits only two-fold symmetry with the asymmetric unit consisting of three glucose residues in one-half turn of the helix. The three residues are nonequivalent principally due to unequal rotational positions of the hydroxymethyl groups. The crystal structure of V-amylose predicted from stereochemical refinement was identical in all details with that obtained from refining against X-ray data. The excellent agreement with the diffraction data was indicated by the crystallographic disagreement index R = 0.25.
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  • 95
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    Biopolymers 15 (1976), S. 2167-2184 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to obtain information about the conformational features of a 2′-O-methylated polyribonucleotide at the nearest neighbor level, a detailed nuclear magnetic resonance study of AmpA was undertaken. AmpA was isolated from alkali hydrolysates of yeast RNA, and proton spectra were recorded at 100 MHz in the Fourier transform mode in D2O solutions, 0.01 M, pH 5.4 and 1.5 at 25°C. 31P spectra were recorded at 40.48 MHz. Complete, accurate sets of nmr parameters derived for each nucleotidyl unit by simulation iteration methods.The nmr data were translated into conformational parameters for all the bonds using procedures developed in earlier studies from these laboratories. It is shown that AmpA exists in aqueous solution with a flexible molecular framework, which shows preferences for certain orientations. The ribose rings exist as a 2E ⇄ 3E equilibrium with the  - pA ribose showing a bias for the 3E pucker. The C(4′) - C(5′) bonds of both nucleotidyl units show significant preference (75-80%) to exist in gg conformation. The dominant conformer (80%) about C(5′) - O(5′) of the 5′-nucleotidyl unit is g′g′. Even though an unambiguous determination of the orientation of the 3′-phosphate group cannot be made, tentative evidence shows that it preferentially occupies g+ domains [O(3′) - P trans to C(3′) - C(2′)] in which the H(3′)  - C(3′) - O(3′) - P(3′) dihedral angle is about 31°. There is reasonable evidence that the 2′-O-methyl preferentially occupies the domain in which the O(2′) - CH3 bond is trans to C(2′) - C(1′).Lowering of pH to 1.5, which results in protonation of both the adenine moieties, causes destacking of AmpA. Such destacking is accompanied by small, but real, perturbations in the conformations about most of the bonds in the backbone.A detailed comparison of the solution conformations of ApA and AmpA clearly shows that 2′-O-methylation strongly influences the conformational preference about the C(3′) - O(3′) bond of the 3′-nucleotidyl unit, in addition to inducing small changes in the overall ribophosphate backbone conformational equilibria. The effect of 2′-O-methylation is such that the C(3′) - O(3′) is forced to occupy preferentially the g+ domain rather than the normally preferred g- domain [O(3′) - P trans to C(3′) - C(4′)] in ApA. The data on ApA and AmpA further reveal that the extent of stacking interaction is less in AmpA compared to ApA.It is suggested that stacked species of AmpA exist as right-handed stacks where the magnitude of ω and ω′ about O(5′) - P and P - O(3′) is about 290°. The reason for the lesser degree of stacking in AmpA compared to ApA is intramolecular interaction between 2′-O-methyl and the flexible O(3′) - P - O(5′) bridge, the interaction causing some perturbation in the magnitudes of ω/ω′, causing destacking. The destacking will lead to an increase in χCN by a few degrees, causing an increase in 2E populations; the latter in turn will shift the 3′ phosphate group from g- to g+ domains. In short, a coupled series of conformational events is envisioned at the onset of destacking, made feasible by the interaction between the 2′-O-methyl group and the swivel O(3′) - P - O(5′) bridge.
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  • 96
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    Biopolymers 15 (1976), S. 2263-2275 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The binding isotherms of sodium decyl sulfate to poly(L-ornithine), poly(D,L-ornithine), and poly(L-lysine) at neutral pH were determined potentiometrically. The nature of a highly cooperative binding in all three cases suggests a micelle-like clustering of the surfactant ions onto the polypeptide side groups. The hydrophobic interaction between the nonpolar groups overshadows the coulombic interaction between the charged groups. The titration curves can be interpreted well by the Zimm-Bragg theory. The average cluster size of bound surfactant ions is sufficiently large to promote the β-structure of (L-Lys)n even at a very low binding ratio of surfactant to polypeptide residue, whereas the onset of the helical structure for (L-Orn)n begins after about 7 surfactant ions are bound to two turns of the helix. The CD results are consistent with this explanation.
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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
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  • 98
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    Biopolymers 15 (1976), S. 2337-2351 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of a cross-linked polypentapeptide (an insoluble product) by means of a cross-linking reaction between a lysine-containing (1%) polypentapeptide and a glutamic acid-containing (2%) polypentapeptide is described, following description of the synthesis and polymerization of the corresponding pentapeptide p-nitrophenyl esters. The pentapeptide p-nitrophenylesters - H-Val1-Pro2-Gly3-Val4-Gly5-ONp, H-Val1-Pro2-Gly3-Lys4(ε-Z)-Gly5-ONp, and H-Val1-Pro2-Gly3-Glu4-Gly5-ONp - prior to polymerizing and the polypentapeptides prior to cross-linking were analyzed by proton and carbon-13 magnetic resonance. The cross-linking reaction was achieved in the coacervate state by intermolecular primary amide bond formation. The coupling reagent was a water-soluble carbodiimide (1-cyclohexyl-3-(2-N-methylmorpholinoethyl)-carbodiimide-p-toluenesulfonate).
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  • 99
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is concluded on the basis of comparison of polyelectrolyte theory with published data that the mean phosphate spacing b along the contour axis of an unfolded polynucleotide single strand is in the range 3-4 Å (polyelectrolyte parameter ξ ≈ 2), regardless of temperature, base composition, or extent of stacking. This result is consistent with the low-angle X-ray scattering measurements of Gulik, Inoue, and Luzzati on poly(C). No conclusion may be drawn from this value of b concerning the structure of the chain skeleton or the spatial arrangement of the bases other than that the chain is far from an all-trans local conformation (for which b would be about 6-7 Å, the length of a nucleotide unit). The structural implications, or lack thereof, are discussed in detail in the following paper.
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  • 100
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    Biopolymers 15 (1976), S. 2421-2437 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The technique of intensity correlation light-scattering spectroscopy has been used to accurately determine the extent of physical swelling of lysozyme, ribonuclease, and chymotrypsinogen produced by thermal denaturation. The change in hydrodynamic radius is deduced from direct measurements of the diffusion coefficient, carried out in the temperature range 20° to 70°C at various values of pH in the range 1.0 to 3.0 at ionic strengths of from 0.01 M to 0.2 M. An average radius increase of 18% is observed for lysozyme and ribonuclease, with an estimate of 26% for chymotrypsinogen. Analysis of the pH dependence of the transition temperature leads to the conclusion that the lysozyme charge increases by approximately +2e during unfolding. We have applied this value of the charge increase along with the 18% average radius increase to estimate the electrostatic contribution to the free-energy change for denaturation of lysozyme. The results are consistent with the experimental observation that the transition temperature is nearly independent of ionic strength.
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