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  • Chemistry  (16,518)
  • 2010-2014
  • 1985-1989  (9,555)
  • 1980-1984  (6,963)
  • 1925-1929
  • 1989  (9,555)
  • 1982  (6,963)
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Years
  • 2010-2014
  • 1985-1989  (9,555)
  • 1980-1984  (6,963)
  • 1925-1929
Year
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Aquatic sciences 51 (1989), S. 108-128 
    ISSN: 1420-9055
    Keywords: Chemistry ; mountain lakes ; silica ; acidity ; sediment
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Alpine lakes in siliceous catchments of Tyrol and Carinthia (Austria) show signs of acidification. About 9% of the studied lakes have no alkalinity, more than 20% are below pH 6. About two thirds of all lakes have acid neutralizing capacities below 100 μeq 1−1. In spite of moderate precipitation acidity, some lakes show considerable concentrations of dissolved reactive aluminum during or shortly after snowmelt. High altitude lakes of the Alps are definitely more acidic than high mountain lakes in remote areas. Large differences in water and soil chemistry of nearby situated lakes were attributed to heterogeneities of bedrock geology. Paleolimnological investigations on former pH values of five lakes, based on diatom assemblages in the sediment, showed different developments: recent and past acidification, stable conditions, and alkalinization.
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  • 2
    ISSN: 1432-0827
    Keywords: Bacterial amphophile ; Purification ; Chemistry ; Resorption ; Ca influx ; Cyclic AMP
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Summary The bone resorptive factor and amphipathic antigen (AcA) previously identified by us in preparations fromActinomyces viscosus have been partially purified, characterized chemically, and compared. They elute at the same location on chromatography with Ac 22. The fatty acid composition of AcA and the bone resorptive factor is the same. Some differences in carbohydrate composition are observed. TheActinomyces factor does not affect calcium influx or cyclic AMP in isolated bone cells. Therefore it is concluded that AcA stimulates resorption either by gaining entrance into bone cells or by way of a yet undetermined second messenger.
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  • 3
    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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  • 4
    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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  • 5
    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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  • 6
    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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  • 7
    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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  • 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: 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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  • 9
    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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  • 10
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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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  • 11
    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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  • 12
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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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  • 13
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 168 (1989), S. 145-155 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Entgegengesetzte Ladungen wurden durch tertiäre Amin- und Carboxylgruppen in Polyurethan (PU) und Polystyrol (PS) eingeführt, um durch gemeinsame Massepolymerisation ein interpenetrierendes PU/PS Polymernetzwerk (IPN) zu erhalten. Vier IPNs wurden hergestellt: ein Voll-IPN, zwei Semi-IPNs und ein lineares Blend. Die Wirkung der geladenen Gruppen auf die mechanischen Eigenschaften und die Morphologie der vier Polymermischungen wurde untersucht.Es wurde gefunden, daß PU/PS IPNs mit geladenen Gruppen keine Phasenseparation und somit homogene Verteilung aufweisen, was durch elektronenmikroskopische (SEM) Aufnahmen nachgewiesen wurde. Dynamisch-mechanische Messungen zeigen, daß die Übergangspeaks des Verlust-Moduls E″ in die Mitte zwischen den beiden Übergangspeaks der beiden Komponenten ohne geladene Gruppen liegen. Dies ist von der Zunahme des Gehaltes an geladenen Gruppen abhängig. Gleichzeitig nimmt der Speichermodul E′ in einer Stufe ab, was im Gegensatz zu der zweistufigen Abnahme bei Proben ohne Ladungsträger steht.Die Zugfestigkeit nimmt in allen vier Polymermischungen mit der Zunahme an Acrylsäure (AA) in Poly(Styrol-Acrylsäue) PSAA zu, was in dem PU/PSAA Voll-IPN besonders deutlich wird.
    Notes: Opposite charges, namely tertiary amine and carboxyl groups, were introduced into polyurethane (PU) and polystyrene (PS), respectively, to prepare PU/PS interpenetrating polymer networks (IPNs) by means of simultaneous bulk polymerization. Four IPNs were synthesized: a full-IPN, two semi-IPNs and a linear blend. The effect of charge groups on the mechanical properties and morphology of the four polymer alloys was investigated.It is found that the PU/PS IPN which was incorporated with charge groups is free of any phase-separation, and sufficiently uniformly distributed, as can be seen from the corresponding scanning electron microscopy (SEM) photographs. Dynamic mechanical analysis indicates that the transition peak of the loss modulus E″ will move towards the centre between the two transition peaks of both components in the absence of charge groups, as a function of an increase in the contents of the opposite charge groups. Meanwhile the storage modulus E′ will decrease in a single-stage way from the previous two-stage mode.The tensile strength in all the four polymer alloys increased markedly along with an increase in the contents of acrylic acid (AA) in the poly(styrene-acrylic acid) (PSAA), which clearly can be seen for the PU/PSAA full-IPN.
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  • 14
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 168 (1989), S. 157-168 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Pyrolysis behaviour and coke characteristics of different precursors for carbon processing: thermosetting resins (resol, novolak), hydrolytic lignin, pitch, tar as well as their blends were studied using differential thermal analysis (DTA) and X-ray diffraction techniques. The blends novolak-pitch, resol-tar and resol-hydrolytic lignin show a higher coke yield after carbonisation up to 1000°C compared to the corresponding individual substances. A good correlation between the integral procedural decomposition temperature T*A of the investigated precursors and their coke yield is found.
    Notes: Mittels Thermo- und Röntgenstrukturanalyse wird eine vergleichende Untersuchung des Pyrolysevorganges und der Mikrostruktur des aus zwei Gruppen organischer Bindemittel und deren Mischungen gewonnenen Koksrückstandes durchgeführt. Gruppe I umfaßt reine und mit Hydrolyselignin gefüllte Resol- und Novolak-Phenol-Formaldehydharze und Gruppe II Steinkohlenpech und -teer. Es wird festgestellt, daß sich die Mischungen Novolakharz-Pech, Resolharz-Teer und Resolharz-Hydrolyselignin beim Erhitzen nicht wie mechanische Gemische verhalten und eine erhöhte Ausbeute an Koksrückstand liefern. Weiterhin wird gefunden, daß die integrale Endtemperatur der Pyrolyse (T*A) dieser Substanzen als quantitatives Maß für die Ausbeute an Koksrückstand im Anschluß an die Carbonisierung der Proben dienen kann.
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  • 15
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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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  • 16
    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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  • 17
    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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  • 18
    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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  • 19
    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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  • 20
    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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  • 21
    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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  • 22
    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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  • 23
    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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  • 24
    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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  • 25
    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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  • 26
    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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  • 27
    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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  • 28
    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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  • 29
    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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  • 30
    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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  • 31
    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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  • 32
    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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  • 33
    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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  • 34
    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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  • 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: 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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  • 36
    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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  • 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: 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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  • 38
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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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  • 39
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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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  • 40
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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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  • 41
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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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  • 42
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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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  • 43
    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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  • 44
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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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  • 45
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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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  • 46
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    Biopolymers 21 (1982), S. 17-24 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Computer simulation shows that the time required to attain near sedimentation equilbrium is dramatically reduced by a two-step initial loading in which a macromolecular solution at low or zero concentration is layered above one at a higher concentration. To achieve the minimum time requires a good estimate of the molecular weight, but at least a 50% reduction in time can be achieved if the molecular weight of the macromolecule is known only within a factor of 2. Numerical solutions to the differential equation of the ultracentrifuge are calculated using the finite element method. An efficient Gaussian elimination algorithm can be used to minimize calculation time and computer storage requirements.
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  • 47
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    Biopolymers 21 (1982), S. 79-88 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The aldehydes present in acid-soluble type I collagen react with pyrenebutyrylhydrazine to form various types of complexes under different reaction conditions. These complexes exhibit one or more of three different pyrene fluorescence bands: monomer, excimer, and aggregate fluorescence. Collagen, whose aldehydes have been reduced with NaBH4, does not react with this fluorescent hydrazine, confirming that the hydrazine reacts specifically with aldehyde groups to form hydrazones. The absence of a reaction with pepsin-treated collagen also shows that the fluorescent labels are primarily in the nonhelical terminal telopeptides. Upon dialysis, the pyrene label bound to a saturated aldehyde in an α-chain is lost; whereas that bound to an unsaturated aldehyde remains on the protein. The pyrene monomer fluorescence in the β-chain of old collagen is stronger than that of young collagen. The formation of the pyrene excimer fluorescence implies the proximity of two pyrene molecules, probably attached to two adjacent aldehydes. Upon changing from acidic to neutral pH, both excimer and aggregate fluorescence bands disappear within a few seconds, revealing a very rapid alteration at the telopeptides.
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  • 48
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    Biopolymers 21 (1982), S. 147-157 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We describe conditions which lead to complete helix formation of poly(I) in the presence of NH4+. Binding of NH4+ is shown to be specific in the presence of Li+, which does not by itself support helix formation under these conditions. The NH4+-poly(I) complex is characterized by uv, CD, and ir spectroscopy. The CD spectrum is strikingly different from those of the Na+ or K+ complexes, the first extremum being changed from negative for the metal ions to positive for NH4+. A stereospecific model is proposed for the NH4+-poly(I) helix in which the N of NH4+ is located on the axis of the four-stranded helix, midway between planar tetramers formed by the bases. The model is consistent with the tetrahedral symmetry of NH4+, the requirement for four acceptable hydrogen bonds, the observed stability of the helix, and the accepted geometry of the backbone.
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    Biopolymers 21 (1982), S. 159-167 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It has recently been proven that the counterion condensate around an isolated line charge in an electrolyte, as characterized by nonlinear Poisson-Boltzmann theory, is an encapsulating δ-function. Here the identical result is shown to hold in the framework of the polyelectrolyte theory of Fuoss, Katchalsky, and Lifson. The proof fully exploits analytic solutions to the differential equation which are not available for the nonlinear, cylindrical Poisson-Boltzmann equation.
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    Biopolymers 21 (1982), S. 203-218 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The extent and modes of binding of the divalent metal ions Mn2+ and Co2+ to DNA and the effects of salt on the binding have been studied by measurements of the effects of these paramagnetic metal ions on the longitudinal and transverse relaxation rates of the protons of the solvent water molecules, a technique that is sensitive to overall binding. The number of water molecules coordinated to the DNA-bound Mn2+ and Co2+ is found to be between five and six, and the electron spin relaxation times and the electron-nuclear hyperfine constants associated with Mn2+ and Co2+ are little or not affected by the binding. These observations indicate little disturbance of the hydration sphere of Mn2+ and Co2+ upon binding to DNA. An average 2-3-fold reduction in the exchange rate of the water of hydration of the bound metal ions and an order-of-magnitude increase in their rotational correlation time are attributed to hydrogen-bond formation with the DNA. The binding constants of Mn2+ to DNA, at metal concentrations approaching zero, are found to be inversely proportional to the second power of the salt concentration, in agreement with the predictions of Manning's polyelectrolyte theory. A remarkable quantitative agreement with the polyelectrolyte theory is also obtained for the anticooperativity in the binding of Mn2+ to DNA, although the experimental results can be well accounted for by another simple electrostatic model. The various modes of binding of divalent metal ions to DNA are discussed.
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    Biopolymers 21 (1982), S. 265-275 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dc electrical conductivity of films of the polyelectrolyte complexes of glycol chitosan (GlChi) with the sodium salts of dextran sulfate (DS), carboxymethyl cellulose (CMC), polygalacturonic acid (GalUA)n, and alginic acid (AlgA) was measured at temperatures above and below room temperature. The maximum field strength in the thinnest film used amounted to 3 × 104 V/cm. A plot of normalized current against the reciprocal of the absolute temperature revealed two regions with different slopes, and activation energies in these two regions have been obtained for all the complexes. The activation energies in the high-temperature region vary from 0.85 to 1.18 eV and in the low-temperature region from 0 to 0.22 eV. Reasons are given to show that the conductivity is probably ionic. Near room temperature, the current-voltage relation is almost linear in the GlChi-DS complex, while in the other three complexes the current varies as a power n of the voltage with the value of n ranging from 1.7 to 2.5. A rise in temperatures causes an increase in the slope of the log I vs log V plot in GlChi-DS and GlChi-CMC complexes. The nonlinear current-voltage relation is ascribed to a space-charge-limited conductivity.
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    Biopolymers 21 (1982), S. 301-319 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Five different glucomannan samples were recrystallized from dilute solution. Depending on the experimental conditions, the crystals obtained could be identified as corresponding to the mannan I (anhydrous precipitate of more or less regular lozenge-shaped crystals) or mannan II (hydrated gel-forming pseudo-fibrillar precipitate). High-molecular-weight material, low temperature of crystallization, or a polar crystallization medium favored the mannan II polymorph, whereas a low-molecular weight, a high temperature of crystallization, and a crystallization medium of low polarity yielded the mannan I polymorph. Since the base-plane unit-cell dimensions are fairly constant with respect to variation of glucose, it is likely that isomorphous replacement of mannose by glucose occurs in glucomannan crystallization; the data also indicate that perfection of the glucomannan crystals was reduced in specimens having a high glucose:mannose ratio. The oriented crystallization of glucomannan on cellulose microfibrils was also studied under conditions where the mannan I polymorph was obtained. This gave shish-kebab structures that were characterized.
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  • 53
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The primary hydration process of native biopolymers is analyzed in a brief review of the literature, pertaining to various aspects of biopolymer-water systems. Based on this analysis, a hydration model is proposed that implies that the solution conformation of native biopolymers is stable at and above a critical degree of hydration (hp′ = 0.06-0.1 g H2O/g polymer). This water content corresponds to the fraction of strongly bound water, and amounts to ∼20% of the primary hydration sphere. In order to test this model, detailed sorption-desorption scanning experiments were performed on a globular protein (α-chymotrypsin). The results obtained are consistent with the proposed hydration model. They show that under certain experimental conditions, sorption isotherms can be obtained that do not exhibit hysteresis. These data represent equilibrium conditions and are thus accessible to thermodynamic treatment. Valid thermodynamic functions, pertinent to the interaction of water with biopolymers in their solution state, can be obtained from these sorption experiments.
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    Biopolymers 21 (1982), S. 451-458 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The light scattering of bovine serum albumin (BSA) has been measured at protein concentration up to 90 g/L and at pH values between 4.4 and 7.6. The dependence of scattering on both protein concentration and pH may be quantitatively accounted for by a simple extension of the hard-sphere model for protein solutions [Ross, P. D. & Minton, A. P. (1977) J. Mol. Biol. 112, 437-452] allowing for electrostatic repulsions between molecules. According to the extended model, the radius of the effective hard spherical particle representing BSA varies with the net electrical charge of the BSA molecule in a manner which may be calculated from electrostatic theory.
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    Biopolymers 21 (1982), S. 475-497 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A complete analysis of all possible conformations with correct hydrogen bonds of the collagen II type was performed on the basis of developed simultaneous equations. Using a unimodal search (by varying Ψ3), the energetically favorable structure was obtained. No other energetically satisfactory structural solutions are possible. The next aim was to obtain a precise model of the molecule. The program used includes a subroutine for continual deformation of the pyrrolidine rings. The set of parameters determining the structure consists of 14 independent variables (8 dihedral and 6 bond angles). As starting points for the energy optimization, conformations produced by scanning and some structures from previous work were used. The final structures (practically the same for both polymers) have helix parameters h = 0.285 nm and t = 52°, which are in excellent agreement with the 7/2 symmetry of diffraction data. The conformations of the pyrrolidine rings are of the B type, i.e., C2-Cβ-exo-Cγ-endo. For both polypeptides, the conformations of imino acids in position 3 of the triplet are the same; in position 2, however, they are slightly different. The difference in diffraction patterns for the 7/2 and 10/3 helices is discussed.
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    Biopolymers 21 (1982), S. 547-563 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The CD spectrum of the enzyme adenylate kinase has been investigated. Theoretical calculations, based on the x-ray crystal structure, have been carried out by means of an origin independent matrix formalism. The entire molecule was included in the calculations in the sense that essentially all electronic transitions that occur at wavelengths longer than 185 nm were included in the basis set. A linear dielectric function was utilized to evaluate the intertransition coupling potentials. The results of the theoretical calculations were in reasonable agreement with experimental CD spectra of the molecule.
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    Biopolymers 21 (1982), S. 633-652 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mode of action of many antitumor agents entails the inhibition of nucleic acid synthesis. Because many of the drugs can intercalate, it is assumed that intercalation is an important step in the mechanism of biological activity. As intercalants contain a planar chromophore as an ingredient essential for intercalation, chromophores that should fit into DNA are desired. This is the main theme of this investigation. Binding to DNA of fundamental moieties, protonated pyridine, aniline, phenol, quinone, and 4H-thiopyran-4-one, is studied to determine their optimum placement in DNA. The optimum orientations for each moiety are superimposed to form polyaromatic systems that can intercalate in a manner in which functional groups on these chromophores are oriented as in the moieties themselves. Ideal intercalants proposed contain three and four fused ring system, have protonated ring nitrogen atoms located to maximize the electrostatic interactions with DNA, hydroxy and amino groups that can hydrogen bond to the OII and O5′ phosphate backbone atoms, and carbonyl and sulfur groups in the central position of the ring system to provide variations in the chromophore and to interact with the relatively positive region in the intercalation site. The optimum orientation occurs when the chromophore and the base pairs overlap to the maximum extent. The ideal intercalants are fundamentally of the type:
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    Biopolymers 21 (1982), S. 665-677 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: DNA reassociation kinetics using the phenol emulsion reassociation technique (PERT) [Kohne, D. E., Levison, S. A. & Byers, M. J. (1977) Biochemistry 16, 5329-5341] has been investigated at high DNA concentrations using an endonuclease S1 assay of reaction progress. Apparent second-order rate constants fall on two intersecting straight lines when presented as a function of DNA concentrations on a log-log plot. In the low DNA concentration range, the rate constants drop about 10-fold when concentration increases 1000-fold. In the high DNA concentration range, the rate constants drop more than 10-fold when concentration increases 10-fold. The slopes of these lines are the same in different solvents and at different temperatures. The intersection between the lines occurs when the available catalytic surface is saturated. At high DNA concentrations, high-complexity heterologous denatured DNA apparently competes 2-4 times better for the surface than homologous DNA because it does not participate in a reassociation reaction. Native and partially native DNA molecules cannot compete with single-stranded DNA for a saturated surface. At high DNA concentrations, reactions using PERT become dependent on the single-strand DNA length. Increasing length lowers reassociation rates.
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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  • 60
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    Biopolymers 21 (1982), S. 859-872 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Classical potential functions (CPF) calculations on 3′-mononucleotides, the building blocks of nucleic acids, predict a correlation between the sugar ring pucker and the torsion angle Φ′ around the C3′—O3′ bond. In ribonucleotides, the value of Φ′ depends on the sugar pucker, viz. the C2′-endo sugar pucker is associated with Φ′ = 210° and 270°, while the C3′-endo sugar pucker favors only Φ′ = 210°. On the other hand, in deoxyribonucleotides, both sugar puckers show a preference for Φ′ = 180°. These theoretical predictions are fully corroborated by the results obtained from x-ray and nmr studies on mono-, di-, and polynucleotides.
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  • 61
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The effect of several surfactants on the secondary structure of bovine β-lactoglobulin B was determined from the circular dichroism spectra. The spectra were measured at several concentrations of surfactant ranging from 1 mg/mL to the critical micelle concentration. The surfactants studied were sodium dodecyl, decyl, and octyl sulfate, sodium dodecyl sarcosinate, dodecyltrimethylammonium bromide. The data were analyzed using the method of Chen et al. [Biochemistry (1974) 13, 3350-3359] to determine the percentage of α-helix, β-sheet, and unordered form at each surfactant concentration. In every case, an increase in structured form and a 20-25% decrease in the amount of unordered form was noted when the surfactant concentration reached the critical micelle concentration. However, the relative amounts of the two structured forms present depend on the surfactant used. The profile of the secondary structure of the protein also varied from surfactant to surfactant as the protein was titrated, probably reflecting the delicate balance between ionic and nonionic forces that governs the secondary structure of β-lactoglobulin and most other globular proteins in aqueous solution.
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  • 62
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Amino acids are known to differ in their individual preferences for each of the four positions of the β-turn conformation formed by tetrapeptide segments. Proline and glycine show relatively high preferences for positions 2 and 3, respectively, of the β-turn. Using tripeptides of the type N-acetyl-Pro-Gly-X-OH, where X = Gly, Ala, Leu, Ile, and Phe, we have sought to study the influence of the 4th residue X on the stability of the β-turn conformation in these tripeptides. Our nmr and CD results show that the β-turn stability is quite significantly governed by the nature of the amino acid residue at this position in the following order: Leu 〉 Ala 〉 Ile, Gly 〉 Phe.
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  • 63
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    Biopolymers 21 (1982), S. 1153-1166 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermodynamic studies of the binding of adamantanecarboxylate to cyclodextrins have been made as a function of temperature and added organic cosolvent (methanol) using flow microcalorimetry. The negative heat capacity change associated with the adamantanecar-boxylate/β-cyclodextrin interaction and the fact that the interaction is weakened by the addition of methanol implicate the binding process as being a hydrophobically driven one. The negative enthalpy change (ΔH0 = -5.5 kcal/mol) and near-zero entropy change (ΔS0 = 1.5 cal/mol deg) are quite different from the values normally expected for a hydrophobic bond, indicating that other bonding forces are important in addition to the hydrophobic effect. The relative contribution of the hydrophobic effect and other bonding forces (most likely van der Waals forces) to the overall binding was judged from an analysis of the dependence of the thermodynamics of the association process on the surface tension of the water-methanol mixtures following a model for “solvophobic” bonding described by Sinanoglu [Molecular Associations in Biology (1968) Academic Press, New York, pp. 427-445]. From this analysis, adamantane-carboxylate/cyclodextrin complex formation is found to be driven to the extent of -1.9 kcal/mol by the hydrophobic effect. Furthermore, the hydrophobic driving force is found to be characterized by a positive ΔS0 of 10 cal/mol deg. The remaining free energy of binding (and the ΔH0 of binding of ∼-6 kcal/mol) is then due to the intrinsic (surface-tension-independent) van der Waals interaction between the ligand and cyclodextrin cavity.
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    Biopolymers 21 (1982) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 65
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Pivaloyl-L-Pro-Aib-N-methylamide has been shown to possess one intramolecular hydrogen bond in (CD3)2SO solution, by 1H-nmr methods, suggesting the existence of β-turns, with Pro-Aib as the corner residues. Theoretical conformational analysis suggests that Type II β-turn conformations are about 2 kcal mol-1 more stable than Type III structures. A crystallographic study has established the Type II β-turn in the solid state. The molecule crystallizes in the space group P21 with a = 5.865 Å, b = 11.421 Å, c = 12.966 Å, β = 97.55°, and Z = 2. The structure has been refined to a final R value of 0.061. The Type II β-turn conformation is stabilized by an intramolecular 4 → 1 hydrogen bond between the methylamide NH and the pivaloyl CO group. The conformational angles are φPro = -57.8°, ψPro = 139.3°, φAib = 61.4°, and ψAib = 25.1°. The Type II β-turn conformation for Pro-Aib in this peptide is compared with the Type III structures observed for the same segment in larger peptides.
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    Biopolymers 21 (1982), S. 1333-1363 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The folding-unfolding process of reduced bovine pancreatic trypsin inhibitor was investigated with an idealized model employing approximate free energies. The protein is regarded to consist of only Cα and Cβ atoms. The backbone dihedral angles are the only conformational variables and are permitted to take discrete values at every 10°. Intraresidue energies consist of two terms: an empirical part taken from the observed frequency distributions of (φ,ψ) and an additional favorable energy assigned to the native conformation of each residue. Interresidue interactions are simplified by assuming that there is an attractive energy operative only between residue pairs in close contact in the native structure. A total of 230,000 molecular conformations, with no atomic overlaps, ranging from the native state to the denatured state, are randomly generated by changing the sampling bias. Each conformation is classified according to its conformational energy, F; a conformational entropy, S(F) is estimated for each value of F from the number of samples. The dependence of S(F) on energy reveals that the folding-unfolding transition for this idealized model is an “all-or-none” type; this is attributable to the specific long-range interactions. Interresidue contact probabilities, averaged over samples representing various stages of folding, serve to characterize folding intermediates. Most probable equilibrium pathways for the folding-unfolding transition are constructed by connecting conformationally similar intermediates. The specific details obtained for bovine pancreatic trypsin inhibitor are as follows: (1) Folding begins with the appearance of nativelike medium-range contacts at a β-turn and at the α-helix. (2) These grow to include the native pair of interacting β-strands. This state includes intact regular secondary conformations, as well as the interstrand sheet contacts, and corresponds to an activated state with the highest free energy on the pathway. (3) Additional native long-range contacts are completely formed either toward the amino terminus or toward the carboxyl terminus. (4) In a final step, the missing contacts appear. Although these folding pathways for this model are not consistent with experimental reports, it does indicate multiple folding pathways. The method is general and can be applied to any set of calculated conformational energies and furthermore permits investigation of gross folding features.
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  • 67
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Peptide NH chemical shifts and their temperature dependences have been monitored as a function of concentration for the decapeptide, Boc-Aib-Pro-Val-Aib-Val-Ala-Aib-Ala-Aib-Aib-OMe in CDCl3 (0.001-0.06M) and (CD3)2SO (0.001-0.03M). The chemical shifts and temperature coefficients for all nine NH groups show no significant concentration dependence in (CD3)2SO. Seven NH groups yield low values of temperature coefficients over the entire range, while one yields an intermediate value. In CDCl3, the Aib(1) NH group shows a large concentration dependence of both chemical shift and temperature coefficient, in contrast to the other eight NH groups. The data suggest that in (CD3)2SO, the peptide adopts a 310 helical conformation and is monomeric over the entire concentration range. In CDCl3, the 310 helical peptide associates at a concentration of 0.01M, with the Aib(1) NH involved in an intermolecular hydrogen bond. Association does not disrupt the intramolecular hydrogen-bonding pattern in the decapeptide.
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    Biopolymers 21 (1982), S. 1469-1472 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 21 (1982), S. 1479-1487 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A formalism for extracting the conformations of a proline ring based on the bistable jump model of R. E. London [(1978) J. Am. Chem. Soc. 100, 2678-2685] from 13C spin-lattice relaxation times (T1) is given. The method is such that the relaxation data are only partially used to generate the conformations; these conformations are constrained to satisfy the rest of the relaxation data and to yield acceptable ring geometry. An alternate equation for T1 of 13C nuclei to that of London is given. The formalism is illustrated through an example.
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    Biopolymers 21 (1982), S. 1521-1534 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have used broadline proton magnetic resonance to study molecular motion in cellulose, a sodium pectate solution, a calcium pectate gel, and isolated bean cell walls. All samples were prepared in D2O to minimize the contribution of water to the observed signals. For each sample, a free induction decay was obtained, and the second moment, spin-lattice relaxation, and dipolar relaxation were measured. Our results show that the large majority of protons in cellulose are immobile. Rigid and mobile domains were also observed in the pectate samples. We have shown that gelation induces large-scale changes in the free induction decay, the second moment, and the relaxation behavior of the pectate. As with the other samples, rigid and more mobile domains were found in bean cell walls. The fraction in the rigid domains is much larger than the fraction of cellulose in the sample, suggesting that the noncellulosic wall components are also organized into rigid and mobile domains.
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  • 71
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Conformational energy computations were carried out on collagenlike triple-stranded conformations of several poly(tripeptide)s with the general structure CH3CO—(Gly—X—Y)3—NHCH3. The sequences considered had various amino acid residues in position X or Y of the central tripeptide, with either Pro or Ala as a neighbor, i.e., Gly-X-Pro, Gly-X-Ala, Gly-Pro-Y, and Gly-Ala-Y. Minimum-energy conformations were computed for the side chains, and their distributions were compared for the four sequences. The residues used were Abu (= α-aminobutyric acid), Leu, Phe, Ser, Asp, Asn, Val, Ile, and Thr. The conformational energy of a —Ch2—CH3 side chain in Abu was mapped as a function of the dihedral angle χ1. Intrastrand interactions with neighboring residues do not affect the conformations of a side chain in position Y, and they have a minor effect on it in the X-Ala sequence, but they strongly restrict the conformational freedom of the side chain in the X-Pro sequence. Conversely, interstrand interactions do not affect side chains in position X, but they strongly restrict the conformational freedom of a side chain in position Y if there is a nearby Pro residue in a neighboring strand. Hydrogen bonds with the backbone can be formed in some conformations of long polar side chains, such as Asp, Asn, or Gln. All amino acid residues can be accommodated in collagen. Because of the interactions mentioned above, steric and energetic constraints can be correlated with observed preferences of certain amino acids for positions X or Y in collagen. Hence, these preferences may be explained, in part, in terms of differences in the conformational freedom of the side chains in the triple-stranded structure.
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    Biopolymers 21 (1982), S. 1657-1666 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ionization constants of the tyrosyl groups of chymotrypsinogen and of nitrated-chymotrypsinogen (two tyrosyl residues nitrated) have been determined by difference spectrophotometry. In chymotrypsinogen, two of the four tyrosyl groups ionize without any time dependence. Above pH greater than ca. 12.5, time-dependent spectral changes are seen for 0.7 group equivalent. The data can be fitted to the values of pK′1 9.75 ± 0.07, pK′2 11.55 ± 0.05, pK′3 13.30 ± 0.05. In nitrated-chymotrypsinogen, the two nitrated tyrosyl residues have pK′1 6.44 and pK′2 8.30. For both proteins, these pK′ values are in agreement with those evaluated from potentiometric titration and calorimetric data using computer-assisted curve-fitting analysis.
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    Biopolymers 21 (1982), S. 2195-2203 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformation of several samples of poly(α,β-L-Asp) with a molar fraction of β-bonds ranging from 0.1 to 0.55 was investigated by means of ir and CD spectroscopy and potentiometric titration and compared with the results obtained previously with poly(α-L-Asp). All samples investigated underwent a conformational change induced by changes in their degree of ionization: unpronounced ir absorption of amide V at 650 cm-1 was shifted to 620 cm-1 and substantially increased on deionization; CD spectra changed with the degree of ionization, passing through an isosbestic point; and the pattern of the titration curves was more complex than that of a simple polyelectrolyte. The conformation developing with the decreasing degree of ionization may be considered to be α-helix, as deduced according to the analogous behavior of other polypeptides. The extent of the conformational change in the individual samples depends on the molar fraction of β-bonds: the higher it is, the lower is the helix-forming ability of the sample.
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    Biopolymers 21 (1982), S. 2225-2239 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The use of 1H-nmr spectroscopy is demonstrated to be a useful analytical method to characterize the structure of synthetic peptides attached to soluble, macromolecular polyoxyethylene (POE) supports in the liquid-phase method (LPM) of peptide synthesis. We report an extensive 360-MHz 1H-nmr study of POE-bound homo-oligo-L-methionine peptides. A combination of high field and selective saturation or Redfield pulse methods allows resolution of individual backbone NH and α-CH resonances of dilute peptides in the presence of strong resonances from macromolecular POE and/or protonated solvents. The nmr spectra for the POE-bound peptides in CDCl3 are qualitatively similar to those of the low-molecular-weight Boc-L-Metn-OMe peptide esters. This corroborates other observations that POE has little effect on peptide stucture. The backbone α-CH region of peptides is overlapped by signals from the terminal oxyethylene group of POE, but the peptide side-chain and low-field backbone NH resonances are well resolved. In trifluoroethanol the Boc-(L-Met)n-NH-POE heptamer and octamer adopt the right-handed α-helical structure, and the present nmr studies provide evidence for two strong intramolecular hydrogen bonds to stabilize the helices. In water, the N-deblocked derivatives, (L-Met)n-NH-POE oligomers adopt β-sheet structure and manifest well-resolved nonequivalent NH resonances with 6-7 Hz 3JNH-CH coupling constants.
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    Biopolymers 21 (1982), S. 2241-2252 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The concerted model of Monod, Wyman, and Changeux is generalized so that all effects of interactions for an enzyme operating at a nonequilibrium stationary state are considered. In contrast to the original model, which is based on an analogy to equilibrium ligand binding, the generalization may show both “positive” and “negative cooperativity” in both catalytic binding and conformational processes. Furthermore, in contrast to any equilibrium binding model, the Hill coefficients may be greater than the number of sites n. For catalysis, the maximum value is 2n, and for conformational changes, n + 1. These points are illustrated by two cases that yield simpler analytic expressions. The first obtains when catalysis occurs on a much faster time scale than the conformational changes, and the second, when this situation is reversed.
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    Biopolymers 21 (1982), S. 2315-2316 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 21 (1982), S. 1473-1477 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 21 (1982) 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 21 (1982), S. 1503-1520 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By combining gel permeation chromatography (GPC) and light-scattering spectroscopy, including photon correlation and angular distribution of absolute scattered intensity, we were able to characterize immunologically active Haemophilus influenzae type b polysaccharide (HIB Ps) bovine serum albumin (BSA) conjugates in terms of equivalent hydrodynamic radius rh ∼ (6.2 ± 0.6) × 102 Å, apparent radius of gyration rg ∼ (5.4 ± 0.3) × 102 Å, apparent molecular weight Mw ∼ (3.5 ± 0.4) × 106 g/mol, and a second virial coefficient A2 ∼ (1.9 ± 0.3) × 10-4 cm3 mol/g2. We could study the effects of each of the processes in the conjugate formation according to the following procedure: BSA (dialysis, modification, fractionation) + HIB Ps → HIB Ps/BSA conjugate (conjugate formation, fractionation). Narrow distributions of HIB Ps BSA conjugate formation can be achieved using fractionated BSA.
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    Biopolymers 21 (1982), S. 1569-1586 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have measured the ir absorption of 5′CMP, 5′IMP, and poly(I)·poly(C) from ∼25 to ∼500 cm-1. From a comparison of the data with the previously measured absorption of the corresponding nucleosides and bases we can identify several “lines” associated with the deformation of the ribose ring. Out-of-plane deformation of the bases contributes strongly to vibrations near 200 cm-1. The same ribose vibrations observed in the nucleotides are found in poly(I)·poly(C). They sharpen with increasing water absorption. A study of the spectra of poly(I)·poly(C) as a function of the adsorbed water indicates that water does not contribute in a purely additive fashion to the polynucleotide spectrum but depends on the conformation of the helix. However, the only spectral feature that shifts drastically with conformation is near 45 cm-1. Measurements at cryogenic temperatures indicate some sharpening of the spectrum of poly(I)·poly(C). Instead, no sharpening is observed in the spectrum of the nucleotides. Shear degradation of poly(I)·poly(C) produces significant spectral changes in the 200-cm-1 region and sharpening of the features assigned to the low-frequency ribose-ring vibrations.
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    Biopolymers 21 (1982), S. 1735-1747 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of the oxygen replacement reaction of carbon monoxide-saturated hemoglobin (HbA0) was carried out using spectroscopic, calorimetric, and pH titration methods. Under fully saturated conditions the replacement reaction can be defined by a single partition constant over all ratios of bound oxygen to carbon monoxide. This indicates that under saturating conditions Haldane's first law for the ligand binding of gas mixtures holds for any CO/O2 ratio. It further shows that there is no appreciable difference in relative CO-O2 affinity between the α- and β-chains. The same partition coefficient was found to hold for different pH, buffer, and allosteric effector conditions. The lack of any pH dependence of the partition coefficient was confirmed by the absence of proton changes for the replacement reaction. The temperature dependence of the partition coefficient and calorimetric results yield a value for the enthalpy of the reaction of -3.65 ± 0.29 kcal/mol/heme.
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    Biopolymers 21 (1982), S. 1763-1780 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We demonstrate that the isotropic absorption and linear dichroism in an unknown flow field can be used to determine base tilt in polynucleotides if three transitions are measured and the directions of the corresponding dipoles are known. The method is applied here to reach conclusions about the base tilt in poly(rA), poly(rA)+·poly(rA), and poly(rC). The respective values are: 28° tilt about the axis + 50° toward C8 from the C1′ → N9, and 25° tilt about the axis + 118° toward C5 from C1′ → N1. The results for poly(rA)+·poly(rA) are consistent with the accepted model. Spectra were measured for poly(rC)+·poly(rC), but definite conclusions must await reliable directions for transition dipoles. The dipole direction for the 218-nm transition in rC is found to be +13° or +43° toward C5 from C1′ → N1. The CD spectra to about 168 nm are presented and discussed.
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    Biopolymers 21 (1982), S. 1811-1832 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Measurements of stress relaxation in uniaxial extension and associated time-dependent birefringence have been made on bovine fibrin film, prepared by gentle compaction of coarse fibrin clots, containing 13-22% fibrin plasticized with either aqueous buffer or glycerol. Both unligated and ligated (i.e., with α-α and γ-γ ligation by fibrinoligase, factor XIIIa) films were studied. Both types showed two stages of stress relaxation, with time scales of approximately 10 and 103-104 s, respectively, with a plateau region between. In the plateau, the nominal (engineering) stress for ligated glycerol-plasticized film is proportional to In λ, where λ is the stretch ratio, up to λ ≅ 2, and it decreases with increasing temperature. For unligated glycerol-plasticized film, the stresses are smaller by a factor of one-half to one-third. For ligated film, the second stage of relaxation is relatively slight, and recovery after release of stress is often nearly complete. For unligated film, the second stage involves a substantial drop in stress, and after recovery there is a significant permanent set. A second relaxation for ligated film reproduces the first, but for unligated film it reproduces the first only if the initial relaxation is terminated before the second stage; otherwise, the second relaxation shows a weaker structure. The behavior of water-plasticized film is similar to that of glycerol-plasticized except that the second stage of relaxation occurs at shorter times. During the first stage of stress relaxation, up to about 100 s, the birefringence and the stress-optical coefficient increase; during the plateau zone of stress relaxation, the birefringence of ligated films is approximately constant and is proportional to 2λ2/(λ2 + 1) - 1, where λ is the stretch ratio. This dependence is predicted by a two-dimensional model in which rodlike elements in the plane of the film are oriented with independent alignment. During the final stage of stress relaxation, the birefringence of ligated films decreases slightly; that of unligated films decreases substantially, but less rapidly than the stress, corresponding to a further increase in the stress-optical coefficient. With additional information from small-angle x-ray scattering reported in an accompanying paper, the first stage of relaxation is attributed to partial release of bending forces in the fibers by orientation, accompanied by increased birefringence. The second stage is attributed, for ligated films, to an internal transition in the fibrin units accompanied by elongation of some of the fibers; and in the unligated films, to a combination of the latter transition with slippage of protofibrils lengthwise within the fiber bundles that causes some loss of orientation, which diminishes the birefringence.
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  • 84
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    Biopolymers 21 (1982), S. 1899-1908 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A microscope capable of measuring the CD of intact single eukaryotic cells, DNA microcrystals, and other microscopic structures has been constructed and tested. It can measure the CD spectra in the 200- and 800-nm wavelength range and consists of a modification to a standard Cary 60 CD machine in combination with a Zeiss uv microspectrometer. Preliminary CD spectra of red blood cells and lymphocytes are presented.
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  • 85
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    Biopolymers 21 (1982), S. 1909-1926 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The distribution of fibers in agarose gels has been studied by electron-microscopic examination of replicas formed from freeze-fracture surfaces. For gels set in water, the results obtained support the model proposed for the gel structure by Arnott et al. (1974) of a random array of long, straight, connected fibers, with each fiber having a diameter equivalent to that of an aggregate of approximately 10-30 agarose helixes, depending on the initial agarose concentration. The density of these fibers, their water content, and the total length of fibers per unit volume have been derived from the measured distribution of intersections per unit area of freeze-fracture surfaces. For gels set in the presence of salt, the distribution of fibers becomes distinctly non-Poissonian, leading to larger interfiber spaces and a gel of greater effective pore size. The larger pore size of gels set in the presence of salt also has been revealed by electrophoretic measurements in which the relative migration rates of plasmid DNA molecules of varying conformations have been determined.
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  • 86
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    Biopolymers 21 (1982), S. 1933-1943 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Energy embedding has been shown recently to be a useful extension of the distance geometry approach to conformational calculations in the case of very small molecules and simple energy functions. This paper tests the ability of energy embedding to locate low energy conformations satisfying both weak and strong geometric constraints when the molecule is the small protein, bovine pancreatic trypsin inhibitor, and the energy function is the complicated Oobatake-Crippen residue-residue potential. Using the potential function alone, the algorithm reaches a structure with energy lower than that of the native conformation, but with little resemblance to it. Aided by numerous geometric constraints, such as preformed secondary structure segments, the algorithm again finds a local minimum with energy better than that of the native, and with only 3.3 Å rms deviation from it. This is significantly closer to the native value than can be obtained using standard distance geometry and the geometric constraints alone. Thus, energy embedding using the Oobatake-Crippen potential function is a significant help in finding native conformations of proteins. However, additional trials on a hairpin bend fragment of trypsin inhibitor demonstrate the potential's shortcomings in encouraging proper secondary structure.
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  • 87
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular-mechanics calculations have been carried out on the base-paired deoxy dodecanucleoside undecaphosphates d(CGCGAATTCGCG)2 and d(A12)·d(T12). These refinements were carried out using the model-built Arnott B-DNA geometry as initial coordinates (with a helix repaeat of 10.0 residues/turn), as well as helix repeats ranging from 9 to 12 residues/turn. There was some variation in the optimum calculated helix repeat, depending on the dielectric model, the presence or absence of counterions, and the method used for inclusion for nonbonded interactions; the most interesting general result of these calculations was the coupling between furanose sugar puckering and twist. This coupling was observed for all models. With a helix repeat of 9.0 residues/turn, all sugars remain C(2′)endo after refinement; as the helix repear increases to 12.0 residues/turn, the number of sugars repuckering to O(1′)endo and C(3′)endo increases also. With our most rigorous model (i.e., a model with no cutoff distance for nonbonded interactions) and a helix repeat of 10.0 residues/turn, we find a greater tendency for pyrimidine than purine repuckering in d(CGCGAATTCGCG)2, in agreement with the x-ray structural data of Drew et al. [(1981) Proc. Natl. Acad. Sci. USA 78, 2179-2185].We also carried out a number of calculations in which we “forced” one of two deoxy sugars to repucker or one of the C3′-O3′-P-O5′ (ω) torsion angles to change from gauche- to trans using dihedral angle constraints. After the constraints were removed, some of these structures “reverted” to the sugar pucker of the initial structures, while others remained repuckered. In all cases, the energies for repuckered structures after refinement were very similar to energies of the initial structure. Experiments and theory suggest that local conformational fluctuations play an essential role in nmr relaxation of 31P and 13C atoms in double-helical DNA. The results of our previous calculations on hexanucleoside phosphates and the calculations presented there are consistent with an important contribution to nmr relaxation processes of conformational changes in the torsion angle ω′ from gauche- to trans and deoxy sugar repuckering from C(2′)endo to C(3′)endo. Specifically, the calculations presented here indicate a very flexible phosphate backbone in helixes having an intermediate helix repeat of 10 to 11 residues/turn. These helixes may accommodate sugars of variable pucker without significantly disrupting base-base hydrogen-bonding and stacking interactions. All of the variant structures are similar in energy, suggesting that conversion between them can occur on a nanosecond time scale, as observed in nmr relaxation experiments.
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  • 88
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The microwave absorption of aqueous solutions of DNA extracted from E. coli has been studied between 8 and 12 GHz by the use of an optical heterodyne technique. By measuring optically the temperature rise produced in an absorbing sample by pulsed microwave radiation, unambiguous, direct measurement of the microwave absorption is possible. Our results show that E. coli DNA absorbs microwaves in the 8-12-GHz region substantially more efficiently than water, which is itself an extremely efficient absorber. The observed absorption is featureless and decreases slightly with increasing frequency. These observations are consistent with an explanation involving direct absorption by longitudinal acoustic modes of the double helix.
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  • 89
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    Biopolymers 21 (1982), S. 251-263 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The formation of polyelectrolyte complexes of glycol chitosan (GlChi) with sodium salts of dextran sulfate (DS), carboxymethyl cellulose (CMC), polygalacturonic acid (GalUA)n, and alginic acid (AlgA) has been studied. The number of ionizable groups per pyranose ring and the degree of dissociation as a function of pH in the polycation and polyanions have been determined using conductometric and potentiometric titrations. The formation of the complexes at different pH values has been followed by turbidity measurements. It is found that stoichiometric complexes of the polycation with CMC, (GalUA)n, and AlgA are formed at a mixing ratio of 0.5, indicating that the conformation may correspond to chains of equal lengths. In the case of the complex of GlChi with DS, the stoichiometric composition corresponds to a mixing ratio of 0.62. Thin transparent films of the complexes have been obtained by dehydration under reduced pressure on a layer of mercury. The dielectric constant ε′ and loss ε″ of thin films of these complexes have been measured in the range of frequencies of 1-100 kHz at different temperatures above and below room temperature. The GlChi-DS complex shows very little change in the values of ε′ and ε″ with frequency or temperature. On the other hand, films of GlChi-CMC and GlChi-(GalUA)n complexes show a significant increase in ε′ and ε″ as the temperature is increased above room temperature. The increase is more prominent at low frequencies. This behavior is attributed to the Maxwell-Wagner interfacial polarization. In the case of GlChi-AlgA film, the values of ε′ and ε″ increase enormously as the temperature increases. This behavior is similar to the increase in ε′ and ε″ observed by Michels et al. [(1965) J. Phys. Chem. 69, 1456-1465] as the salt concentration increases in another polyelectrolyte complex studied by them. The electric double-layer mechanism proposed by Schwarz [(1962) J. Phys. Chem. 66, 2636-2642] to account for the dielectric properties of biocolloids is shown to account quantitatively for the observations on the GlChi-AlgA film.
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  • 90
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    Biopolymers 28 (1989), S. 773-781 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A second example of insertion of a water molecule into the helical backbone of an apolar peptide is presented here and compared to a similar occurrence in a longer peptide with the same type of sequence of residues, i.e., Boc-Aib-(Ala-Leu-Aib)3-OMe. The backbone of the title compound assumes an approximate 310-helical form with three 4 → 1 hydrogen bonds. In the place of a fourth 4 → 1 hydrogen bond, a water molecule is inserted between O(1) and N(4), and acts as a bridge by forming hydrogen bonds N(4) … W(1) (2.95 Å) and W(1) … O(1) (2.81 Å). The water molecule participates in a third hydrogen bond with a neighboring peptide molecule, W(1) … O(4) (2.91 Å). The insertion of the water molecule causes the apolar peptide to mimic an amphiphilic helix. Crystals grown from ethyl acetate/petroleum ether (reported here) or from methanol/water solution are in space group P212121 with a = 12.024(4) Å, b = 15.714(6) Å, c = 21.411(7) Å, Z = 4 and dcalc = 1.124 g/cm3 for C32H58N6O9 · H2O. The overall agreement factor R is 6.3% for 2707 reflections observed with intensities 〉 3σ(F) and the resolution is 0.90 Å.
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  • 91
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chemical shifts of base and H1′ protons of the single-stranded hexamers d(ATTACC) and d(GGTAAT), of the 1 : 1 mixtures of these complementary hexamers, and of the self-complementary dodecamer d(ATTACCGGTAAT) were measured at various temperatures in aqueous solution. Four different sample concentrations were used in the case of the dodecamer and of the mixture of the complementary hexamers; the individual hexamers were measured at two different DNA concentrations. Absorbance temperature profiles at five different NaCl concentrations were measured for the dodecamer in order to quantify the effect of the ionic strength on the duplex formation.Under suitable conditions of nucleotide concentration, temperature, and ionic strength, the dodecamer adopts either a B-DNA duplex or a hairpin-loop structure. Chemical shift vs temperature profiles, constructed for all samples, were used to obtain thermodynamic parameters either for the various stacking interactions in the single strands or for the duplex or the hairpin-loop formation. In the analysis of the duplex formation of the hexamers, a two-state approach appeared too simple, because systematic deviations were revealed. Therefore, a new three-state model (DUPSTAK) was developed. In order to investigate the magnitude of error arising from the use of the two-state approach in cases where the DUPSTAK model appears more appropriate, a series of test calculations was made. The magnitude of error in the enthalpy and in the entropy of duplex melting is found to depend linearly upon the actual melting temperature and not upon the individual ΔHOd and ΔSOd values.Thermodynamic analysis of the chemical shift vs temperature profiles in D2O solution (no added salt) yields an average Tmd value of 341 K (1M DNA) and ΔHOd of -121 kJ · mol-1 for the dimer/random-coil transition of the hexamer duplex d(ATTACC) · d(GGTAAT). For the duplex ⇄ random-coil transition of the 12-mer d(ATTACCGGTAAT) an average Tmd value of 336 K (1M DNA) and ΔHOd of -372 kJ · mol-1 are found. The hairpin/random-coil transition of d(ATTACCGGTAAT) is characterized by a rather large ΔHOh value, -130 kJ · mol-1, and an average Tmh value of 304 K.
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  • 92
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A computational method is elaborated for studying the water environment around regular polynucleotide duplexes; it allows rigorous structural information on the hydration shell of DNA to be obtained. The crucial aspect of this Monte Carlo simulation is the use of periodical boundary conditions. The output data consists of local maxima of water density in the space near the DNA molecule and the properties of one- and two-membered water bridges as function of pairs of polar groups of DNA.In the present paper the results for poly(dG) · poly(dC) and poly(dG-dC) · poly(dG-dC) are presented. The differences in their hydration shells are of a purely structural nature and are caused by the symmetry of the polar groups of the polymers under study, the symmetry being reflected by the hydration shell.The homopolymer duplex hydration shell mirrors the mononucleotide repeat. The water molecules contacting the polynucleotide in the minor groove are located nearly in the plane midway between the planes of successive base pairs. One water molecule per base pair forms a water bridge facing two polar groups of bases from adjacent base pairs and on different strands making a “spine”-like structure. In contrast, the major groove hydration is stabilized exclusively by two-membered water bridges; the water molecules deepest in the groove are concentrated near the plane of the corresponding base pair.The alternating polymer is characterized by a marked dyad symmetry of the hydration shell corresponding to the axis between two successive base pairs. The minor groove hydration of the dCpdG step resembles the characteristic features of the homopolymer, but the bridge between the O2 oxygens of the other base-stacking type is formed by two water molecules. The major groove hydration is characterized by high probability of one-membered water bridges and by localization of a water molecule on the dyad axis of the dGpdC step.The found structural elements are discussed as reasonable invariants of a dynamic hydration shell.
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  • 93
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    Biopolymers 28 (1989) 
    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: We report dynamic light scattering measurements over a wide range of scattering vectors for fractionated samples of porcine submaxillary mucin (PSM) glycoproteins in two different solvents: 0.1M NaCl, and 6M GdnHCl. The relaxation spectrum has been successfully resolved into a slow mode corresponding to pure translational diffusion and a fast mode containing information on the relaxation times for intramolecular motion. Analysis of the slow mode permits a light scattering evaluation of the polydispersity of these high molecular weight mucin glycoprotein fractions. Determination of the longest intramolecular relaxation times τ1 shows that these are much longer for the PSM fractions in 0.1M NaCl compared to 6M GdnHCl. These data are consistent with earlier studies showing that the chain conformation is the same in both solvents, but that in 0.1M NaCl, the PSM glycoprotein undergoes a self-association process that is end-to-end in nature. Since the τ1 value is intimately related to the viscoelastic behavior of PSM solutions and gels, it is interesting to speculate that the end-to-end association process may be physiologically important.
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  • 95
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    Biopolymers 28 (1989), S. 835-849 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Theoretical computations are performed of the intercalative binding to a model d(CpG)2 minihelix of 7-H pyrido[4.3C]carbazole, the precursor of the antitumor bisintercalating drug ditercalinium. The conformations of the intercalation site are generated by the AGNAS procedure (algorithm to generate nucleic acid structures) of Miller and co-workers. The ligand-nucleotide interactions and the nucleotide conformational energies are computed with the SIBFA procedures (sum of interactions between fragments ab intio computed), which use formulas of empirical origin that reproduce ab initio SCF (self-consistent field) computations. Among the candidate intercalation sites most favored energetically, one has a pattern of conformational angles related to the one determined crystallographically by Sobell et al. in a series of x-ray structural studies of small intercalator-dinucleotide monophosphate complexes. Optimal values of the unwinding angle, found in the range of -12° to -14°, are consistent with available experimental data on DNA.
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  • 96
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of concanavalin A (Con A) on the thermotropic behavior of positively charged, glycosyl-free lipids and their mixtures with zwitterionic lipids was investigated by differential scanning calorimetry.The gel to liquid-crystal phase transition enthalpy of pure dipalmitoylcholine (DPC) was found to be significantly increased in the presence of Con A (ΔH = 31.2 and 42.5 KJ mol-1 lipid in the presence and in absence of Con A, respectively). Addition of the lectin to DPC liposomes, furthermore, induces the appearance of a new phase transition centered at 320 K. These results are interpretable by a partial hydrophobic interdigitation of the lectin molecule into the liposomal bilayer.The effect of Con A on the phase behavior of three 2:1 mixtures of zwitterionic and of positively charged lipids was also investigated. Phase diagrams of the systems dipalmitoylphosphatidylcholine-dihydrosphingosine (DPPC-DHS), sphingomyelin-dipalmitoylcholine (SPM-DPC), and dimyristoylphosphatidylcholine-dipalmitoylcholine (DMPC-DPC) are presented. In lipid mixtures of limited miscibility (DPPC-DHS and SPM-DPC), Con A induces pronounced phase-separation effects. These effects are attributable to a direct hydrophobic interaction of the lectin with the liposomal bilayer and do not require the presence of specific receptor groups.The possible relationship between lectin-induced phase separations in the lipid matrix of biomembranes, and the observed changes in membrane permeability, membranal enzymatic activities, etc., is briefly discussed.
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  • 97
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two-dimensional nuclear Overhauser enhancement (2D NOESY) data are reported for the polypentapeptide of elastin, poly(VPGVG), and the cyclopentadecapeptide, cyclo(VPGVG)3. In both, the repeating type II Pro2-Gly3 β-turn can be derived from the NOE data, providing confirmation of many previous studies. In addition, other through-space connectivities are detailed that also compare favorably with previously determined crystal and solution structures for cyclo(VPGVG)3. Also, near identical data for the cyclopentadecapeptide and the polypentapeptide demonstrate the cyclic conformation-linear (helical) conformational correlate relationship between the two molecules. The 2D NOESY experiment is seen to be an effective means of establishing the presence or absence of a conformational relationship between a cyclic repeating sequence and its higher molecular weight linear counterpart. This is an approach of substantial practical value when developing the conformation of sequential polypeptides and when attempting to identify the presence of the conformation of a repeating peptide sequence within a more complex primary structure.Having established the basic conformational relationship between a cyclic conformation and its linear helical counterpart, cross peaks present in the linear helical structure that are not present in the cyclic conformational correlate can provide information on the interactions between adjacent turns of the helix. In this connection, a ValγCH3 ↔ ProβCH2 interaction is reported that can be the basis for determining the number of pentamers per turn of helix once it is determined whether it is dominantly the Val1 or Val4γCH3 that is interacting with the Pro2βCH2.
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  • 98
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    Biopolymers 28 (1989), S. 901-905 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 99
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    Biopolymers 28 (1989), S. 965-973 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oligo-DNAs are synthesized on a solid support using the 9-fluorenylmethyloxycarbonyl group as a 5′-OH base labile protection. The synthesis of the pure protected nucleotides, a relevant phosphoramidite-type strategy of coupling, and the optimization of the deprotection steps are described. This new synthetic method is an alternative to the standard protocol that avoids acidic conditions.
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  • 100
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have applied the formalism developed previously for the kinetics of domain-localized reaction [S. Mazur and M. T. Record, Jr. (1986) Biopolymers 25, 985-1008] to describe complex mechanisms of association of a protein with a specific site on a large DNA molecule also containing many nonspecific binding sites. These nonspecific sites participate in the mechanism of formation of the specific complex through competitive binding and the facilitating mechanisms of sliding and transfer. The effects of localizing the sites in a domain are represented by a simple algebraic expression, and the sequence of interactions within the domain are described by equations closely related to a conventional, homogeneous solution mechanism. We apply this formalism to examine the interplay between sliding and direct transfer in domain-localized interactions in general and in the lac repressor-lac operator interaction in particular. Experimental investigation of the effect of the molecular location of the specific site (e.g., end vs middle of the polymer chain) on the kinetics of association may allow the contributions of sliding and direct transfer to be resolved.
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