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  • Polymer and Materials Science  (9)
  • General Chemistry  (4)
  • Inorganic Chemistry  (2)
  • Life and Medical Sciences  (2)
  • 1985-1989
  • 1970-1974  (17)
  • 1974  (17)
Collection
Publisher
Years
  • 1985-1989
  • 1970-1974  (17)
Year
  • 1
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Darstellung von Poly(γ-p-biphenylmethyl-L-Glutamat), PBPLG, (Poly{L-imino-1-[2-(4-biphenylmethoxycarbonyl)äthyl]-2-oxoäthylen}), (1d) wird beschrieben. Das Viskositätsverhalten dieses Polymers in Mischungen aus Benzol und Dichloressigsäure (c=0,2.10 - 3 - 1,4.10 - 3g/cm3) bei 25°CC wird untersucht. Die Ergebnisse werden verglichen mit Messungen unter den gleichen Bedingungen an Poly(γ-benzyl-L-Glutamat),PBLG, (Poly[ L-imino-l-(2-benzyloxycarbonylathyl)-2-oxoathylen]), (lc). In beiden Fallenfindet ein zweistufiger Ubergang von einer starren, von Wasserstoffbrucken stabilisiertenHelix in ein statistisches, solvatisiertes Knduel statt : PBPLG (erste Stufe CrSSX,, zweite Stufe 55-100%, Dichloressigsaure und PBLG (erste Stufe 0-70%, zweite Stufe 70-100%,Dichloressigsaure)).Die Einfiihrung eines p-Phenylsubstituenten in PBLG fuhrt deshalb in Mischungen aus Benzol- und Dichloressigsaure zu einer weniger stabilisierten Helix.Die Stabilitat und das Viskositatsverhalten von PBLG in Mischungen aus Benzol und Dichloressigsaure (c=0,2.10-3 -14.10-3g/cm3) sind denjenigen von PBLG in Mi-schungen aus m-Kresol und Dichloressigslure ( c = 1,0.10-3-4,0. 10-3g/cm3) ähnlich.
    Notes: The synthesis of poly(γ-p-biphenylmethyl-L-glutamate), PBPLG, (poly{L-imino-1-[2-(4-biphenylylmethoxycarbonyl)ethyl]-2-oxoethylene}), (1d) is described. The viscosity behavior of this polymer in benzene/dichloroacetic acid mixtures (c=0,2.10 - 3 - 1,4.10 - 3 g/cm3) at 25°CC is investigated. The results are compared with measurements on poly(γ-benzyl-L-glutamate), PBLG, (poly[L-imino-1-(2-benzyloxycarbonylethyl)-2-oxoethylene]), (1c) under the same conditions. A transition from a rigid hydrogen bonded helix to a random solvated coil occurs in two stages for both: PBPLG (first stage 0 - 55%, second stage 55 - 100% dichloroacetic acid) and PBLG (first stage 0 - 70%, second stage 70 - 100% dichloroacetic acid).Therefore, the introduction of a p-phenyl substituent in PBLG leads to a less stable helix in benzene/dichloroacetic acid mixtures.The stability and viscosity behavior of PBLG in benzene/dichloroacetic acid mixtures (c=0,2.10 - 3 - 1,4.10 - 3g/cm3) is quite similar to the behavior of PBLG in m-cresol/dichloroacetic acid mixtures (c=1,0.10 - 3 - 4,0.10 - 3 g/cm3).
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1684-1701 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Dispiro[2.0.2.4]deca-7,9-diene and Related Model Compounds: Synthesis, U.V, N.M.R, and Photoelectron-Spectroscopic InvestigationsDispiro[2.0.2.4]deca-7,9-diene (4) and spiro[2.5]octa-4,6-diene (5 can be obtained from the corresponding monoolefins 6 and 10, respectively, by bromine addition and subsequent dehydrobromination. The u. v. spectra of 5 and 4 with λmax = 269 nm (log ε = 3.4) and 284 nm (3.7), respectively, show bathochromic shifts of their longest wavelength bands as compared to 1,3-cyclohexadiene. An analysis of the 1H n. m. r. chemical shifts and H, H-coupling constants for the olefinic protons in 4 indicates that there is no cyclic electron delocalization in this ring system. The six-membered ring in 4 is only slightly flatter than the one in 1,3- cyclohexadiene. The photoelectron spectroscopic data of 4, 5, spiro[2.5]octane (13), spiro[2.5]oct-4-ene (15), dispiro[2.0.2.4]decane (14), and dispiro[2.0.2.4]dec-7-ene (16) demonstrate the effect of the interaction between π-orbitals and cyclopropyl Walsh-orbitals; an assignment for the first bands in the p. e. spectra of these compounds is proposed.
    Notes: Dispiro[2.0.2.4] deca-7,9-dien (4) und Spiro[2.5]octa-4,6-dien (5) lassen sich aus den entsprechenden Monoolefinen 6 bzw. 10 durch Bromierung und anschließende Dehydrobromierung gewinnen. Die UV-Absorptionen von 5 und 4 mit λmax = 269 nm (log ε = 3.4) bzw. 284 nm (3.7) sind bathochrom verschoben gegenüber denjenigen des 1,3-Cyclohexadiens. Aus einer Analyse der Chemischen Verschiebungen und H,H-Kopplungskonstanten der olefinischen Protonen im 1H-NMR-Spektrum von 4 ist zu schließen, daß 4 kein cyclisch delokalisiertes Elektronensystem enthält. Der Sechsring in 4 ist nur wenig stärker eingeebnet als derjenige im 1,3-Cyclohexadien. Anhand der Photoelektronen-Spektren von 4, 5 sowie Spiro[2.5]octan (13), Spiro[2.5]oct-4-en (15), Dispiro[2.0.2.4]decan (14) und Dispiro[2.0.2.4]dec-7-en (16) wird der Effekt der Wechselwirkung zwischen π-Orbitalen und Cyclopropyl-Walsh-Orbitalen aufgezeigt; für die jeweils ersten Banden in den PE-Spektren dieser Verbindungen wird eine Zuordnung vorgeschlagen.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1702-1713 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Dispiro[2.0.2.4]deca-7,9-diene and Spiro[2.5]octa-4,6-diene: Their Chemical Reactions, Thermal and Photochemical RearrangementsSome [4 + 2]cycloaddition reactions of the title compounds 1 and 2 have been investigated. In all cases normal addition onto the 1,3-diene system is observed. 1 in the presence of proton acids at elevated temperatures yields o-ethylstyrene (16) and derivatives of 2-(o-ethylphenyl)ethane. The thermolysis of 1 above 120°C gives a mixture of 16 and tetraline (20). Higher temperatures are required for the thermal rearrangement of 2 to ethylbenzene. photo-chemically 1 yields a mixture of 16 and 20 in a ratio of about 2:1 both on direct and sensitized excitation. Possible mechanisms for these rearrangements are discussed.
    Notes: Einige [4 + 2]-Cycloadditionen der Titelverbindungen 1 und 2 werden untersucht; in allen Fällen beobachtet man normale Addition an das 1,3-Diensystem. Mit Säuren liefert 1 bei erhöhter Temperatur unter Öffnung beider Cyclopropanringe o-Äthylstyrol (16) und Derivate des 2-(o-Äthlphenyl)äthans. Die Thermolyse von 1 oberhalb 120°C führt zu 16 und Tetralin (20). Die thermische Umlagerung von 2 zu Äthylbenzol erfordert höhere Temperaturen. Photochemisch bilden sich aus 1 sowohl bei direkter als auch bei sensibilisierter Anregung 16 und 20 im Verhältnis von ca. 2:1. Mögliche Mechanismen dieser Umlagerungen werden diskutiert.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 175 (1974), S. 2983-2989 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In der vorliegenden Arbeit wurde die Kristallisationskinetik von zwei verschiedenen Netzwerken aus Naturkautschuk untersucht. Diese Netzwerke wurden durch Vulkanisation unter gewöhnlichen Bedingungen bzw. im gequollenen Zustand erhalten.Die Ergebnisse werden auf molekularer Ebene diskutiert und geben wertvolle Aufschlüsse über die bekannten Abweichungen von der Gaußschen Theorie der Gummielastizität.
    Notes: In the present paper the crystallization kinetics of two networks of natural rubber was analyzed. The two networks were prepared following two different vulcanization techniques, as usual the first, and under swelling conditions the second.The results are discussed at the molecular level and give some important information about the well known deviations from the Gaussian theory on rubber elasticity.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 175 (1974), S. 2029-2038 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Kinetik der isothermen Kristallisation von Polybutadienen mit hohem 1,4-cis-Gehalt und hoher Taktizität, dargestellt mit Uranverbindungen als Katalysator, wurde dilatometrisch im Temperaturbereich von -30 bis 0°C untersucht.Die experimentellen Schmelztemperaturen (T*m) von solchen Polybutadienen liegen zwischen 3 und 12,5°C.Eine Beziehung zwischen der Halbwertzeit (t1/2) der isothermen Kristallisation bei + C und dem Molekulargewicht wurde erhalten.Hochmolekulare Fraktionen kristallisieren schneller als solche mit niedrigen Molekulargewichten, wie bereits beim 1,4-cis-Polyisoprene gefunden wurde.Die Polybutadiene wurden durch Kristallisation aus verdünnter Toluol-Lösung unter Kühlung und Rühren fraktioniert. Naturkautschuk kristallisiert unter diesen Bedingungen nicht.
    Notes: Bulk isothermal crystallization kinetics of some highly tactic 1,4-cis-polybutadienes obtained with a new catalyst based on uranium derivatives were dilatometrically measured over a crystallization temperature (Tc) range from -30 to 0°C.The corresponding experimental melting temperatures (T*m) of uranium polybutadiene range from 3 to 12,5°C. A relationship between the isothermal bulk half-crystallization time (t1/2) at -10°C and the molecular weight (MW) has been obtained.High MW fractions crystallize faster than low MW fractions as previously reported for 1,4-cis-polyisoprene. Uranium polybutadiene has been fractionated by crystallization. by cooling and stirring a dilute toluene solution. Under the same experimental conditions + rubber does not crystallize.
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  • 6
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurden die Bildung, die optischen Eigenschaften und die Strukturen der Bis(o-hydroxybenzylidenamin)Kupfer(II)-Chelate von Poly(L-lysin), Poly(L-ornithin) und Poly(L-α,γ-diaminobuttersäure) untersucht.Aus den Versuchsergebnissen ging hervor, daß diese Polykomplexe in alkoholisch wäßriger Lösung eine bestimmte Struktur besitzen. Aus den strukturellen Eigenschaften resultierte, daß die asymmetrischen Polypeptid-Ketten die Metall-Chelate stereospezifisch binden.Auf Grund dieser Ergebnisse kann man stereoselektive Reaktionen der Kupfer(II)-polykomplexe von Bis(o-hydroxybenzylidenamin) erwarten.
    Notes: Formation, optical properties and structures of bis(o-hydroxybenzylideneamine)copper(II) chelates of poly(L-lysine), poly(L-ornithine), and poly(L-α,β-diaminobutyric acid) were investigated.Experimental evidence was obtained for a definite structure of these polycomplexes in alcoholic/aqueous solution. Structural features showed that asymmetric polypeptide matrices bind metal chelates stereospecifically. On the basis of these results stereoselective reactions on bis(o-hydroxybenzylideneamine)copper(II) polycomplexes are expected.
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  • 7
  • 8
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 9
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 10
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformational analysis of DNA-basic polypeptide complexes, based on stereo-chemical criteria and energy calculations and experimental results, is reported. Three types of polypeptide conformations were selected: the distorted β conformation similar to that proposed by Feughelmann et al.; a structure characterized by a repetition of a right-handed and left-handed α helix-type conformation; and an intermediate structure. A model of the complex between DNA and basic polypeptides was proposed, where the polypeptide chain fits the narrow groove of the B form of DNA. Van der Waals, hydrogen bond, electrostatic, and hydrophobic forces cooperate to stabilize the association complex. This structure also seems to be suitable to represent the molecular model of nucleoprotamines. In the case of nucleohistones, both grooves of DNA are involved in the interaction with the proteins. These have the nonbasic-rich portion in the α-helical conformation, whereas the part where a greater proportion of basic amino acids occurs presents a structure similar to nucleoprotamines and complexes between DNA and basic homopolypeptides. The distribution of basic residues of the F2A1(IV) histone on DNA is markedly disproportionate for the two opposite cylindrical sectors of the double helix. This suggests a new mechanism of supercoiling in nucleo-histones.
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