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  • Polymer and Materials Science  (9)
  • Organic Chemistry  (5)
  • General Chemistry  (4)
  • Inorganic Chemistry  (2)
  • Life and Medical Sciences  (2)
  • 1985-1989
  • 1970-1974  (22)
  • 1974  (22)
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  • 1985-1989
  • 1970-1974  (22)
Year
  • 1
    Electronic Resource
    Electronic Resource
    Synthesis and viscosity behavior of poly(γ-p-biphenylmethyl-L-glutamate) in benzene/dichloroacetic acid mixtures, a comparison with poly(γ-benzyl-L-glutamate) (1974)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 175 (1974), S. 3193-3206 
    Details
    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).
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1974.021751113
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  • 2
    Electronic Resource
    Electronic Resource
    The Stabilization Energy of [18] Annulene. A thermochemical determination (1974)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 57 (1974), S. 2276-2288 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal rearrangement of [18]annulene in solution gives benzene and 1,2-benzo-1,3,7-cyclooctatriene. This reaction has been investigated using a differential scanning calorimeter and the associated enthalpy change has been measured. The enthalpy of the reaction (in the gase phase at 298°K) is \documentclass{article}\pagestyle{empty}\begin{document}$$ \Delta {\rm H}_{\rm r} \left({{\rm g},\,298^ \circ } \right) = - 50.7 \pm 5\,{\rm kcal mol}^{{\rm - 1}} $$\end{document} From this value and the enthalpies of formation of the reaction products, the enthalpy of formation of [18]annulene is obtained: \documentclass{article}\pagestyle{empty}\begin{document}$$ \Delta {\rm H}_{\rm f} \,^ \circ \left({{\rm 1,}\,{\rm g},\,298^ \circ } \right) = 124 \pm 5.5\,{\rm kcal mol}^{{\rm - 1}} $$\end{document} The stabilization energy of [18]annulene, defined as the difference between the enthalpy of formation of the hypothetical Kékulé [18]annulene (with single and double bonds of normal lengths) and the heat of formation of the real molecule is then \documentclass{article}\pagestyle{empty}\begin{document}$$ \Delta {\rm H}_{{\rm stab}{\rm .}} \left({\rm 1} \right) = 37 \pm 6\,{\rm kcal mol}^{{\rm - 1}} $$\end{document} a value close to the corresponding quantity found for benzene.The very large stabilization energy of [18]annulen (100 ± 6 kcal mol-1) previously reported in the literature, based on measurements of the heat of combustion, is not correct since the annulene is certainly oxidized in the bomb prior to combustion.The isodynamic conformational mobility of [18]annulene is not incompatible with a stabilization energy of 37 kcal mol-1; the activation enthalpy observed for this process (ΔH≠ = 16.1 kcal mol-1) indicates that the stabilization is not completely destroyed in the transition state.The mechanism of the thermolysis of [18]annulen, investigated by kinetic measurements and by analysis of the shape of the thermograms, is discussed.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19740570745
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  • 3
    Electronic Resource
    Electronic Resource
    Dispiro[2.0.2.4] deca-7,9-dien und Vergleichsverbindungen: Darstellung, UV-, NMR- und Photoelektronen-spektroskopische Untersuchungen (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1684-1701 
    Details
    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.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070527
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  • 4
    Electronic Resource
    Electronic Resource
    Dispiro[2.0.2.4]deca-7,9-dien und Spiro[2.5]octa-4,6-dien: Chemische Umsetzungen, thermische und photochemische Umlagerungen (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 1702-1713 
    Details
    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.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070528
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  • 5
    Electronic Resource
    Electronic Resource
    Crystallization kinetics of natural rubber under stress (1974)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 175 (1974), S. 2983-2989 
    Details
    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.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1974.021751017
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  • 6
    Electronic Resource
    Electronic Resource
    High 1,4-cis-polybutadiene by uranium catalysts, 2Part 1: cf.5.. Bulk and solution crystallization of polymers (1974)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 175 (1974), S. 2029-2038 
    Details
    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.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1974.021750707
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  • 7
    Electronic Resource
    Electronic Resource
    Formation, properties and structures of bis (o-hydroxybenzylideneamine)copper(II) chelates of polypeptide ligands (1974)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 175 (1974), S. 327-337 
    Details
    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.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1974.021750201
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  • 8
    Electronic Resource
    Electronic Resource
    Comparative cardiac anatomy of the reptilia. II. A critique of the literature on the Squamata and RhynchocephaliaWe are indebted to a Commonwealth Scholarship (to G. J. W. Webb) and to the National Heart Foundation of Australia (grant No. G838) for financial aid, to Louise Wissman and Alex Stock for assisting in the translation of foreign literature, to J. P. Kennedy and W. E. Adams for providing papers not otherwise available, to Harry Wadleigh and Harry Spencer for technical aid, to Pam O'Hara, Elizabeth Cherry and Audry Heatwole for typing and to Malcolm Mackinnon for suggestions and criticism. E. T. B. Francis drew our attention to the significance of Acolat's ('35) paper. (1974)
    New York, NY : Wiley-Blackwell
    Journal of Morphology 142 (1974), S. 1-20 
    Details
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jmor.1051420102
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  • 9
    Electronic Resource
    Electronic Resource
    Allgemeine Methode zur Synthese von 2-Azetidinonen und 2-AzetidinylidenammoniumsalzenDiese Arbeit wurde von der UCB, Pharmaceutical Division, unterstützt. M. De Poortere und J. Marchand-Brynaert danken dem Institut pour l'Encouragement de la Recherche scientifique dans l'Industrie et l'Agriculture für Stipendien. (1974)
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 86 (1974), S. 272-273 
    Details
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ange.19740860707
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  • 10
    Electronic Resource
    Electronic Resource
    Photoisomerisierung des Tricyclo[5.2.1.04.10]deca-2,5,8-triens (Triquinacens)Auszugsweise vorgetragen auf der Chemiedozententagung in Stuttgart, 31.3.-4.4. 1974 und auf der 15th Conference on Reaction Mechanisms in Fort Collins, Colorado (USA), 24.6.-28.6. 1974.  -  Diese Arbeit wurde von der Deutschen Forschungsgemeinschaft und dem Fonds der Chemischen Industrie unterstützt. (1974)
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 86 (1974), S. 706-707 
    Details
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ange.19740861909
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