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  • Chemistry  (72)
  • Cell & Developmental Biology  (5)
  • Physics  (3)
  • Condensed Matter: Electronic Properties, etc.
  • 2015-2019
  • 1970-1974  (80)
  • 1974  (34)
  • 1971  (46)
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  • 2015-2019
  • 1970-1974  (80)
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  • 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
    Poly(γ-p-nitrobenzyl-L-glulainate): synthetic aspects, sedimentation, and viscosity studies (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 2509-2523 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of poly(γ-p-nitrobenzyl-L-glutamates), PNBG, has been synthesized by the polymerization of N-carboxyanhydride (NCA) derivatives of γ-p-nitrobenzyl-L-glutamate, NBG, using triethylamine as an initiator. We studied the influence of (a) the solvents dioxane, nitrobenzene, dimethylformamide (DMF), and DMF-1,2-dichloroethane mixture and (b) the anhydride-initiator ratio (A/I) for the polymerization in nitrobenzene (A/I varying from 50 to 750) on the properties of the polymers obtained. In order to improve its synthesis, NBG, was prepared by three different methods. Ten samples of PNBG, ranging in Mw from 10,000 to 50,000, were examined viscometrically in DMF and dichloroacetic acid (DCA) and by ultracentrifugation in DMF. The data for [η] and So (limiting sedimentation coefficient) as functions of Mw for PNBG in DMF were utilized, applying theories of Kuhn and Kuhn,13 Schachman,14 and Perrin, 15 for the estimation of the length per monomeric residue h. Viscosity data gave a h value of about 2.3 Å, Whereas sedimentation yielded 1.5 Å. Treating viscosity and sedimentation data for poly(γ-benzyl-L-glutamate), PBLG, in the same way leads to somewhat higher hvalues (2.4 Å and 1.7 Å, respectively).Although a nitroaromatic effect was shown to be absent for PNBG in DMF, it can be concluded that in this medium PNBG has a somewhat more compact structure than PBLG.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360101212
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  • 3
    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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  • 4
    Electronic Resource
    Electronic Resource
    Intrinsic carbon-13 NMR solvent shifts in hydrocarbons. Relevance of long range substituent parameters (1974)
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 6 (1974), S. 601-602 
    Details
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbon-13 NMR chemical shifts have been measured in a number of binary mixtures of normal alkanes. Intrinsic solvent shifts are deduced from the shifts and the relevance of some small substituent effects in alkanes is discussed. A comparison is made between solvent effects and thermally induced chemical shift differences in alkanes.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/mrc.1270061111
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  • 5
    Electronic Resource
    Electronic Resource
    Thermal bulk polymerization of cholesteryl acrylate (1971)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 9 (1971), S. 1893-1899 
    Details
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal bulk polymerization of cholesteryl acrylate was carried out in the solid phase, the mesomorphic phase, and the liquid phase to study the effect of monomer ordering on polymerization rate and polymer properties. The rate increased with decreasing ordering (or enhanced mobility) of the monomer. Formation of inhibitive by-products during the polymerization limited conversions to 35%. The sedimentation constant S0 = 6.2 S was the same for the polymers obtained in the three phases. The weight-average molecular weight (M̄w) was 480,000 as determined by ultracentrifugation. Poly-(cholesteryl acrylate) formed in bulk is randomly coiled when dissolved in tetrahydrofuran. The thermal properties of the monomer are given.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1971.150090709
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  • 6
    Electronic Resource
    Electronic Resource
    Conformation of gramicidin S (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 699-710 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A molecular conformation of Gramicidin S was derived on the basis of conformational calculations taking into account the available experimental data.The conformation is characterized by a dyad axis which relates the two chemically equivalent halves of the molecule and contains four hydrogen bonds; other structural features agree with experimental results. X Ray Crystallographic evidences for the relative position of the Ornithine residues is also reported which supports an important feature of the structure of Gramicidin S.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360100408
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  • 7
    Electronic Resource
    Electronic Resource
    On the conformations of poly-N-methyl-L-alanine (PNMA) in solution (1971)
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 2581-2590 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-resolution nuclear magnetic resonance spectra at 100 MHz have been obtained on poly-N-methyl-L-alanine in the chloroform-trifluoroacetic acid system under various conditions of solvent composition. Different spectra are observed for the CH3-Cα, Cα-H, and N-CH3 protons. On the basis of conformational analysis an interpretation of the NMR results was attempted.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360101217
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  • 8
    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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  • 9
    Electronic Resource
    Electronic Resource
    Synthesen mit heterocyclischen Aminen, VII. Über die Reaktion von Acrylsäureestern mit heterocyclischen Aminen. Struktur der Reaktionsprodukte (1971)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 104 (1971), S. 3961-3964 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses with Heterocyclic Amines, VII. Reactions of Acrylates with Heterocyclic Amines. The Structure of the Reaction ProductsThe addition of acrylic esters to 3(5)-aminopyrazole, 3-amino-1.2.4-triazole (4), and 3-amino-s-triazolo[3.4-a]isoquinoline (9) takes place at the ring nitrogen just as in the case of propiolic ester. The condensed oxo-tetrahydro-pyrimidines 1, 5, 6, and 10 are formed. Their structure is proved by catalytic hydrogenation of the addition products 3, 7, 8, and 11, which have been obtained with propiolic ester.
    Notes: Die Addition von Acrylsäureestern an 3(5)-Amino-pyrazol, 3-Amino-1.2.4-triazol (4) und 3-Amino-s-triazolo[3.4-a]isochinolin (9) erfolgt wie im Falle des Propiolsäureesters am Ringstickstoff. Es entstehen die kondensierten Oxo-tetrahydro-pyrimidine 1, 5, 6 und 10. Ihre Struktur wird durch katalytische Hydrierung der mit Propiolsäureester erhaltenen Additionsprodukte 3, 7, 8 und 11 bewiesen.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19711041226
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  • 10
    Electronic Resource
    Electronic Resource
    Kondensierte Isochinoline, III Untersuchungen über die Reaktivität der s-Triazolo[3.4-a]isochinoline (1971)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 104 (1971), S. 3925-3939 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Condensed Isoquinolines, III. Studies on the Reactivity of s-Triazolo[3.4-a]isoquinolinesHMO-Calculations of s-triazolo[3.4-a]isoquinoline (1) reveal a high doublebond character of the C-5/C-6 bond. Halogenaddition, catalytic hydrogenation and oxidation reactions are in experimental agreement. It appears from oxidation reactions of derivatives of 1 that unsaturated side chains are also oxidatively degradated at the same time under the same conditions.
    Notes: Aus HMO-Berechnungen des s-Triazolo[3.4-a]isochinolins (1) geht u. a. ein hoher Doppelbindungscharakter der C-5/C-6-Bindung hervor, was auch experimentell bei Halogenaddition, katalytischer Hydrierung und Permanganat-Oxydation beobachtet wird. Oxydationsreaktionen der Derivate von 1 zeigen, daß ungesättigte Seitenketten unter gleichen Bedingungen gleichzeitig oxydativ abgebaut werden.
    Additional Material: 8 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19711041222
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