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  • Artikel: DFG Deutsche Nationallizenzen  (21)
  • Polymer and Materials Science  (11)
  • Analytical Chemistry and Spectroscopy  (10)
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  • Artikel: DFG Deutsche Nationallizenzen  (21)
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  • 1
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Empirical conformational energy calculations have been carried out for N-methyl derivatives of alanine and phenylalanine dipeptide models and N-methyl-substituted active analogs of three biologically active peptides, namely thyrotropin-releasing hormone (TRH), enkephalin (ENK), and luteinizing hormone-releasing hormone (LHRH). The isoenergetic contour maps and the local dipeptide minima obtained, when the peptide bond (ω) preceding the N-methylated residue is in the trans configuration show that (1) N-methylation constricts the conformational freedom of both the ith and (i + 1)th residues; (2), the lowest energy position for both residues occurs around φ = -135° ± 5° and ψ = 75° ± 5°, and (3) the αL conformational state is the second lowest energy state for the (i + 1)th residue, whereas for the ith residue the C5 (extended) conformation is second lowest in energy. When the peptide bond (ωi) is in the cis configuration the ith residue is energetically forbidden in the range φ = 0° to 180° and ψ = -180° to +180°. Conformations of low energy for ωi = 0° are found to be similar to those obtained for the trans peptide bond. In all the model systems (irrespective of cis or trans), the αR conformational state is energetically very high. Significant deviations from planarity are found for the peptide bond when the amide hydrogen is replaced by a methyl group. Two low-energy conformers are found for [(N-Me)His2]TRH. These conformers differ only in the φ and ψ values at the (N-Me)His2 residue. Among the different low-energy conformers found for each of the ENK analogs [D-Ala2,(N-Me)Phe4, Met5]ENK amide and [D-Ala2,(N-Me)Met5]ENK amide, one low-energy conformer was found to be common for both analogs with respect to the side-chain orientations. The stability of the low-energy structures is discussed in the light of the activity of other analogs. Two low-energy conformers were found for [(N-Me)Leu7]LHRH. These conformations differ in the types of bend around the positions 6 and 7 of LHRH. One bend type is eliminated when the active analog [D-Ala6,(M-Me)Leu7]LHRH is considered.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
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  • 2
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Energy pathways between the αR, β′, C7eq, and β-regions of the conformational energy surface of N-acetyl-N′-methylalanyl amide were obtained by SCF ab initio calculations on the 4-21G level, with gradient geometry optimization at each point. The calculations indicate that no barrier exists at this computational level between αR and β′. The variation of geometry (bond distances and bond angles) with conformation is analyzed in detail, and the most important geometrical parameters that should be treated as variables in both empirical energy calculations and in the fitting of polypeptide chains in proteins by x-ray methods are identified. In addition to the φ,ψ correlation discussed previously for the helical state, a correlation of these dihedral angles in the β-region is described.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 1 (1975), S. 227-234 
    ISSN: 0025-116X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: IR-spektroskopische Untersuchungen von Polyäthylen-Proben, dargestellt durch Reduktion von Polyvinylchlorid mit Lithiumaluminiumhydrid, ließen darauf schließen, daß Polyvinylchlorid Seitenketten enthält, die seine Morphologie und Festkörpereigenschaften wesentlich beeinflussen. Die Natur dieser Seitenketten war bisher unbekannt. Es wird anhand von 13C-NMR Spektren gezeigt, daß die Verzweigungen in reduziertem Polyvinylchlorid aus Methylgruppen bestehen, die vermutlich aus Chlormethylgruppen des ursprünglichen Polymeren entstanden sind. Die untersuchte Probe enthielt ca. 3 CH3-Gruppen pro 1000 CH2-Gruppen, jedoch is dieses Verhältnis vermutlich von der Polymerisationstemperatur abhängig. Zusätzlich wurden Anzeichen für längere Seitenketten gefunden, die allerdings nur in einem Ausmaß von weniger als 1 pro 1000 CH2-Gruppen vorhanden sein dürften.
    Notizen: The presence of branches in poly(vinyl chloride) as indicated by previous IR measurements on the polymer reduced to polyethylene by means of lithium aluminum hydride is believed to affect materially the morphology and solid state properties of poly(vinyl chloride); however, up to the present, the nature of these branches has not been known. By use of 13C-NMR on reduced poly(vinyl chloride) it is demonstrated that the brances are methyl groups, presumably corresponding to chloromethyl groups in the original polymer. In the sample studied, the frequency is ca. 3 methyl groups per 1000 CH2 groups, but this is expected to depend on the temperature of polymerization. There is also some evidence for long branches, probably not exceeding 1 per 1000 CH2 groups.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 25 (1987), S. 426-427 
    ISSN: 0887-6258
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 5
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A simulation study is described of the behaviour of ions confined in a quadrupole ion trap during each of two separate operations of a tandem mass spectrometric experiment. The two operations are those of mass-selective ion isolation and mass-selective resonance excitation to the point of ion ejection from the ion trap. The method of mass-selective ion isolation simulated is that of consecutive ion isolation. Simulation data indicate that the collisional history of the ions prior to the isolation process can greatly influence the degree to which ions survive this process. Simulation data for mass-selective resonance ejection are compared with experimental data obtained with a Finnigan-MAT ion trap mass spectrometer. In each operation, the facility with which ions absorb energy from the field within the ion trap, whether this field is derived from the R.F. drive potential or a supplementary potential, can determine the extent to which ions are retained within the ion trap during the two mass-selective operations described.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 6
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Described herein are proton nmr experiments on chemically modified derivatives of ribonuclease A designed to elucidate the origin of an exchangeable resonance, assigned previously to a histidine ring N proton that titrates between 11 to 13 ppm with a pKa of 6.1 in H2O solution. Histidines 48 and 105, which are distant from the active site, are eliminated as candidates for this resonance from inhibitor binding studies on the enzyme in acetate-water solutions. This exchangeable resonance titrates with modified pKa's and constant area over the above pH range in His-119-N1-carboxymethylated-RNase A and des-(121-124)-RNase A, thus eliminating the imidazole N3 proton in the His 119-Asp 121 hydrogen bond. In His-12-N1-carboxymethylated-RNase A, this resonance is also observable, but broadens on raising the pH above 7 and at elevated temperatures above neutrality. It exhibits a pH-independent chemical shift characteristic of the protonated state of histidine. On the basis of these findings, this exchangeable resonance, designated a, is assigned to the imidazole N1 proton of His 12, which is hydrogen-bonded to the carbonyl oxygen of Thr 45 in the crystal.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 7
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 14 (1975), S. 987-997 
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The C2H resonance of the active site histidine residue designated AS-2, which has the lower pKa of the two active site histidines, has been correlated in both RNase A and RNase S by comparing the pH 3 to 5.5 regions of the chemical shift titration curves, the effect of the inhibitor CMP-3′ on the chemical shifts at pH 4.0, and the effect of Cu II on the line widths at pH 3.6. It has been demonstrated that resonance AS-2 is absent in the spectrum of RNase S′ reconstituted using S-peptide deuterated at the C2 of His 12, and in that of the RNase S′-CMP-3′ complex. We thus demonstrate that histidine AS-2 is in fact His 12 in both enzymes. This finding is in agreement with out previous assignment of the exchangeable NH proton in RNase A to His 12, but reverses the assignments of the active site histidine C2H resonances made earlier by other authors.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 22 (1983), S. 787-805 
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Solutions are obtained that describe the time dependence of the reversible binding of a ligand to a two-site lattice. The binding may be cooperative. Three methods are used to obtain these solutions: the separation of on/off processes with a variable transformation, the asymptotic series analysis, and the singular perturbation procedure. Applications to parameter calculation from experimental data are presented. This kinetic system is such that it is difficult to extract all kinetic parameters from data analysis, and the implications for each method are also discussed.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 9
    ISSN: 0951-4198
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Notizen: Commercial gas chromatography quadrupole ion-trap mass spectrometer (GC/ITMS) instruments have been used in a novel way for the study of negative ions formed from perfluorotributyl-amine and polychlorinated biphenyl compounds. Negative ions, formed during a normal electron impact ionization period in which 70 eV electrons were used, were isolated in an ion trap by the application of a negative DC voltage to the ring electrode that caused all positive ions to be ejected from the ion trap; in the subsequent analytical scan, negatives ions were detected with an electron multiplier biased normally so as to detect positive ions. The major negative-ion species detected from FC-43 were m/z 252 to m/z 633; 34 other negative-ion species were detected also, though in low abundance. The observed negative-ion mass range extended from m/z 252 to m/z 633. The signal-to-noise ratio of negative-ion mass spectra was enhanced by operation of the GC/MS instrument in GC mode and averaging the mass spectra acquired. In an examination of 3 hexachlorobiphenyl compounds, the molecular anion cluster around m/z 360 for the non-ortho-substituted congener 169 was observed with a signal-to-noise ratio of ca. 20 for 90 pg injected on column: the response for congener 169 was greater than that for congener 156 (mono-ortho-substituted) which, in turn, was greater than that for congener 153 (di-ortho-substituted).
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 851-865 
    ISSN: 0021-8995
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Physik
    Notizen: Untreated and fire-retardant-treated white α-cellulose samples were isothermally pyrolyzed in a fluidized bath in a nitrogen environment at 298-360°C. Results were reported in terms of volatilization (based on weight loss-time measurements) and the degradation products (based on gas chromatographic-mass spectrometric analysis). The findings products (based on gas chromatographic-mass spectrometric analysis). The findings on untreated cellulose indicate that: (1) pyrolysis occurs in three distinct phases in the temperature range 276-360°C; (2) there is a single activation energy of 42 kcal/mole over this temperature range; (3) the initial rapid weight loss is not due to the desoprtion of water, but primarily to decomposition of the cellulose; molecules: (4) there is little difference in either the quality or relative quantity of the volatiles generated during the three different phases of pyrolysis. The findings on treated cellulose show that the fire retardant, KHCO3, does not markedly change the types of degradation products having molecular weights below about 110, althought it does change their relative concentrations. Furthermore, the rate of product generation and the quantity of residual char are increased.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
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