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  • Chemistry  (85)
  • Biochemistry and Biotechnology  (12)
  • Atomic, Molecular and Optical Physics  (3)
  • 1
    Electronic Resource
    Electronic Resource
    Reaktionen an Indolderivaten, XI. Die stereoselektive Totalsynthese von DL-Ajmalicin, DL-19-epi-Ajmalicin, DL-Formosanin und Isoformosanin (1969)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 102 (1969), S. 3558-3572 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ausgehend vom ungesättigten Keton 1 gelingt die stereoselektive Totalsynthese mehrerer heterocyclischer Indol- und Oxindol-Alkaloide. Speziell der stereoselektive Aufbau der C-19-Konfiguration sowie der Einfluß dieses Zentrums auf die Folgereaktionen werden diskutiert. Die Massenspektren der verschiedenen stereoisomeren Zwischenprodukte werden gegenübergestellt.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19691021034
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  • 2
    Electronic Resource
    Electronic Resource
    Examination of the semi-classical theory of circular dichroismSupported by NIH Grant No. GM-14936. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 6 (1972), S. 787-791 
    Details
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solution of the time dependent Schrödinger equation, including renormalization of the wave function, is used to obtain quantum mechanical expressions for the optical rotation and the circular dichroism. The use and form of the radiative damping term is examined with respect to its effects in the circular dichroism formula.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/qua.560060419
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  • 3
    Electronic Resource
    Electronic Resource
    Solvent stabilization of the edge inversion transition state in tetrahedral molecules (1988)
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 34 (1988), S. 85-98 
    Details
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The edge inversion process in phosphoric acid, PO(OH)3 has been studied by large scale ab initio molecular orbital theory. Edge inversion of the tetrahedral ground state via a square-planar transition state requires 69.5 kcal/mol (MP-2). Addition of two NH3 solvent molecules to the vacant NLUMO stabilizes the transition state by 45 kcal/mol (MP-2). The value for ΔH(300K) for the reaction 2NH3 + PO(OH)3 → PO(OH)3 · (NH3)2 is 24.1 kcal/mol (MP-2). The complex with two NH3 molecules is an intermediate. Addition of one NH3 to PO(OH)3 leads to an energy lowering of the planar form of 31 kcal/mol. This structure is now a transition state. The value for ΔH(300K) for the reaction NH3 + PO(OH)3 → PO(OH)3 · NH3 is 38.6 kcal/mol (MP-2). The complex of PF3O with two NH3 molecules was studied and is an intermediate. The value for ΔH(300K) for the reaction 2NH3 + POF3 → POF3 · (NH3)2 is only 3.3 kcal/mol (MP-2). Electron-donor solvents clearly will stabilize the edge inversion transition state for tetracoordinate main group compounds.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/qua.560340814
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  • 4
    Electronic Resource
    Electronic Resource
    Auf der Suche nach Stabilen Carbenen (1998)
    Weinheim : Wiley-Blackwell
    Chemie in unserer Zeit 32 (1998), S. 6-14 
    Details
    ISSN: 0009-2851
    Keywords: Chemistry ; Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This article follows a thread through the history of the quest for stable carbenes. The story begins in 1835 with the attempts by Dumas to dehydrate methanol to produce methylene. It continues through modern times to a point where the accumulation of many false starts in stable carbene synthesis led to the conventional wisdom that carbenes are so highly reactive that they exist only as labile, short-lived molecules. The report of the isolation of the first stable crystalline carbene in 1991 began a renaissance in the chemistry of isolable carbenes. Much of the older chemistry is currently being revisited and reinterpreted with the aid of modern analytical techniques. Easily handled carbenes are opening many new opportunities in both exploratory chemistry and industrial applications.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ciuz.19980320103
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  • 5
    Electronic Resource
    Electronic Resource
    Application of local-density functional theory to molecules containing a hypervalent bond (1991)
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 269-279 
    Details
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The molecular and electronic structures of ADPO 1, a model thiapentalene 2, and [Xe2F3]+ have been calculated in the local-density functional (LDF) formalism with polarized double numerical basis sets. The molecules were calculated to have planar C2ν structures in agreement with experiment and in contrast to Hartree-Fock molecular-orbital calculations. The vibrational spectra of all species were calculated to show that the optimized structures are indeed minima. The calculated spectrum of [Xe2F3]+ is compared with the experimental one and excellent agreement is found. These results demonstrate that the LDF method can be applied to the prediction of molecular structures containing hypervalent bonds.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/qua.560400827
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  • 6
    Electronic Resource
    Electronic Resource
    Monitoring the quality of mix of polymer melts with particulate fillers using fluorescence spectroscopy (1989)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 29 (1989), S. 1759-1765 
    Details
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Fluorescence spectroscopy has been employed to monitor the mixing of polymer melts with filler material. The polymer melts were low molecular weight polybutadiene and PBAN, a terpolymer consisting of 85% butadiene, 11% acrylonitrile, 4% acrylic acid, and the filler material was aluminum oxide. To carry out the fluorescence observations, a dopant chromophore was mixed into the polymer melt at very low concentrations, 10-4 to 10-6 molar or 11 to 0.11 ppm by weight. The mixing experiments were carried out using a small laboratory mixer which had glass walls for viewing the fluorescence spectra from the dopant chromophore. Fluctuations in fluorescence intensity were observed to decrease as a function of mixing time indicating that the spatial distribution of the fluorescent chromophores was becoming more uniform. Concerning the mixing of polymer melt and filler, we hypothesize that uniform mixing of ingredients is achieved when fluorescence intensity as a function of time is constant. In order to obtain quantitative support for this hypothesis, we used a fluorescence microscope to measure fluorescence intensity and optical transmittance from microscopic regions of well-mixed and poorly mixed specimens.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760292405
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  • 7
    Electronic Resource
    Electronic Resource
    Mechanism of accelerated photofading of thioether anthraquinone dyes in styrene butadiene resinsPresented, in part, at the IUPAC Photochemistry Symposium at Interlaken, Switzerland, July 1984. (1988)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 36 (1988), S. 1205-1219 
    Details
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Many anthraquinone dyes fade in visible light up to 100 times faster in styrene butadiene copolymers than in polyester resins or polystyrene. A mechanistic investigation of the photofading of 1,5-dihydroxy-2,6-diisobutyl-4-thiophenylanthraquinone has established that the dye sensitizes formation of singlet oxygen, a very reactive species, which attacks the double bonds in the styrene butadiene, resulting in extensive chain cleavage and peroxide formation. The major process is the oxidation of the polymer, and the dye fading is a minor process whereby the dye is apparently attacked by polymeric peroxides. The mechanism appears to be general for anthraquinone dyes, especially those with thioether, amino, hydroxy, or double-bond functionality. Unfortunately the fading is unaffected by most anticxidant stabilizers: the best result achieved was a doubling of half-life with 1 wt% Spinuvex A-36. This is still insufficient to give colored styrene butadiene copolymer resins the intrinsic dye stability available in other polymers, rendering styrene butadiene unsuitable for applications requiring high photostability of anthraquinone dyes.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1988.070360520
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  • 8
    Electronic Resource
    Electronic Resource
    The effect of mislabeled samples on the performance of the linear learning machine (1990)
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 4 (1990), S. 47-50 
    Details
    ISSN: 0886-9383
    Keywords: Classification ; Pattern recognition ; Preprocessing ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Over the past 15 years the linear learning machine has been applied to a large number of chemical problems. The learning machine approach is conceptually simple and does not require knowledge about the statistical distribution of the data. However, there are problems associated with this approach. One problem which has not been investigated is the influence of mislabeled samples on the positioning of the hyperplane in feature space. If a few samples in a data set are incorrectly tagged prior to training (i.e. the samples are labeled as members of class 2 even though they are actually members of class 1), it is still possible using the linear learning machine to achieve a classification success rate of 100% for the training set. However, unfavorable results will be obtained for the prediction set. The magnitude of this effect and its potential implications regarding the proper use of the linear learning machine are discussed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cem.1180040106
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  • 9
    Electronic Resource
    Electronic Resource
    The controlled flocculation of submicron emulsion particles. I. A three-step synthetic route to supermicron polymer particles (1996)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 3061-3069 
    Details
    ISSN: 0887-624X
    Keywords: aggregation ; emulusion polymerization ; flocculation ; latex ; particles ; polymer ; size distribution ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The basic features of a three-step experimental process to produce supermicron polymer particles are described. First, a submicron emulsifier-free latex is prepared by a well-known technique. Second, the latex is aggregated by destabilizing with cetyl pyridinium chloride under constant stirring conditions, to yield roughly spherical clusters of 6-12 μ diameter. Third, the aggregates are stabilized with poly(vinyl alcohol) and internally coalesced by heating at or above the glass transition temperature. The final product particles have relatively smooth surfaces. Results are qualitatively interpreted in terms of a dynamic equilibrium where the aggregate size is determined by a balance between attractive interparticle potentials and stirring shear forces. Bimodal aggregate size distributions suggest the aggregate break-up mechanism may involve the erosion of individual latex particles and small fragments from the surface of aggregates. © 1996 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1996.866
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  • 10
    Electronic Resource
    Electronic Resource
    Dispersion polymerization of styrene in polar solvents. IV. Solvency control of particle size from hydroxypropyl cellulose stabilized polymerizationsPresented in part at the Canadian High Polymer Forum, Ottawa, August, 1987, and the NATO ASI on Polymer Colloids, Strasbourg, July, 1988; for Paper I of this series, see Ref. 1 (1990)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 28 (1990), S. 2485-2500 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Changing solvent has a dramatic effect on the outcome of HPC stabilized dispersion polymerization of styrene in polar solvents. In methoxyethanol/ethanol mixtures, particle size varies from essentially infinity for unstabilized reactions (below 30% ethanol) to about 3 microns in ethanol. In a series of n-alcohols, there was a maximum in particle size at intermediate chain length: particle size increased from 2 microns in methanol to 8.3 microns in pentanol, then decreased again to 1 micron in octadecanol. These results were rationalized in terms of the three-component Hansen solubility parameters. The largest particles were obtained in solvents with Hanson polarity and hydrogen bonding terms closest to HPC. The generality of the three-component solubility parameter approach was examined by reactions performed in eight mixed solvents with the same values of all three Hansen terms. Seven of the eight solvents gave particles of similar size and molecular weight. The two critical effects of solvent on both particle size and molecular weight appear to be: (a) the solubility properties of the grafted HPC-PS formed, and (b) the partitioning of monomer and initiator between solution and particle phases subsequent to nucleation.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1990.080280921
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