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  • 1
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The main fragmentation pathway of vinyl triflates in mass spectra involves the loss of CF3SO2·, followed by the loss of olefin and/or CO. The loss of TfOH takes place with fragmentation of a vinylic C—H bond. TfOH2+ ions are formed via regiospecific double hydrogen transfer from five- and six-membered cyclic triflates.
    Additional Material: 3 Tab.
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  • 2
    ISSN: 1042-7163
    Keywords: Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have prepared two new tetracyclic phenylboronic esters 4 and 5 derived from myo-inositol and from 1,2-O-isopropylidene-myo-inositol, respectively. The structures of these compounds were established from NMR and IR spectra, elemental analyses, and an X-ray diffraction study in the case of 4. Compound 4 is a tetracyclic derivative of the less stable conformer of inositol (five axial hydroxy groups and one equatorial) with two dioxaboroline rings at opposite faces of the six-membered ring, one formed between the boron atom and the axial hydroxyl groups at C-3 and C-5 and the other between the boron atom and the hydroxyl groups at C-4 and C-6, and a dioxaborolidine ring bridging C-1 and C-2 at axial and equatorial positions. A similar structure was found for 5 with the difference that bridging C-1 and C-2 there is a dioxolane ring. The boron atoms are planar with their attached atoms, stabilized by retrocoordination between the boron and oxygen and carbon atoms, respectively. The two phenyl rings that are in the same face of the molecule are essentially parallel, with a dihedral angle between planes of 28.26 ± 0.79°.
    Additional Material: 2 Ill.
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  • 3
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
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  • 4
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: This work suggests a theoretical approach for the description of a primary x-ray beam by means of the K fluorescence which it excites on a set of thin targets made of pure elements. Physical quantities, defined as weighted integrals over hv of the photon spectral distribution, are obtained directly as weighted integrals of the Kα yields over the variable Ez (the ionization energy of the K shell of the element with atomic number Z), without needing any explicit reconstruction of the spectral distribution. The set of Kα yields produced by an x-ray beam as a function of Ez is a functional description of the exciting beam. Theoretically, such a description is suited to x-ray fluorescence analysis.
    Additional Material: 2 Ill.
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  • 5
    ISSN: 0749-1581
    Keywords: 1H, 13C, 15N and 113Cd NMR ; Two-dimensional NMR ; CP/MAS NMR ; Hg and Cd complexes 4(1H) -Quinazolinone-2,3-dihydro-2-thioxo ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Cd(II) and Hg(II) complexes of 4(1H)-quinazolinone-2,3-dihydro-2-thioxo (1) and the free ligand were studied by 1D and 2D multinuclear magnetic resonance in solution and 13C cross polarization magic angle spinning NMR in the solid state. Compound 1 adopts only one of five possible tautomeric structures in solution, namely the thiouracyl-like structure. It was found that the metal atom is linked to two molecules of deprotonated 1 by N-1 and coordinated by the sulphur atom. The compounds retain the same structure in the solid state and in dimethyl sulphoxide solution.
    Additional Material: 2 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 89-98 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The occurrence of instabilities in chemically reacting systems, resulting in unsteady and spatially inhomogeneous reaction rates, is a widespread phenomenon. In this article, we use nonlinear signal processing techniques to extract a simple, but accurate, dynamic model from experimental data of a system with spatiotemporal variations. The approach consists of a combination of two steps. The proper orthogonal decomposition [POD or Karhunen-Loève (KL) expansion] allows us to determine active degrees of freedom (important spatial structures) of the system. Projection onto these “modes” reduces the data to a small number of time series. Processing these time series through an artificial neural network (ANN) results in a low-dimensional, nonlinear dynamic model with almost quantitative predictive capabilities.This approach is demonstrated using spatiotemporal data from CO oxidation on a Pt (110) crystal surface. In this special case, the dynamics of the two-dimensional reaction profile can be successfully described by four modes; the ANN-based model not only correctly predicts the spatiotemporal short-term behavior, but also accurately captures the long-term dynamics (the attractor). While this approach does not substitute for fundamental modeling, it provides a systematic framework for processing experimental data from a wide variety of spatiotemporally varying reaction engineering processes.
    Additional Material: 11 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1794-1803 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Time-dependent viscous flows driven by capillarity act to minimize the surface area of a fluid bounded in a plane geometry with initial gradients in surface curvature. These free-surface flows are solved by a finite-element model applied to describe the viscous sintering of two-dimensional ceramic particles. The numerical model is validated by comparison to the analytical solution obtained by Hopper (1990) for the coalescence of two infinite cylinders of equal cross section and is applied to several other geometries pertinent to the study of particle sintering for which analytical results are not available. Details of the flow fields and morphological evolution lend insight to the physical behavior of these systems and provide a basis for the more complete understanding of viscous sintering phenomena.
    Additional Material: 8 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 16 (1993), S. 35-39 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Experimental data are reported for ion exchange equilibria of binary systems on Amberlite IR-120 resin, at different temperatures and total ionic concentrations in aqueous solutions. These systems exhibit non-ideal behaviour in both phases, and the equilibrium characterization has been based on the law of mass action, using Wilson and Meisssner, and Kusik equations to correlate the activity coefficients in the resin and aqueous solutions, respectively. Equilibrium constants, standard thermodynamic properties (Gibbs free enthalpy changes, enthalpy and entropy) and Wilson binary parameters were obtained as functions of temperature.
    Additional Material: 4 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 210-215 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The kinetics of the pseudohomogeneous liquid phase synthesis of a high molecular weight ester in a stirred tank reactor using cobalt chloride as catalyst has been studied at various temperatures, catalyst concentrations, and acid/alcohol molar ratios. A kinetic model has been determined that predicts the experimental results quite well.
    Additional Material: 7 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 39 (1992), S. 141-147 
    ISSN: 0006-3592
    Keywords: protein engineering ; enzymes in organic solvents ; protein stabilization ; subtilisin E ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Subtilisin E was rationally engineered to improve its stability in polar organic solvents such as dimethylformamide (DMF). A charged surface residue, Asp248, was substituted by three amino acids of increasing hydrophobicity, Asn, Ala, and Leu; all three variants were stabilized with respect to wild type in 80% DMF. This stabilization was only observed in the presence of high concentrations of the organic solvent: no stability enhancements were observed in 40% DMF. In contrast, the mutation Asn218 → Ser alters internal hydrogen bonding interactions and stabilizes subtilisin E in both 40% and 80% DMF. This study provides additional evidence that substitution of surface-charged residues is a generally useful mechanism for stabilizing enzymes in organic media and that the stabilizing effects of such substitutions are unique to highly altered solvent environments. The effects of the single amino acid substitutions on free energies of stabilization are additive in the Asp248 → Asn + Asn218 → Ser combination variant, yielding an enzyme that is 3.4 times more stable than wild type in 80% DMF.
    Additional Material: 3 Ill.
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