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  • Wiley-Blackwell  (196)
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  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 446-455 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Studies of heat and mass transfer in packed beds, which disagree substantially in their findings, have nearly all been done with beds of regular particles of uniform size, whereas oil-shale retorting involves particles of diverse irregular shapes and sizes. We, in 349 runs, measured mass-transfer rates from naphthalene particles buried in packed beds by passing through air at room temperature. An exact analogy between convection of heat and mass makes it possible to infer heat-transfer coefficients from measured mass-trans-fer coefficients and fluid properties. Some beds consisted of spheres, naphthalene and inert, of the same, contrasting or distributed sizes. In some runs, naphthalene spheres were buried in beds of crushed shale, some in narrow screen ranges and others with a wide size range. In others, naphthalene lozenges of different shapes were buried in beds of crushed shale in various bed axis orientations. This technique permits calculation of the mass-transfer coefficient for each active particle in the bed rather than, as in most past studies, for the bed as a whole.The data are analyzed by the traditional correlation of Colburn jD vs. Reynolds number and by multiple regression of the mass-transfer coefficient on air rate, sizes of active and inert particles, void fraction, and temperature. Principal findings are: local Reynolds number should be based on the active-particle size, not the average for the whole bed; differences between shallow and deep beds are not appreciable; mass transfer is 26% faster for spheres and lozenges buried in shale than in all-sphere beds; orientation of lozenges in shale beds has little or no effect on mass-transfer rate; and for mass or heat transfer in shale beds, log(j·∊) = - 0.0747 - 0.6344logNRe + 0.0592log2 NRe.
    Additional Material: 15 Ill.
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  • 2
    ISSN: 0947-3440
    Keywords: Diastereoselectivity ; Hetero Diels-Alder reactions ; Enamino ketones ; High-pressure kinetics ; Kinetics, high-pressure ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hetero Diels-Alder reaction of the enamino ketones 1b and 1c with ethyl vinyl ether (2) in dichloromethane to give the dihydropyrans 3b/4b and 3c/4c is studied at high pressure up to 5 kbar. The kinetics is measured by on-line FT-IR spectroscopy up to 3 kbar. The cycloadditions show a relatively high pressure-dependent increase in diastereoselectivity in favor of the trans adducts 4b and 4c, respectively. The activation volumes at atmospheric pressure, ΔVo≠, are determined to be -(43.3 ± 2.1) and -(43.9 ± 2.9) cm3 mol-1 for the reactions of 1b and 1c at 100°C in dichloromethane solution. The activation enthalpies, ΔH≠ for the two cycloadditions at 1500 bar are (64.4 ± 0.4) kJ mol-1 and (64.0 ± 0.6) kJ mol-1. The ΔΔVo≠ values are (3.8 ± 0.3) and (4.6 ± 0.3) cm3 mol-1 and the ΔΔH≠ values (1.5 ± 0.2) and (2.1 ± 0.3) kJ mol-1, respectively.
    Additional Material: 9 Ill.
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  • 3
    ISSN: 0947-3440
    Keywords: Hetero Diels-Alder reactions, intramolecular ; High-pressure reactions ; Diastereoselectivity ; Pyrans ; 1-Oxa-1,3-butadiens ; Isoxazolones ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The intramolecular hetero Diels-Alder reaction of the benzylidene-isoxazolone 3 giving the adducts 4 and 5 is studied in dichlormethane under high pressure up to 5 kbar. The kinetics is measured by on-line FT-IR spectroscopy up to 3 kbar. The cycloaddition shows a clear pressure-induced increase in diastereoselectivity. For the difference in activation volume ΔΔV≠ of the reactions affording the two diastereomers, a value of -(1.6 ± 0.2) cm3 · mol-1 is obtained. The activation volume ΔVcis≠ is determined to be -(19.4 ± 0.5) cm3 · mol-1 at 343 K. The activation enthalpy and entropy, as derived from the overall rate coefficient k measured at 1000 bar, are (62.9 ± 1.7) kJ · mol-1 (at 343 K) and -(135 ± 11) J · mol-1 · K-1.
    Additional Material: 3 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1995 (1995), S. 739-743 
    ISSN: 0947-3440
    Keywords: Interlocked rings ; Macrocycles ; Mechanical bond ; Rotaxanes ; Template effect ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The first rotaxanes 6a, 6b and 11 with an amide structure are described. Their (supramolecular template) syntheses are strikingly simple. The central part of the „axle“ is added to the „wheel“ and subsequently capped. The macromonocycle („wheel“) provides the receptor cavity for the „axle“ and the triphenylmethane stoppers confirm the mechanical bond between „wheel“ and „axle“.
    Additional Material: 3 Ill.
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  • 5
    ISSN: 0947-3440
    Keywords: D-Galacturonic acid derivatives ; Regioselective deacetylation ; 1,2-O-Isopropylidene derivatives of D-galacturonic acid ; Lipases ; Enzyme catalysis ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A number of D-galacturonic acid derivatives (1, 3, 7 and 9) have been selectively deacetylated in enzyme-catalyzed reactions. The 2-O-acetyl groups were selectively hydrolyzed from 2,3,4-tri-O-acetyl-β-D-galactopyranurono-6,1-lactone (1), and methyl [methyl (3) and benzyl (7) 2,3,4-tri-O-acetyl-β-D-galactopyranosid]uronates, affording the specifically deacetylated products in good to excellent yields. The methyl 1,2,3,4-tetra-O-acetyl-α-D-galactopyranuronate (9) was hydrolyzed at the anomeric position in 48% yield using the acylase from Aspergillus melleus (E1), whereas the lipases from wheat germ (E5 and E7) catalyzed the selective cleavage of the acetyl groups in both the 1- and 2-O-positions, furnishing the methyl 3,4-di-O-acetyl-D-galactopyranuronate (12) in 46% isolated yield. The latter compound was obtained in nearly quantitative yield by selective enzymatic deacetylation at the 2-O-position of 7, followed by hydrogenolytic cleavage of the anomeric O-benzyl group. Isopropylidenation of 12 furnished the hitherto unknown methyl 3,4-di-O-acetyl-1,2-O-isopropylidene-α-D-galactopyranuronate (13).
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  • 6
    ISSN: 0899-0042
    Keywords: avoparcin ; macrocyclic antibiotics ; enantiomeric separations ; chiral stationary phases ; verapamil ; thyroxine ; mephenytoin ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Avoparcin is a macrocyclic glycopeptide antibiotic structurally related to vancomycin, teicoplanin, and ristocetin A. When attached to 5-μm spherical silica gel, the avoparcin proved to be an effective chiral stationary phase (CSP) that could be used in the reversed-phase, normal-phase, and polar-organic modes. The avoparcin CSP was complimentary to the other macrocyclic glycopeptide CSPs in that it could resolve some racemates that the others could not, and vice versa. Some important compounds resolved on the avoparcin CSP include verapamil, thyroxine, mephenytoin, and 2-imidazolidone-4-carboxylic acid. The use of this CSP and the optimization of separations on it are discussed. Avoparcin appears to be a useful addition to this family of CSPs. Chirality 10:627-660, 1998. © 1998 Wiley-Liss, Inc.
    Additional Material: 10 Ill.
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  • 7
    ISSN: 0899-0042
    Keywords: ristocetin A ; macrocyclic antibiotic ; enantiomeric separations ; underivatized amino acids ; chiral stationary phase ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The macrocyclic glycopeptide, ristocetin A, was covalently bonded to a silica gel support and evaluated as a liquid chromatographic (LC) chiral stationary phase (CSP). Over 230 racemates were resolved in either the reversed-phase mode, the normal-phase mode, or the polar-organic mode. The retention behavior and selectivity of this CSP were examined in each mode. Optimization of separations on this column is discussed. The ristocetin A CSP appeared to be complimentary to other glycopeptide CSPs (i.e., vancomycin and teicoplanin). Column stability was excellent. The CSP was not irreversibly altered when going from one mobile phase mode to another. Chirality 10:434-483, 1998. © 1998 Wiley-Liss, Inc.
    Additional Material: 10 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 188 (1930), S. 47-51 
    ISSN: 0863-1786
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 8 (1996), S. 49-57 
    ISSN: 0899-0042
    Keywords: racemization ; fermented beverages ; beer ; D-amino acids ; D-leucine ; D-phenylalanine ; D-proline ; cyclodextrin columns ; column switching ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Even though amino acids are important trace components in the brewing of beers, they have not been extensively evaluated in these beverages. Studies involving the enantiomeric composition of these amino acids are even less prevalent. A brief summary of the brewing process for malt beverages is given. The total concentration and enantiomeric composition of three amino acids (leucine, phenylalanine, and proline) were determined in 25 different beers. Proline tended to have the highest average absolute concentration and the lowest percentage of the D-enantiomer in most samples. In some cases the relative amounts of D-phenylalanine and D-leucine exceeded 10% of the individual amino acids. The enantiomeric composition of the amino acids in different beer samples did not vary as extensively as the absolute concentrations. The reason for the concentration differences between proline and the other amino acids is discussed. A knowledge of amino acid concentrations and enantiomeric compositions appears to be useful in characterizing specific beers and brewing processes. © 1996 Wiley-Liss, Inc.
    Additional Material: 4 Ill.
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  • 10
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The differences in thermal expansion between rubber-particle and matrix-resin in graft polymers (ABS) cause thermal stresses which influence the glass transition of the rubber phase. Such effects were observed hitherto only in grafted material so that the graft-adhesion between the two phases is hold responsible for this mechanical interaction. The present investigations show that thermal stresses may also arise in ungrafted material if the samples are properly prepared. In such special cases it is obviously not reasonable to use the thermal stresses as a proof of grafting. After estimating the volume dilatation of the rubber phase during cooling the influence of swelling, thermal pretreatment and rubber content on the temperature dependence of the shear modulus is investigated. In addition stress-strain measurements and anisotropic thermal expansion of grafted and ungrafted samples are discussed. Toughness behaviour cannot be derived in a direct manner from the size of the thermal stresses; additional data must be considered.
    Notes: Zwischen Elastomerteilchen und Matrix eines ABS-Pfropfpolymerisates können mechanische Wechselwirkungen auftreten, die wegen der unterschiedlichen thermischen Ausdehnungskoeffizienten der beiden Phasen beim Abkühlen zu thermischen Spannungen führen und dadurch den Glasübergang der Elastomerphase beeinflussen. Da bei einem ungepfropften Material ein solcher Effekt nicht auftritt, wird in Übereinstimmung mit verschiedenen Angaben in der Literatur geschlossen, daß diese Wechselwirkungen durch die Pfropfhülle verursacht werden. Die vorliegenden Untersuchungen zeigen aber darüber hinaus, daß je nach Herstellungs-bedingungen auch bei einem ungepfropften Material eine ausreichende Adhäsion zwischen Teilchen und Matrix erreicht werden kann, um hinsichtlich der thermischen Spannungen ähnliche Effekte wie bei einem gepfropften Material zu ergeben. In einem solchen Fall kann natürlich die thermische Spannung nicht zum makroskopischen Nachweis der Pfropfung herangezogen werden. Eine Pfropfhülle ist demnach keine notwendige Bedingung für das Auftreten dieser mechanischen Wechselwirkungen. Nach einer Abschätzung der' Volumendilatation der Elastomerphase beim Abkühlen wird anhand von Schubmoduluntersuchungen auf den Einfluß von Quellung, unterschiedlicher thermischer Vorbehandlung und unter-schiedlichem Elastomergehalt eingegangen. Abschließend werden Kraft-Dehnungs-untersuchungen und Anisotropieerscheinungen in der thermischen Ausdehnung an gepfropften und ungepfropften Proben diskutiert. Das Zähigkeitsverhalten der untersuchten ABS-Polymerisate kann nicht ohne zusätzliche Angaben nach der Größe der thermischen Spannungen zwischen Teilchen und Matrix beurteilt werden.
    Additional Material: 16 Ill.
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