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  • Articles  (122)
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  • Articles  (122)
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  • 1
    Electronic Resource
    Electronic Resource
    Darstellung und Eigenschaften von Tetrakis(trifluormethyl)-1,3-dithietan-S-oxiden und des Bis(trifluormethyl)sulfins (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 116-123 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Properties of Tetrakis(trifluoromethyl)-1,3-dithietane S-Oxides and Bis(triflouromethyl)sulfineThe corresponding S-oxides 2-6 could be obtained by oxidation of 2,2,4,4-tetrakis(trifluoromethyl)-1,3-dithietane (1). Similar oxidation of 2,2,4,4-tetrakis(trifluoromethyl)thiirane (8) yields the episulfoxide 12, but not the episulfone 14. Pyrolysis of 2, 3, 5, and 6 have been investigated and bis(trifluoromethyl)sulfine (7) could be isolated as the first member of perfluoroalkylsulfines as well as the sulfonylfluoride 13 being the product of isomerization of bis(trifluoromethyl)-sulfene (9). 7 could also be obtained by ring opening from 3 with bases and by oxidation of hexafluorothioacetone (11), respectively. Solvolytic ring opening in 5 and 6 yields the sulfones 16 and 17.
    Notes: Durch Oxidation des 2,2,4,4-Tetrakis(trifluormethyl)-1,3-dithietans (1) erhält man dessen S-Oxide 2-6. Auf gleiche Weise gelingt die Oxidation des 2,2,4,4-Tetrakis(trifluormethyl)thiirans (8) zum Episulfoxid 12, nicht jedoch zum Episulfon 14. Die Pyrolysen von 2, 3, 5 und 6 wurden untersucht, wobei als erster Vertreter der Perfluoralkylsulfine das Bis(trifluormethyl)sulfin (7) sowie das Sulfonylfluorid 13 als Isomerisierungsprodukt des Bis(trifluormethyl)sulfens (9) isoliert wurden. 7 entsteht auch durch Ringöffnung aus 3 mit Basen bzw. bei der Oxidation des Hexafluorthioacetons (11). Die Solvolyse von 5 und 6 liefert unter Ringöffnung die Sulfone 16 und 17.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180112
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  • 2
    Electronic Resource
    Electronic Resource
    Sterisch überladene Cyclohexane, 3. 4,4,8,8,12,12-Hexamethyltrispiro[2.1.2.1.2.1]dodecan und 4,4,8,8,9,9,10,10-Octamethyldispiro[2.1.2.3]decan - Zwei per(cyclo)alkylierte Cyclohexane in Twistbootkonformation (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 1144-1161 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Sterically Crowded Cyclohexanes, 3. 4,4,8,8,12,12-Hexamethyltrispiro[2.1.2.1.2.1]dodecane and 4,4,8,8,9,9,10,10-Octamethyldispiro[2.1.2.3]decane - Two Per(cyclo)alkylated Cyclohexanes Adopting a Twistboat ConformationSynthesis, conformation, and dynamics of the title compounds 1 and 8 are described. 1 and [1-13C]-1 were obtained by sequential methylenation and cyclopropanation of 9. The hydrogenation of 1 yielded not only 7 and 8 but also 21 and 22. On the contrary, the hydrogenations of 15 and 19 yielded 16 and 20 exclusively. The conformation and dynamics of 1 followed from an analysis of the 13C DNMR spectra of [1-13C]-1, the conformation and dynamics of 8 from an analysis of the 1H and 13C DNMR spectra of unlabelled material. Both compounds adopt a twistboat conformation. The activation parameters of the twistboat-to-twistboat interconversion of 1 were determined by bandshape analysis, those of 8 by the coalescence method. The results were as follows: 1: ΔH≠ = 8.5 · 0.2 kcal/mol, ΔS≠ = 12.8 ± 1.5 cal/mol · grd, ΔG298≠ = 4.7 ± 0.2 kcal/mol; 8: ΔG300≠ 13.6 kcal/mol. The unusual conformations of 1 and 8 are discussed on the basis of nonbonding interactions.
    Notes: Synthese, Konformation und Dynamik der Titelverbindungen 1 und 8 werden beschrieben. 1 und [1-13C]-1 wurden durch Methylenierung und anschließende Cyclopropanierung von 9 erhalten. Die Hydrierung von 1 lieferte neben 7 und 8 auch 21 und 22. Die Hydrierungen von 15 und 19 lieferten dagegen ausschließlich 16 bzw. 20. Die Konformation und Dynamik von 1 ergab sich aus einer Analyse der 13C-DNMR-Spektren von [1-13C]-1, die Konformation und Dynamik von 8 aus einer Analyse der aH- und 13C-DNMR-Spektren unmarkierten Materials. Beide Verbindungen liegen in einer Twistbootkonformation vor. Die Aktivierungsparameter der Twistboot-Twistboot-Inversion wurden bei 1 über eine Bandenformanalyse, bei 8 nach der Koaleszenztemperaturmethode bestimmt. Danach ergaben sich folgende Werte: 1: ΔH≠ = 8.5 ± 0.2 kcal/mol, ΔS≠ = 12.8 ± 1.5 cal/mol · grd, ΔG298≠ = 4.7 ± 0.2 kcal/mol; 8: ΔG300≠ = 13.6 kcal/mol. Die ungewöhnlichen Konformationen von 1 und 8 werden auf der Grundlage nichtbindender Wechselwirkungen diskutiert.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190406
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  • 3
    Electronic Resource
    Electronic Resource
    Numerical methods for heat transfer in hydraulic fracturing (1987)
    Chichester [u.a.] : Wiley-Blackwell
    International Journal for Numerical Methods in Engineering 24 (1987), S. 75-87 
    Details
    ISSN: 0029-5981
    Keywords: Engineering ; Engineering General
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: During the propagation of a hydraulically induced fracture in a porous material, fluid leak-off occurs from the fracture to the formation. Conduction and convection of heat also take place, owing to the large difference between the fluid injection temperature and that of the reservoir. The paper describes a quasi-two-dimensional heat transfer model coupled with a filtration model. It is then coupled into different coupled fracture propagation models (two-dimensional and quasi-three-dimensional).The rheological characteristics of the fracturing fluid are temperature-dependent with a sharp breakdown. The fluid diffusion model combines cake growth at the fracture face with two-fluid flow in the formation. Temperature profiles along the fracture and the formation are computed during fracture propagation.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/nme.1620240106
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  • 4
    Electronic Resource
    Electronic Resource
    Comparison of hydrolysis and esterification behavior of Humicola lanuginosa and Rhizomucor miehei lipases in AOT-stabilized water-in-oil microemulsions: II. Effect of temperature on reaction kinetics and general considerations of stability and productivity (1995)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 48 (1995), S. 190-196 
    Details
    ISSN: 0006-3592
    Keywords: hydrolysis ; esterification ; Humicola lanuginosa ; Rhizomucor miehei ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Humicola lanuginosa lipase (HIL) and Rhizomucor miehei lipase (RrnL), isolated from commercial preparations of Lipolase and Lipozyme, respectively, were solubilized in AOT-stabilized water-in-oil (w/o) microemulsions in n-heptane and aspects of their hydrolysis and condensation activity examined. The temperature dependence of HIL hydrolysis activity in unbuffered R = 10 microemulsions matched very closely that for tributyrin hydrolysis by Lipolase in an aqueous emulsion assay. Apparent activation energies were measured as 13 ± 2 and 15 ± 2 kJ mol / respectively. Condensation activity, however, was essentially independent of temperature over the range 5° to 37°C. The stability of HIL over a 30-day period was very good at all pH levels (6.1, 7.2, 9.3) and R values studied (5, 7.5, 10, 20), except when high pHs and low R values were combined. The excellent stability was reflected by the linearity of the productivity profiles which facilitate system optimization. The temperature dependence of RmL hydrolysis activity toward pNPC4 showed a maximum at 40°C and an apparent Eact = 20 ± 2 kJ mol-1 was calculated based on the linear region of the profile (5° to 40°C). RmL esterification activity showed only a slight dependence on temperature over the studied range (0° to 40°C) and an apparent Eact = 5 ± 1 kJ mol-1 was measured for octyl decanoate synthesis. Both RmL and HIL, therefore, have potential for application in low temperature biotransformations in microemulsion-based media. The stability of RmL over a 30-day period was good in R = 7.5 and R = 10 microemulsions containing pH 6.1 buffer, and this was reflected in the linearity of their respective productivity profiles. RmL stability was markedly poorer at more alkaline pH, however, and proved to be sensitive to relatively small changes in the R value. © 1995 John Wiley & Sons, Inc.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bit.260480304
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  • 5
    Electronic Resource
    Electronic Resource
    Comparison of hydrolysis and esterification behavior of Humicola lanuginosa and Rhizomucor miehei lipases in AOT-stabilized water-in-oil microemulsions: I. Effect of pH and water content on reaction kinetics (1995)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 48 (1995), S. 78-88 
    Details
    ISSN: 0006-3592
    Keywords: hydrolysis ; esterification ; Humicola lanuginosa ; Rhizomucor miehei ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Lipolase and Lipozyme are produced in large quantities (as a result of genetic engineering and overexpression) for the detergents market and provide a cheap source of highly active biocatalysts. Humicola lanuginosa lipase (HIL) and Rhizomucor miehei lipase (RmL) have been isolated in partially purified form from commercial preparations of Lipolase and Lipozyme, respectively. These lipases were solubilized in Aerosol-OT (AOT)-stabilized water-in-oil (w/o) microemulsions in n-heptane. HIL and RmL activity in these microemulsions was assayed by spectrophotometric measurement of the initial rate of p-nitophenyl butyrate hydrolysis, and by chromatographic determination of the initial rate of octyl decanoate synthesis from 1-octanol and decanoic acid. The hydrolytic activity of HIL in microemulsions measured as a function of buffer pH prior to dispersal, followed a sigmoidal profile with the highest activities observed at alkaline pHs. This broadly matches the pH-activity profile for tributyrin hydrolysis by Lipolase in an aqueous emulsion assay. The hydrolytic activity of RmL in the same microemulsions, measured as a function of pH, gave a bell-shaped profile with a maximum activity at pH 7.5. Again, the observed pH-activity profile was similar to that reported for a purified RmL in a tributyrin-based aqueous emulsion assay. In contrast, the esterification activity exhibited by both HIL and RmL in AOT microemulsions over the available range pH 6.1 to 10.4, decreases as the pH increases, most likely reflecting the effect of substrate ionization. The dependence of the hydrolytic and condensation activity of HIL on R, the mole ratio of water to surfactant, were similar with both profiles exhibiting a maximum at R = 5. The hydrolytic and esterification activities of RmL followed similar R-dependent profiles, but the profiles in this case exhibited a maximum at R = 10. The water activities at these R values were directly measured as 0.78 and 0.9, respectively. Measured water activities were unperturbed by the presence of lipase at the concentrations used in these studies. © 1995 John Wiley & Sons, Inc.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bit.260480111
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  • 6
    Electronic Resource
    Electronic Resource
    Evaluation of startup and operation of four anaerobic processes treating a synthetic meat waste (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 28 (1986), S. 372-380 
    Details
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two continuous stirred tanks reactors (CSTR) and four anaerobic fluidized bed reactors (AFBR) were used to study the treatment of a synthetic meat waste during single-and two-stage anaerobic treatment. Four configurations were investigated; a single-stage CSTR and AFBR and the two-stage systems CSTR-AFBR and AFBR-AFBR. Startup of the anaerobic reactors was achieved within 50 days by use of a regime that included stepped increases in influent COD, methanol substitution of the substrate, and addition of essential trace metals such as cobalt and nickel. Two-stage reactors removed up to 85% of influent COD concentrations of 5000 mg/L, whereas the single-stage AFBR and CSTR removed 76 and 9%, respectively. The proportion of methane in the effluent gases increased as the influent COD concentration was increased. Volumetric production of methane was greatest for the first stage of the AFBR-AFBR system. Solids retention times calculated for the AFBRs ranged from 7 to 12 days, sufficient to support methanogenesis. The AFBRs and two-stage systems were more resistant to an influent pH shock from the operating value of pH 6.8 down to pH 3 than the CSTRs and single-stage reactors. It was concluded that high-rate anaerobic treatment systems were applicable to meat industry wastewaters and that two-stage digestion produced a better quality effluent.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bit.260280310
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  • 7
    Electronic Resource
    Electronic Resource
    Reconciliation of process data with process simulation (1986)
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 32 (1986), S. 247-254 
    Details
    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 SACDA group at the University of Western Ontario has developed an equations-oriented modular process simulation program called MASSBAL. A model of a process is constructed by selecting and flowsheeting standard building blocks describing fundamental operations such as the mixing and separating of streams. Building blocks are also provided by which equipment operating or design equations may be incorporated into the model. Reconciliation of the inconsistency and redundancy of process measurements is an optional feature of the program. The measurements are reconciled by minimizing a weighted least-squares criterion while satisfying the model equations and any modeling constraints. The minimum is obtained directly, avoiding the need for laborious searching techniques.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/aic.690320211
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  • 8
    Electronic Resource
    Electronic Resource
    The application of membrane biological reactors for the treatment of wastewaters (1996)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 49 (1996), S. 601-610 
    Details
    ISSN: 0006-3592
    Keywords: aerobic ; anaerobic ; biomass separation ; bioreactor ; bubbleless ; oxygen mass transfer ; extraction of organic pollutants ; membrane ; wastewaters ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Combining membrane technology with biological reactors for the treatment of municipal and industrial wastewaters has led to the development of three generic membrane processes within bioreactors: for separation and recycle of solids; for bubbleless aeration of the bioreactor; and for extraction of priority organic pollutants from hostile industrial wastewaters. Commercial aerobic and anaerobic membrane separation bioreactors already provide a small footprint alternative to conventional biological treatment methods, producing a high-quality effluent at high organic loading rates. Both the bubbleless aeration and extractive membrane bioreactors are in the development stages. The former uses gas-permeable membranes to improve the mass transfer of oxygen to the bioreactor by providing bubbleless oxygen. By using a silicone membrane process, extractive membrane bioreactors transfer organic pollutants from chemically hostile wastewaters to a nutrient medium for subsequent biodegradation. All three membrane bioreactor (MBR) processes are comparatively and critically reviewed. © 1996 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Estimation of the speed of propagation of intergranular stress waves using a simple elastic contact model (1987)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1310-1316 
    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: A model of a granular bed is used to obtain an estimate of the speed of propagation of intergranular stress waves. In the analysis, a simple elastic contact between neighboring grains is assumed. The model may be extended to include more complex Intergranular interaction mechanisms, but at the expense of such a simple analytical solution as that obtained here. The predicted dependence of compression of a granular bed on compressive load is compared with experimental measurements and is found to describe the relationship very well. The simplified analysis gives a general insight into the dependency of wave speed on bed geometry, indicating for example that while wave speed is independent of grain size, it does depend on the Initial porosity of the bed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760271707
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  • 10
    Electronic Resource
    Electronic Resource
    Synthesis of [1.1.1]Propellanes by Bridging of Bicyclo[1.1.0]butanes (1996)
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1996 (1996), S. 1705-1715 
    Details
    ISSN: 0947-3440
    Keywords: [1.1.1]Propellanes ; 13C-13C coupling constants ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several [1.1.1]propellanes were synthesized by bridging the 1,3-positions of the corresponding bicyclo[1.1.0]butane. The synthesis of 1-bromo-3-(chloromethyl)bicyclobutanes and the bridging were carried out in a one-pot reaction by addition of 2.0 equiv. of MeLi to 1,1-dibromo-2,2-bis(chlormethyl)-cyclopropanes 10. Three routes to 10 were investigated: Firstly, the Wittig reaction of 1,3-dichloroacetone leading to (chloromethyl)allyl chlorides 6 was, with the exception of 6m, successful only with Wittig reagents derived from primary alkyl halides, Secondly, reduction of diethyl alkylidenemalonates with LiAlH4 in benzene afforded carbinols 12 which were converted into 6 by reaction with N-chlorosuccinimide/dimethyl sulfide. The cyclopropanation of 6 to 10 was achieved by reaction with bromoform/NaOH under phase-transfer catalysis conditions. Finally, starting from diethyl alkylidenemalonates, the sequence of reduction and cyclopropanation could be interchanged, according to the sequence 11 → 13 → 14 → 10. Propellanes 5b and 3 were reduced with LiAlH4 to bicyclo[1.1.1]pentanes 15b and e. 2-D INADEQUATE NMR spectra of 5d and 5p indicate that the coupling constants J(13C-13C) between the bridgehead positions are very small, i.e. 0.47 and 0.53 Hz, respectively.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jlac.199619961103
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