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  • 1
    Electronic Resource
    Electronic Resource
    Advantages in using immobilized thermophilic β-glycosidase in nonisothermal bioreactors (1998)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 59 (1998), S. 108-115 
    Details
    ISSN: 0006-3592
    Keywords: thermophilic β-glycosidase ; catalytic membranes ; nonisothermal bioreactors ; thermodialysis ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Catalytic membranes, obtained by immobilizing thermophilic β-glycosidase onto nylon supports, were used in a nonisothermal bioreactor to study the effect of temperature gradients on the rate of enzyme reaction. Two experimental approaches were carried out to explain the molecular mechanisms by which the temperature gradients affect enzyme activity. The results showed that the thermophilic enzyme behaved as the mesophilic β-galactosidase, exhibiting an activity increase which was linearly proportional to the transmembrane temperature difference. The efficiency of the system proposed was determined by calculating two constants, α and β, which represent respectively the percentage increase of enzyme activity when a temperature difference of 1°C or a temperature gradient of 1°C cm-1 were applied across the catalytic membrane. The increase of enzyme activity in nonisothermal bioreactors entailed a proportional reduction of production times. The advantages in using thermophilic enzymes immobilized in nonisothermal bioreactors are also discussed. © 1998 John Wiley & Sons, Inc. Biotechnol Bioeng 59:108-115, 1998.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    XPS study of laser-annealed ion-implanted GaAs (1993)
    Chichester [u.a.] : Wiley-Blackwell
    Surface and Interface Analysis 20 (1993), S. 955-958 
    Details
    ISSN: 0142-2421
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Data on the effects of 140 keV Zn+ implanation of (100)GaAs and the consequent low-power pulsed laser annealing (LPPLA) on the composition of the surface layers are presented. The implantation does was 1014 cm -2 and the sample temperature was kept at 110 ± 10°C. THE LPPLA was carried out by 10-30 pulses of a Q-switched ruby laser (λ = 694.3 nm, τ = 25 ns and P0 = 4-6 MW cm-2) equipped with a spatial homogenizer. The crystal surface was studied by XPS analysis combined with depth profiling with the use of 1 keV Ar+.The results presented include the depth redistribution of oxygen and the As/Ga ratio as well as the oxide thickness for (a) virgin, (b) as-implanted and (c) implanted and then annealed samples.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/sia.740201205
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  • 3
    Electronic Resource
    Electronic Resource
    N2O5 photolysis products investigated by fluorescence and optoacoustic techniques (1985)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 17 (1985), S. 991-1006 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pulsed laser photolysis of N2O5 near 290 nm coupled with fluorescence detection (calibrated by NO2 photolysis) showed that the O(3P) quantum yield is ≤0.1. A pulsed laser optoacoustic technique in a flow tube (ca. 6 torr of N2) was tested by photolysis of NO2 and then applied to N2O5. Nitric oxide was added to react with NO3 free radical and the resulting increase in the optoacoustic signal confirmed the presence of NO3 free radicals. Based on the relative optoacoustic signals observed for NO2 and N2O5, the quantum yield for NO3 production is 0.8 ± 0.2.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550170906
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  • 4
    Electronic Resource
    Electronic Resource
    Homogeneous decomposition of vinyl ethers. The heat of formation of ethanal-2-yl (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 715-730 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal unimolecular decomposition of three vinylethers has been studied in a VLPP apparatus. The high-pressure rate constant for the retro-ene reaction of ethylvinylether was fit by log k (sec-1) = (11.47 + 0.25) - (43.4 ± 1.0)/2.303 RT at 〈T〉 = 900 K and that of t - butylvinylether by log k (sec-1) = (12.00 ± 0.27) - (38.4 ± 1.0)/2.303 RT at 〈T〉 = 800 K. No evidence for the competition of the higher energy homolytic bond-fission process could be obtained from the experimental data. The rate constant compatible with the C—O bond scission reaction in the case of benzylvinylether was log k (sec-1) = (16.63 ± 0.30) - (53.74 ± 1.0)/2.303 RT at 〈T〉 = 750 K. Together with ΔHf,3000(benzyl·) = 47.0 kcal/mol, the activation energy for this reaction results in ΔHf,3000(CH2CHO) = +3.0 ± 2.0 kcal/mol and a corresponding resonance stabilization energy of 3.2 ± 2.0 kcal/mol for 2-ethanalyl radical.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110705
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  • 5
    Electronic Resource
    Electronic Resource
    Laser-induced kinetics: Arrhenius parameters for t-C4H9 + XI → i-C4H9X + I (X = H,D) and the Heat of Formation of the t-butyl radical (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1283-1300 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The metathesis reaction of DI with t-C4H9 generated by 351-nm photolysis of 2,2′-azoisopropane was studied in a low-pressure reactor (VLPφ Knudsen cell) in the temperature range of 302-411 K. The data obeyed the following Arrhenius relation when combined with recent data by Rossi and Golden gathered by the same technique (t-C4H9 by thermal decomposition of 2,2′-azoisobutane): log k2D(M-1s-1) = 9.60 - 1.90/θ, where θ = 2.303RT kcal/mol for 302 K 〈 T 〉 722 K. The metathesis reaction of HI with t-C4H9 was studied at 301 K and resulted in k2H(M-1·s-1) = (3.20 ± 0.62) × 108. An analogous Arrhenius relation was calculated for the protiated system if the small primary isotope effect k2H/k2D was assumed to be √2 at 700 K. It was of the following form: log k2H(M-1·s-1) = 9.73 - 1.68/θ.Preliminary data of Bracey and Walsh indicate that earlier Arrhenius parameters determined for the reverse reaction are somewhat in error. Their value of log k1(M-1·s-1) = 11.5 - 23.8/θ yields 7delta;Hf,3000(t-butyl) = 9.2 kcal/mol and S3000(t-butyl) = 74.2 cal/mol7°K when taken in conjuction with this study.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151204
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  • 6
    Electronic Resource
    Electronic Resource
    The influence of reductive pretreatments on CuO/MnO2 catalytic activity: An XPS study (1986)
    Chichester [u.a.] : Wiley-Blackwell
    Surface and Interface Analysis 9 (1986), S. 249-250 
    Details
    ISSN: 0142-2421
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/sia.740090413
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  • 7
    Electronic Resource
    Electronic Resource
    Functional alterations of the endoplasmic reticulum and the detoxification systems during diethyl-nitrosamine carcinogenesis in rat liver (1984)
    New York, NY [u.a.] : Wiley-Blackwell
    Cell Biochemistry and Function 2 (1984), S. 177-181 
    Details
    ISSN: 0263-6484
    Keywords: Cancer ; tumours ; DEN carcinogenesis ; cytochrome P450 ; aminopyrine demethylase ; total glutathione ; oxidized glutathione ; γ-glutamyltranspeptidase ; glutathione peroxidase ; glutathione reductase ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The mixed-function oxidase system shows a number of variations in the liver of diethyl-nitrosamine (DEN) treated rats. These include a decrease of the cytochrome P450 content and of the aminopyrine demethylase activity both in the hyperplastic nodules and in the hepatoma. Processes of detoxification, such as the glutathione system, show some modifications. These alterations are in accordance with the decrease of glutathione peroxidase and the increase of γ-glutamyltranspeptidase during diethyl-nitrosamine carcinogenesis.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cbf.290020312
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  • 8
    Electronic Resource
    Electronic Resource
    Rate of decomposition of hexafluoroazomethane and the absolute rate of recombination of trifluoromethyl radical at higher temperatures (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 775-788 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The unimolecular homogeneous decomposition of hexafluoroazomethane was studied in a VLPP apparatus in the temperature range 720-1050 K and is consistent with the following Arrhenius parameters: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k(\sec ^{ - 1}) = 16.2 - 55.2/\theta $$\end{document} at 900 K, where the A factor was assumed to be the same as for 2,2′-azoisobutane. The homogeneous rate of recombination of ·CF3 radicals at temperatures around 1000 K was also studied under VLPP conditions and was found to be in the fall-off region, corresponding to k/k∞ = 8.5 × 10-3 when a rotational transition-state model was used. This model predicts an essentially constant value of kr∞ of 109.7 over the temperature range 300-1000 K.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110709
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  • 9
    Electronic Resource
    Electronic Resource
    Laser-induced chemical kinetics: Absolute rate constants for the reactions Ċ2F2 + Br2 → C2F5Br + Ḃr and n-Ċ3F7 + Br2 → n-C3F7Br + Ḃr (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 499-506 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate constants at room temperature for the metathesis reaction have been measured under VLPP conditions: k1 = (2.0 ± 0.5) × 108M-1·s-1, k2 = (3.0 ± 0.7) × 108M-1·s-1. The radicals were generated through collisionless infrared-multiphoton decomposition of the corresponding iodides by irradiation from a high-power CO2-TEA laser. The reaction of Ċ2F5 and Ċ3F7 with \documentclass{article}\pagestyle{empty}\begin{document}$$\mathop {\rm N}\limits^{\rm .} {\rm O}_{\rm 2} $$\end{document} are briefly discussed in relation to the reaction of Ċ3 with \documentclass{article}\pagestyle{empty}\begin{document}$$\mathop {\rm N}\limits^{\rm .} {\rm O}_{\rm 2} $$\end{document}, which had been measured previously.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140507
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  • 10
    Electronic Resource
    Electronic Resource
    Relationship between bond dissociation energies and activation energies for bond scission reactionsThis article is dedicated to the memory of Bob Back, with whom we had the good fortune to share some time during his sabbatical visit at SRI. (1994)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 26 (1994), S. 211-217 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bond dissociation energies are frequently derived from values of the high pressure activation energy for bond scission reactions. The value derived depends on the transition state structure chosen for the reaction. We consider several models of the transition state and show that the variation in derived BDE values can be quite substantial, 3 to 6 kcal/mol at the high temperatures of pyrolysis kinetics. Application of the restricted Gorin model of the transition state results in BDE values in good agreement with current thermochemistry, while the other models tested result in lower to much lower values. © 1994 John Wiley & Sons, Inc.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550260120
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