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  • 1
    Electronic Resource
    Electronic Resource
    Vesicles from mixtures of bipolar archaebacterial lipids with egg phosphatidylcholine
    Amsterdam : Elsevier
    Biochimica et Biophysica Acta (BBA)/Biomembranes 732 (1983), S. 714-718 
    Details
    ISSN: 0005-2736
    Keywords: (Caldariella acidophila) ; Archaebacterial lipid ; Asymmetric distribution ; Bipolar lipid ; Liposome ; Phosphatidylcholine
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Biology , Chemistry and Pharmacology , Medicine , Physics
    Type of Medium: Electronic Resource
    URL: http://linkinghub.elsevier.com/retrieve/pii/0005-2736(83)90252-3
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  • 2
    Electronic Resource
    Electronic Resource
    Phase transitions of bipolar lipids of thermophilic archaebacteria
    Amsterdam : Elsevier
    Biochimica et Biophysica Acta (BBA)/Biomembranes 861 (1986), S. 420-428 
    Details
    ISSN: 0005-2736
    Keywords: (S. solfataricus) ; Archaebacterium ; Bipolar lipid ; Differential scanning calorimetry ; Lipid polymorphism ; Phase transition
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Biology , Chemistry and Pharmacology , Medicine , Physics
    Type of Medium: Electronic Resource
    URL: http://linkinghub.elsevier.com/retrieve/pii/0005-2736(86)90450-5
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  • 3
    Electronic Resource
    Electronic Resource
    Thermotropic properties of bipolar lipids of Sulfolobus solfataricus and of their mixtures with dipalmitoylphosphatidylcholine
    Amsterdam : Elsevier
    Biophysical Chemistry 22 (1985), S. 27-35 
    Details
    ISSN: 0301-4622
    Keywords: Bipolar lipid ; DSC ; Hydration ; Interaction ; Orientation
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Biology , Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://linkinghub.elsevier.com/retrieve/pii/0301-4622(85)80023-5
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  • 4
    Electronic Resource
    Electronic Resource
    Acidity constants of benzamide and some Ortho-substituted derivatives (1993)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 101-106 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Acidity constants of benzamide and seven ortho-substituted derivatives were determined. Except for o-nitrobenzamide, all the amides exhibit medium effects. The data were treated by vector analysis. o-Aminobenzamide displays two protonation equilibria. The second acidity constant was determined by vector analysis and by the excess acidity function, since the acid strength provided by perchloric acid is insufficient for complete protonation. Different acidity functions and the ortho substituent effect on ionization of the amide group are compared.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610060206
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  • 5
    Electronic Resource
    Electronic Resource
    Elimination kinetics and mechanism of primary, secondary and tertiary α-hydroxycarboxylic acids in the gas phase (1993)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 54-58 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rates of elimination of primary, secondary and tertiary α-hydroxycarboxylic acids were determined in a seasoned, static reaction vessel over the temperature range 280-390°C and the pressure range 30-201 Torr. The reactions, in the presence of a free radical inhibitor, are homogeneous, unimolecular and follow a first-order rate law. The rate coefficients are given by the following equations: for glycolic acid, log k1 (s-1) = (14·03 ± 0·24) - (209·3 ± 1·5) kJ mol-1 (2·303RT)-1; for lactic acid, log k1 (s-1) = (12·24 ± 0·11) - (182·8 ± 1·3) kJ mol-1 (2·303RT)-1; and for 2-hydroxyisobutyric acid, log k1 (s-1) = (12·91 ± 0·13) - (174·7 ± 1·5) kJ mol-1 (2·303RT)-1. The basicity and the ease with which the hydroxy group is removed from primary to tertiary α-hydroxycarboxylic acids are reflected in rate enhancement. The mechanism of these eliminations appears to proceed through a semi-polar five-membered cyclic transition state.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610060109
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  • 6
    Electronic Resource
    Electronic Resource
    Several mechanisms in the elimination kinetics of ω-chlorocarboxylic acids in the gas phase (1995)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 133-138 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the gas-phase pyrolysis of ω-chlorocarboxylic acids were examined in a seasoned static reaction vessel and in the presence of at least twice the amount of the free radical inhibitor cyclohexene or toluene. In conformity with the available experimental data on rate determination, these reactions proved to be unimolecular and obeyed a first-order rate law. The presence of the primary chlorine leaving group in Cl(CH2)nCOOH (n = 1-4) showed a change in mechanism from intramolecular displacement of the Cl leaving group by the acidic hydrogen of the COOH to anchimeric assistance of the carbonyl COOH to the C—Cl bond polarization in the transition state. This mechanistic consideration is nearly the same for the series of 2-, 3-, and 4-chlorobutyric acids. The chlorine atom at the 2-position of acetic, propionic and butyric acids is dehydrochlorinated through a prevailing reaction path involving a polar five-membered cyclic transition state.
    Additional Material: 9 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610080302
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  • 7
    Electronic Resource
    Electronic Resource
    Molecular rearrangements in homogeneous gas-phase elimination reactions. Pyrolysis kinetics of alkyl methanesulphonates (1993)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 85-94 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rates of elimination of several alkyl methanesulphonates were determined in a seasoned, static reaction vessel over the temperature range 300-420°C and the pressure range 28-163 Torr. The reactions are homogeneous, unimolecular and follow a first-order rate law. The overall rate coefficients are given by the following equations: for isobutyl methanesulphonate, log k1 (s-1) = (12·51 ± 0·38) - (177·0 ± 2·1) kJ mol-1 (2·303RT)-1; for 2-phenyl-1-propyl methanesulphonate, log k1(s-1) = (12·62 ± 0·04) - (176·2 ± 0·5) kJ mol-1 (2·303RT)-1; for neopentyl methane-sulphonate, log k1(s-1) = (13·35 ± 0·42) - (198·2 ± 5·2) kJ mol-1 (2·303RT)-1; and for 3-chloro-2,2-dimethyl-1-propyl methanesulphonate, log k1(s-1) = (13·87 ± 0·42) - (218·2 ± 5·4) kJ mol-1 (2·303RT)-1. Rearrangements in these methanesulphonate pyrolyses may proceed via an intimate ion-pair type of mechanism. Consequently, the results appear to confirm that intramolecular migration through autosolvation is possible in gas-phase elimination reactions of certain types of organic molecules.
    Additional Material: 11 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610060204
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  • 8
    Electronic Resource
    Electronic Resource
    The pyrolysis kinetics of 4-chloro-2-butanone in the gas phase (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 403-410 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates of pyrolysis of 4-chloro-2-butanone in the gas phase have been determined in a static system seasoned with the products of decomposition of allyl bromide. The reaction is catalyzed by hydrogen chloride. Under maximum catalysis of HCl, the kinetics were found to be of order 1.5 in the substrate suggesting that a complex elimination is involved. The reaction, when maximally inhibited with propene, appears to undergo a unimolecular elimination and follows a first-order law kinetics. The products are methylvinyl ketone and hydrogen chloride. The kinetics have been measured over the temperature range of 402.0-424.4°C.The rate coefficients are given by the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$ \log k_1 (\sec ^{ - 1}) = (13.67 \pm 0.69) - (225.2 \pm 8.6)\,{\rm kj}/{\rm mol}/2.303RT\angle $\end{document}. Thepyrolysis of 4-chloro-2-butanone is 31 times greater in rate than that of ethyl chloride at 440°C. This large difference in rate may be attributed to the -M effect of the acetyl substituent in the pyrolysis of the former halo compound.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130406
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  • 9
    Electronic Resource
    Electronic Resource
    The intimate ion pair mechanism in the maximally inhibited elimination kinetics of methyl 4-chlorobutyrate and methyl 5-chlorovalerate in the gas phase (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 203-213 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase elimination of methyl 4-chlorobutyrate and methyl 5-chlorovalerate has been reexamined, in a static system and seasoned vessel, over the temperature range of 419.6-472.1°C and pressure range of 45-108 torr. The reactions, under maximum inhibition with propene, are homogeneous, unimolecular, and obey a first-order rate law. The rate coefficients are given by the following Arrhenius equations: for methyl 4-chlorobutyrate, log (k1(s-1) = (13.41 ± 0.60) - (226.8 ± 8.2) kJ/mol/2.303RT; and for methyl 5-chlorovalerate, log k1(s-1) = (13.20 ± 0.02) - (227.6 ± 0.3) kJ / mol / 2.303RT. The pyrolysis rates are found to be about a half of the rates reported in a previous work. As already advanced, the carbomethoxy substituent appears to provide anchimeric assistance in the elimination process, where normal dehydrochlorination and lactone formation arise from an intimate ion pair type mechanism. The partial rates towards each of these products have been determined and reported.
    Additional Material: 10 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180206
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  • 10
    Electronic Resource
    Electronic Resource
    The mechanism of the elimination kinetics of 2-bromo-2-butene in the gas phase (1990)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 211-217 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas phase elimination of 2-bromo-2-butene were determined in a static system over the temperature range of 340-380°C and pressure range of 37-134 torr. The reaction in seasoned vessels, even in the presence of a free radical inhibitor, is catalyzed by hydrogen bromide. Under maximum catalysis of HBr, the kinetics were found to be of order 1.0. The reaction, when maximally catalyzed with HBr, appears to undergo a molecular elimination of HBr which follows first-order kinetics. The products are 1,2-butadiene and hydrogen bromide. The rate coefficients. under maximum catalysis, are given by the Arrhenius equation log k1(s-1) = (13.57 ± 0.56) - (200.4 ± 6.8) kJ mol-1 (2.303RT)-1. The catalyzed pyrolysis of 2-bromo-2-butene appears to proceed through a six-membered cyclic transition-state type of mechanism.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550220302
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