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  • Artikel: DFG Deutsche Nationallizenzen  (369)
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  • Artikel: DFG Deutsche Nationallizenzen  (369)
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  • 2020-2022
  • 1990-1994  (368)
  • 1965-1969  (1)
  • 1945-1949
  • 1935-1939
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Jahr
  • 101
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990) 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
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  • 102
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 443-448 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Two types of equivalents for the aldo and the keto groups have been developed, the Schleyer and the bond separation energy (BSE) equivalents. The equivalents were used to give the heats of formation and the BSE of unstrained models. These equivalents were then used in the calculations of the strain energies for aldehydes and ketones. The results obtained were compared with MM2 values. The equivalents were also used in calculations of the stabilization (destabilization) energies for conjugated carbonyl compounds. The results obtained correlate well with the available experimental data.
    Zusätzliches Material: 5 Tab.
    Materialart: Digitale Medien
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  • 103
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 428-434 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The effect of added alkali metal perchlorates on the rate of lactonization of ω-bromoalkanoate ions was investigated in 99% dimethyl sulphoxide (four-membered ring formation) and in dimethylformamide (DMF) (four- and sixteen-membered ring formation). In all cases the effect of the added metal salts is rate depressing, as a result of the lower reactivity of metal ion-associated species relative to the free ions. Ion-pairing association constants were determined, but the reactivity of ion pairs were so low as to elude direct measurement in most cases. Evidence was also obtained for the formation of ion triplets with Li+ in DMF. The relevance of the present results in connection with the ‘caesium effect’ is briefly discussed.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 104
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 470-476 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Ab initio theoretical calculations were carried out on the three tautomers, NH, OH and CH, of 1,2,6-thiadiazine 1,1-dioxides. Different basis sets were employed in order to obtain an adequate description of these cyclic sulphamide derivatives. A coherent picture is obtained which includes relative stability of tautomers (NH 〉 CH 〉 OH), non-planarity of NH and CH tautomers and electronic distribution (Boys' localized orbitals).
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 105
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990) 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
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  • 106
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 687-693 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The electrochemical behaviour of seven N-hydroxy-N-arylacetamides (RNOHCOCH3, R = phenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 4-ethoxyphenyl, 4-biphenylyl, 2-fluorenyl and 2-phenanthryl) was investigated by cyclovoltammetry. Each compound showed two different oxidation potentials, attributed to a quasi-reversible one-electron transfer in the range between 0·55 and 0·63 V and an irreversible transfer of a second electron between 0·80 and 1·20 V. Since the one-electron oxidation of N-hydroxy-N-arylacetamides gives the corresponding nitroxides, the kinetics of the self-reaction of these radicals and the concentration dependence of the product pattern were also studied.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 107
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990) 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
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  • 108
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 13-16 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A model is proposed for the quantification of resonance in thioamides. The percentage resonance and CS and CN bond distances predicted from the model are reported and the results are compared with those for the corresponding amides.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 109
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 55-61 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Rates of loss of tritium from p-nitrophenylnitromethane-α-t in toluene solution catalyzed by a series of amine bases show that hydrogen exchange in this system occurs at the same rate as ionization of the carbon acid, and that internal return is not taking place. This substantiates a previous suggestion that very large deuterium isotope effects reported for some of these reactions and attributed to extensive tunnelling were determined under conditions where the isotopic label was being lost and are therefore artifacts. This study provides isotope effects which are generally much smaller than those reported previously, but some tunnelling may still be taking place in some of these reactions.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 110
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 41-47 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The kinetics of the reactions of 1-chloro-, 1-fluoro- and 1-phenoxy-2,4-dinitrobenzene with piperidine, n-butylamine and benzylamine, and in the case of the ether, morpholine were studied as functions of nucleophile, DABCO and pyridine concentrations in tetrahydrofuran and ethyl acetate. The reactions of the ether with n-butylamine and benzylamine in benzene were also studied as functions of nucleophile, DABCO and pyridine concentrations. A comparison with results in the literature indicated that the reactions in tetrahydrofuran and ethyl acetate resemble those in dipolar aprotic solvents when primary amines are the nucleophiles and those in aprotic solvents when the nucleophile is a secondary amine. An explanation is suggested for the observation that whereas the reactions of 1-phenoxy-2,4-dinitrobenzene with piperidine and morpholine in both tetrahydrofuran and ethyl acetate are strongly catalysed by the nucleophiles, they are not catalysed by pyridine and there is either extremely weak or no catalysis by DABCO.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 111
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990) 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
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  • 112
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 81-88 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: MNDOC-CI results are reported for the photochemical α-cleavage reaction of carbonyl compounds. Potential energy surfaces for some excited singlet and triplet states and cross-sections along the bitopic reaction path show that the activation energy of the α-cleavage reaction is determined by the relative energetic position of the lowest two triplet states. The reactivity of aliphatic ketones depends only on the degree of branching at the α-carbon, because the triplet barrier is due to an (avoided) crossing of two surfaces corresponding to an nπ* and ππ* excitation respectively, which correlates with the stability of the leaving alkyl radical. For conjugated carbonyl compounds, on the other hand, the position of the crossing point is independent of the 3nπ* excitation energy, but if the 3ππ* surface is below the 3nπ* surface all the way along the reaction coordinate, the reaction is determined by the barrier on the 3ππ* surface and any additional stabilization of the 3ππ* state increases the barrier.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 113
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 119-125 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Nuclear spin polarization effects observed during the electron transfer-induced cleavage of the trans head-to-head dimer of 3,3-dimethylindene are incompatible with the intermediacy of a single dimer radical cation. Instead, they are compatible with the ‘cooperative’ involvement of a localized, doubly linked and a delocalized, singly linked dimer radical cation. The mechanistic consequences for the cycloaddition and cycloreversion of radical cations are discussed.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 114
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990) 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
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  • 115
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 143-146 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Analysis of the topological properties of the electron density distribution of cis-1,2-dinitrosoethene (I) shows that there is a normal covalent, albeit very long, single bond between the nitrogen atoms in the molecule, which is in fact the di-N-oxide of 1,2-diazacyclobutadiene (II). Despite its extraordinary length, the N—N bond is shown to be consistent with the strong correlation between the electron density at the bond critical points and the calculated bond lengths of N—N bonds. The geometry and electronic structure exhibit a number of remarkable features.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 116
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 174-180 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The kinetics of the oxidation of a number of monosubstituted aryl methyl, alkyl phenyl, dialkyl and diphenyl sulphides by N-chloroacetamide (NCA) to yield the corresponding sulphoxides were studied. The reaction is first order with respect to the sulphide, NCA and hydrogen ions. There is no effect of added acetamide. Protonated NCA has been postulated as the reactive oxidizing species. The rates of oxidation of meta- and para-substituted phenyl methyl sulphides were correlated with Taft's and Swain's dual substituent parameter equations. For the para-substituted compounds, the best correlation is obtained with σI and σR+; the meta-substituted compounds correlate best with σI and σR° values. The reaction constants are negative. The oxidation rates of the ortho-substituted sulphides yield an excellent correlation in a triparametric equation involving Taft's σI and σR+ values and Charton's steric parameter, V. The oxidation of alkyl phenyl sulphides is susceptible to both polar and steric effects of the alkyl group. A mechanism involving the formation of a halogenosulphonium cation in the rate-determining step is proposed.
    Zusätzliches Material: 8 Tab.
    Materialart: Digitale Medien
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  • 117
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 190-194 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Vector analysis of dipole moments of two series of nitrones revealed a mesomeric dipole moment compatible with a relatively great contribution of a zwitterionic structure and possible some contribution from a hypervalent structure. The latter was also suggested from a detailed comparison of bond lengths among several classes of compounds, involving the CNO grouping. Since both the C=N and N—O bonds seem to possess an appreciable double bond character, it is suggested that the N atom might be allocated more then eight valence electrons.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 118
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 205-208 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The equilibrium adduct from the Michael reaction between lithium dimethylphenylacetamide enolate and methyl cinnamate has been studied by means of 7Li, 13C and 1H NMR and IR spectroscopy as well as by electrical conductivity measurements in THF and diethyl ether. The 7Li NMR and the electrical conductivity measurements data are consistent with a triple ion structure of [A-M+A-]- M+ type, favoured in THF. All other spectral data support an intramolecular chelation in the triplet fragment.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 119
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 230-234 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The Stern-Volmer quenching equation for a photochemical reaction in the presence of internal filtering was obtained by applying the steady-state approximation to the system. The equation was used for the kinetic analysis of the Type II photoreaction of 2-benzoylcyclohexanone yielding 1-phenylhept-6-ene-1,3-dione, the enol form of which acts as an effective internal filter. The kqτ value for quenching of the photoreaction by 2,5-dimethylhexa-2,4-diene was determined to be 9·1 ± 0·5 l mol-1.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 120
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 255-259 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The lone-pair charge, Qlpf, of a base B is a (theoretically calculated) measure of the amount of charge on the lone pair of B that binds to an acid Av (v = 0, 1) in an acid-base reaction. It is shown how they can be used for the quantitative study of structural effects on gas-phase proton affinities, vertical ionization potentials and hydrogen-bonding basicities.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 121
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 419-427 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A method for relating averaged NMR parameters with point-by-point geometries for MM2 calculations is given for mobile molecules, e.g. δ-lactones. This method permits the identification of cis/trans geometry in cases where a complete set of isomers is not available. 2-Oxa-3r,4c,5t-triphenylcyclohexanone is prepared by condensation of 1,2-diphenylethanone with 3-phenylpropenal. The initially formed formed biscarbonyl adduct undergoes an internal Cannizzaro reaction forming a hydroxy ester, which lactonizes during work-up. The stereochemistry of the hydride transfer in the Cannizzaro reaction is consistent with the Felkin rule for asymmetric induction. The configurations of this and related lactones were studied through observation of NMR coupling constants, reductions to hemiacetals and molecular mechanics calculations. The most stable conformations are found to be a boat form for the parent lactone and a half-chair form for two isomers. The half-chair and boat forms lie near in energy for all isomers. The calculation techniques outlined illustrate that it is incorrect to consider only chair and boat forms; many intermediate conformations exist. Difficulties with previous IR methods of analysis are discussed.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
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  • 122
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The nature of the (Na-DB30C10)+ complex has been studied by 23Na NMR in four non-aqueous solvents: nitromethane (NM), acetonitrile (AN), acetone (AC) and pyridine (PY). The equilibrium constant of formation (Kf) of (Na-DB30C10)+ in AC, AN and PY was determined at 300 K: log Kf = 3·9 ± 0·3, 3·4 ± 0·5 and 3·0 ± 0·1, respectively. In cases such as in pyridine, where exact values of the rate constants for the chemical exchange could not be calculated, limiting values were determined giving k-1 (the rate constant for complex dissociation) 〉 6·6 × 10-4 s-1 and kc (the rate constant for the formation of the complex) 〉 5 × 107 l mol-1 s-1. Evidence was found for the formation of a 2 : 1 (Na2-DB30C10)+2 complex in nitromethane. It has been previously shown that for (Na-DB24C8)+ the first coordination sphere of Na+ is exclusively filled by the oxygens of the crown ether, whereas for (Na-DB18C6)+ there is participation of at least one solvent molecule. The first coordination sphere of Na+ in (Na-DB30C10)+ consists of one or several molecules of solvent in addition to a number of oxygens from the crown ether. The soft wrapping of the Na+ by DB30C10 is in constrast with the hard wrapping of Na+ by DB24C8 and of K+ by DB30C10.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 123
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The kinetics of the gas-phase elimination of two 2-haloethyl methanesulphonates were determined in a static system over the temperature range 310-380°C and pressure range 26-174 Torr. The reactions in seasoned vessels, with the free-radical inhibitor propene and/or toluene always present, are homogeneous and unimolecular, and follow a first-order rate law. The rate coefficients are given by the Arrhenius equations: for 2-bromoethyl methanesulphonate log k1 (s-1) = (11·70 ± 0·43)-(172·8 ± 4·8) kJ mol-1 (2·303RT)-1 and for 2-chloroethyl methanesulphonate log k1 (s-1) = (11·67 ± 0·50)-(173·9 ± 6·0) kJ mol-1 (2·303RT)-1. The bromo compound was found to be more reactive than the chloro compound. At 340°C, for Br k1 = 9·46 × 10-4 s-1 and for Cl k1 = 7·12 × 10-4 s-1. Apparently, electronic factors seem to be operating in these elimination reactions.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 124
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 477-481 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Ab initio calculations were carried out on systems with a geometrically constrained relationship between a double bond and a homoallylic substituent X, as in YC=CCCX. The axial-equatorial equilibria in 3-substituted methylenecyclohexanes and 4-substituted cyclohexenes are determined largely by the homoallylic interaction between X and the double bond. The homoallyic substituent was chosen to be OCH3, and the nature of the double bond was varied by changing Y (H, CH3, F, Cl, CN). NMR experiments previously had found very significant dependences of the axial-equatorial equilibrium on the nature of the X and Y substituents. Electrostatic calculations, based on Mulliken charges, reproduce the experimental (NMR) substituent effects on the axial-equatorial equilibrium and suffice to explain all the observations.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 125
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 493-502 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The stoichiometry of solvates formed in some binary solvent systems is presented and types of interactions in such systems are discussed based on changes in viscosity and dielectric properties.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 126
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 587-593 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: An analysis of the energy components of the conjugation energy between the substituent and the phenyl group in aniline and nitrobenzene showed that there are two types of conjugation: the conjugation energy in aniline, with an electron-donating substituent, is given by the decrease in the kinetic energy of elctrons, whereas that in nitrobenzene, with an electron-withdrawing substituent, is caused by the decrease in the potential energy. Physical interpretations are given of the arrows in the organic electron theory of these compounds.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 127
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 611-619 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: An MNDO study was made of the gas-phase thermal isomerization of isoxazole to explore theoretically the proposed reaction mechanism. The results showed that isoxazole isomerizes through an azirine, as an intermediate, to oxazole via a nitrile ylide or to ketenimine, with similar activation energies, and that the first step is rate limiting, in agreement with the experimental results. These results also show that isomerization to a nitrile is possible, but in this case the energy barrier is grater than the corresponding isomerization to oxazole. The MNDO study also supports a concerted process for the rate-limiting step, as reported earlier on the basis of experimental studies.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 128
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 635-638 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Ab initio calculations with the 6-31G* basis set were carried out on planar and pyramidalized geometries of the 1,1,3,3-tetrafluoropropenyl anion and on two geometries with one CF2 group rotated out of conjugation. Structures with at least one pyramidalized CF2 group are substantially lower in energy than the corresponding unpyramidalized structures for both rotated and unrotated geometries. At the MP2/6-31G* level of theory, three structures of approximately equal energy all lie 17-18 kcal mol-1 below the planar C2v structure. These include a Cs geometry with one CF2 group rotated out of conjugation, an unrotated C1 structure with unequal CC bond lengths and an unrotated, pyramidalized C2 structure with equal CC bond lengths.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 129
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 651-658 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The spectroscopic and physicochemical properties of parent azoles substituted on the nitrogen by a proton, a methyl group, a p-aminophenyl group and an acetyl group have been gathered. This information on azol-1-yl substituents has been treated by principal component analysis and partial least-squares analysis. The first result of these analyses is that it has been possible to complete some missing properties of azol-1-yl substituents, such as pKa for proton loss of some azoles and hydrolysis rates of certain azolides. Another significant result of the chemometric approach is the assignment of the 1-acetyltetrazole IR and NMR data to one of the two possible isomers.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 130
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Formation constants, K, for hydrogen bonding of weak C—H donors with hexamethylphosphoric triamide were measured in cyclohexane at 35°C by PMR spectroscopy; data were analyzed by the Higuchi method. Donors include terminal alkynes and series of polyfluoro-, polychloro- and polybromobenzenes. The K values for many of these are too small to measure in CCl4. For RC≡CH, K decreases in the order R = BrCH2 〉 C6H5 〉 C2H5O 〉 tert-butyl. For polyhalobenzenes, K is generally larger for F than Cl or Br, and meta halogens facilitate hydrogen bonding most effectively. Among tetrahalobenzenes, 1,2,3,4-isomers show the least evidence of 2:1 complex formation. Pentachlorobenzene has a smaller K than its 1,2,3,4-tetrachlor analog even after statistical correction; for C6HX5, K decreases in the order F 〉 Cl 〉 Br; the K values for 1,3,5-trihalobenzenes are closely similar; and 1,3,5-tribromo-2,4-dimethylbenzene shows no evidence of hydrogen bonding by PMR. The last three observations suggest that buttressing is important in the C6HX5 structure, at least with Cl and Br. A value of K for benzene was measured, suggesting for the first time that the H atoms of benzene engage in hydrogen bonding. The result compares well with values extrapolated from data for polyfluoro- but not polychlorobenzenes, again probably because of buttressing in the latter.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 131
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 694-696 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Benzyloxyfluorocarbene resists fragmentation to benzyl fluoride, and can be intercepted by water, fluoride ion, methanol or acrylonitrile. In contrast, benzyloxybromocarbene and benzyloxychlorocarbene fragment to the corresponding benzyl halides, and are not efficiently trapped.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 132
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990) 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 133
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 1-18 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Counterpoise corrected ab initio calculations are reported for (H2O)2 and H2O-H2CO. Geometry searches were done in the moment-optimized basis DZP' at the SCF, MP2, and CEPA-1 levels of theory, followed by more accurate single-point calculations in basis ESPB, which includes bondfunctions to saturate the dispersion energy. The final equilibrium binding energies obtained are -4.7 ±0.3 kcal/mol for a near-linear (H2O)2 structure and -4.6 ±0.3 kcal/mol for a strongly bent HOH ‥ OCH2 structure. The energy difference between these systems is much smaller than in all previous ab initio work. Cyclic (C2h) and bifurcated (C2v) transition structures for (H2O)2 are located at 1.0 ±0.1 kcal/mol and 1.9 ±0.3 kcal/mol above the global minimum, respectively. A new partitioning scheme is presented that rigorously partitions the MP2 correlation interaction energy in intra and intermolecular (dispersion) contributions. These terms are large (up to 2 kcal/mol) but of opposite sign for most geometries studied and hence their overall effect upon the final structures is relatively small. The relative merits of the MP2 and CEPA-1 approaches are discussed are discussed and it is concluded that for economical reasons MP2 is to be preferred, especially for larger systems.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 134
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 45-57 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: A data compression method is presented that is generally applicable to first-order convergent iterative procedures that employ subspace expansions or extrapolations based on successive correction vectors. This method is based on the truncation of insignificant information in successive correction vectors. Although the correction vectors themselves may be severely truncated with the proposed approach, the final solution vector may be represented to arbitrary accuracy. A feature of the proposed method is that more slowly convergent iterative procedures allow the correction vectors to be more severely truncated without affecting the overall convergence rate. The method is implemented and applied to the iterative Davidson diagonalization method. If the compressed representation of the expansion vectors can be held in main computer memory, then a significant reduction in the I/O requirements is achieved.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 135
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 67-75 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: By examining the displacement coordinate metric three modes of constrained optimization for large molecules and clusters are suggested. The first method corresponds to a conventional optimization using internal coordinates. The second mode has applications with respect to both internal and cartesian coordinates. The final mode is particularly interesting because it can result in computational savings. A mixture of both internal and cartesian coordinates is specified where these coordinates are usually a subset of the molecules or clusters total coordinate set. In the optimization only a subset of the energy derivatives need be evaluated reducing the computational effort associated with the gradient calculation.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 136
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 82-87 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: A finite-field method for the calculation of polarizabilities and hyperpolarizabilities is developed based on both an energy expansion and a dipole moment expansion. This procedure is implemented in the MOPAC semiempirical program. Values and components of the dipole moment (μ), polarizability (α), first hyperpolarizability (β), and second hyperpolarizability (γ) are calculated as an extension of the usual MOPAC run. Applications to benzene and substituted benzenes are shown as test cases utilizing both MNDO and AM1 Hamiltonians.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 137
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 121-151 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: A procedure has been developed for global energy minimization of surface loops of proteins in the presence of a fixed core. The ECEPP potential function has been modified to allow more accurate representations of hydrogen bond interactions and intrinsic torsional energies. A computationally efficient representation of hydration free energy has been introduced. A local minimization procedure has been developed that uses a cutoff distance, minimization with respect to subsets of degrees of freedom, analytical second derivatives, and distance constraints between rigid segments to achieve efficiency in applications to surface loops. Efficient procedures have been developed for deforming segments of the initial backbone structure and for removing overlaps. Global energy minimization of a surface loop is accomplished by generating a sequence (or a trajectory) of local minima, the component steps of which are generated by searching collections of local minima obtained by deforming seven-residue segments of the surface loop. The search at each component step consists of the following calculations: (1) A large collection of backbone structures is generated by deforming a seven-residue segment of the initial backbone structure. (2) A collection of low-energy backbone structures is generated by applying local energy minimization to the resulting collection of backbone structures (interactions involving side chains that will be searched in this component step are not included in the energy). (3) One low-energy side-chain structure is generated for each of the resulting low-energy backbone structures. (4) A collection of low-energy local minima is generated by applying local energy minimization to the resulting collection of structures. (5) The local minimum with the lowest energy is retained as the next point of the trajectory. Applications of our global search procedure to surface segments of bovine pancreatic trypsin inhibitor (BPTI) and bovine trypsin suggest that component-step searches are reasonably complete. The computational efficiency of component-step searches is such that trajectories consisting of about 10 component steps are feasible using an FPS-5200 array processor. Our procedure for global energy minimization of surface loops is being used to identify and correct problems with the potential function and to calculate protein structure using a combination of sequence homology and global energy minimization.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 138
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 416-430 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: A systematic analysis of the molecular electrostatic potential (MEP) is presented. This study has been performed with a twofold purpose: first, to study the MEP dependence with regard to the quality of the basis set used to compute the ab initio SCF wavefunction and second, to develop and to assess a new strategy for computing isoelectrostatic potential maps using the semiempirical MNDO wavefunction. The only differences between this procedure and the ab initio SCF MEP computation lie in the freezing of the inner electrons and in the origin of the first-order density matrix. The statistical analysis of MEPs computed for a large number of molecules from MNDO wavefunction and ab initio SCF wavefunctions obtained using STO-3G, 4-31G, 6-31G, 4-31G*, 6-31G*, and 6-31G** basis sets points out the ability of any wavefunction to reproduce the general topological characteristics of the MEP surfaces. Nevertheless, split-valence basis sets including polarization functions are necessary to obtain accurate MEP minimum energy values. MNDO wavefunction tends to overestimate the MEP minima depth by a constant factor and shows an excellent ability to reflect the relative variation of MEP minima energies derived from a rather sophisticated (6-31G*) basis set, lacking of the shortcomings detected in the semiempirical CNDO approximation.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 139
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 487-492 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Expressions are derived for computing the kinetic energy of a peptide with fixed geometry, in terms of dihedral angles as generalized coordinates; other expressions required for the solution of Lagrange's equations are also presented. The peptide is regarded as held stationary at one end. We also outline the computations that are needed in calculating the components of the third derivative of a potential energy function that consists of a sum of pairwise interatomic interactions.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 140
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 819-828 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Complexes of alkali and alkaline earth cations with organic compounds are modeled by describing ionligand interaction energies with pair potentials and intraligand as well as interligand energies with the MM2 potential. New pair potentials for the interaction of Li+, Na+, K+, Mg2+, and Ca2+ ions are derived on the basis of 30,000 ab initio interaction energy values with 70 selected model ligand molecules. Various problems of the combination of these two basically different potentials are discussed. An application for the K+ complex of 18-crown-6 is presented. For more flexible ligands the introduction of three-body correction terms of the pair potentials seems necessary.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 141
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 924-929 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: The geometry, electronic structure, and photoelectron spectra of Sb2 and Sb4 have been investigated employing the LCGTO-MP-LSD method. For both molecules the geometrical and spectroscopic constants computed using the VWN potential are in very good agreement with the available experimental data. The HeI photoelectron spectra were computed with different potentials (Xα, GL, HL, BH, and VWN). The calculated spectra are in excellent agreement with the experimental ones and the use of the VWN potential gives the most accurate results. The reliable results for molecules complement those for the Sb atom and show that the proposed LSD Model Potential is able to give an accurate description of the structural and spectroscopic properties of the title molecules.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 142
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 958-971 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Intermolecular potential functions have been developed for use in computer simulations of alkyl ethers. The simple OPLS model was adopted and parameterized to yield good descriptions of bimolecular and ion-molecule complexes as well as to reproduce experimental thermodynamic properties of liquid ethers. The principal testing featured Monte Carlo statistical mechanics simulations for liquid dimethyl ether (DME), ethyl methyl ether (EME), diethyl ether (DEE), and tetrahydrofuran (THF). Average errors of 1-3% are obtained for the computed densities and heats of vaporization including results for THF at pressures up to 5000 atm. The torsional motion about the central C—O bonds in EME and DEE was included in the simulations using rotational potential functions fit to results of molecular mechanics (MM2) calculations. The liquid-state environment is found to have negligible effect on the conformational equilibria.
    Zusätzliches Material: 15 Ill.
    Materialart: Digitale Medien
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  • 143
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 972-977 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: A quadrature-point-driven implementation of the standard Rys polynomial method for computing two-electron repulsion integrals of gaussian basis functions has been found to be both concise and openended with respect to the angular momentum of the gaussian functions (i.e., s,p,d,f,g,…). These are important features in certain applications, such as molecular properties and property gradients.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 144
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 994-1002 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Free energy perturbation calculations were performed to determine the free energy of binding associated with the presence of perhaps an unusual hydroxyl group in the transition state analog of nebularine, an inhibitor of the enzyme adenosine deaminase. The presence of a single hydroxyl group in this inhibitor has been found to contribute -9.8 kcal/mol to the free energy of binding, with a 108-fold increase in the binding affinity by the enzyme. In this work, we calculate the difference in solvation free energy for the 1,6-dihydropurine complex versus that of the 6-hydroxyl-1,6-dihydropurine complex to determine if this marked increase in binding affinity is attributed to an unusually hydrophobic hydroxyl group. The calculated ΔG associated for the solvation free energy is -11.8 kcal/mol. This large change in the solvation free energy suggests that this hydroxyl is instead unusually hydrophilic and that the difference in free energy of interaction for the two inhibitors to the enzyme must be at least ca. 20 kcal/mol. Although the crystal structure for adenosine deaminase is currently not known, we attempt to mimic the nature of the active site by constructing models which simulate the enzyme-inhibitor complex. We present a first attempt at determining the change in free energy of binding for a system in which structural data for the enzyme is incomplete. To do this, we construct what we believe is a minimal model of the binding between adenosine deaminase and an inhibitor. The active site is simulated as a single charged carboxyl group which can form a hydrogen bond with the hydroxyl group of the analog. Two different carboxyl anion models are used. In the first model, the association is modeled between an acetic acid anion and the modified inhibitor. The second model consists of a hydrophobic amino acid pocket with an interior Glu residue in the active site. From these models we calculate the change in free energy of association and the overall change in free energy of binding. We calculate the free energies of interaction both in the absence and presence of water. We conclude from this that the presence of a single suitably placed-CO-2 group probably cannot explain the binding effect of the-OH group and that additional interactions will be found in the adenosine deaminase active site.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 145
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 1029-1037 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Pseudopotentials and valence basis sets to be used in calculations for organometallic compounds of zinc and magnesium have been tested in calculations for the M(CH3)n (M = Zn, Mg; n = 1,2) molecules. Valence correlation effects are treated at the SDCI and CEPA levels. The capability of a polarization potential on zinc to account for the valence shell contracting effect of core valence correlation is studied. Properties considered are geometries, force constants, Mulliken populations, ionization potentials, atomization, and binding energies. Differences in bonding between the two dimethyl compounds are discussed.
    Zusätzliches Material: 1 Ill.
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  • 146
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 1094-1100 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: The acid-catalyzed hydrolysis mechanisms of maleamic (4-amino-4-oxo-2-butenoic) acids were studied using AM1 method. The reaction proceeded mainly in two steps: (1) nucleophilic attack of the undissociated carboxyl group on the adjacent aminocarbonyl carbon via a zwitterionic intermediate; and (2) the rate-determining proton transfer to form the zwitterionic tetrahedral intermediate. In each step, the hydration of water and hydronium ion molecules was important in stabilizing the polarized intermediates. The substituent effects at the amide moiety and the 2,3-positions of the maleamic acids were qualitatively estimated for each step.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 147
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990) 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Materialart: Digitale Medien
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  • 148
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 1139-1146 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: A prescription for applying the method of molecular similarity calculations based on electrostatic potentials and fields is developed by consideration of a typical structure-activity series. Firm conclusions are drawn about the nature of the grid of points surrounding the molecules and about the choice of geometry, but options for point charges are less clearcut.
    Zusätzliches Material: 1 Ill.
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  • 149
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 899-908 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: An expanded form of the Wiener number is suggested for characterization of molecular graphs and structure-property correlations. The simple, computer-oriented method for counting of the novel index is briefly discussed.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 150
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 1193-1205 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: A common requirement in conformational analysis is the identification of a molecule's lowest energy conformations. The application of the A* algorithm to this problem is examined. The algorithm uses heuristic information about the problem domain to direct the search and has been implemented in a system for performing automated conformational analysis. The method is detailed and sample results presented. Some limitations of the approach are identified.
    Zusätzliches Material: 13 Ill.
    Materialart: Digitale Medien
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  • 151
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 1009-1016 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Heats of formation and net atomic charges of some 120 structures involving substituted phenols, anilines, and benzoic acids and the corresponding anions were calculated by MNDO, AM1, and PM3 semiempirical methods. The gas phase acidities of substituted phenols and anilines and the net atomic charges on the anionic heteroatoms of the corresponding anions have been successfully correlated with σ- constants. Moreover, good correlations with σ were found for the charges on the acidic hydrogens of substituted phenols and anilines. In contrast, the gas phase acidities of substituted benzoic acids and the charges on the anionic oxygens of the corresponding anions are better correlated with Taft σ° constants. Comparisons of these results with experimental data and ab initio theoretical calculations indicate that AM1 and PM3 methods are much better than MNDO in predicting the acidity of aromatic compounds.
    Zusätzliches Material: 8 Tab.
    Materialart: Digitale Medien
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  • 152
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 1038-1046 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: We studied geometries and energies of complexes between water and neutral or protonated imidazole by ab initio molecular orbital calculations using the 4-31G basis set with and without the counterpoise correction. Positions of hydration sites and relative binding energies could be also estimated by using the electrostatic field map of imidazole as calculated by our bond increment method. The reliability of the calculations is confirmed by comparing the geometries of the imidazole-water complex to the experimental ones from the Cambridge Structural Database. These were obtained by X-ray diffraction studies on crystals with water bound to a molecule containing the imidazole fragment.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 153
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 1061-1071 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: A new method for the evaluation of metal complexes with molecular mechanics calculations is described. The method has been employed to determine the global minimum energy conformations of three seven-coordinate lanthanide complexes. The method searches the potential energy surface of the metal complexes for the global minimum structure using the recently reported Random Incremental Pulse Search (RIPS). The molecular mechanics calculations were performed using the MM2 metal-extended force field (MM2MX). This force field excludes 1-3 bending terms about the metal center and, instead, explicitly includes 1-3 nonbonded van der Waals interactions. This affords a model based mainly on steric interactions about the ligating atoms, and removes the necessity of specifying ligand-metal-ligand bond angles for seven-coordinate and higher metal complexes in which no preferred bond angle can be proficiently determined. The calculated minimum-energy structures were well known seven-coordinate conformations in all cases, and a comparison with X-ray crystallographic is presented.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 154
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 1076-1079 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: The method of approximation of the frozen molecular fragment (FMF) we derived has been applied to calculations of proton affinities. Results are in good agreement with experimental data and extended basis set calculations.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 155
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 1087-1093 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Myelin basic protein (MBP) is the major extrinsic protein of the myelin sheath in the central nervous system. It is this protein that is destroyed in such demyelinating diseases as multiple sclerosis. We have examined the predicted structures of one segment of MBP using the molecular mechanics program ECEPP83 developed by Scheraga and co-workers as modified by Chuman, Momany, and Schafer. We have focused upon a segment, 87-118, containing the Pro-Pro-Pro sequence (residues 100-102), which has been predicted from standard algorithms to exist in a hairpin loop connecting anti-parallel beta-strands. Several local energy minima have been found and reported. Tripoline sequences are not rare in proteins, but their structure and function is still uncertain.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 156
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 1101-1110 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Two new computational methods for the evaluation and partitioning of projected, planar, and averaged slab electron densities, implemented in the program PRODEN, are presented. The new algorithms for the projection, demarcation, and integration of electron densities are described and evaluated in terms of speed and numerical accuracy. Integrated Projected Populations are analyzed and some of the advantages and limitations of the methods are discussed.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 157
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 930-942 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: The effect of the addition of diffuse functions of sp type on the first row atoms (and/or of d type on phosphorus) to a MINI-1 minimal basis set is evaluated by comparing the SCF description of the interaction energy and its decomposition, counterpoise (CP) corrected and uncorrected for basis set superposition errors (BSSEs), with that produced by extended basis sets (6-31G** and 3-21G+) as well as by basis sets (6-31G** + VPS and (2d)S), previously successfully tested, designed to minimize the BSSE. The systems considered are a few anions (F-, HCOO-, H2PO-4) H-bonded to water; the basis set performance on a different geometry (bifurcated instead of linear) of the phosphate-water adduct was also considered. An additional comparison with the interaction energy in a neutral dimer, (HF)2, was carried out. The addition of diffuse functions to the MINI-1 basis set, instead of resorting to extended basis sets, seems to be a sensible choice for anions. The equilibrium distance is shifted towards the reference basis set value at the CP corrected level as well as at the uncorrected one. The spread of the energy due to the basis set is hardly distinguishable when the CP corrected values are plotted. The description of the interaction energy in dimers involving phosphorus is improved using d type diffuse functions.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
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  • 158
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990) 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 159
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 1017-1020 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Ab initio CI calculations using pseudopotentials to describe germanium inner electrons are carried out on the low-lying excited singlet states (T2) of GeH4. A theoretical analysis of these states in terms of Mulliken population of Rydberg orbitals for each state and oscillator strengths allow us to reinterpret its experimental Vacuum UV electronic spectrum.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 160
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 1047-1060 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: The algorithm used by the program GEPOL to compute the Molecular Surface (MS), as defined by Richards, is presented in detail. GEPOL starts like other algorithms from a set of spheres with van der Waals radii, centered on the atoms or group of atoms of the molecule. GEPOL computes the MS by first searching the spaces inaccessible to the solvent and consequently filling them with a new set of spheres. Here we study the behavior of the method with its parameters, presenting several examples of application.
    Zusätzliches Material: 13 Ill.
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  • 161
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 1080-1086 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: A boundary element method is developed to compute the electrostatic potential inside and around molecules in an electrolyte solution. A set of boundary integral equations are derived based on the integral formulations of the Poisson equation and the linearized Poisson-Boltzmann equation. The boundary integral equations are then solved numerically after discretizing the molecular surface into a number of flat triangular elements. The method is applied to a spherical molecule for which analytical solutions are available. Use is made of both constant and linearly varying unknowns over the boundary elements, and the method is tested for various values of parameters such as the dielectric constant of the molecule, ionic strength, and the location of the interior point charge. The use of the boundary integral method incorporating the nonlinear Poisson-Boltzmann equation is also briefly discussed.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 162
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The method for determining the rates of formation of gaseous pyrolysis products during thermal decompositions by simultaneous thermogravimetric modulated beam mass spectrometry is presented. The analysis procedure that handles both molecular and continuum flow from the reaction cell is described. The technique is illustrated with the isothermal decomposition of HMX. The temporal behaviors of the rates of formation of the pyrolysis products, H2O, HCN, CO, CH2O, NO, N2O, methylformamide, C2H6N2O, and octahydro-1-nitroso-3, 5, 7-trinitro-1, 3, 5, 7-tetrazocene, formed during the isothermal decomposition of HMX at 211°C, are presented. The results show that a complex condensed-phase reaction mechanism controls the decomposition.
    Zusätzliches Material: 4 Ill.
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  • 163
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 243-252 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Rate constants and activation parameters for the direct addition reaction of methyloxirane or ethyloxirane to alkyl-2-hydroxyalkyl sulfides or successive oxypropylene and oxybutylene adducts in the presence of basic catalysts were determined at 373-403 K. This reaction was found to be of the first order with respect to alkyloxirane, sulfide, and catalyst.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 164
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 321-329 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Kinetic parameters of the reaction of ozone with aliphatic alcohols of different structures are obtained. The ratio between the relative reactivities of the primary: secondary: tertiary alcohols was found to be 1:15:138. The bond energy changes in the same sense as the activation energy. The rate-controlling step of ozone reaction with alcohols is the abstraction of a hydrogen atom being in α-position with respect to the OH group. The pre-exponential factors (A) are calculated by the collision and activated complex methods and compared with the experimentally obtained values. The results from the calculations represent convincing evidence that the mechanism of the rate-controlling step of the reaction is associated with the formation of an activiated complex which has a linear shape ensuring free rotation of its fragments.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 165
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Excitation of Ru(bipy)32+ ion by visible radiation of wavelength λ = 436 nm in aqueous medium in presence of inorganic peroxides, peroxomonosulfate (PMS), peroxodisulfate (PDS), and peroxodiphosphate (PDP) was found to generate Ru(bipy)33+. The kinetics of this photochemical oxidation of Ru(bipy)32+ by each peroxide was followed spectrophotometrically and found to obey a total second-order, first-order each in [Ru(bipy)32+] and [peroxide]. In the absence of light, thermal reaction of PMS and PDS with Ru(bipy)32+ occurred but only when at 1.0 M [H+] and 〉 10-2M [peroxide]. The reaction of PMS with the complex is found to be cyclic, ie., Ru(bipy)33+ formed oxidizes PMS itself and such a reaction was not observed in the case of PDS and PDP. The effects of pH, [peroxide], and [Ru(bipy)32+] on the visible light induced oxidation of Ru(bipy)32+ by these peroxides are investigated. The results are discussed with suitable reaction mechanisms.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 166
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reaction rates of ethanolysis of ionized phenyl salicylate, PS-, have been studied in the presence of different concentrations of various inorganic and organic salts in ethanol-water solvent of different compositions. The observed pseudo first-order rate constants,k1, reveal a nonlinear increase with increase of thecontent of ethanol until it becomes ca. 85%, v/v. The rate constants, k1, begin to decrease with increase of ethanol content beyond ca. 85%, v/v. The observed data obtained at ethanol contents of 〈ca. 55%, v/v, follow the relationships k1 = k[EtOH]T/(1 + K[EtOH]T ) where k and K represent the second-order rate constant for thereaction of PS- with monomeric ethanol, EtOH, and association constant for dimerization of monomers of ethanol, respectively, and [EtOH]T is the total concentration of ethanol. The calculated values of k and K obtained in the presence of 0.01 M tetraalkylammonium ions, R4N+, show ca. 15% and 40%, respectively, decrease with increase of the chain lengths of alkyl groups, R. The following conclusions have been derived from the observed data. (i) Lithium chloride causes ethanol structure-making effect while NaCl, KCl, and CsCl show ethanol structure-breaking effect. (ii) Tetraalkylammonium halide salts such as Me4NCl, Et4NI, andn-Bu4NI reveal ethanol structure-breaking effect due to the transfer of some water molecules from solvation shells of ethanol and R4N+ when favorable hydrophobic interaction between hydrophobic sites of ethanol and R4N+ results in. This effect is, however, partially off set by the direct interaction between monomeric ethanol and R4N+. Both inorganic and organic cations are preferentially solvated by only water molecules in EtOH-H2O solvents with EtOH contents of 〈ca. 55%, v/v. The effects of 0.01 M LiOH on k1 values obtained within the ethanol content range of 35% to 97%, v/v, seemed to be unaffected due to the presence of 0.01 M NaCl.
    Zusätzliches Material: 6 Ill.
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  • 167
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990) 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 168
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 175-186 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The photolysis of trans-3,4-dimethylcyclopentanone has been investigated in the gas phase at 100°C using light of 206 and 193 nm. The photolytic products are propene, 1,2-dimethylcyclobutane, and the butene isomers. Small quantities of 3,4-dimethylpent-4-enal were also detected. Relative yields of these products were determined as a function of the ketone pressure and also of that of added nitrogen. A mechanism for the photochemical decomposition based on that suggested for the photolysis of cyclopentanone using short wavelength radiation, is consistent with the experimental results and is simpler than that required to account for the long wavelength photolysis reported earlier.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 169
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 379-397 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of reactions (1)-(4) as a function of temperature. In all cases, the concentration of the excess reagent, i.e., HBr or Br2, was measured in situ in the slow flow system by UV-visible photometry. Heterogeneous dark reactions between XBr (X = H or Br) and the photolytic precursors for Cl(2P) and O(3P) (Cl2 and O3, respectively) were avoided by injecting minimal amounts of precursor into the reaction mixture immediately upstream from the reaction zone. The following Arrhenius expressions summarize our results (errors are 2σ and represent precision only, units are cm3 molecule-1 s-1): k1 = (1.76 ± 0.80) × 10-11 exp[(40 ± 100)/T]; k2 = (2.40 ± 1.25) × 10-10 exp[-(144 ± 176)/T]; k3 = (5.11 ± 2.82) × 10-12 exp[-(1450 ± 160)/T]; k4 = (2.25 ± 0.56) × 10-11 exp[-(400 ± 80)/T]. The consistency (or lack thereof) of our results with those reported in previous kinetics and dynamics studies of reactions (1)-(4) is discussed.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 170
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 431-448 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Reaction rate constants for the hydrolysis of organic esters and amides were determined at temperatures of 100-240°C in aqueous solutions buffered at pH values between 5.5 and 7.3. Experiments are modeled assuming alkaline hydrolysis with a thermodynamic solution model included to account for the temperature dependence of hydroxide ion concentration. In most cases, the ester hydrolysis second order rate constants agree well with published values from experiments in strongly basic solutions at pH values from 11 to 14 and temperatures from 25-80°C, despite the large extrapolations required to compare the data sets. The amide hydrolysis rate constants are about one order of magnitude higher than the extrapolated results from other investigators, but the reaction rate increased proportionally with hydroxide ion concentration, suggesting that an alkaline hydrolysis mechanism is also appropriate. These data establish the validity of the alkaline hydrolysis mechanism and can be used to predict hydrolysis reaction rates in neutrally-buffered solutions such as many groundwater and geothermal fluids.
    Zusätzliches Material: 10 Ill.
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  • 171
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 253-259 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The basis dehydrobromination of p-substituted 2-phenylethyl bromides promoted by hydroxide ion has been studied in micelles of N-hexadecyl-N,N,N-trimethylammonium nitrate (CTANO3). The pseudophase ion exchange model can be adapted to explain the kinetic results at low hydroxide ion concentration, i.e., less than 0.075 M of NaOH. At high hydroxide ion concentration in solution the applied model does not describe the kinetic results unless the empirical variations are applied for the mol ratio of reactive ion to micellar head group (β) and the binding constant of the organic reagent to the micelle (Ks).
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 172
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 399-414 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the important stratospheric reactions Cl(2PJ) + O3 → ClO + O2 and Br(2P3/2) + O3 → BrO + O2 as a function of temperature. The temperature dependence observed for the Cl(2PJ) + O3 reaction is nonArrhenius, but can be adequately described by the following two Arrhenius expressions (units are cm3 molecule-1 s-1, errors are 2σ and represent precision only): k1(T) = (1.19 ± 0.21) × 10-11 exp [(-33 ± 37)/T] for T = 189-269K and k1(T) = (2.49 ± 0.38) × 10-11 exp[(-233 ± 46)/T] for T = 269-385 K. At temperatures below 230 K, the rate coefficients determined in this study are faster than any reported previously. Incorporation of our values for k1(T) into stratospheric models would increase calculated ClO levels and decrease calculated HCl levels; hence the calculated efficiency of ClOx catalyzed ozone destruction would increase. The temperature dependence observed for the (2P3/2) + O3 reaction is adequately described by the following Arrhenius expression (units are cm3 molecule-1 s-1, errors are 2σ and represent precision only): k2(T) = (1.50 ± 0.16) × 10-1 exp[(-775 ± 30)/T] for T = 195-392 K. While not in quantitative agreement with Arrhenius parameters reported in most previous studies, our results almost exactly reproduce the average of all earlier studies and, therefore, will not affect the choice of k2(T) for use in modeling stratospheric BrOx chemistry.
    Zusätzliches Material: 4 Ill.
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  • 173
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 483-490 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Rates of hydrolysis of hydroxamic acids with perfluorooctanoic acid as a reactive counterion surfactant and also with sodium sulfonate surfactants plus HCl have been determined in both water and aqueous acetonitrile solvents. The pseudophase ion exchange model satisfactorily explains the micellar effects for both the reactive and non-reactive counterion surfactants in both solvent systems.
    Zusätzliches Material: 4 Ill.
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  • 174
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990) 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 175
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 449-453 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of hydrolysis of Cu(II)-salicylamide complex have been studied in sodium hydroxide solution (0.5 to 2.5M). The observed pseudo-first-order rate constants vary according to the empirical equation 1/kobs = B1 + B2/[ŌH] up to 2.0 M sodium hydroxide concentration. The mechanism of base-catalyzed hydrolysis has been proposed and it is concluded that the reaction proceeds by the interaction of complex with the nucleophile, forming tetrahedral intermediate which then breaks down to products. The rate equation has been derived. Thermodynamic parameters have also been reported.
    Zusätzliches Material: 2 Ill.
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  • 176
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 491-504 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of the thermal decomposition of acetylacetone has been studied in a shock tube in the temperature range of 1120-1660 K. Detailed analyses of CO and H2O formation data indicate that H2O is formed by a four-center molecular channel, whereas CO is formed by the rapid dissociation of CH3CO produced by the C—C bond dissociation of acetylacetone. The Arrhenius equations for H2O and CH3CO formation channels are k2 = 1014.24±0.21 exp(-60,800 ± 1,220/RT)sec-1 and k3 = 1017.05±0.28 exp(-74,600 ± 1,680/RT) sec-1, respectively. The results of the study suggest that the six-center molecular channel for the production of acetone and ketene is not important under the condition used in this investigation.
    Zusätzliches Material: 5 Ill.
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  • 177
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 513-535 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The mechanism of NH3 pyrolysis was investigated over a wide range of conditions behind reflected shock waves. Quantitative time-history measurements of the species NH and NH2 were made using narrow-linewidth laser absorption. These records were used to establish an improved model mechanism for ammonia pyrolysis. The risetime and peak concentrations of NH and NH2 in this experimental database have also been summarized graphically.Rate coefficients for several reactions which influence the NH and NH2 profiles were fitted in the temperature range 2200 K to 2800 K. The reaction and the corresponding best fit rate coefficients are as follows: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm NH}_{\rm 2} + {\rm H} \to {\rm NH + H}_{\rm 2} $$\end{document} with a rate coefficient of 4.0 × 1013 exp(-3650/RT) cm3 mol-1 s-1, \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm NH}_{\rm 2} + {\rm NH} \to {\rm N}_{\rm 2} {\rm H}_{\rm 2} + {\rm H}$$\end{document} with a rate coefficient of 1.5 × 1015T-0.5 cm3 mol-1 s-1 and \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm NH}_{\rm 2} + {\rm NH}_{\rm 2} \to {\rm NH + NH}_{\rm 3} $$\end{document} with a rate coefficient of 5.0 × 1013 exp(-10000/RT) cm3 mol-1 s-1. The uncertainty in rate coefficient magnitude in each case is estimated to be ±50%. The temperature dependences of these rate coefficients are based on previous estimates.The experimental data from four earlier measurements of the dissociation reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm NH}_{\rm 3} + {\rm M} \to {\rm NH}_{\rm 2} {\rm + H + M} $$\end{document} were reanalyzed in light of recent data for the rate of NH3 + H → NH21 + H2, and an improved rate coefficient of 2.2 × 1016 exp(-93470/RT) cm3 mol-1 s-1 in the temperature range 1740 to 3300 K was obtained. The uncertainty in the rate coefficient magnitude is estimated to be ± 15%.
    Zusätzliches Material: 17 Ill.
    Materialart: Digitale Medien
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  • 178
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 633-639 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reaction rates of SO3 with CH3OH in He were measured at total pressures of 0.7-1.6 torr in flow tubes. The concentration of SO3 was monitored by the SO2* fluorescence from excitation of SO3 at 147 nm. The reaction rate constant of SO3 + CH3OH in the gas phase is determined to be (1.17 ± 0.16) × 10-13 cm3 molec-1 s-1 at room temperature.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 179
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Rate constants for the reactions of OH radicals and Cl atoms with diethyl sulfide (DES), di-n-propyl sulfide (DPS), and di-n-butyl sulfide (DBS) have been determined at 295 ± 3 K and a total pressure of 1 atm. Hydroxyl radical rate data was obtained using the absolute technique of pulse radiolysis combined with kinetic spectroscopy. The chlorine atom rate constants were measured using a conventional photolytic relative rate method. The rate constant for the reaction of Cl atoms with dimethyl sulfide (DMS) was also determined. The following rate constants were obtained: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} k({\rm OH + DES) = (}11.6 \pm 2) \times 10^{ - 12} {\rm cm}^{\rm 3} {\rm molecule}^{{\rm - 1}} {\rm s}^{{\rm - 1}} \\ k({\rm OH + DPS) = (}21.5 \pm 3) \times 10^{ - 12} {\rm cm}^{\rm 3} {\rm molecule}^{{\rm - 1}} {\rm s}^{{\rm - 1}} \\ k({\rm OH + DBS) = (}37.4 \pm 5) \times 10^{ - 12} {\rm cm}^{\rm 3} {\rm molecule}^{{\rm - 1}} {\rm s}^{{\rm - 1}} \\ k({\rm Cl + DMS) = (}32.2 \pm 3) \times 10^{ - 11} {\rm cm}^{\rm 3} {\rm molecule}^{{\rm - 1}} {\rm s}^{{\rm - 1}} \\ k({\rm Cl + DES) = (}44.1 \pm 4) \times 10^{ - 11} {\rm cm}^{\rm 3} {\rm molecule}^{{\rm - 1}} {\rm s}^{{\rm - 1}} \\ k({\rm Cl + DPS) = (}51.8 \pm 4) \times 10^{ - 11} {\rm cm}^{\rm 3} {\rm molecule}^{{\rm - 1}} {\rm s}^{{\rm - 1}} \\ k({\rm Cl + DBS) = (}64.6 \pm 2) \times 10^{ - 11} {\rm cm}^{\rm 3} {\rm molecule}^{{\rm - 1}} {\rm s}^{{\rm - 1}} \\ \end{array} $$\end{document}
    Zusätzliches Material: 4 Ill.
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  • 180
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 665-671 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The relative rate technique has been used to measure rate constants for the reaction of chlorine atoms with nitro methane, nitro ethane, nitro propane, nitro butane, nitro pentane, ethyl nitrate, isopropyl nitrate, n-propyl nitrate, 2-pentyl nitrate, and 2-heptyl nitrate. Decay rates of these organic species were measured relative to one or more of the following reference compounds; n-butane, ethane, chloroethane, and methane. Using rate constants of 2.25 × 10-10 5.7 × 10-11, 8.04 × 10-12, and 1.0 × 10-13 cm3 molecule-1 s-1 for the reaction of Cl atoms with n-butane, ethane, chloroethane, and methane, respectively, the following rate constants were derived, in units of cm3 molecule-1 s-1: nitro methane, 〈7 × 10-15; nitro ethane, (2.05 ± 0.14) × 10-13; nitro propane, (1.13 ± 0.05) × 10-11; nitro butane, (5.13 ± 0.68) × 10-11; nitro pentane, (1.40 ± 0.14) × 10-10; ethyl nitrate, (3.70 ± 0.24) × 10-12; n-propyl nitrate, (2.15 ± 0.13) × 10-11; i-propyl nitrate, (3.94 ± 0.48) × 10-12; 2-pentyl nitrate, (1.00 ± 0.06) × 10-10; and 2-heptyl nitrate, (2.84 ± 0.50) × 10-10. Quoted errors represent 2σ and do not include possible systematic errors due to errors in the reference rate constants. Experiments were performed at 295 ± 2 K and atmospheric pressure (≃740 torr) of synthetic air. The results are discussed with respect to the previous literature data and to the modeling of these compounds in the atmosphere.
    Zusätzliches Material: 1 Ill.
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  • 181
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 711-717 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Rate constants for the gas phase reCedex 2, Franceactions of O(3P) atoms with a series of symmetric aliphatic ethers have been determined using the flash photolysis resonance fluorescence technique over the temperature range 240-400 K. The Arrhenius parameters derived from these data are (in units of cm3 molecule -1 s-1): \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{rcl} {\rm dimethyl ether,}k &=& (5.39 \pm 1.94) \times 10^{ - 12} {\rm exp[(} - {\rm 1320} \pm 120)/T]; \\ {\rm diethyl ether,}k &=& (1.42 \pm 0.18) \times 10^{ - 11} {\rm exp[(} - {\rm 1070} \pm 40)/T]; \\ {\rm di -}n{\rm - propyle ether,}k &=& (1.41 \pm 0.21) \times 10^{ - 11} {\rm exp[(} - {\rm 960} \pm 50)/T]; \\ {\rm di -}n{\rm - butyl ether,}k &=& (1.37 \pm 0.29) \times 10^{ - 11} {\rm exp[(} - {\rm 880} \pm 70)/T]; \\ {\rm di -}n{\rm - pentyl ether,}k &=& (1.26 \pm 0.84) \times 10^{ - 11} {\rm exp[(} - {\rm 780} \pm 200)/T]; \\ \end{array} $$\end{document}The error limits are two standard deviations derived from the least-squares fit. Rate constants for several other ethers were determined only at 298 K. The values obtained were (in units of 10-14 cm3 molecule-1 s-1): tetrahydrofuran (37.5 ± 1.1); 1,4-dioxane 1(6.81 ± 0.46); diethoxymethane (40.4 ± 1.8); ethyl -t-butyl ether (37.0 ± 1.3); and methyl-t-amylether (57.3 ± 2.3).
    Zusätzliches Material: 3 Ill.
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  • 182
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 905-914 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The stability of some Schiff-bases formed between PLP and different amino acids has been investigated in a wide range of pH. The kinetic constants of formation of these compounds and their hydrolysis rate constants have been determined. Results show that the α-position of the carboxyl group of amino acid plays an important role on the mechanism of water attack upon the C=N—bond. The absence of ionic groups in the surroundings of that bond must be an important factor of stability. Bulky hydrophobic substituents in the amino acid, near the amine part, protect the imine bond against hydrolysis.
    Zusätzliches Material: 3 Ill.
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  • 183
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 999-1014 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics and nitroarene product yields of the gas-phase reactions of naphthalene-d8, fluoranthene-d10, and pyrene with OH radicals in the presence of NOx and in N2O5—NO3—NO2—air mixtures have been investigated at 296 ± 2 K and atmospheric pressure of air. Using a relative rate method, naphthalene-d8 was shown to react in N2O5—NO3—NO2—air mixtures a factor of 1.22 ± 0.10 times faster than did naphthalene, with the 1- and 2-nitronaphthalene-d7 product yields being similar to those of 1- and 2-nitronaphthalene from naphthalene. From the measured PAH concentrations and the nitroarene product yields, formation yields of 2-, 7-, and 8-nitrofluoranthene-d9 and 2- and 4-nitropyrene of 0.03, 0.01, 0.003, 0.005, and 0.0006, respectively, were determined from the OH radical-initiated reactions. Effective rate constants for the reactions of fluoranthene-d10 and pyrene with N2O5 in N2O5—;NO3—NO2—air mixtures of ca. 1.8 × 10-17 cm3 molecule-1 s-1 and ca. 5.6 × 10-17 cm3 molecule-1 s-1, respectively, were derived. Formation yields of 2-nitrofluoranthene-d9 and 4-nitropyrene of ca. 0.24 and ca. 0.0006, respectively, were estimated for these reaction systems. 2-Nitropyrene was also observed to be formed in these N2O5—NO3—NO2 reactions, but was found to be a function of the NO2 concentration and, therefore, would be a negligible product under ambient NO2 concentrations. These product and kinetic data are consistent with ambient air measurements of the nitroarene concentrations.
    Zusätzliches Material: 2 Ill.
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  • 184
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 105-111 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: A universal computational approach for evaluating integrals over gaussian basis functions for general operators of the form \documentclass{article}\pagestyle{empty}\begin{document}$$x^{k_x } y^{k_y } z^{k_z } \{ (\frac{\partial }{{\partial x'}})^{l_x } (\frac{\partial }{{\partial y'}})^{l_y } (\frac{\partial }{{\partial z'}})^{l_z } \frac{1}{{r'}}\} (\frac{\partial }{{\partial x}})^{m_x } (\frac{\partial }{{\partial y}})^{m_y } (\frac{\partial }{{\partial z'}})^{m_z } x^{n_x } y^{n_y } z^{n_z }$$\end{document} is presented. The implementation is open-ended with respect to the types of basis functions (s, p, d, f, g, h…) and with respect to the integers that specify the operator. These one-electron integrals comprise operators associated with electrical and magnetic properties of molecules and include those needed to find multipole polarizabilities, multipole susceptibilities, chemical shifts, and so on. The scheme also generates the usual kinetic, nuclear attraction, and overlap operators.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 185
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 181-193 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: A general computational scheme for the rational design of chiral stationary phases for the chromatographic separation of enantiomers has been established. The developed scheme was based on applying different interaction models (force field methods versus semi empirical quantum chemical methods), different docking algorithms (systematic grid search methods versus interactive methods guided by rules based on binding modes) and different levels of approximations (rigid versus flexible docking) to a representative test problem containing the 3,5-dinitrobenzoyl group. The computational methods in use covered the most sophisticated methods which could presently be applied to problems of such a size (about 80 atoms). It has been shown that the current computational approaches using rigid body approximations for the docked molecules and simple molecular mechanics (not taking pi-“effects” into account) are invalid in view of the required predictive precision of about 1-2 Kcal/mole for the differential binding energy. Another surprising result was the failure of the commonly used systematic search methods in determining the most favorable binding modes. Based on our calculations on the representative test problem we propose a new arrangement for the most stable complexes without parallel stacking of the aromatic pi-donor and the 3,5-dinitrobenzoyl pi-acceptor systems.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 186
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 223-235 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: A novel efficient computer-oriented approach, based on the DAST (dualist angle-restricted spanning tree) code, is introduced for enumeration and generation of planar polyhex hydrocarbons. It is much faster than other approaches in the literature. The numbers of planar polyhex hydrocarbons with 14 hexagons are reported for the first time.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 187
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 242-248 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Variations of a procedure have been examined for minimization of the energies, calculated using MM2, of two docked molecules. After doing the intramolecular minimization of the individual molecules, randomized orientations of the rigid molecules were brought together to form complexes and the nonbonded energies of interaction were then minimized. Next, pairs having energies within 4.0 kcal/mol of the most stable pair were minimized further by atom-by-atom relaxation of the complex. Only two repetitions of the last two steps were found to give values within 0.001 kcal/mol in more than 90% of the cases. Compared to two other variations of the procedure, this method appeared to avoid erroneous (local, not global) minima. Finally, this overall procedure was tested against chromatographic data in the literature. Using only the most stable comformer of each species, the results appeared to be in qualitative agreement with fractionation data for enantiomeric aminoethanes on a chiral packing very similar to the one modeled here.
    Zusätzliches Material: 2 Ill.
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  • 188
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 249-264 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Structural optimizations of the apically substituted isomer of PH4O- and the diapically substituted isomer of PH3FO- with diffuse-function augmented 3-21G* basis sets and with the 6-31 + G* and 6-31 + + G* basis sets result in P-η4-coordination in these anions. The structures obtained are those of a hydride or fluoride ion “solvated” by or complexed with phosphine oxide, rather than phosphoranes. In contrast, 3-21G* basis sets without diffuse functions on the atom in the trans-apical position with regard to the oxy-substituent yield P-η5-phosphorane structures that appear to be computational artifacts of the small basis set; the formation of the P-η4-geometries is curtailed by the insufficient functional description of the potential trans-apical nucleophilic leaving group. The overall neutral apical isomers of PH4O- · E(E = Li+, NH4+), the diapical isomer of PH3FO-Li+, as well as the model-solvated apical isomer of PH4O- · HF favor P-η5-phosphorane geometries at all of these computational levels. The mechanism by which the E-group alters the electronic structures within PH4Oa- is discussed based on the geometries, the molecular orbitals, and electron density analysis techniques.
    Zusätzliches Material: 9 Ill.
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  • 189
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 291-296 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: The adsorption of methane, ethane, propane, n-butane, ethylene, propene, 1-butene, 1,3-butadiene, acetylene, benzene, toluene, naphthalene, anthracene, and pyrene on the basal plane of graphite has been studied by means of a semiempirical method proposed by Fraga based on a 1/R expansion of atom-atom pair potentials. The energies of interaction obtained agree reasonably well with experimental data and statistical calculations. The orientation of the adsorbed molecules relative to the graphite surface rendered by Fraga's method improves the picture provided by other calculations with empirical potentials. These results display Fraga's method as an economical alternative for the study of physisorption of hydrocarbons on the graphite surface.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 190
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 311-313 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: A common approximation used in ab initio molecular orbital calculations assumes that the changes in energy due to use of a larger basis set (as in the inclusion of polarization orbitals) and to allowance for electron correlation are additives. Thus, small basis sets may be used for correlated ab initio calculations, resulting in a great savings in time. While this approach has been shown to perform acceptably in some cases, a systematic study has not been published. We examined 35 species and computed the heats of reaction for 15 processes at the 6-31G level of theory using polarization and correlation correction up to the MP4 level. The same items were then treated by an additive procedure to attain the same level of theory. We also examined the conrotrary ring opening of cyclobutene. Our results indicate that the errors do cancel to some extent but that the uncertainty associated with open shell species is significantly larger than closed shell systems. This calls into question the use of the procedure in predicting the properties of transition states.
    Zusätzliches Material: 3 Tab.
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  • 191
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 336-345 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Simplified formulas for first and second derivatives of the internal coordinates with respect to Cartesian coordinates are reported for linear and out-of-plane bending motion. They are expressed in a local coordinate system and then rotated to a space-fixed Cartesian coordinate system. For linear motion the important points are: (1) the invariance of the energy with respect to translational and rotational coordinate transformations and (2) the presentation of derivatives of the energy in terms of (α - π)2 rather than (α - π), where α is the bond angle, to avoid indeterminant forms. By factoring the second derivatives of the energy with respect to (α - π) and sinα, analysis in this local coordinate system avoids division by sinα as α → π. The formulas describe linear systems without the need to project the motion onto two perpendicular planes. When the angle is exactly π two degenerate directions arise, and the coordinate axes perpendicular to the axis of the linear sequence of atoms may be chosen arbitrarily. Further refinements and clarifications of methods reported previously to obtain matrix elements for linear and out-of-plane motion are presented.
    Zusätzliches Material: 1 Ill.
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  • 192
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 382-395 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: The coefficients in power series, in the variable time, describing coupled nonlinear chemical reactions are easily obtained from a recursion relation. Since these series have a limited radius of convergence they are not very useful as such. If the series are inverted to give time as a function of the appropriate power of a progress variable, the new series converge over the entire time course of the reaction. If, further, the long-time asymptotic behavior, obtained from the linearized kinetic equations, is used, one can obtain a series expansion for a function that describes the correct short-time behavior. This function can be estimated very well using truncated series. The method works well for consecutive nonlinear reactions where the progress variables are monotonic functions of time; this includes many cases where the concentrations of intermediate species go through a maximum as the reaction progresses.
    Zusätzliches Material: 19 Ill.
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  • 193
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 401-409 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: The accurate calculation of forces from finite difference potentials is very important, especially in the area of Brownian dynamics simulations. Test charge methods are typically used to calculate these forces. In these methods, the potential is calculated with one group of charges present, then the force on a second set of charges is calculated as the negative of the gradient of the potential times the charge. The test charge methods for calculating forces between solute molecules have been compared with more accurate methods and then regions of validity of the test charge methods explored. The test charge methods neglect certain reaction field effects. It is found for the simple charged systems studied that beyond a center-to-center separation of about twice the sum of the molecular radii the test charge approximations can be quite good. For polar molecules with no net charges, however, the corrections can be significant to even longer ranges.
    Zusätzliches Material: 8 Ill.
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  • 194
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 431-439 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: It is demonstrated that semiempirical methods give electrostatic potential (ESP) derived atomic point charges that are in reasonable agreement with ab initio ESP charges. Furthermore, we find that MNDO ESP charges are superior to AM1 ESP charges in correlating with ESP charges derived from the 6-31G* basis set. Thus, it is possible to obtain 6-31G* quality point charges by simply scaling MNDO ESP charges. The charges are scaled in a linear (y = Mx) manner to conserve charge. In this way researchers desiring to carry out force field simulations or minimizations can obtain charges by using MNDO, which requires much less computer time than the corresponding 6-31G* calculation.
    Zusätzliches Material: 4 Tab.
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  • 195
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 468-486 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: A new algorithm is presented for performing molecular dynamics simulations of peptides with fixed geometry, with the aim of simulating conformational changes and of exploring conformational space. The principle of the method is to expand the potential energy as a Taylor's series in the coordinates around the current point, retaining the force and its first two derivatives, and obtain a series solution of the resulting differential equations using a method due to Lyapunov. By choosing the time step so that the second term in the series is small compared to the first, the true solution can in principle be approximated to any desired degree of accuracy. The algorithm has been used to solve numerically Lagrange's equations of motion for N-acetyl alanine amide and N-acetyl methionide amide, regarded as fixed at their C-termini, under the influence of the ECEPP/2 potential energy function, and time steps of 15-30 fsec have been achieved with little variation in the total energy. Possible directions for future development are discussed.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 196
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 314-325 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: We have undertaken an energy minimization study of the binding of a small ligand, water, to amino acid side-chains. These calculations have been performed on a Meiko Computing surface containing a small number of transputers and on a larger transputer array installed at Edinburgh University. The aim of this study is twofold. First, we wished to compare these potential energy maps for a given side-chain as a function of the local secondary structure and also of the neighboring residue types. Secondly, the energy maps are found to be in good agreement with experimental distributions on the binding of water molecules to amino acid side-chains. The use of our in-house Meiko computing surface increases the speed of these calculations by a factor of about 25 over a VAX 11/750. With larger arrays of transputers, such as that at Edinburgh “concurrent” Supercomputer Project, we achieve increases in speed of over 200 such that these energy maps can be calculated at interactive speeds.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 197
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 493-510 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: A new approach based on computation of the molecular surface interactions (MSI) to estimate several physical properties of pure organic substances is described. MSI are derived from molecular structural data and consist of total molecular surface area, electrostatic molecular surface interactions, and a hydrogen bonding term. This new approach estimates the critical temperature and the molar critical volume of pure organic substances with molecular weights in the range of 40-500 a.u‥ In addition, the following properties can be calculated: the critical pressure, the boiling temperature, the molar volume in liquid state at normal pressure and temperature. The method can be used to predict physical properties of compounds having flexible or rigid, symmetric or asymmetric, polar or nonpolar molecular structures, and compounds with or without hydrogen bonding groups.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 198
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 524-530 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: The reaction mechanisms of the alkaline hydrolysis of N-methylcarbamates were studied using the AM1 method by assuming two possible pathways: (1) nucleophilic attack of hydroxide ion on the carbonyl carbon to give a tetrahedral complex followed by its breakdown to carbamic acid (BAC2); and (2) proton abstraction by hydroxide ion at the nitrogen atom followed by elimination of the alkoxide ion to form N-methyl isocyanate (E1cB). Reaction coordinate analysis showed that the reaction mechanism is determined by both the stability of an intermediate and the energy barrier for elimination.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 199
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 541-542 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: A reparameterized version (PM3) of AM1 has recently been reported and the results for several hundred molecules compared with those from AM1 itself. The comparison implied that PM3 represents a significant improvement over the earlier treatment. The apparently poor performance of AM1 is, however, due to the inclusion of “AM1 results” for elements (A1,P,S) for which AM1 parameters were unavailable. If these are omitted, PM3 is seen to be only marginally better than AM1. Since this conclusion refers only to a specific set of stable molecules, it is not clear whether even this small improvement will apply to other species or studies of reactions. It is in any case insufficient to justify the confusion caused by the release of the new treatment.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 200
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 11 (1990), S. 545-547 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: An algorithm based on a small matrix approach to the solution of a system of inhomogeneous linear algebraic equations is developed and tested in this short communication. The solution is assumed to lie in an initial subspace and the dimension of the subspace is augmented iteratively by adding the component of the correction vector obtained from the Jacobi scheme on the coefficient matrix A (ATA, if the matrix A is nondefinite) that is orthogonal to the subspace. If the dimension of the subspace becomes inconveniently large, the iterative scheme can be restarted. The scheme is applicable to both symmetric and nonsymmetric matrices. The small matrix is symmetric (nonsymmetric), if the coefficient matrix is symmetric (nonsymmetric). The scheme has rapid convergence even for large nonsymmetric sparse systems.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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