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91.
Ibrahim Y Alsharaeh E Dias K Meot-Ner Mautner M El-Shall MS 《Journal of the American Chemical Society》2004,126(40):12766-12767
We studied the stepwise hydration and solvent-mediated deprotonation of the benzene*+ cation (Bz*+) and found several unusual features. The solvent binding energies DeltaH on-1,n for the reactions Bz*+(H2O)n-1 + H2O --> Bz*+(H2O)n are nearly constant at 9 +/- 1 kcal mol-1 for n = 1 to 8. We observed a remarkable sudden decrease in the entropy of association accompanying the formation of Bz*+(H2O)7 and Bz*+(H2O)8, indicating strong orientational restraint in the hydration shells of these clusters consistent with the formation of cagelike structures. We observed the size-dependent deprotonation of Bz*+ in a cooperative multibody process, where n H2O molecules (n >/= 4) can remove a proton from Bz*+ to form protonated water clusters. We measured, for the first time, the temperature dependence of such a process and found a negative temperature coefficient of a magnitude unprecedented in any chemical reaction, of the form k = AT-67+/- 4, or in an Arrhenius form having an activation energy of -34 +/- 1 kcal mol-1. The temperature effect may be explained by Bz*+ and four H2O molecules needing to be assembled from gas-phase components to form the reactive species. Such large temperature effects may be therefore general in solvent cluster-mediated reactions. 相似文献
92.
Modifications of the SCF-LCAO-π-MO method analysed in the previous paper are described in which provision is made for the incorporation of Variable Bond Order and Variable Electronegativity procedures. A comparison is made with the results of other π-electron calculations and values are reported for twenty hydrocarbon systems. 相似文献
93.
John M. Adams Keith Martin Richard W. McCabe 《Journal of inclusion phenomena and macrocyclic chemistry》1987,5(6):663-674
Suitably modified smectite clays can be very selective catalysts for a wide range of organic reactions. While it has long been known that such materials can act as Bronsted and Lewis acids, it has been shown recently that they are also effective Diels-Alder catalysts. A selection of illustrative reactions is given which emphasises their wide range of use, their selectivity, and the ease of work-up after reaction. In each case, mechanistic information is presented, e.g., on the site of reaction (whether interlayer or surface), rate determining steps, etc. The regiochemical consequences of the restricted reaction space are stressed.Based on material presented at the Fourth International Symposium on Inclusion Phenomena and the Third International Symposium on Cyclodextrins, Lancaster, U.K., 20–25 July 1986. 相似文献
94.
Keith A. Hunter Margaret R. Leonard Peter D. Carpenter J. David Smith 《Colloids and surfaces. A, Physicochemical and engineering aspects》1997,120(1-3):111-121
The kinetics of iron colloid aggregation in estuaries have been simulated with a model estuary in which seawater is continuously pumped into a reservoir initially containing river water. Profiles of colloidal Fe concentration versus salinity produced in this apparatus closely resembled field data for actual estuaries. Synthetic Fe colloids prepared by peptising Fe(OH)3 with humic acid and phosphate showed very similar kinetic behaviour. Aggregation rate was found to be almost independent of velocity shear rate, implying that most aggregations are induced by brownian interparticle collisions. A heterogeneous kinetic model is proposed to explain the kinetic behaviour of Fe colloids during seawater-induced aggregation. This model describes kinetic behaviour in terms of a log-normal distribution of rate constants characterised by a mean value k and a standard deviation γ. Experiments showed that k is linearly related to the rate constant for salinity increase during mixing. This coupling of salinity changes and aggregation rate leads to Fe-salinity profiles that are nearly independent of the rate of salinity change, but which are dependent on γ. 相似文献
95.
The electronic absorption spectra of a series of alkoxy-styryl substituted terthiophenes, their corresponding sexithiophenes, and the oxidation products of both have been measured. The terthiophenes studied sigma-dimerize to sexithiophenes during the oxidation process and there is clear evidence of sexithiophene radical cations, dications, and pi-dimers in the electronic absorption spectra. The oxidation of concentrated solutions produces predominantly pi-dimer bands, as expected. The absorption spectrum of the styryl-functionalized sexithiophene dication without alkoxy substitution closely resembles that of unsubstituted sexithiophene, while alkoxy substitution induces changes in the wavelength of the dication band maximum and the overall band shape. Time-dependent density functional theory (TDDFT) calculations have shown that styryl-based molecular orbitals are important in the transitions of the neutral molecules as well as the charged species, the dication in particular. Kinetics analyses confirm the stabilization effect induced by the alkoxy substituents. The presence of a reversible pi-dimer equilibrium was verified by cyclic voltammetry. It is clear from the experimental observations and the theoretical calculations that both the styryl and alkoxy groups are influencing the electronic properties of this class of molecules. 相似文献
96.
Keith E. Johnson Richard M. Pagni John Bartmess 《Monatshefte für Chemie / Chemical Monthly》2007,138(11):1077-1101
Summary. A background for studying acids in various solvents is developed, emphasizing the importance of knowing to what extent a solvent
conducts electricity and is therefore ionized, the dissociation equilibria of common molecular solvents and the acidic and
basic species generated by solvent leveling. Acidity measurements in the atypical solvent water are discussed and the common
method of expressing acidity in other systems – by Hammett values – is introduced. Representative examples of reactions involving Br?nsted acids in ionic liquids are presented and attention paid to the questions of speciation and acidity values. It is found that
the gas phase proton affinity of a base is often a better guide to the acidity of its conjugate acid in an ionic liquid than
is the dissociation constant of the said acid in water. 相似文献
97.
Effects of petroleum resins on asphaltene aggregation and water-in-oil emulsion formation 总被引:4,自引:0,他引:4
P. Matthew Spiecker Keith L. Gawrys Chad B. Trail Peter K. Kilpatrick 《Colloids and surfaces. A, Physicochemical and engineering aspects》2003,220(1-3):9-27
Asphaltenes from four crude oils were fractionated by precipitation in mixtures of heptane and toluene. Solubility profiles generated in the presence of resins (1:1 mass ratio) indicated the onset of asphaltene precipitation occurred at lower toluene volume fractions (0.1–0.2) than without resins. Small-angle neutron scattering (SANS) was performed on solutions of asphaltene fractions in mixtures of heptane and toluene with added resins to determine aggregate sizes. Water-in-oil emulsions of asphaltene–resin solutions were prepared and separated by a centrifuge method to determine the vol.% water resolved. In general, the addition of resins to asphaltenes reduced the aggregate size by disrupting the π–π and polar bonding interactions between asphaltene monomers. Interaction of resins with asphaltenic aggregates rendered the aggregates less interfacially active and thus reduced emulsion stability. The smallest aggregate sizes observed and the weakest emulsion stability at high resin to asphaltene (R/A) ratios presumably corresponded to asphaltenic monomers or small oligomers strongly interacting with resin molecules. It was often observed that, in the absence of resins, the more polar or higher molecular weight asphaltenes were insoluble in solutions of heptane and toluene. The addition of resins dissolved these insolubles and aggregate size by SANS increased until the solubility limit was reached. This corresponded approximately to the point of maximum emulsion stability. Asphaltene chemistry plays a vital role in dictating emulsion stability. The most polar species typically required significantly higher resin concentrations to disrupt asphaltene interactions and completely destabilize emulsions. Aggregation and film formation are likely driven by polar heteroatom interactions, such as hydrogen bonding, which allow asphaltenes to absorb, consolidate, and form cohesive films at the oil–water interface. 相似文献
98.
A highly effective synthesis of (±)-12-HETE (1) from the components 2, 3 and 6 is described which employs a new class of cuprate reagents. 相似文献
99.
Keith R. Roby 《Theoretical chemistry accounts》1974,33(2):105-113
The mathematical basis of LCAO MO theory is studied, both within the Hartree-Fock approximation and in more exact formulations. The basic LCAO expansion for molecular orbitals ¦> in terms of atomic orbitals ¦x> is conveniently written ¦> = ¦x>
S
–1
B where S is the overlap matrix for atomic orbitals and B is the matrix of atomic orbital-molecular orbital overlaps. It is suggested that matrices P and Q, defined by P=B B and Q=BnB where n is the matrix of molecular orbital occupation numbers, are appropriate to the interpretation of molecular calculations in terms of atomic orbital components, electronic populations and the degree of bonding. Implications for Hartree-Fock calculations are investigated. 相似文献
100.
Xiaoyi Wang Mark D. Wilkinson Xiaoyan Lin Ren Ren Keith R. Willison Aleksandar P. Ivanov Jake Baum Joshua B. Edel 《Chemical science》2020,11(4):970
Actin is a key protein in the dynamic processes within the eukaryotic cell. To date, methods exploring the molecular state of actin are limited to insights gained from structural approaches, providing a snapshot of protein folding, or methods that require chemical modifications compromising actin monomer thermostability. Nanopore sensing permits label-free investigation of native proteins and is ideally suited to study proteins such as actin that require specialised buffers and cofactors. Using nanopores, we determined the state of actin at the macromolecular level (filamentous or globular) and in its monomeric form bound to inhibitors. We revealed urea-dependent and voltage-dependent transitional states and observed the unfolding process within which sub-populations of transient actin oligomers are visible. We detected, in real-time, filament-growth, and drug-binding at the single-molecule level demonstrating the promise of nanopore sensing for in-depth understanding of protein folding landscapes and for drug discovery.Nanopipettes were used for real-time investigation into actin dynamics and drug binding at single-molecule resolution, showing promise for a better understanding of the mechanism of protein–protein interactions and drug discovery. 相似文献