Calculation of hydrophobic interactions from molecular dynamics,surface areas,and experimental hydrocarbon solubilities

Using experimental solubilities and partial pressures for hydrocarbon solution in water and molecular dynamics calculations of hydrocarbon water interaction energies, hydrocarbon–water cavity potentials are obtained and then plotted vs. accessible surface area. The data used is mainly for aliphatic hydrocarbons, but benzene is included. Molecular dynamics calculations of pairs of hydrocarbon molecules together with the cavity potential curve are then used to obtain hydrophobic interaction free energies between the hydrocarbon pairs. While the cavity potential change is related to a change in surface area for hydrocarbon systems, the hydrocarbon–water interaction energy is not, so that the hydrophobic binding energy is not. The results are in agreement with previous results by a different method (R.B. Hermann, In Seventh Jerusalem Symposium on Quantum Pharmacology, E. Bergman and B. Pullman, Eds., D. Reidel, Dordrecht, 1974, p. 441) in that there is little or no solvent-induced binding free energy between small hydrocarbon molecules in a dilute aqueous solution. It is proposed that the cavity potential vs. accessible surface area curve obtained here can be used together with OPLS parameters to calculate both hydrocarbon–water solvation free energies and hydrophobic interactions. © 1993 John Wiley & Sons, Inc.     

Template evaporation method for controlling anatase nanocrystal size in ordered macroporous TiO2

The importance of pure-phase titanium oxide materials as catalysts, sensors, and photonic band-gap materials has been growing steadily. Recently, more attention has been focused on nanostructured titanium oxide showing controlled and periodic porosity on a nanometric scale. The nanocrystal size control of porous nanostructured titanium oxide in an anatase form is a crucial step for the organic template method. Simple template removal by evaporation in an inert atmosphere is reported in this article and compared with the calcination technique usually reported in the literature. The proposed method allows the formation of a double-porous (macro and meso) anatase phase. We demonstrate that it highly preserves the macropore order into a titanium oxide material and induces narrowly dispersed mesopores by controlling the nano-crystal size that is kept around 6 nm. For the proposed method, polystyrene beads are particularly suitable as templates, being evaporated in the temperature range of anatase existence. The final high surface area makes the materials appealing for applications as photocatalysts or sensors.     

Representations of double coset hypergroups and induced representations

The principal goal of this paper is to investigate the representation theory of double coset hypergroups. IfK=G//H is a double coset hypergroup, representations ofK can canonically be obtained from those ofG. However, not every representation ofK originates from this construction in general, i.e., extends to a representation ofG. Properties of this construction are discussed, and as the main result it turns out that extending representations ofK is compatible with the inducing process (as introduced in [7]). It follows that a representation weakly contained in the left-regular representation ofK always admits an extension toG. Furthermore, we realize the Gelfand pair (where are a local field andR its ring of integers) as a polynomial hypergroup on ℕ₀ and characterize the (proper) subset of its dual consisting of extensible representations.     

The SO(3,3) group as a common basis for Dirac's and Proca's equations

Dirac's and Proca's equations are unified in the sense that the algebras of Dirac -matrices and Duffin-Kemmer-matrices are shown to furnish two distinct matrix representations of the Lie algebra of the SO(3,3)-group. This fact is then interpreted as evidence for the classical picture of particles described by the above-mentioned equations to be a relativistic top. It is also argued that the shape of the top is rod-like.     

Shift-coupling in continuous time

Summary The result linking shift-coupling to time-average total variation convergence and to the invariant -field is extended to continuous time and an analogous result established linking -couplings to smooth total variation convergence and to a smooth tail -field. Shift- and -coupling inequalities are presented.     

Generation of Ethyl Metathiophosphate by Thermal Fragmentation of O-Ethyl N-Substituted Phosphoramidothioates

O-Ethyl N-1-adamantylphosphoramidothioate was synthesized and found to fragment on heating in inert solvents to form the pyrophosphate AdNHP(S)(OEt)OP(S)(OEt)OH. The proposed mechanism involves an elimination of the amine portion with release of ethyl metathiophosphate (EtOP(S)O), as was confirmed in previous work for the comparable structure with oxygen. This transient compound then phosphorylates the starting phosphoramidothioate. O-Ethyl N,N-diethylphosphoramidothioate was also synthesized, and while it gave a similar pyro compound on heating, the reaction mixture was more complex. Both phosphoramidothioates, however, served effectively as thiophosphorylating agents toward alcohols, a silanol, and the silanol groups on the surface of silica gel. Exploratory experiments showed that these phosphoramidothioates also could thiophosphorylate the OH group of a monoester of phosphoric acid, as well as that of phosphinic acids, forming anhydrides with the partial structure     

Intermolecular contact interactions and their temperature dependence

A model, based on inverse gas chromatography experiments, has been developed for intermolecular interaction and its temperature dependence. The model ascribes to each substance a four-component solubility parameter; the four components reflect the van der Waals, polar, electron donor, and electron acceptor interactive properties. Their values depend on temperature in the same manner as does the cohesive energy. The latter was found to depend only on the critical temperature, the acentric factor, and the reduced temperature. The model was used for evaluation of the solubility parameters from polymer-solvent interaction coefficients and their temperature dependence with high accuracy. For binary solventsolvent mixtures, the free energy of mixing and its temperature dependence, as well as enthalpy of mixing can be derived from this model with a good accuracy.     

Non-Watson-Crick base pairing in RNA. quantum chemical analysis of the cis Watson-Crick/sugar edge base pair family

Large RNA molecules exhibit an astonishing variability of base-pairing patterns, while many of the RNA base-pairing families have no counterparts in DNA. The cis Watson-Crick/sugar edge (cis WC/SE) RNA base pairing is investigated by ab initio quantum chemical calculations. A detailed structural and energetic characterization of all 13 crystallographically detected members of this family is provided by means of B3LYP/6-31G and RIMP2/aug-cc-pVDZ calculations. Further, a prediction is made for the remaining 3 cis WC/SE base pairs which are yet to be seen in the experiments. The interaction energy calculations point at the key role of the 2'-OH group in stabilizing the sugar-base contact and predict all 16 cis WC/SE base-pairing patterns to be nearly isoenergetic. The perfect correlation of the main geometrical parameters in the gas-phase optimized and X-ray structures shows that the principle of isosteric substitutions in RNA is rooted from the intrinsic structural similarity of the isolated base pairs. The present quantum chemical calculations for the first time analyze base pairs involving the ribose 2'-OH group and unambiguously correlate the structural information known from experiments with the energetics of interactions. The calculations further show that the relative importance and absolute value of the dispersion energy in the cis WC/SE base pairs are enhanced compared to the standard base pairs. This may by an important factor contributing to the strength of such interactions when RNA folds in its polar environment. The calculations further demonstrate that the Cornell et al. force field commonly used in molecular modeling and simulations provides satisfactory performance for this type of RNA interactions.