Electric polarizabilities,magnetic susceptibilities and dispersion coefficients for hydrocarbons

Using wavefunctions given in the companion paper bond properties and interactions are computed. Results are in agreement with other theoretical estimates and provide good molecular results. Differences between similar bonds can be accounted for by change in bond length. Simple formulae can be used to normalize bond contributions according to bond length. Parameters should be applicable to macromolecules.     

Volumetric properties of H2O, D2O, and methanol in acetonitrile at 278.15—318.15 K

The densities of H₂O, D₂O, and MeOH solutions in acetonitrile with the solute concentrations up to 0.07 molar fractions at 278.15, 288.15, 298.15, 308.15, and 318.15 K were measured using vibrating-tube densimetry with an error 8·10^–6 g cm^–3. The limiting partial molar volumes for the H/D isotopomers of water and IaII in acetonitrile (V^– ₂ ) and the isotope effects in V^– ₂ and in excess molar volumes of acetonitrile—water mixtures were calculated. Molecules of H₂O, D₂O, and IaII form associates with acetonitrile molecules via hydrogen bonds. The associates have the packing volumes close to those in the individual solute. The water and methanol molecules were assumed to be incorporated into the acetonitrile structure without substantial changes in the latter. However, this process results in some compression of the system with a simultaneous increase in its expansibility.     

The nature of the AuI ... AuI Interactions between Cationic [AuL2]+ Complexes in the Solid State

The interaction energy of a [Au{C(NHMe)₂}₂]⁺ ... [Au{C(NHMe)₂}₂]⁺ dimer is investigated using the MP2 method and the LANL2DZ basis set when isolated or embedded in ionic an [Au{C(NHMe)₂}₂]₂anion₂ aggregate, a good model for the environment that these dimers feel in ionic crystals. A repulsive interaction energy is obtained when the dimer is isolated. However, it is possible to find short Au^I ... Au^I separations in [Au{C(NHMe)₂}₂]₂anion₂ aggregates, because in these aggregates the sum of the cation ... anion interactions overweight the sum of the cation ... cation plus anion...anion interactions. This explains why short Au^I ... Au^I separations are found in ionic crystals. The Au^I ... Au^I interaction found in [Au{C(NHMe)₂}₂]₂ anion₂ aggregates shows the same features observed in energetically stable dimers presenting Au^I... Au^I bonds. This makes appropriate to use the name counterion-mediated bonds for the Au^I... Au^I interactions found in [Au{C(NHMe)₂}₂]₂ anion₂ aggregates and ionic crystals.     

Three-dimensional hydrogen-bond geometry and probability information from a crystal survey

Summary An extensive crystal survey of the Cambridge Structural Database has been carried out to provide hydrogen-bond data for use in drug-design strategies. Previous crystal surveys have generated 1D frequency distributions of hydrogen-bond distances and angles, which are not sufficient to model the hydrogen bond as a ligand-receptor interaction. For each hydrogen-bonding group of interest to the drug designer, geometric hydrogen-bond criteria have been derived. The 3D distribution of complementary atoms about each hydrogen-bonding group has been ascertained by dividing the space about each group into bins of equal volume and counting the number of observed hydrogen-bonding contacts in each bin. Finally, the propensity of each group to form a hydrogen bond has been calculated. Together, these data can be used to predict the potential site points with which a ligand could interact and there-fore could be used in molecular-similarity studies, pharmacophore query searching of databases, or de novo design algorithms.     

A new method for predicting conduction anesthesia

A new method for predicting conduction anesthesia has been suggested. The method is based on calculation of theP matrix probabilities of interatomic contacts for each molecule of the compounds considered. TheP matrix enables one to evaluate the main tendencies of atoms and atomic groups to interact in biochemical sorption on the nerve fiber surface. The minimum effective concentrations calculated for 25 compounds are in good agreement with the experimental data. The correlation coefficient between the experimental and calculated values is 0.98 when the standard deviation is 0.1 mmol L⁻¹. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1781–1784, October, 1997.     

Binding of hexacyanoferrate(II) by aliphatic amines in aqueous solution

The stability of hexacyanoferrate(II)-amine(methylamine, ethylenediamine, diethylenetriamine and tetraethylenepentamine) was determined potentiometrically. Species Fe(CN)₆(A)H _j ^(j–4) (A=amine) are formed in all the systems investigated, with j=1...n+2 (n=number of aminogroups). Some other complexes Fe(CN)₆(A)_iH_j (with i>1) were also found. The stability of these complexes is fairly high: the full protonated amine species, show for the reaction Fe(CN)₆ ^4- + H_nAⁿ⁺ = Fe(CN)₆(A)H_n ^(n-4) an equilibrium constant given by logK=0.686+2.10n. Factors affecting the stability are discussed in comparison with similar systems, together with the importance of interferences.     

From anisole to 1,2,4,5‐tetramethoxybenzene: Theoretical study of the factors that determine the conformation of methoxy groups on a benzene ring

Unhindered ortho‐dimethoxy‐substituted phenyl rings often display a coplanar conformation. A theoretical study of a series of methoxybenzenes consisting of methoxybenzene (anisole), the three dimethoxybenzenes, and 1,2,4,5‐tetramethoxybenzene, at the DFT/B3LYP/6‐311++G** level of theory, allows us to identify the factors influencing the conformational preference and attribute the coplanarity of such methoxy groups to mesomeric effects. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

使用疏水作用色谱研究蛋白质的构象变化

研究了高效疏水作用液相色谱中(HIC)色谱条件改变对蛋白质构象的影响。发现固定相配体的疏水性、温度及流动相中盐的阴离子、阳离子和pH值都影响蛋白质的构象。     

The Role of Binary and Many-centre Molecular Interactions in Spin Crossover in the Solid State. Part I. Equation for Free Energy

Summary. A formalism has been developed that describes spin crossover equilibrium in the solid state by taking into account the effects of n nearest neighbours of a given molecule on its partition function. In this way binary and many-body interactions of the order n + 1 are included into the theoretical model and represented by non-ideality parameters connected with the splitting of free energy levels. Binary interactions are characterised by the main splittings whereas higher order interactions manifest themselves in asymmetries of splittings within multiplets. The contribution of molecular interactions can also be written in terms of formal excess free energies of the second, third, fourth and higher orders. Simple relationships between excess free energies and parameters of multiplets have been found for binary, ternary and quaternary interactions. This formalism is reduced to that of the model of binary interactions when effects of surroundings are additive leading to equidistant free energy multiplets. Higher order interactions may cause an abrupt spin crossover but in a limited range of compositions around the transition point. The regression of experimental transition curves of one-step spin crossover may yield estimates of excess energies up to the fifth order.