Freezing temperatures and densities of solutions of some hydrocarbons and sodium oleate inN-methylacetamide. Evidence for a solvophobic interaction

The freezing temperatures and densities (at 31°C) of solutions of octane, nonane, decane, 3,3-diethylpentane, and sodium oleate inN-methylacetamide (NMA) have been measured. The molality of the freezing solution was calculated from the density. The solubilities of octane, nonane, and decane inN-methylacetamide are also reported. Apparent molal volumes calculated from the densities are close to the values in the pure hydrocarbons and are not strong functions of the concentration. This indicates the absence of any unusual packing effect. The calculated free energies of transfer of the hydrocarbons from pure hydrocarbon to NMA solution are much less negative than the corresponding values for water, showing that the bulk solvophobic interaction inN-methylacetamide is smaller than in water. This is consistent with the freezing temperatures of sodium oleate which show that micelles do not form below 0.1 mole-kg^–1. The osmotic coefficients of the hydrocarbons calculated from the freezing temperatures showed negative deviations from ideality that were larger for the hydrocarbons with the higher molecular weights. Two estimates of the pairwise solvophobic interaction inN-methylacetamide indicate that it is also smaller than in water. The solvophobic effect in this solvent does not include the large entropy and enthalpy effects found in aqueous solutions.     

正已醇-邻、间、对二甲苯二元系固液相平衡

Melting temperatures have been measured and the solid-liquid phase diagrams constructed for 1-hexanol＋o-xylene, 1-hexanol＋m-xylene and 1-hexanol＋p-xylene. They are simple eutectic systems. Excess mole Gibbs free energies were calculated at 298.15K, showing larger positive deviations from ideal-solution behavior. The largest values of GmE are 711、 650 and 800 J•mol-1 for {o-C6H4(CH3)2＋C6H13OH}、 {m-C6H4(CH3)2 ＋ C6H13OH} and {p-C6H4(CH3)2＋C6H13OH} respectively.     

Surface forces in foam films from ABA block copolymer: a dynamic method study

The thinning of foam films from aqueous solutions of an ABA triblock copolymer of polyethylene oxide and polypropylene oxide (average molecular weight 14,000 g/mol) is studied experimentally. The dependence of the surface forces on film thickness is obtained by the dynamic method of Scheludko and Exerowa.The total surface force measured in foam films (radius 60–70 m) from 10^–5 M (0.014 wt%) polymer solution with 0.1 M NaCl is positive at thicknesses from about 800 down to 460 . The electrostatic repulsion is negligible while the contribution of van der Waals attraction is small (within 15%). Therefore a positive surface force component predominates. Most probably it arises from steric interactions between the hydrophilic polyethylene oxide tails of the polymer. The dynamic method appears to be a suitable technique for exploring the stabilization of foam films from ABA copolymers.     

Application of recoverable nanosized palladium(0) catalyst in Sonogashira reaction

In the absence of ligand, copper and amine, a recoverable nanoparticle palladium(0) catalyzed Sonogashira reaction of aryl iodides and bromides with terminal alkynes was developed. The protocol involved the use of an environmental-friendly reaction system with ethanol as the solvent, potassium carbonate as a base, and poly(vinylpyrrolidone) (PVP) supported nanosized palladium metal colloids as the catalyst. The palladium metal was recovered and recycled by a simple decantation of the reaction solution and used for eight consecutive trials without significant loss of its reactivity.     

Transition state geometry in radical abstraction reactions: comparison of interatomic distances in the intersecting parabolas and Morse curves models with quantum-chemical calculations

Interatomic distances in the transition state were estimated for the reactions of radical abstraction: H^· + H₂, H^· + HCl, H^· + CH₄, N^·H₂ + NH₃, HO^· + H₂O, HO₂ ^· + HOOH, and C^·H₃ + SiH₄. The calculation was performed by the quantum-chemical density functional method or coupled clusters method (QCH), as well as by the methods of intersecting parabolas (IPM) and Morse curves (IMM), using experimental data (activation energies and reaction enthalpies). The results of the latter two methods are close to the quantum-chemical calculation and differ only by the increment a: r(IPM or IMM) = a + r(QCH), where a = –4.5·10^–12 m for IPM and a = +1.9·10^–12 m for IMM.     

2-(N'-乙基咔唑-3'-烯基)-8-羟基喹啉的合成及理论研究

设计合成了2-(N'-乙基咔唑-3'-烯基)-8-羟基喹啉. 以UV-Vis, ¹H NMR, FT-IR, 元素分析和MS进行了结构表征, 并测定了产物的光致发光(PL)性质. 运用Gaussian98量子化学程序包, 采用B3LYP密度泛函(DFT)的方法, 在6-31G(d,p)水平上对分子的几何构型进行结构优化; 预测目标产物的振动光谱, 结果表明与实验值相符.     

Free energy perturbation approach to the critical assessment of selective cyclooxygenase-2 inhibitors

The discovery of selective cyclooxygenase-2 (COX-2) inhibitors represents a major achievement of the efforts over the past few decades to develop therapeutic treatments for inflammation. To gain insights into designing new COX-2-selective inhibitors, we address the energetic and structural basis for the selective inhibition of COX isozymes by means of a combined computational protocol involving docking experiment, force field design for the heme prothetic group, and free energy perturbation (FEP) simulation. We consider both COX-2- and COX-1-selective inhibitors taking the V523I mutant of COX-2 to be a relevant structural model for COX-1 as confirmed by a variety of experimental and theoretical evidences. For all COX-2-selective inhibitors under consideration, we find that free energies of binding become less favorable as the receptor changes from COX-2 to COX-1, due to the weakening and/or loss of hydrogen bond and hydrophobic interactions that stabilize the inhibitors in the COX-2 active site. On the other hand, COX-1-selective oxicam inhibitors gain extra stabilization energy with the change of residue 523 from valine to isoleucine because of the formations of new hydrogen bonds in the enzyme-inhibitor complexes. The utility of the combined computational approach, as a valuable tool for in silico screening of COX-2-selective inhibitors, is further exemplified by identifying the physicochemical origins of the enantiospecific selective inhibition of COX-2 by -substituted indomethacin ethanolamide inhibitors.     

Importance of the Debye interaction in organic solutions: Henry's law constants for polar liquids in nonpolar solvents and vice versa

Henry's law constants have been determined for -butyrolactone (BL), ethyl acetate (EA), and 2-methyl-3-pentanol (MEP) in mixtures of iso-octane (ISO) and toluene (TOL), for BL, EA, TOL, and ISO in cinnamaldehyde (CIN) and for TOL and ISO in each other and in BL. From these data and published vapor pressures, the activity coefficients at infinite dilution and the standard molar Gibbs free energy of transfer, G ₂ ⁰ of the solutes from dilute solution in ISO to dilute solution in each solvent medium have been calculated. The different behavior patterns of BL and EA are attributed to differences in their abilities to exist in different conformations possessing different dipole moments. For polar solutes, G ₂ ⁰ decreases with increasing polarizability of the solvent and with increasing dipole moment of the solute, suggesting increased contributions from dipole-induced dipole (Debye) interactions. The sigmoidal plot of G ₂ ⁰ against the change in pair potential energy calculated from the classical expressions suggests that G ₂ ⁰ seriously underestimates the strength of the Debye interactions in comparison with the London interactions.     

The free loop space and the algebraic k-theory of spaces

Let A(X) be the space defined by Waldhausen whose homotopy groups define the algebraic K-groups of the space X and let . Here (X) denotes the free loop space of X and Q denotes the functor . For X = Y, the suspension of a connected space Y, we shall prove that the homotopy fibers Ã(X), B(X) of the maps A(X) A (point), B(X) B (point) are equivalent as infinite loop spaces.