Mixed micelles formed by n-octyl-beta-D-glucopyranoside and tetradecyltrimethylammonium bromide in aqueous media

Speed of sound, density, conductivity, and fluorescence spectroscopy experiments were run to analyze the mixed aggregation process of a nonionic-cationic surfactant system in aqueous media at 298.15 K. The mixed system comprises a nonionic surfactant, n-octyl-beta-D-glucopyranoside (OBG), and a cationic surfactant, tetradecyltrimethylammonium bromide (C14TAB), with 8 and 14 carbon atoms on the hydrophobic tails, respectively. From these data, the total and partial critical micellar concentrations, the total and partial aggregation numbers, apparent molar volumes and isentropic compressibilities, hydration numbers, and the corresponding changes in the latest properties due to the mixed aggregation process were determined. Pure and mixed micelles were analyzed from a geometrical point of view by determining the packing parameter of the aggregates. Furthermore, the experimental characterization of both the monomeric and micellar phases was completed with a theoretical study of the mixed micellization phenomena studied herein, by means of some of the most relevant theoretical models.     

The formation of cation-ligand complexes of tributylammonium cation with diethyl carbonate,ethylene carbonate,propylene carbonate, 4-butyrolactone,ethyl acetate,and cyclopentanone ino-dichlorobenzene at 25°C

The effects of adding millimolar quantities of a series of compounds containing the carbonyl function on the conductances of solutions (0.2 mM) of tri-n-butylammonium picrate ino-dichlorobenzene solvent at 25°C have been measured. Values of the complex formation constants K ₁ ⁺ for 1:1 cation-ligand complexes are derived from these data. The corresponding values of –G ₁ ⁰ at 25°C are (in kcal-mole ^–1 ): 4-butyrolactone, 4.29; propylene carbonate, 3.87; ethylene carbonate, 3.59; cyclopentanone, 3.42; ethyl acetate, 2.84; and diethyl carbonate, 2.78. These results together with earlier results from this laboratory are discussed in terms of the effects of structure on cation-ligand affinity.     

K-theory for the leaf space of foliations by Reeb components

The K-theory of the C¹-algebra $\text{C}{}^1\text{(V, F)}$ associated to C^∞-foliations (V, F) of a manifold V in the simplest non-trivial case, i.e., dim V = 2, is studied. Since the case of the Kronecker foliation was settled by Pimsner and Voiculescu (J. Operator Theory4 (1980), 93–118), the remaining problem deals with foliations by Reeb components. The K-theory of $\text{C}{}^1\text{(V, F)}$ for the Reeb foliation of S³ is also computed. In these cases the C¹-algebra $\text{C}{}^1\text{(V, F)}$ is obtained from simpler C¹-algebras by means of pullback diagrams and short exact sequences. The K-groups $\text{K}{}_1\text{(C}{}^1\text{(V, F))}$ are computed using the associated Mayer-Vietoris and six-term exact sequences. The results characterize the C¹-algebra of the Reeb foliation of $\text{T}$² uniquely as an extension of C(S¹) by C(S¹). For the foliations of $\text{T}$² it is found that the K-groups count the number of Reeb components separated by stable compact leaves. A C^∞-foliation of $\text{T}$² such that K₁(C¹($\text{T}$², F)) has infinite rank is also constructed. Finally it is proved, by explicit calculation using (M. Penington, “K-Theory and C¹-Algebras of Lie Groups and Foliations,” D. Phil. thesis, Oxford, 1983), that the natural map $\text{μ: K}{}_1\text{,}{}_{\mathrm{\tau }}\text{(BG) → K}{}_1\text{(C}{}^1\text{(V, F))}$ is an isomorphism for foliations by Reeb components of $\text{T}$² and S³. In particular this proves the Baum-Connes conjecture (P. Baum and A. Connes, Geometric K-theory for Lie groups, preprint, 1982; A. Connes, Proc. Symp. Pure Math.38 (1982), 521–628) when V = $\text{T}$².     

Connections among quantum logics. Part 1. Quantum propositional logics

In this paper, we propose a theory of quantum logics which is general enough to enable us to reexamine previous work on quantum logics in the context of this theory. It is then easy to assess the differences between the different systems studied. The quantum logical systems which we incorporate are divided into two groups which we call quantum propositional logics and quantum event logics. We include the work of Kochen and Specker (partial Boolean algebras), Greechie and Gudder (orthomodular partially ordered sets), Domotar (quantum mechanical systems), and Foulis and Randall (operational logics) in quantum propositional logics; and Abbott (semi-Boolean algebras) and Foulis and Randall (manuals) in quantum event logics. In this part of the paper, we develop an axiom system for quantum propositional logics and examine the above structures in the context of this system.     

Solid-state binding of dimethyl sulphoxide involving carboxylic host molecules. X-ray crystal structures of four inclusion species

The crystal structures of four dimethyl sulphoxide (DMSO) inclusion compounds with different carboxylic acid hosts,1–4, have been studied by single crystal X-ray analysis. Crystals of thetrans-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid inclusion compound (1a), [1 · DMSO (1: 1)] show monoclinic (P2₁/n) symmetry with the unit cell dimensionsa = 11.522(4),b = 18.658(2),c = 8.709(1) Å and = 98.92(2)°. The clathrate of the 9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid (2a), [2 · DMSO (1: 2)] is triclinic (P) with the cell dimensionsa = 15.043(7),b =9.657(4),c = 8.118(7) Å, = 101.81(5), = 96.05(4) and = 100.04(4)°. Triclinic (P) symmetry is shown also by the inclusion compound of 9,10-dihydro-9,10-ethanoanthracene-11-monocarboxylic acid (3a) [3 · DMSO (1:1)] with the cell dimensionsa=6.3132(1),b=7.9846(2),c=17.5314(4) Å, = 96.46(2), = 87.08(2) and = 106.02(2)°. The 9,9-bianthryl-2-monocarboxylic acid clathrate (4a) [4 · DMSO (1:1)] is monoclinic (P2₁/n) and the cell dimensions area = 19.625(18),b = 8.817(1),c = 14.076(8) Å and = 97.92(6)°. In all these structures, the hosts show the same basic recognition pattern for the DMSO guest, involving a strong O-H ... O bond from the COON to the S=O group, and a possible C-H ... O type interaction between the carbonyl O atom of the host and a CH₃ group of the guest. The crystals consist of discrete host-guest aggregates which are mainly held together by weak intermolecular interactions of the Van der Waals' type. The stoichiometries of the aggregates are, however, different.     

New gem-dicyanocyclobutane-containing hydroxyesters

Six new gem-dicyanocyclobutanes containing carbomethoxy and hydroxyl/acetoxy functions were synthesized by cycloaddition of the appropriate vinyl ethers or alkoxystyrenes to methyl β,β-dicyanoacrylate. They proved to be too thermally labile to allow polycondensation to potentially piezoelectric linear polyesters.     

Systematic control of photochemistry: the dynamics of photoisomerization of a model cyanine dye

On-the-fly CASSCF nonadiabatic dynamics have been used to model the trans-cis isomerization of a model cyanine dye. Our results show that the photochemical generation of the trans versus cis product is dynamically controlled by the presence of an extended cis-trans conical intersection seam that persists along all torsional angles. This in turn suggests that the photochemistry could be completely controlled by controlling the distribution of momentum components in a wave packet excited by laser photolysis in a coherent control experiment.     

Nonpeptide inhibitors of cathepsin G: optimization of a novel beta-ketophosphonic acid lead by structure-based drug design

The serine protease cathepsin G (EC 3.4.21.20; Cat G), which is stored in the azurophilic granules of neutrophils (polymorphonuclear leukocytes) and released on degranulation, has been implicated in various pathological conditions associated with inflammation. By employing high-throughput screening, we identified beta-ketophosphonic acid 1 as a moderate inhibitor of Cat G (IC(50) = 4.1 microM). We were fortunate to obtain a cocrystal of 1 with Cat G and solve its structure by X-ray crystallography (3.5 A). Structural details from the X-ray analysis of 1.Cat G served as a platform for optimization of this lead compound by structure-based drug design. With the aid of molecular modeling, substituents were attached to the 3-position of the 2-naphthyl ring of 1, which occupies the S1 pocket of Cat G, to provide an extension into the hydrophobic S3 region. Thus, we arrived at analogue 7 with an 80-fold potency improvement over 1 (IC(50) = 53 nM). From these results, it is evident that the beta-ketophosphonic acid unit can form the basis for a novel class of serine protease inhibitors.     

Cu K-edge EXAFS characterisation of copper(I) arenethiolate complexes in both the solid and liquid state: detection of Cu-Cu coordination

Herein we describe a structural characterisation with EXAFS of copper(I) arenethiolate complexes in both the solid and liquid state. Previously noted difficulties in the detection of the Cu-Cu interaction have been attributed to anti-phase behaviour of different Cu-Cu neighbour contributions. A data analysis procedure solely based on EXAFS parameters is presented which resolves these problems. A careful analysis of the individual coordination shells and the use of different k-weightings during the data analysis are shown to be an absolute necessity to obtain reliable results. During R-space fitting, the difference file technique is used to separate, examine and compare the individual contributions. Using this technique their statistical significance and correctness can be determined. Anti-phase behaviour can be detected and accounted for in this way. An additional mixed organocopper aggregate [Cu4(SAr)2(Mes)2] with different Cu sites is analysed, which proves the value of the analysis procedure described above. Moreover, this newly developed EXAFS data analysis procedure is applicable to any other EXAFS spectrum obtained. The structural analysis of these organocopper complexes with EXAFS provides information about their actual structure and dynamic behaviour in solution. The technique can now be used to obtain insights into the reactivity of these complexes and the way in which they form catalytic reaction intermediates.     

Pervaporative transport modelling in a ternary system: ethyltertiarybutylether/ethanol/polyurethaneimide

The study deals with the analysis of diffusion and mass transfer modelling during pervaporation in a true ternary system involving a polar liquid mixture (ETBE/EtOH) and a polar block copolymer (polyurethaneimide or PUI). A survey of methods of pervaporative transfer modelling in ternary systems is first developed. From differential permeation experiments carried out with both pure liquids, it appears that both permeants obey a Fickian law. Moreover, the diffusional behaviour is consistent with Long's model, which has thus been assumed for the related ternary system. An extension of the Brun's model is then derived, which takes into account the diffusion coupling as well the significant deviation from sorption ideality. From a practical point of view, the calculated values of fluxes show generally good agreement with the experimental results, although a small deviation occurs for mixtures of low ethanol content. Diffusion coefficients of both pure solvents corresponding to transient or steady state are compared. A very good agreement is found for the aprotic permeant (ETBE). whereas the diffusion coefficient of ethanol in transient state is only the quarter of the value corresponding to steady state. The results are discussed in comparison with related investigations in the literature, involving specific liquid-polymer interactions.