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.     

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.     

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.     

Study of the ESI-mass spectrometry ionization mechanism of Fischer carbene complexes

By means of deuterium-labeling experiments, we have carried out a systematic ESI-MS study to determine the mechanism of ESI ionization of alkenyl and alkynyl group 6 Fischer carbene complexes. These compounds can be ionized under ESI conditions only in the presence of additives such as hydroquinone (HQ) or tetrathiafulvalene (TTF). Our results demonstrate that in the ESI source an anion-radical is formed after the initial HQ- or TTF-mediated electron transfer to the metallic carbene complex. For alkenyl carbene complexes, this species evolves by extrusion of a hydrogen radical to form an allenylchromium anion that is detected as the [M - H](-) ion in the mass spectrum. The preference for this mechanistic pathway could be rationalized by DFT calculations. In the case of alkynyl carbene complexes, experiments combining deuterated substrate, additive, and solvent demonstrate that the previously proposed allene-anion carbene complex is not formed. Instead, the H transfer from the ethoxy group in the anion radical, followed by extrusion of a hydrogen radical, leads to an allenyl anion that is detected in the ESI-MS as [M - H - CO](-).     

Copper sorption on a straw lignin: experiments and EPR characterization

Spectroscopic and physicochemical data, X-ray photoelectron spectroscopy (XPS), solid-state (13)C cross-polarization magic-angle-spinning NMR, GC/MS, specific surface area, site density, and surface acidity constants have been recorded or determined for a ligno-cellulosic substrate (LS) extracted from straw. Its copper(II)-bound ability has also been studied. The LS solid that exhibits two types of binding sites, carboxylic and phenolic groups, has a great affinity for copper(II), with a maximum of adsorption at around 4 mg g(-1) as early as the pH reaches 6. The structural characterization of the Cu(II) surface complexes has been investigated using EPR spectroscopy. The CuO(4) chromophore of the inner-sphere surface complexes is a slightly distorted square. A surface oxidation occurred simultaneously, which leads to semiquinonic radicals. Furthermore, our empirical approach, which used a correlation between thermodynamics data and EPR parameters, has led to a surface complexation constant log beta equal to 12.6. This indicates that copper(II) surface complexes are relatively stable.     

The 1,2,4-triazolyl cation: thermolytic and photolytic studies

The generation of the 1,2,4-triazolyl cation (1) has been attempted by the thermolysis and photolysis of 1-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridinium tetrafluoroborate (2) and the thermolysis of 1- and 4-diazonium-1,2,4-triazoles, using mainly mesitylene as the trapping agent. Thermolysis of 2 gave mostly 1,2,4-triazole, together with 3-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridine, 4-(1,2,4-triazol-4-ylmethyl)-2,6-dimethylpyridine, and 4-(2,4,6-trimethylbenzyl)-2,6-dimethylpyridine. Thermolysis of each of the diazonium salts in the presence of mesitylene again gave mainly triazole together with very low yields of 1-(1,2,4-triazol-1-yl)-2,4,6-trimethylbenzene and the corresponding -4-yl isomer in about the same ratio. On the other hand, photolysis of 2 in mesitylene gave mainly 1-(1,2,4-triazol-1-yl)-2,4,6-trimethylbenzene. A photoinduced electron transfer from mesitylene to 2 has been observed and preliminary laser flash photolyses of 2 and the corresponding 2,4,6-triphenylpyridinium salt have been carried out. The observed transients are explained as arising from the first excited states of the pyridinium salts rather than from 1. Ab initio MO calculations are reported and indicate that the predicted electronic ground-state of the triazolyl cation is a triplet state of B1 symmetry with five pi electrons, which corresponds to a diradical cation (1c). Possible mechanisms for the formation of the various products are proposed.     

Synthesis of donor-acceptor alkynylcyclopropanes by diastereoselective cyclopropanation of electron-deficient alkenes with alkoxyalkynyl Fischer carbene complexes

The reaction of electron-deficient alkenes with alkoxyalkynyl Fischer carbene complexes (FCCs) represents a straightforward route to a new type of captodative (donor-acceptor) alkynylcyclopropanes, which have been prepared in moderate to high yields and in a diastereoselective manner. Some studies regarding the employment of additives to facilitate the recovery of the metal moiety after the reaction are also described. Finally, the first example of a cyclopropanation reaction through employing Fischer carbene complexes under microwave irradiation is presented; this method proved to be an advantageous alternative to the thermal reaction.     

Interaction of UO2 2+ with sodium dodecyl sulfate micelles: association of phenols to micelles through fluorescence quenching data

Time-resolved laser-induced fluorescence (TRLIF) has been used to study the interaction of uranyl ion with sodium dodecyl sulfate (SDS) micelles in H(3)PO(4) 1 M. The titration curve consists of two curved regions with different slopes, one of them more pronounced at low concentration of SDS and the other, with a less pronounced positive slope at larger [SDS] until a plateau is reached. The fluorescence quenching of uranyl ion by para-substituted phenol compounds was studied by TRLIF and steady-state emission intensity measurements. The results were interpreted in terms of binding of phenolic compounds to the micelle. The binding constant (K(Q)) as well as the entrance and exit rate constants were determined for all the quenchers used.     

Isobaric vapor–liquid equilibria for the quaternary reactive system: Ethanol + water + ethyl lactate + lactic acid at 101.33 kPa

Isobaric vapor–liquid equilibrium (VLE) data of the reactive quaternary system ethanol (1) + water (2) + ethyl lactate (3) + lactic acid (4) have been determined experimentally. Additionally, the reaction equilibrium constant was calculated for each VLE experimental data. The experimental VLE data were correlated using the UNIQUAC equation to describe the chemical and phase equilibria simultaneously. For some of the non-reactive binary systems, UNIQUAC binary interaction parameters were obtained from the literature. The rest of the binary UNIQUAC parameters were obtained by correlating the experimental quaternary VLE data obtained in this work. A maximum pressure azeotrope at high water concentration for the binary reactive system ethyl lactate + water has been calculated.