Capillary attraction of colloidal particles at an aqueous interface

We study the capillary forces arising from charged colloidal particles trapped at an oil-water interface. Since it is quadratic in the electric field, the electric stress acting on the interface cannot be written as the superposition of one-particle terms. Indeed, we find that the interfacial pressure is dominated by two-particle terms, which induce capillary forces involving one, two, three, or four particles. The dominant interaction is attractive and varies with the inverse cube of the particle distance.     

Synthesis and molecular structure of methyl 4-O-methyl-alpha-D-glucopyranuronate

A method for the preparation of methyl 4-O-methyl-alpha-D-glucopyranuronate and its single crystal X-ray structure determination are reported. The molecule adopts an almost ideal (4)C1 ((degree)C3) conformation.     

Surface Characterization of Sepiolite by Inverse Gas Chromatography

Inverse gas chromatography (IGC) was applied to characterize the surface of sepiolite. The adsorption thermodynamic parameters (the standard enthalpy (ΔH ⁰), entropy (ΔS ⁰) and free energy of adsorption (ΔG ⁰)), the dispersive component of the surface energy (γ _S ^d ), and the acid/base character of sepiolite surface were estimated by using the retention time of different non-polar and polar probes at infinite dilution region. The specific free energy of adsorption (ΔG ^sp ), the specific enthalpy of adsorption (ΔH ^sp ), and the specific entropy of adsorption (ΔS ^sp ) of polar probes on sepiolite were determined. ΔH ^sp were correlated with the donor and modified acceptor numbers of the probes to quantify the acidic K _A and the basic K _D parameters of the sepiolite surface. The values obtained for the parameters K _A and K _D indicated an acidic character for sepiolite surface.     

The aqueous cationic system sodium undecenoate-dodecyltrimethylammonium bromide at low concentration

The aqueous sodium undecenoate (SUD) –dodecyltrimethylammonium bromide (DTAB) catanionic system was studied at low concentration. The system did not precipitate, even at a 1:1 SUD:DTAB proportion, but showed the formation of a coacervate in a range of surfactant mixture compositions. Micelles have a preferential composition of 0.37 mole fraction of SUD. This behavior is attributed to the presence of the double bond at the distal extreme of the SUD molecule, which can form hydrogen bonds with water. Consequently, the –CH=CH₂ group is situated at the interface between the hydrocarbon micelle core and water, reducing the interfacial free energy. Structural computations demonstrate that the mentioned SUD proportion produces complete coverage of the micelle surface by the double bonds.     

Substituent-dependent reactivity in the photodimerization of N-substituted dibenz[b,f]azepines

The photoprocesses of a series of N-substituted dibenz[b,f]azepines (iminostilbenes) were studied by absorption and emission spectroscopy, by laser flash photolysis, and by preparative irradiation with NMR analysis. In solutions, 2pi+2pi photodimers of N-cyano and N-acyl dibenzazepines are formed via the triplet state upon acetone- or benzophenone-sensitized energy transfer. T-T absorption spectra were measured and absorption coefficients were determined. The triplet energy transfer is equally efficient for N-alkyl dibenzazepines, which do not dimerize. Excited states of npi* character in the latter cases are discussed to rationalize the different reactivities. In spite of negligible intersystem crossing of 21 dibenzazepine derivatives, photodimers of N-acyl and N-cyano dibenzazepines are formed upon direct excitation in concentrated solutions (0.01-0.1 mol dm(-3)) as well as in the solid state. A selective anti-configuration of the photodimers was found throughout.     

Analysis of Colubroidea snake venoms by liquid chromatography with mass spectrometry: evolutionary and toxinological implications

The evolution of the venomous function of snakes and the diversification of the toxins has been of tremendous research interest and considerable debate. It has become recently evident that the evolution of the toxins in the advanced snakes (Colubroidea) predated the evolution of the advanced, front-fanged delivery mechanisms. Historically, the venoms of snakes lacking front-fanged venom-delivery systems (conventionally grouped into the paraphyletic family Colubridae) have been largely neglected. In this study we used liquid chromatography with mass spectrometry (LC/MS) to analyze a large number of venoms from a wide array of species representing the major advanced snake clades Atractaspididae, Colubrinae, Elapidae, Homalopsinae, Natricinae, Psammophiinae, Pseudoxyrhophiinae, Xenodontinae, and Viperidae. We also present the first sequences of toxins from Azemiops feae as well as additional toxin sequences from the Colubrinae. The large body of data on molecular masses and retention times thus assembled demonstrates a hitherto unsuspected diversity of toxins in all lineages, having implications ranging from clinical management of envenomings to venom evolution to the use of isolated toxins as leads for drug design and development. Although definitive assignment of a toxin to a protein family can only be done through demonstrated structural studies such as N-terminal sequencing, the molecular mass data complemented by LC retention information, presented here, do permit formulation of reasonable hypotheses concerning snake venom evolution and potential clinical effects to a degree not possible till now, and some hypotheses of this kind are proposed here. The data will also be useful in biodiscovery.     

Diastereomer-differentiating hydrolysis of 1,3-diol-acetonides: a simplified procedure for the separation of syn- and anti-1,3-diols

[reaction: see text] A new method to facilitate the separation of diastereomeric syn- and anti-1,3-diols is described. The method relies on the different hydrolysis rates of the corresponding diastereomeric acetonides. Treatment of a dichloromethane solution of syn- and anti-1,3-diol-acetonide with a catalytic amount of diluted aqueous hydrochloric acid leads to the selective cleavage of the anti diastereomer. The resulting anti-1,3-diol can be easily separated from the unchanged syn-1,3-diol-acetonide.     

Comparative investigation of ruthenium-based metathesis catalysts bearing N-heterocyclic carbene (NHC) ligands

Exchange of one PCy3 unit of the classical Grubbs catalyst 1 by N-heterocyclic carbene (NHC) ligands leads to "second-generation" metathesis catalysts of superior reactivity and increased stability. Several complexes of this type have been prepared and fully characterized, six of them by X-ray crystallography. These include the unique chelate complexes 13 and 14 in which the NHC- and the Ru-CR entities are tethered to form a metallacycle. A particularly favorable design feature is that the reactivity of such catalysts can be easily adjusted by changing the electronic and steric properties of the NHC ligands. The catalytic activity also strongly depends on the solvent used; NMR investigations provide a tentative explanation of this effect. Applications of the "second-generation" catalysts to ring closing alkene metathesis and intramolecular enyne cycloisomerization reactions provide insights into their catalytic performance. From these comparative studies it is deduced that no single catalyst is optimal for different types of applications. The search for the most reactive catalyst for a specific transformation is facilitated by IR thermography allowing a rapid and semi-quantitative ranking among a given set of catalysts.     

Exact spin-pairing energies at the crossovers in octahedral d 4, d 5, d 6, and d 7 transition metal complexes

Exact spin-pairing energies are calculated by direct diagonalization of the relevant ligand field plus interelectronic repulsion matrices for the configurations d ⁴, d ⁵, d ⁶, and d ⁷ of octahedral transition metal ions. The results are presented in terms of /B as function of = C/B for the range of values =3.0 to 8.0. Comparison with the quantity resulting from a simplified approach in which configuration interaction is neglected or considered on an approximate basis only reveals significant differences. Useful estimates of spin-pairing energies are provided, in addition, on the basis of empirical magnetic and electronic spectral data.

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Zusammenfassung Exakte Spinpaarungsenergien für die Konfigurationen d ⁴, d ⁵, d ⁶ und d ⁷ oktaedrischer Übergangsmetallionen werden durch direkte Diagonalisierung der entsprechenden Matrizen des Ligandenfeldes sowie der Elektronenwechselwirkung berechnet. Die Ergebnisse für /B werden in Abhängigkeit von = C/B für den Wertebereich =3.0 bis 8.0 angegeben. Ein Vergleich mit der Größe , die bei einer vereinfachten Behandlung unter Vernachlässigung oder näherungsweiser Berücksichtigung der Konfigurationswechselwirkung erhalten wird, zeigt auffallende Unterschiede. Nützliche Abschätzungen der Spinpaarungsenergie werden außerdem unter Benutzung empirischer magnetischer und elektronenspektroskopischer Daten erhalten.

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Résumé Les énergies exactes de couplage de spin sont calculées par diagonalisation directe du champ de ligand correspondant en plus des matrices de répulsion électronique pour les configurations d ⁴, d ⁵, d ⁶ et d ⁷ des ions octaédriques des métaux de transition. Les résultats sont présentés en termes de /B en fonction de = C/B dan l'intervalle =3,0 à 8,0. On trouve des différences significatives par comparaison de avec les valeurs résultant d'une approche simplifiée sans interaction de configuration ou avec interaction de configuration approchée. De plus, des estimations des énergies de couplage de spin sont obtenues à partir de données empiriques magnétiques et spectrales.