Transport properties of alkyltrimethylammonium bromide surfactants in aqueous solutions

Differential mutual diffusion coefficients of n-alkyltrimethylammonium bromides [CH₃(CH₂)_n–1N(CH₃)₃Br, C_nTAB] (n=10, 12, 14, 16) have been measured in aqueous solutions at 298.15 K using a conductimetric cell and an automatic apparatus to follow diffusion. The cell is based on an open-ended capillary, and the technique follows the diffusion process by measuring the resistance of a solution inside the capillaries at various times. The electrical conductances of those solutions have also been measured to calculate the critical micellar concentration (cmc). Thermodynamic analysis of the data suggests that the free ion concentration decreases at concentrations above the cmc, in agreement with theoretical predictions. The obtained values of the micellization parameters were used to model the mutual diffusion coefficients of C_nTAB aqueous solutions.     

Cluster Build-up Reactions using Di-gold Cationic Fragments: Synthesis and Structural Characterization of [Os7(CO)19(Au2dppm)]

The reaction of the di-gold cation [Au₂(dppx)]²⁺ with the heptanuclear cluster dianion [Os₇(CO)₂₀]^2– affords the mixed metal cluster [Os₇(CO)₂₀{Au₂(dppx)}] (x=m (1), e (2), b (3)). On standing, in solution, this complex undergoes decarbonylation to give the cluster [Os₇(CO)₁₉{Au₂(dppx)}] (x=m (4), e (5), b (6)). The complexes have been characterised spectroscopically, and an X-ray structure determination of the dppm derivative shows that it contains a metal core based on an Os₇ edge-bridged bicapped tetrahedron with the two ₃-Au atoms capping adjacent triangular Os₃ faces of the central tetrahedron. In an analogous reaction, the carbido anion [Os₇(H)C(CO)₁₉]^– affords the neutral cluster [Os₇C(CO)₁₉{Au₂(dppm)}] (7) when treated with [Au₂(dppm)]²⁺ in the presence of base.     

Kinetically inert transition metal complexes that reversibly bind to DNA

Transition metal complexes that reversibly bind to DNA have been studied for almost 30 years. In the last few years a variety of new systems have been developed, employing a range of metal ions and ligand architectures. In many cases, high affinity binding and specific selectivities have been observed. These complexes display properties that make them attractive as probes of DNA structure and function, suggesting that they may find a r?le as prototypical tools for a spectrum of applications, from basic molecular biology to medicine. This review presents an overview of some of the structures and properties of such complexes.     

Synthesis and conformational analysis of novel N(OCH3)-linked disaccharide analogues

N(OMe)-linked disaccharide analogues, isosteric to the corresponding natural disaccharides, have been synthesized by chemoselective assembly of unprotected natural monosaccharides with methyl 6-deoxy-6-methoxyamino-alpha-D-glucopyranoside in an aqueous environment. The coupling reactions were found to be chemo- and stereoselective affording beta-(1-->6) disaccharide mimics when using Glc and GlcNAc; in the case of Gal, the beta-anomer was prevalent (beta:alpha=7:1). An iterative method for the synthesis of linear N(OMe) oligosaccharide analogues was demonstrated, based on the use of an unprotected monosaccharide building block in which an oxime functionality at C-6 is converted during the synthesis into the corresponding methoxyamino group. The conformational analysis of these compounds was carried out by using NMR spectroscopy, ab initio, molecular mechanics, and molecular dynamics methods. Optimized geometries and energies of fourteen conformers for each compound have been calculated at the B3LYP/6-31G* level. Predicted conformational equilibria were compared with the results based on NMR experiments and good agreement was found. It appears that N(OMe)-linked disaccharide analogues exhibit a slightly different conformational behavior to their parent natural disaccharides.     

Complex emulsion inversion pattern associated with the partitioning of nonionic surfactant mixtures in the presence of alcohol cosurfactant

Commercial ethoxylated nonionic surfactant mixtures containing alcohol cosurfactant exhibit a three-phase behavior whose formulation strongly varies with the water/oil ratio. As a consequence, a change in water/oil ratio can result in a sequence of up to three different emulsion inversion processes, through a combination of formulation and composition effects.     

Reactions of pyrrolidine enamines of cyclic and acyclic 3,4-dioxobutanoic acid Derivatives with dimethyl acetylenedicarboxylate. A new case of atropoisomerism.

Reaction conditions and structure of the starting enamines (cyclic or open-chain) determine greatly the final products of the title reactions. Whereas in benzene and acetonitrile, DMAD and 1 give a mixture of the diastereoisomeric dienamines 5, in methanol they afford pirrolizine 3. Enaminofuranones 2 and 10 furnish the corresponding “Michael adducts” 7a,b,c and 11a,b,c but fail to yield pirrolizines. It has been demonstrated that above b and c adducts differ exclusively on the arrangement of groups around a chiral axis.     

DABCO-directed self-assembly of bisporphyrins (DABCO=1,4-diazabicyclo[2.2.2]octane)

Three isomeric zinc bisporphyrins have been prepared by covalently linking together two aminoporphyrins with an isophthalic acid derivative. The porphyrins differ in the substitution pattern on the meso phenyl groups, that is, ortho, meta, or para. Titrations carried out by UV-visible and 1H NMR spectroscopy have been used to map out the stabilities and the stoichiometries of the complexes formed with 1,4-diazabicyclo[2.2.2]octane (DABCO) in chloroform. The ortho- and meta-substituted bisporphyrins form 1:1 intramolecular sandwich complexes. The para-substituted bisporphyrin cannot adopt the cofacial conformation required for this type of complex and forms a higher order 2:2 intermolecular assembly, which is stable over a wide range of DABCO concentrations.     

Trehalose-based cyclodextrin analogs: cyclotrehalans (CTs)

A new concept for the de novo synthesis of artificial glyconanocavities is presented. The use of alternating α,α′-trehalose building blocks and (thio)urea segments allows the efficient synthesis of a new family of cyclooligosaccharides, namely cyclotrehalans (CTs), featuring a convex-shaped cavity with an apolar environment. CTs are designed to exhibit molecular inclusion abilities similar to that of cyclodextrins (CDs). Contrary to CDs, CTs expose the monosaccharide β-face to the inner cavity, while the (thio)urea tethers provides some conformational adaptability. High-yielding syntheses of a series of CTs and a preliminary evaluation of their inclusion properties are reported.     

Theoretical study of p‐methacryloyl‐aminophenylarsonic acid

Conformations of p‐methacryloylaminophenylarsonic acid (p‐MAPHA) are determined through molecular mechanics and DFT/B3LYP calculations. Solvation effects are studied within the self‐consistent isodensity continuum model (SCI‐PCM). The stationary points were found to correspond to minima as verified by the analysis of vibrational frequencies in the molecule. The molecular optical absorption was obtained by using different solvent environments. The present results are in good agreement with the available experimental data. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

Conformational dynamics of a bispyridinium cyclophane

A complete study of the conformational behavior of 4,8-diaza-3(1,4),9(4,1)-dipyridina-1,6(1,4)-dibenzenacyclodecaphan-3(1),9(1)-bis(ilium) bishexafluorophosphate is described. This study allows us to conclude that the process observed by which the different chemical shifts of the pyridinium protons show coalescence at a high-temperature 1H NMR is the rotation around the C-N bond, whereas the conformational equilibrium between the four conformers is produced at low temperature.