Electric-field-driven surface aggregation of a model zwitterionic surfactant

Electrochemical measurements, atomic force microscopy, and scanning tunneling microscopy have been combined to describe the electric-field-controlled surface aggregation of N-dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (DDAPS), a model zwitterionic surfactant, at a Au(111) electrode surface. At concentrations below the critical micelle concentration (CMC), the monomer adsorbs and aggregates at the surface. The charge on the metal (sigmaM) controls the orientation of adsorbed molecules and consequently the film structure. At high negative (sigmaM < -5 microC cm-2) charge densities, a spongy, disordered film is formed in which the polar heads are turned toward the solution. At high positive (sigmaM > +5 microC cm-2) charge densities, a planar film with "blisters" is observed with the polar heads of DDAPS turned to the metal. Hemicylindrical aggregates are observed in the intermediate charge density range (-5 < sigmaM < +5 microC cm-2). At bulk concentrations higher than the CMC, micelles adsorb and the structure of these films is controlled by the fusion of the adsorbed micelles. STM and AFM images provided direct visualization of this field-driven surface aggregation of the zwitterionic surfactant.     

The structure-based design of Mdm2/Mdmx-p53 inhibitors gets serious

The p53 protein is the cell's principal bastion of defense against tumor-associated DNA damage. Commonly referred as a "guardian of the genome", p53 is responsible for determining the fate of the cell when the integrity of its genome is damaged. The development of tumors requires breaching this defense line. All known tumor cells either mutate the p53 gene, or in a similar number of cases, use internal cell p53 modulators, Mdm2 and Mdmx proteins, to disable its function. The release of functional p53 from the inhibition by Mdm2 and Mdmx should in principle provide an efficient, nongenotoxic means of cancer therapy. In recent years substantial progress has been made in developing novel p53-activating molecules thanks to several reported crystal structures of Mdm2/x in complex with p53-mimicking peptides and nonpeptidic drug candidates. Understanding the structural attributes of ligand binding holds the key to developing novel, highly effective, and selective drug candidates. Two low-molecular-weight compounds have just recently progressed into early clinical studies.     

Thin-layer chromatography of alkaloids on cyanopropyl bonded stationary phases. Part I

Selected alkaloids are chromatographed on cyanopropyl-silica thin layers using various nonaqueous and aqueous eluents. Because of the strong retention of these basic compounds, nonaqueous eluents containing medium polar diluents, strongly polar modifiers, and silanol blockers (ammonia or diethylamine) are required for separation. Likewise, aqueous eluents containing modifiers (acetonitrile, methanol, and tetrahydrofuran), buffered aqueous solutions at pH 2-8, ion-pair reagents [octane sulfonic acid sodium salt, sodium dodecyl sulphate, and bis-(2-ethylhexyl)phosphoric acid], or silanol blockers (ammonia, tetrabutyl ammonium chloride, and diethyl amine) are investigated. The separation selectivity as well as spot symmetry and efficiency system in the applied eluent systems are analyzed. The most selective and efficient systems are used in two-dimensional separations of isoquinoline alkaloids' mixture and the plant extracts Chelidonium majus, Fumaria officinalis, and Glaucium flavum. Two-dimensional thin-layer chromatography on cyanopropyl layer with diode array detection densitometry enables the separation and identification of some alkaloids in plant extracts.     

A strategy for selection of reference materials in stable oxygen isotope analyses of solid materials

The propagation of uncertainties associated with the stable oxygen isotope reference materials through a multi-point normalisation procedure was evaluated in this study using Monte Carlo (MC) simulation. We quantified the normalisation error for a particular selection of reference materials and their number of replicates, when the choice of standards is restricted to either nitrates, sulphates or organic reference materials alone, and in comparison with when this restriction was relaxed. A lower uncertainty in stable oxygen isotope analyses of solid materials performed using High-Temperature Pyrolysis (HTP) can be readily achieved through an optimal selection of reference materials. Among the currently available certified reference materials the best performing pairs minimising the normalisation errors are USGS35 and USGS34 for nitrates; IAEA-SO-6 and IAEA-SO-5 for sulphates; and IAEA-601 and IAEA-602 for organic materials. The normalisation error can be reduced further--by approximately half--if each of these two analysed reference materials is replicated four times. The overall optimal selection among all nine considered reference materials is the IAEA-602 and IAEA-SO-6 pair. If each of these two reference materials is replicated four times the maximum predicted normalisation error will equal 0.22‰, the minimum normalisation error 0.12‰, and the mean normalisation error 0.15‰ over the natural range of δ(18)O variability. We argue that the proposed approach provides useful insights into reference material selection and in assessing the propagation of analytical error through normalisation procedures in stable oxygen isotope studies.     

Transition-metal-catalyzed chemoselective methylenation of dicarbonyl substrates

Rhodium- and copper-catalyzed methylenation reactions with trimethylsilyldiazomethane, triphenylphosphine, and 2-propanol were used to react chemoselectively with aldehydes, alkoxymethylketones, and trifluoromethylketones in substrates also containing a less reactive carbonyl group. Terminal alkenes were obtained in high yields, and no protecting group was necessary in the methylenation process.     

The entropy effects in binary mixtures of polar mesogenic solvent/nonpolar solute

The paper concerns two aspects of the entropy in mesogenic systems: (i) the entropy jump (Delta S (0) NI) at the phase transition from the isotropic liquid (I) to the nematic liquid crystalline state (N), and (ii) the entropy increment (Delta S) caused by the ordering action of the probing electric field applied to the dipolar system. The system studied are the mixtures of strongly polar mesogenic solvent n-hexylcyanobiphenyl (C 6H 13PhPhCN, 6CB) and the nonpolar nonmesogenic admixture 4-ethylcyclohexyl-4'- n-nonylphenyl (C 2H 5CyHxPhC 9H 19, 2CyPh9). The entropy jump at the I-N phase transition in pure 6CB [Delta S (0) NI= 1.52 J/(mol K)] was evaluated from the analysis of the phase diagram of the mixture 6CB + 2CyPh9 with use of the Landau-Lifshitz theory; the resulting value of the transition enthalpy (Delta H (0) NI = T NIDelta S (0) NI = 0.50 kJ/mol) agrees well to that obtained with the calorimetric methods. The field-induced entropy increment (Delta S) was calculated, at the given temperature, from the static dielectric permittivity derivative value (depsilon s/d T), with use of the Fr?hlich theory. The singularities in dependence of the entropy increment on the temperature and on the mixtures composition are discussed in terms of the prenematic molecular self-organization extent in mesogenic liquids of different density of dipoles.     

Harmonic measure and expansion on the boundary of the connectedness locus

The paper develops a technique for proving properties that are typical in the boundary of the connectedness locus with respect to the harmonic measure. A typical expansion condition along the critical orbit is proved. This condition implies a number of properties, including the Collet-Eckmann condition, Hausdorff dimension less than 2 for the Julia set, and the radial continuity in the parameter space of the Hausdorff dimensions of totally disconnected Julia sets. Oblatum 6-XI-1998 & 12-V-2000?Published online: 11 October 2000     

Synthesis and Reactions of a New Cyclobutanethione Derivative

The 3,3‐dichloro‐2,2,4,4‐tetramethylcyclobutanethione ( 4b ) was prepared from the parent diketone by successive reaction with PCl₅ and Lawesson reagent in pyridine. This new thioketone 4b was transformed into 1‐chlorocyclobutanesulfanyl chloride 5 and chloro 1‐chlorocyclobutyl disulfide 9 by treatment with PCl₅ and SCl₂, respectively, in chlorinated solvents (Schemes 1 and 2). These products reacted with S‐ and P‐nucleophiles by substitution of Cl⁻ at the S‐atom; e.g., the reaction with 4b yielded the di‐ and trisulfides 6b and 11 , respectively. Surprisingly, only pentasulfide 12 was formed in the reaction of 9 with thiobenzophenone (Scheme 3). In contrast to 5 and 9 , the corresponding chloro 1‐chlorocyclobutyl trisulfide 13 could not be detected, but reacted immediately with the starting thioketone 4b to give the tetrasulfide 14 (Scheme 4). Oxidation of 4b with 3‐chloroperbenzoic acid (mCPBA) yielded the corresponding thione oxides (= sulfine) 15 , which underwent 1,3‐dipolar cycloadditions with thioketones 3a and 4b (Scheme 5). Furthermore, 4b was shown to be a good dipolarophile in reactions with thiocarbonylium methanides (Scheme 6) and iminium ylides (= azomethine ylides; Scheme 7). In the case of phenyl azide, the reaction with 4b gave the symmetrical trithiolane 25 (Scheme 8).