Synthesis of series of 1- and 3-differently substituted xanthines from imidazoles

A new and general method is described for the synthesis, in three steps and in good overall yields, of tetrasubstituted xanthines from an easily prepared imidazole precursor. The method is especially useful for the preparation in standardized conditions of series of xanthines combining a broad variety of primary or secondary alkyl, benzyl or aryl groups at N1 and of alkyl or arylmethyl groups at N3, that are not readily available by other methods.     

1,1',3,3',6,6',8,8'-Octachloro-9,9'-bifluorenylidene and perchloro-9,9'-bifluorenylidene,two exceedingly twisted ethylenes

The syntheses of 1,1',3,3',6,6',8,8'-octachloro-9,9'-bifluorenylidene (1), its precursors, and the byproduct 3,3',5,5'-tetrachloro-4-(trichloromethyl)biphenyl (5) are described. Accurate structural X-ray data on 1 and on perchloro-9,9'-bifluorenylidene (2) are reported and discussed. Because of chlorine overcrowding, the dihedral angles between their two identical fluorenylidene moieties are abnormally large, the central-ethylene twist angles being 55 and 66 degrees, respectively. Significant out-of-plane carbon-chlorine bond bending is likewise exhibited. Their ESR spectra and magnetic measurements prove that they are singlet species. The exceptionally large bathochromic displacements of their UV-vis absorption spectrum with respect to that of their parent hydrocarbon are mainly attributed to bond bending and molecular warping.     

Adhesion hysteresis in dynamic atomic force microscopy

The effects of adhesion hysteresis in the dynamic‐dissipation curves measured in amplitude‐modulation atomic force microscopy are discussed. Hysteresis in the interaction forces is shown to modify the dynamics of the cantilever leading to different power dissipation curves in the repulsive and attractive regimes. Experimental results together with numerical simulations show that power dissipation, as measured in force microscopy, is not always proportional to the energy dissipated in the tip–sample interaction process. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Abschätzung mittlerer Schwingungsamplituden der Metall—Sauerstoff-Bindungen einiger Hexaoxometallate

Mean amplitudes of vibration of a series of hexaoxometalates have been estimated using an approximation method and recently reported spectroscopic data arising from the study of the respective lithium salts.     

Bassianolone: an antimicrobial precursor of cephalosporolides E and F from the entomoparasitic fungus Beauveria bassiana

We have established the chemical structure of (+)-bassianolone (3), the antimicrobial compound precursor of cephalosporolides E and F, and that of the furan metabolite 4 from the entomopathogenic fungus Beauveria bassiana.     

2-Methoxy-6-oxo-1,4,5,6-tetrahydropyridine-3-carbonitriles: versatile starting materials for the synthesis of libraries with diverse heterocyclic scaffolds

Heterocyclic demonstration libraries for agrochemical screening were prepared from the common intermediates 2-methoxy-6-oxo-1,4,5,6-tetrahydropyridine-3-carbonitriles (1), using standard solution-phase techniques. A total of 18 screening libraries were prepared in good to excellent yields. Several members of these libraries were active in the first level of agrochemical screening, especially in the fungicide screen.     

Synthesis and characterization of nanocapsules with shells made up of Al13 tridecamers

The synthesis of samples by the sol-gel method with aluminum tri-sec-butoxide as cation precursor, 2-propanol as solvent, and sulfuric acid as hydrolysis catalyst gave rise to nanocapsules with an average diameter of 20 nm and a shell thickness of 3.5 nm. The analysis of the X-ray diffraction patterns and the 27Al MAS NMR spectra showed that the shell of the nanocapsules was made up of Al13 tridecamers ordered in a noncrystalline symmetry. The interaction between the capsule's shells opened the capsule structure, producing curved fibers, but maintaining the atomic local order. This opening of the capsules favored the reordering of the atomic local order of Al13 tridecamers into the one of crystalline boehmite, when the sample was aged at room temperature for several days; it also increased the pore volume and the specific surface area of the sample. The crystallization transformed the curved fibers into rods made of small crystalline boehmite bars. The capsule morphology was preserved after calcining the nonaged sample at 700 degrees C, indicating that the transformation of the phase made up of ordered Al13 tridecamers into a noncrystalline alumina was pseudomorphic. We describe and partially explain one of the possible atomic ordering evolutions from the one of an isolated Al13 tridecamer, to the phase forming the nanocapsules shell, until eventually coming to the ordering corresponding to boehmite crystalline rods.     

Characterization of the surface structure of gold nanoparticles and nanorods using structure sensitive reactions

The surface structure of gold nanorods has been determined by studying the behavior of electrochemical reactions sensitive to the structure and compared to that obtained by other structure characterization techniques. Lead underpotential deposition (UPD) reveals that the surface of the nanorods is composed by (111) and (110) domains, while (100) domains are practically absent from the surface. In the case of the oxygen reduction reaction, the formation of hydrogen peroxide as a final product of the reaction in the whole potential range also indicates that (100) domains are absent on the surface of the nanoparticles, corroborating the previous result. These results are compared with other surface structure information provided by other techniques.     

Design and synthesis of two pyrazole libraries based on o-hydroxyacetophenones

Two new solid-phase syntheses of substituted pyrazoles are described. The first includes supporting an o-hydroxyacetophenone on Merrifield resin, Vilsmeier-Haack formylation on the methyl group and cyclization with a substituted hydrazine to afford a pyrazole ring with two diversity centers. The second starts from o-hydroxyacetophenone supported on Wang resin, which undergoes a Claisen condensation with a carboxylic acid ester to yield a 1,3-dicarbonyl compound that cyclizes to a pyrazole using a hydrazine. Both methods have been used to synthesize two small pyrazole libraries.