Peroxycarbenium-mediated C-C bond formation: applications to the synthesis of hydroperoxides and peroxides

The Lewis acid-mediated reaction of alkene nucleophiles with peroxyacetals provides an effective route for the synthesis of homologated peroxides and hydroperoxides. In the presence of Lewis acids such as TiCl(4), SnCl(4), and trimethylsilyl triflate, peroxyacetals and peroxyketals undergo reaction with allyltrimethylsilane, silyl enol ethers, and silyl ketene acetals to afford homoallyl peroxides, 3-peroxyketones, and 3-peroxyalkanoates, respectively. Reactions of peroxyacetals are Lewis acid dependent; TiCl(4) promotes formation of ethers while SnCl(4) and trimethylsilyl triflate promote formation of peroxides. Lewis acid-promoted reactions of silylated hydroperoxyacetals furnish silylated hydroperoxides, which can be deprotected to homologated hydroperoxides. Hydroperoxyketals undergo Lewis acid-mediated allylation to furnish 1,2-dioxolanes via attack of hydroperoxide on the intermediate carbocation. Lewis acid-mediated cyclization of unsaturated peroxyacetals furnishes 1,2-dioxanes, 1,2-dioxepanes, and 1,2-dioxacanes through 6-endo/exo, 7-endo/endo, and 8-endo/endo pathways. The corresponding reactions involving 6-endo/endo and 5-endo/exo pathways were unsuccessful.     

Functional molecular wires

The properties of self-assembled molecules may be tuned by sequentially coupling components on a gold surface, the molecular electronics toolbox of chemically reactive building blocks yielding molecular wires with diode-like current-voltage (I-V) characteristics. The bias for rectification in each case is dependent upon the sequence of electron-donating and electron-accepting moieties and similar behaviour has been achieved for four different contacting techniques.     

Several constants arising in statistical mechanics

This is a brief survey of certain constants associated with random lattice models, including self-avoiding walks, polyominoes, the Lenz-Ising model, monomers and dimers, ice models, hard squares and hexagons, and percolation models.     

Neural correlates of semantic and syntactic processes in the comprehension of case marked pronouns: Evidence from German and Dutch

Background  

It is well known that both semantic and syntactic information play a role in pronoun resolution in sentences. However, it is unclear what the relative contribution of these sources of information is for the establishment of a coreferential relationship between the pronoun and the antecedent in combination with a local structural case constraint on the pronoun (i.e. case assignment of a pronoun under preposition governing). In a prepositional phrase in German and Dutch, it is the preposition that assigns case to the pronoun. Furthermore, in these languages different overtly case-marked pronouns are used to refer to male and female persons. Thus, one can manipulate biological/syntactic gender features separately from case marking features.     

Measurement of thickness and composition of a solvent film on a bubble

Solvent-coated air bubbles in the air-assisted solvent extraction (AASX) process achieve the dual role of high solvent specific surface area and ease of phase separation. The properties and thickness of the solvent film control the process. As an approach to the study, the layer interferometry (in the UV-vis region) and FT-IR spectroscopy were used to measure the time dependent thickness and chemical composition, respectively, of a film formed by blowing an air bubble in kerosene-based solvents. The film was stabilized by the presence of 1.5 ppm silicone oil, as employed in AASX. The film appears to comprise two layers; an outer layer of almost constant thickness and an inner layer which decreased in thickness with time. The latter is considered relevant to AASX. Generally, the initial thickness was approximately 3 microm which decreased over several minutes to a final rupture thickness of 500 nm. The initial thickness is of the order determined indirectly. The chemical composition of the layer did not change with time.