Synthesis, Chemical Characterization, and Molecular Structure of Au8{Fe(CO)4}4(dppe)2 and Au6Cu2{Fe(CO)4}4(dppe)2

The new Au₈{Fe(CO)₄}₄(P^P)₂ and Au₆Cu₂{Fe(CO)₄}₄(P^P)₂ (P^P=dppm, dppe) neutral cluster compounds were isolated in good yields by condensation of the [Au₃{Fe(CO)₄}₂(P^P)]^- anions with Au(SEt₂)Cl and CuCl, respectively, and have been characterized by IR, NMR and microanalyses. The molecular structures of Au₈{Fe(CO)₄}₄(dppe)₂ and Au₆Cu₂{Fe(CO)₄}₄(dppe)₂ have been determined by X-ray diffraction studies. Both molecules adopt a stereogeometry of the heavy atoms consisting of a triangulated and corrugated ribbon twisted around the elongation direction. Contrary to the expectations the latter displays the two copper atoms in the sites of highest connectivity. This implies that site exchange between copper and gold occurs during the synthesis.     

RuO4-promoted oxidative polycyclization of isoprenoid polyenes. A further insight into the stereochemistry of the process

Further studies on the RuO₄-catalyzed oxidative polycyclization of isoprenoid polyenes have been carried out. The configuration of the tris-THF product from the oxidation of geranylgeranyl acetate has been determined by a combination of spectral and chemical correlation methods. The oxidation of (E,Z)-farnesyl acetate, synthesized from nerol, has been carried out. This process stops at the first cyclization indicating that an E configuration of the Δ⁶ double bond is needed for the second cyclization to occur. The results are discussed in comparison with previous knowledge on the related Re(VII) polycyclization of polyenic bis-homoallylic alcohols.     

Reversed-phase capillary electrochromatography for the simultaneous determination of acetylsalicylic acid, paracetamol, and caffeine in analgesic tablets

The separation and simultaneous determination of caffeine, paracetamol, and acetylsalicylic acid in two analgesic tablet formulations was investigated by capillary electrochromatography (CEC). The effect of mobile phase composition on the separation and peak efficiency of the three analytes was studied and evaluated; in particular, the influence of buffer type, buffer pH, and acetonitrile content of the mobile phase was investigated. The analyses were carried out under optimized separation conditions, using a full-packed silica capillary (75 microm ID; 30.0 cm and 21.5 cm total and effective lengths, respectively) with a 5 microm C8 stationary phase. A mixture of 25 mM ammonium formate at pH 3.0 and acetonitrile (30:70 v/v) was used as the mobile phase. UV detection was at 210 nm. Good linearity was found in the range of 50-200, 20-160, and 4-20 microg/mL for acetylsalicylic acid (r2=0.9988), paracetamol (r2=0.9990) and caffeine (r2=0.9990), respectively. Intermediate precision (RSD interday) as low as 0.1-0.8% was found for retention times, while the RSD values for the peak area ratios (Aanalyte/AIS) were in the range of 1.9-2.9%. The optimized CEC method was applied to the analysis of the studied compounds present in commercial tablets.     

Synthesis of Piperidine Nucleosides as Conformationally Restricted Immucillin Mimics

The de novo synthesis of piperidine nucleosides from our homologating agent 5,6-dihydro-1,4-dithiin is herein reported. The structure and conformation of nucleosides were conceived to faithfully resemble the well-known nucleoside drugs Immucillins H and A in their bioactive conformation. NMR analysis of the synthesized compounds confirmed that they adopt an iminosugar conformation bearing the nucleobases and the hydroxyl groups in the appropriate orientation.     

Improving charge transport in poly(3‐hexylthiophene) transistors via blending with an alkyl‐substituted phenylene–thiophene–thiophene–phenylene molecule

A prototypical semiconducting bicomponent system consisting of a conjugated polymer, that is, poly(3‐hexylthiophene) (P3HT), blended with a small thiophene containing conjugated molecule, that is, an alkyl‐substituted bisphenyl‐bithiophene [phenylene–thiophene–thiophene–phenylene (PTTP)], has been used as an electroactive active layer in field‐effect transistors (FETs). The self‐assembly of this bicomponent system at surfaces has been studied at different length scales, from the nanoscale to the macroscale, and compared with the behavior of monocomponent films of PTTP and P3HT. The correlation between morphology and electric properties of the semiconducting material is explored by fabricating prototypes of FETs varying the relative concentrations of the two‐component blend. The maximum charge carrier mobility value, achieved with a few percent of PTTP component, is not simply due to a uniform dispersion of the molecules in the polymer matrix, but rather to the generation of very long percolation paths, whose composition and electrical properties can be tuned with the PTTP concentration. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012