Nanostructured polymetallaynes of controlled length: Synthesis and characterization of oligomers and polymers from 1,1′‐bis‐(ethynyl)4,4′‐biphenyl bridging Pt(II) or Pd(II) centers

The reactivity of square planar palladium(II) and platinum(II) complexes in trans or cis configuration, namely trans or cis‐[dichlorobis(tributylphosphine)platinum(II)] and trans‐[dichlorobis(tributylphosphine)palladium(II)] with 1,1′‐bis(ethynyl) 4,4′‐biphenyl, DEBP, leading to π‐conjugated organometallic oligomeric and polymeric metallaynes, was investigated by a systematic variation of the reaction conditions. The formation of polymers and oligomers with defined chain length [? M(PBu₃)₂ (C?C? C₆H₄? C₆H₄? C?C? )]_n (n = 3–10 for the oligomers, n = 20–50 for the polymers) depends on the configuration of the precursor Pt(II) and Pd(II) complexes, the presence/absence of the catalyst CuI, and the reaction time. A series of model reactions monitored by XPS, GPC, and NMR ³¹P spectroscopy showed the route to modulate the chain growth. As expected, the nature of the transition metal (Pt or Pd) and the molecular weight of the polymers markedly influence the photophysical characteristics of the polymetallaynes, such as optical absorption and emission behavior. Polymetallaynes with nanostructured morphology could be obtained by a simple casting procedure of polymer solutions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3311–3329, 2007     

Modification of surface properties of electrospun polyamide nanofibers by means of a perfluorinated acridine

Polyamide 6 (PA6) nanofibers were prepared from formic acid solutions by using electrospinning technique. The fibers were smooth, defects free and with diameters smaller than 200 nm. Small amounts of a perfluorinated acridine were added as dopant to the feed solution to modify the wettability of the fibers. The effect of doping on the contact angle values is well apparent. The contact angle values go from 50° of pure PA6 to 120° when 6% of acridine is added. A comparison between fibers and films of pure and doped polyamide 6 was carried out in order to determine the effect of morphology on wettability. Thermal annealing near the T_g of the polymer promoted the segregation of the molecules to the surface, reaching contact angles of 131° with smaller amounts (4%) of acridine. The surface segregation was also promoted by time aging.     

Synthesis and spectroscopic properties of highly water-soluble perylene derivatives

Most known perylene diimides are lipophilic, with few exceptions of hydrophilic derivatives. Even in the latter case, the compounds have limited water solubility and show a strong tendency to self-aggregation. In this paper we present the synthesis of four new perylene derivatives with three and four basic side chains, obtained by functionalizing the bay-area of perylene. These molecules show great solubility in aqueous media as hydrochlorides and their tendency to self-aggregate is remarkably reduced with respect to the previously synthesized two-chained perylene diimides. Their different spectroscopic properties in various solvents and conditions are reported and discussed.     

A Formal Total Synthesis of (+)-Methyl Trachyloban-18-oate and (+)-Methyl 16-Oxo-17-norkauran-18-oate: Regio- and Diastereoselective Preparation of Methyl (13S)-13-Hydroxyisoatisiren-18-oate from (−)-Abietic Acid

A novel preparation of methyl (13S)-13-hydroxyisoatisiren-18-oate ( 4 ), a key-intermediate in a synthesis of (+)-methyl trachyloban-18-oate ((+)- 1 ), from (?)-abietic acid, is described. Since (?)- 1 has been previously converted into (?)-methyl 16-oxo-17-norkauran-18-oate ((?)- 16 ), our preparation of 4 constitutes also a formal total synthesis, from (?)-abietic acid, of (+)- 16 . Key steps in this approach were the allene photoaddition to podocarp-8(14)-en-13-one ( 5 ) and the conversion of the endo-toluene-4-sulfonate 11 into the exo-benzoate 12b .     

High-performance liquid chromatography with post-column derivatisation and fluorescence detection for sensitive determination of aflatoxin M1 in milk and cheese

A new HPLC method with fluorescence detection using pyridinium hydrobromide perbromide as a post-column derivatising agent has been developed to determine aflatoxin M1 in milk and cheese. The detection limits were 1 ng/kg for milk and 5 ng/kg for cheese. The calibration curve was linear from 0.001 to 0.1 ng injected. The method includes a preliminary C18-SPE clean-up and the average recoveries of Aflatoxin M1 from milk and cheese, spiked at levels of 25-75 ng/kg and 100-300 ng/kg, respectively, were 90 and 76%; the precision (RSDr) ranged from 1.7 to 2.6% for milk and from 3.5 to 6.5% for cheese. The method is rapid, easily automatable and therefore useful for accurate and precise screening of aflatoxin M1 in milk and cheese.     

Perfluoropoly-ether/peroxide compounds: spectroscopic studies and quantum chemical calculations

Perfluoropolyethers (PFPEs) are a class of high performance materials used in a wide range of applications (refrigeration, lubrication, semiconductor industry, etc.). PFPEs containing peroxidic units are intermediate materials for the preparation of commercial end products. In this work we study the spectroscopic properties of ether and peroxides linkages in this class of compounds; nuclear magnetic resonance (NMR) spectra are discussed, FT-Raman data presented. Quantum chemical calculations on model molecules were used as a tool for the interpretation of the Raman experimental data and physical-chemical properties.     

Determination of picotamide in human plasma and urine by high-performance liquid chromatography.

A high-performance liquid chromatographic method for the determination of picotamide in human plasma and urine is described. After addition of an internal standard (bamifylline), the plasma and urine samples were subjected to liquid-liquid extraction and clean-up procedures. The final extracts were evaporated to dryness and the resulting residues were reconstituted in 100 microliters of methanol-water (50:50, v/v) and chromatographed on a LiChrosorb RP-SELECT B reversed-phase column coupled to an ultraviolet detector monitored at 230 nm. Chromatographic analysis takes about 10 min per sample. The assay was linear over a wide range and has a limit of detection of 0.005 and 0.1 micrograms/ml in plasma and urine, respectively. It was selective for picotamide, accurate and robust and thus suitable for routine assays after therapeutic doses of picotamide.     

2-(2-Hydroxyaryl)cinnamic amides: a new class of axially chiral molecules

The syntheses of several differently substituted amides formally derived from a chiral amine, either E-2-(2-hydroxyphenyl)cinnamic acid or both E- and Z-2-(2-hydroxynaphthyl)cinnamic acid, are reported. These molecules display a restricted rotation about the C₂-C_aryl bond. The barriers to rotation about the C₂-C_aryl bond were measured by the dynamic ¹H NMR and were found to vary between 11.8 and 24.5 kcal mol⁻¹, depending on the substitution. In particular, E-2-(2-hydroxynapthyl)cinnamic amides, displayed a high barrier to rotation (ΔG_c^‡=24.4 kcal mol⁻¹) and could be isolated in both diastereomerically pure forms at room temperature. The X-ray structure of one E-2-(2-hydroxynapthyl)cinnamic amide, was resolved, enabling for the determination of the absolute configuration of the chiral axis (aR).