Nanoscopic optical sensors based on functional supramolecular hybrid materials

This review highlights how the combination of supramolecular principles and nanoscopic solid structures enables the design of new hybrid sensing ensembles with improved sensitivity and/or selectivity and for the targeting of analytes for which selectivity is hard to achieve by conventional methods. Such ideas are bridging the gap between molecules, materials sciences and nanotechnology. Relevant examples will be detailed, taking into account functional aspects such as (1) enhanced coordination of functionalized solids, (2) enhanced signalling through preorganization, (3) signalling by assembly–disassembly of nanoscopic objects, (4) biomimetic probes utilizing discrimination by polarity and size and (5) distinct switching and gating protocols. These strategies are opening new prospects for sensor research and signalling paradigms at the frontier between nanotechnology, smart materials and supramolecular chemistry.     

DNS of backward‐facing step flow with fully turbulent inflow

Direct numerical simulation (DNS) has been performed to study the channel flow over a backward‐facing step at a Reynolds number Re_b=5600 based on the step height h and the inflow bulk velocity U_b. A dynamic method has been used in order to generate realistic turbulent inflow conditions. The results upstream of the step compared well with the fully developed channel flow. Downstream of the step our results show excellent agreement with experimental data. Copyright © 2009 John Wiley & Sons, Ltd.     

An attempt to understand the observed plateau of the magnetization in tetranuclear iron(II) complexes of thiacalixarene macrocycles

The next-nearest-neighbour (NNN) effect in tetranuclear iron(II) complexes of thiacalixarene macrocycles using the isotropic Heisenberg model has been investigated in order to understand its effects on the observed plateau of magnetization. Although NNN effect is generally very weak in these kinds of systems, it was calculated that its response is quite significant to the external perturbations in certain temperature regions. Using the isotropic Heisenberg exchange Hamiltonian, zero-field energy spectra have been calculated for this particular tetranuclear system. The average magnetic moments with and without next-nearest-neighbour interactions were also calculated. In order to verify the calculations, the results were compared with experimental data taken from the literature, whence, it is suggested that observed magnetic behaviour can be improved by taking into account the NNN effect.     

Cloud point extraction procedure for flame atomic absorption spectrometric determination of lead(II) in sediment and water samples

The conditions for cloud point extraction of lead(II) from aqueous solutions were investigated and optimized. The procedure is based on the separation of Pb(II) – brillant cresyl blue (BCB) complexes into the micellar media by adding the surfactant Triton X-114. After phase separation, the surfactant-rich phase was dissolved with 1 mol L⁻¹ HNO₃ in ethanol and diluted with 1 mol L⁻¹ HNO₃ solution before lead was determined by flame atomic absorption spectrometry. Optimization of the pH, ligand and surfactant quantities, incubation time, temperature, viscosity, sample volume, and interfering ions was performed. The effects of the matrix ions were also examined. The detection limits for three times the standard deviations of the blank for lead were 7.5 μg L⁻¹ for water samples and 0.33 μg g⁻¹ for sediment samples. The validity of cloud point extraction was checked by employing certified reference samples of Lake Sediment IAEA-SL-1 and Sewage Sludge BCR-CRM 144R. The procedure was applied to natural waters and sediment samples with satisfactory results (recoveries >95%, relative standard deviations <6.4%).     

Synthesis of novel iodo derived bicalutamide analogs

A series of optically active nonsteroidal selective androgen receptor modulators with structures analogous to bicalutamide was prepared by replacing the trifluoromethyl group with iodine and the sulfonyl linker by oxygen.     

Role of copper species in the oxidative dimerization of arylboronic acids: synthesis of symmetrical biaryls

Certain Cu(I) and Cu(II) salts are able to mediate the dimerization of arylboronic acids in DMF. They provide the corresponding symmetrical biaryls in moderate to very good yields. It is possible to run the reaction catalytically under an oxygen atmosphere without a significant loss of yields.