Ligand trans-effect: using an old concept as a novel approach to bis(dipolar) NLO-phores

In plane parallel arrangement and enhancement of NLO-activity are observed upon coordination of heteroditopic dipoles containing a phosphole ring on square-planar d8-palladium centre.     

New stereoselective reaction of methylglyoxal with 2-aminopyridine and adenine derivatives: formation of imino acid-nucleic base derivatives in water under mild conditions

A remarkable stereoselective reaction of methylglyoxal with 2-aminopyridine, the nucleic base adenine and adenine nucleosides leads in good yield to heterocycles of a new family in water under mild conditions and should be of interest in the understanding of the biological effects of methylglyoxal which is toxic, mutagenic and involved in diabetic complications.     

Observation of diffraction excitation in pp → (pπ+π−)+X at the CERN-ISR and tests of limiting fragmentation

In a single-arm magnetic spectrometer experiment at the CERN Intersecting Storage Rings (ISR), a prominent diffractive enhancement is observed for inclusive production of (pπ⁺π^?) systems near x ～ 1 at √s = 53 and 35 GeV. In testing limiting fragmentation and scaling for this system, inclusive pπ⁺π^? diffractive excitation into a fixed invariant mass range is found to possess a cross-section independent of s to within (3 ± 5)%. The main component in the (pπ⁺π^?) system is Δ(1236)π, with a charge structure compatible with the break-up of an isotopic spin $\text{1}\text{2}$ system.     

Cytotoxic effect and electrophysiological activity of S-irniine, a synthesised isomer of the natural R-irniine, on human MRC-5 fibroblasts

Numerous original alkaloids are present in tubers of Arisarum vulgare Targ. a species belonging to the Araceae family known in Morocco for its toxicity. Some previous works deal with the activity of these natural compounds as R-irniine. As the enantioselective total synthesis of irniine has been realised, the R- and S-forms were obtained and this last one could be tested. Thus, a study of the cytotoxicity and the electrophysiological activity of S-irniine was carried out on human MRC-5 fibroblasts. A cytotoxic effect of S-irniine at 40 microg/mL was detected on MRC-5 fibroblasts. An electrophysiological study was also carried out on the MRC-5 cells by using the patch-clamp technique and no effect of this compound at this concentration on the outward potassium current of MRC-5 fibroblasts was observed. Thus, this study showed, as it was for R-irniine, that the cytotoxicity of S-irniine was not explained by an effect on the potassium currents.     

First synthesis and structure of beta-ketoimine calix[4]arenes: complexation and extraction studies

The synthesis of a new series of beta-ketoimine calix[4]arene derivatives is described. The reaction of calix[4]arene or p-tert-butylcalix[4]arene with bromoacetonitrile or bromobutyronitrile afforded di-, tri-, and tetranitrile calixarene derivatives (3-8, 3a), which were then reduced into the corresponding amine (9-13, 3b). The condensation of these aminocalixarenes with acetylacetone led to six beta-ketoimine calix[4]arene derivatives (14-18, 3c) as a class of selective receptors toward transition metals. Molecular structures of 4, 7, and 17 have been determined by X-ray diffraction. The packing of 17 revealed a network of intramolecular and intermolecular hydrogen bonds. The complexation properties of receptors 15, 17, and 3c toward different metal ions have been investigated by UV-vis titrations in organic media. The stoichiometries of complexes with 17 were determined by both the mole ratio method and Job plots. These novel receptors selectively complex Cu2+, Hg2+, and Ag+. Moreover, the extraction properties of 17 toward cations have been studied by liquid-liquid extraction and atomic absorption spectrometry. Compound 17 has good affinity and selectivity toward Pb2+.     

Photophysics of Calix[4]biscrown-Based Ditopic Receptors of Caesium Containing One or Two Dioxocoumarin Fluorophores

The ditopic receptors Calix-COU1 and Calix-COU2 consist of a calix[4]biscrown containing one or two dioxycoumarin fluorophores, respectively, inserted into the crown. They can form 1:1 and 2:1 (metal:ligand) complexes with caesium ions. The photophysical properties of the 1:1 complexes can be explained by (i) cation tunneling through the tube-shaped cavity (composed of the four phenyl rings) of the calix[4]biscrown, (ii) photodisruption of the interaction between the bound cation and the oxygen atoms belonging to both the coumarin moiety and the crown, (iii) photoinduced motions of the cation.     

Organization of nanoscale objects via polymer demixing

We present an extremely versatile method for the lateral organization of nano-scale objects (NOs) based on the phenomenon of polymer demixing. NOs are suspended in a solution of two immiscible polymers, which is used to form a thin polymer film by spin coating. During spin coating the two polymers separate to give a microphase structure, whose length scale depends on the experimental conditions. The NOs spontaneously partition into one or other of the polymer phases resulting in their lateral organization. In this work, the organization of CdSe nanoparticles and fluorescent organic dyes was studied by fluorescence microscopy. The NOs were organized in the polymer film in stochastic patterns or in ordered designs on substrates pre-patterned by soft-lithography techniques. Single-particle measurements, using confocal microscopy, showed that at low concentrations there was little aggregation of the particles.     

Modeling the frequency dependence (5-120 MHz) of ultrasound backscattering by red cell aggregates in shear flow at a normal hematocrit

The frequency dependence of the ultrasound signal backscattered by blood in shear flow was studied using a simulation model. The ultrasound backscattered signal was computed with a linear model that considers the characteristics of the ultrasound system and tissue acoustic properties. The tissue scattering properties were related to the position and shape of the red blood cells (RBCs). A 2D microrheological model simulated the RBC dynamics in a Couette shear flow system. This iterative model, described earlier [Biophys. J. 82, 1696-1710 (2002)], integrates the hydrodynamic effect of the flow, as well as adhesive and repulsive forces between RBCs. RBC aggregation was simulated at 40% hematocrit and shear rates of 0.05-2 s(-1). The RBC aggregate sizes ranged, on average, from 3.3 RBCs at 2 s(-1) to 33.5 cells at 0.05 s(-1). The ultrasound backscattered power was studied at frequencies between 5-120 MHz and insonification angles between 0-180 degrees. At frequencies below approximately 30 MHz, the ultrasound backscattered power increased as the shear rate was decreased and the size of the aggregates was raised. A totally different scattering behavior was noted above 30 MHz. Typical spectral slopes of the backscattered power (log-log scale) between 5-25 MHz equaled 3.8, whereas slopes down to 0.6 were measured at 0.05 s(-1), between 40-60 MHz. The ultrasound backscattered power was shown to be angle dependent at low frequencies (5-25 MHz). The anisotropy persisted at high frequencies (>25 MHz) for small aggregates (at 2 s(-1)). In conclusion, this study sheds some light on the blood backscattering behavior with an emphasis on the non-Rayleigh regime. Additional experimental studies may be necessary to validate the simulation results, and to fully understand the relation between the ultrasound backscattered power, level of RBC aggregation, shear rate, frequency, and insonification angle.