Boron-nitrogen macrocycles: a new generation of calix[3]arenes

The simple condensation reaction of 3,5-di-tert-butyl salicylaldehyde and 3-aminophenylboronic acid leads to a trimeric macrocyclic compound. The ability of this molecule to include small organic molecules was in a first approximation analyzed by (1)H NMR spectroscopy and X-ray crystallography.     

An extended mixture model for the simultaneous treatment of small‐scale and large‐scale interfaces

The aim of this work is to present a new model based on the volume of fluid method and the algebraic slip mixture model in order to solve multiphase gas–fluid flows with different interface scales and the transition among them. The interface scale is characterized by a measure of the grid, which acts as a geometrical filter and is related with the accuracy in the solution; in this sense, the presented coupled model allows to reduce the grid requirements for a given accuracy. With this objective in mind, a generalization of the algebraic slip mixture model is proposed to solve problems involving small‐scale and large‐scale interfaces in an unified framework taking special care in preserving the conservativeness of the fluxes. This model is implemented using the OpenFOAM^® libraries to generate a tool capable of solving large problems on high‐performance computing facilities. Several examples are solved as a validation for the presented model, including new quantitative measurements to assess the advantages of the method. Copyright © 2014 John Wiley & Sons, Ltd.     

Incorporation of Ce3+ in crystalline Gd-silicate nanoclusters formed in silica

Structural and optical properties of sol–gel silica based glassceramics doped with 0.1 mol% Ce and codoped with Gd at high concentrations, from 5 mol% up to 40 mol%, are investigated and compared to those of analogous samples doped only with Ce. Raman scattering, transmission electron microscopy, and x-ray diffraction reveal the formation of Gd apatite-like silicate (Gd_4.67O(SiO₄)₃) and of Gd pyrosilicate (Gd₂Si₂O₇) nanophases whose morphology and crystallinity depend on the Gd concentration and thermal treatments. Optical absorption measurements demonstrate the role of the densification atmosphere in modifying the charge state of Ce ions. The incorporation of Ce³⁺ ions in the nanophases is put in evidence by photo- and radio-luminescence results.     

Tuning the Cell Uptake and Subcellular Distribution in BODIPY–Carboranyl Dyads: An Experimental and Theoretical Study

A set of BODIPY-carboranyl dyads synthesized by a Sonogashira cross-coupling reaction, where different C-substituted ortho- and meta-carboranyl fragments have been linked to a BODIPY fluorophore is described. Chemical, photophysical and physicochemical analyses are presented, including NMR and single XRD experiments, optical absorption/emission studies and partition coefficient (log P) measurements. These studies, supported by DFT computations (M06-2X/6-31G**), provide an explanation to the largely divergent cell income that these fluorescent carboranyl-based fluorophores display, for which a structural or physicochemical explanation remains elusive. By studying the cell uptake efficiency and subcellular localization for our set of dyads on living HeLa cells, we tracked the origins of these differences to significant variations in their static dipole moments and partition coefficients, which tune their ability to interact with lipophilic microenvironments in cells. Remarkably, m-carboranyl-BODIPY derivatives with a higher lipophilicity are much better internalised by cells than their homologous with o-carborane, suggesting that m-isomers are potentially better theranostic agents for in vitro bioimaging and boron carriers for boron neutron capture therapy.     

Clusters in strong polyelectrolyte solutions in the condensation theory approach

The interaction free energy of parallel clusters of like-charged rod polyelectrolytes in solution is calculated in the framework of the extended condensation theory. For sufficiently high linear charge density of the polyelectrolyte, clustering takes place. The greater is the number of polyelectrolytes participating to the cluster, the smaller is the equilibrium interpolyelectrolyte distance, and the deeper is the corresponding free energy minimum. It is a counterintuitive organization due to the increasing of the counterion condensed charge and condensation volume, taking place as the polyelectyrolytes approach each other.     

Basic hydrolysis of quinolinyl N,N‐dimethylcarbamates: a two‐step mechanism

The reactivity of 6‐quinolinyl and 8‐quinolinyl N,N‐dimethylcarbamates was examined in several aqueous basic media. A quadratic dependence was observed for the constant rates upon hydroxide concentration for both compounds, which is a typical behaviour of a mechanism involving a base‐catalysed deprotonation of the tetrahedral intermediate with the formation of a dianion at high concentrations of hydroxide ion, while at lower concentrations a specific‐base catalysed addition–elimination mechanism seems to be predominant. The reactivity of 8‐quinolinyl N,N‐dimethylcarbamate was also studied in several amine buffers, showing specific base catalysis. The reactivity of 6‐quinolinyl N,N‐dimethylcarbamate was studied in H₂O and in D₂O and the solvent isotope effect supports the proposal of a mechanism involving a specific‐base hydrolysis. All results confirm the existence of a mechanism with a rate determining step involving the substrate anion and a second mole of hydroxide ion. This mechanism was so far unknown for carbamate reactivity, being only known to occur with amides. Copyright © 2011 John Wiley & Sons, Ltd.     

Computer simulation model of the structure of ion implanted impurities in semiconductors

A system of ion implanted impurities in a semiconductor is described by a Monte Carlo simulation of a non-equilibrium system of random distributed hard spheres. The radial distribution function of this system is found. The comparison is made with the fluid hard sphere case. The assumption that the absence either of annealing or diffusion of the impurities after the implantation process is also made.