Synthesis and coordination properties of highly preorganised polyamine macrocycles

Synthesis and characterisation of the new macrocyclic ligands L1‐L4 are reported. The ligands present one or two pentaamine moieties, each containing two piperazine rings, linked by benzene or anthracene spacers. Interaction of L1 with H⁺, Cu(II), Zn(II), Hg(II), and Pd(II) and of L3 with H⁺, and Cu(II) has been studied by potentiometric titrations in 0.15 mol dm^?3 NaCl aqueous solution at 298.1 ±0.1 K. The thermodynamic data suggest that in the metal complexes only three nitrogen donor atoms bind each metal ion. As a consequence of the low coordination number, these complexes are promising receptors for different molecules.     

Novel coating for solid-phase microextraction: Electropolymerization of a molecular receptor functionalized with 2,2′-bithiophene for the determination of environmental pollutants at trace levels

A novel solid-phase microextraction coating based on the electropolymerization of a molecular receptor properly functionalized with 2,2′-bithiophene was developed for the determination of environmental pollutants in air and water samples. The 2,2′-bithiophene-based film was electrochemically deposed on the surface of a gold wire using cyclic voltammetry. The fibres showed a porous structure with an average thickness of 12 ± 3 μm (n = 5): a good intra-batch and inter-batch repeatability with RSD lower than 14% was also observed. The selective interactions via hydrogen bonding with organic molecules containing electronegative atoms was proved: LOD values in the low ng/l range allowed the determination of vinyl chloride and chlorobenzenes at trace levels in environmental matrices.     

Geometrische Darstellung der Gruppen linearer Substitutionen mit ganzen complexen Coefficienten nebst Anwendungen auf die Zahlentheorie

Ohne Zusammenfassung     

Nonlinear modelling of data in photomineralization kinetics of organic micropollutants by photocatalytic membranes immobilizing titanium dioxide in membrane reactors

Kinetic fitting of substrate disappearance and of total organic carbon (TOC) mineralization of organic micropollutants, in water and air, by photocatalytic membranes immobilizing titanium dioxide, was carried out. A model was used in which mineralization of substrate to CO₂ is supposed to occur, with kinetic constant k₁, through one single intermediate, mediating the behaviour of all the numerous real intermediates formed in the path to CO₂, kinetic constant of formation of the latter being k₂. A competitive Langmuirian‐type adsorption of both substrate and ‘intermediate’ was also supposed to be operative, as expressed by pseudo‐thermodynamic constants K₁ and K₂ respectively, these constants possessing a, partly at least, kinetic significance. Nonlinear models could be fitted to data by using the least‐squares method. The very satisfactory matching is shown for the laboratory‐scale mineralization kinetics of methane, as model molecule of aliphatic contaminants, both in the gas phase and in aqueous solution. Furthermore, in pilot plant experiments, using phenol, as model molecule of aromatics, modelling of quantum yields was carried out, as a function of concentration and of adsorbed radiant power. Kinetics of hydroxyl radicals reacting between themselves, leading to hydrogen peroxide, other than with substrate or intermediates leading to mineralization, was considered, paralleled by a second competition kinetics due to superoxide anion radical and its conjugate acid, equally leading to mineralization. In this model the contribution of hydroxyl radicals to mineralization decreases with irradiance, while the contribution of superoxide anion radical and its conjugate acid increases. If the regression equations of these two contributions are considered together, in a linear combination, the surface model perfectly fits the experimental data. Copyright © 2008 John Wiley & Sons, Ltd.     

Moisture Absorption in Capillary Active Materials: Analytical Solution for a Multiple Step Diffusivity Function

This paper deals with the double-constraint methodology for calibration of steady-state groundwater flow models. The methodology is based on updating the hydraulic conductivity of the model domain by comparing the results of two forward groundwater flow models: a model in which known fluxes are specified as boundary conditions and a model in which known heads are specified as boundary conditions. A new zone-integrated double-constraint approach is presented by partitioning the model domain in zones with presumed constant hydraulic conductivity (soft data), and the double-constraint methodology is reformulated accordingly. The feasibility of the method is illustrated by a practical case study involving a numerical steady-state groundwater flow model with about 3 million grid blocks, subdivided into four zones corresponding to the major hydrogeological formations. The results of the zone-integrated double-constraint method for estimating the horizontal and vertical hydraulic conductivities of the zones compare favourably with a classical model calibration based on minimisation of the differences between calculated and measured heads, while the double-constraint method proves to be more robust and computationally less cumbersome.     

The length operator in Loop Quantum Gravity

The dual picture of quantum geometry provided by a spin network state is discussed. From this perspective, we introduce a new operator in Loop Quantum Gravity—the length operator. We describe its quantum geometrical meaning and derive some of its properties. In particular we show that the operator has a discrete spectrum and is diagonalized by appropriate superpositions of spin network states. A series of eigenstates and eigenvalues is presented and an explicit check of its semiclassical properties is discussed.     

Independence of friction self-locking from kinematic singularity

Self-locking analysis in closed kinematic chains is sometimes likened to kinematic singularity. Here a novel approach to tackle self-locking analysis due to joints friction is exploited, that is completely different from the classical kinematic analysis based on the jacobian conditioning. It is shown that an inverse kinematic singularity always entails a self-locking phenomenon because of the general increasing of joints reactions and, then, friction forces; hence, a self-locking domain can be always identified including such a locus. On the other side, this paper is aimed at demonstrating that the aforementioned condition is not necessary: namely, self-locking may occurs also if the mechanism kinematics is well-conditioned. Then, the theoretical result is clarified performing the self-locking analysis on a simple crank-slider mechanism.