Protonated macrobicyclic hosts containing pyridine head units for anion recognition

In this paper, we report two macrobicyclic receptors containing pyridine head units derived from 1,10-diaza-15-crown[5] (L1) or 4,13-diaza-18-crown[6] (L2) that can be protonated in MeCN and used for anion recognition. The interaction of these protonated lateral macrobicycles with different anions has been investigated by means of spectrophotometric titrations in MeCN. The association constants for the complexes of halide anions with the protonated macrobicycles follow the sequences Cl(-)>Br(-)>I(-)>F(-) (L1) and Cl(-)>F(-)>I(-)>Br(-) (L2), whereby an increase of more than two logarithmic units is observed from F(-) to Cl(-) for the binding constants of the receptor derived from L1. The association constants also indicate an important degree of selectivity of these macrobicyclic receptors for Cl(-) over Br(-) or I(-). The X-ray crystal structure analyses of the chloride and bromide complexes confirms the formation of the envisaged supramolecular complexes. Moreover, the binding constants indicate that these receptors present a high sulfate-to-nitrate binding selectivity. The stability trend observed for the recognition of halide anions by the macrobicycles presented herein as well as the sulfate-to-nitrate binding selectivity have been rationalised by means of DFT calculations at the B3LYP/LanL2DZ level. These studies indicate that the especially high binding selectivity for Cl(-) is the result of the optimum fit between the protonated macrobicyclic cavity and the size of the anion, whereas the sulfate-to-nitrate selectivity results from shape complementarity between the hydrogen-binding acceptor sites on sulfate and the hydrogen-bond donors of the macrobicycle.     

A discrete long-term location–price problem under the assumption of discriminatory pricing: Formulations and parametric analysis

We consider a competitive location problem in which a new firm has to make decisions on the locations of several new facilities as well as on its price setting in order to maximise profit. Under the assumption of discriminatory prices, competing firms set a specific price for each market area. The customers buy one unit of a single homogeneous price-inelastic product from the facility that offers the lowest price in the area the consumers belong to. Three customer choice rules are considered in order to break ties in the offered prices. We prove that, considering long-term competition on price, this problem can be reduced to a problem with decisions on location only. For each one of the choice rules the location problem is formulated as an integer programming model and a parametric analysis of these models is given. To conclude, an application with real data is presented.     

On Gorenstein injective discrete modules over profinite groups

Gorenstein homological algebra was introduced in categories of modules. But it has proved to be a fruitful way to study various other categories such as categories of complexes and of sheaves. In this paper, the research of relative homological algebra in categories of discrete modules over profinite groups is initiated. This seems appropriate since (in some sense) the subject of Gorenstein homological algebra had its beginning with Tate homology and cohomology over finite groups. We prove that if the profinite group has virtually finite cohomological dimension then every discrete module has a Gorenstein injective envelope, a Gorenstein injective cover and we study various cohomological dimensions relative to Gorenstein injective discrete modules. We also study the connection between relative and Tate cohomology theories.     

The optimal combination: Grammatical swarm,particle swarm optimization and neural networks

Social behaviour is mainly based on swarm colonies, in which each individual shares its knowledge about the environment with other individuals to get optimal solutions. Such co-operative model differs from competitive models in the way that individuals die and are born by combining information of alive ones. This paper presents the particle swarm optimization with differential evolution algorithm in order to train a neural network instead the classic back propagation algorithm. The performance of a neural network for particular problems is critically dependant on the choice of the processing elements, the net architecture and the learning algorithm. This work is focused in the development of methods for the evolutionary design of artificial neural networks. This paper focuses in optimizing the topology and structure of connectivity for these networks.     

Search for new d0 half-metallic materials: theoretical investigation on KCaC1−xSix (x = 0; 0.25; 0.5; 0.75 and 1) compounds

In recent years, the investigations on d⁰ half-metallic materials have become the new trend in the search of novel materials for applications in spintronic devices. In this work, the structural, electronic and magnetic properties of KCaC${}_{1?x}$Si_x (x = 0; 0.25; 0.5; 0.75 and 1) compounds have been theoretically studied using the full-potential linearized augmented plane wave (FP-LAPW) method within framework of the density functional theory. The generalized gradient approximation scheme as proposed by Wu-Cohen (GGA-WC) and Tran-Blaha modified Becke-Johnson exchange potential with improved parameterization by Koller are adopted for the treatment of electron exchange-correlation. All considered materials show half-metallic characteristics with semiconducting majority spin channel and metallic minority one. The total spin magnetic moment is 1μ_B for ternary alloys and 4μ_B for quaternary compounds. Our obtained results suggest that these materials could be promising candidate for spintronic applications.     

Lanthanide(III) complexes with ligands derived from a cyclen framework containing pyridinecarboxylate pendants. The effect of steric hindrance on the hydration number

Two new macrocyclic ligands, 6,6′-((1,4,7,10-tetraazacyclododecane-1,7-diyl)bis(methylene))dipicolinic acid (H2DODPA) and 6,6′-((4,10-dimethyl-1,4,7,10-tetraazacyclododecane-1,7-diyl)bis(methylene))dipicolinic acid (H2Me-DODPA), designed for complexation of lanthanide ions in aqueous solution, have been synthesized and studied. The X-ray crystal structure of [Yb(DODPA)](PF6)·H2O shows that the metal ion is directly bound to the eight donor atoms of the ligand, which results in a square-antiprismatic coordination around the metal ion. The hydration numbers (q) obtained from luminescence lifetime measurements in aqueous solution of the Eu(III) and Tb(III) complexes indicate that the DODPA complexes contain one inner-sphere water molecule, while those of the methylated analogue H2Me-DODPA are q = 0. The structure of the complexes in solution has been investigated by 1H and 13C NMR spectroscopy, as well as by theoretical calculations performed at the density functional theory (DFT; mPWB95) level. The minimum energy conformation calculated for the Yb(III) complex [Λ(λλλλ)] is in good agreement with the experimental structure in solution, as demonstrated by the analysis of the Yb(III)-induced paramagnetic 1H shifts. The nuclear magnetic relaxation dispersion (NMRD) profiles recorded for [Gd(Me-DODPA)]+ are typical of a complex with q = 0, where the observed relaxivity can be accounted for by the outer-sphere mechanism. However, [Gd(DODPA)]+ shows NMRD profiles consistent with the presence of both inner- and outer-sphere contributions to relaxivity. A simultaneous fitting of the NMRD profiles and variable temperature 17O NMR chemical shifts and transversal relaxation rates provided the parameters governing the relaxivity in [Gd(DODPA)]+. The results show that this system is endowed with a relatively fast water exchange rate k(ex)(298) = 58 × 10(6) s(–1).     

Lanthanide(III) Nitrate Complexes of Two 17 Membered N3O2-Donor Macrocycles

The interaction of lanthanide(III) ions with two N₃O₃-macrocycles, L¹ and L², derived from 2,6-bis(2-formylphenoxymethyl)pyridine and 1,2-diaminoethane has been investigated. Schiff-base macrocyclic lanthanide(III) complexes LnL¹(NO₃)₃ · xH₂O (Ln = Nd, Sm, Eu or Lu) have been prepared by direct reaction of L¹ and the appropriate hydrated lanthanide nitrate. The direct reaction between the diamine macrocycle L² and the hydrated lanthanide(III) nitrates yields complexes LnL²(NO₃)₃· H₂O only for Ln = Dy or Lu. The reduction of the Schiff-base macrocycle decreases the complexation capacity of the ligand towards the Ln(III) ions. The complexes have been characterised by elemental analysis, molar conductivity data, FAB mass spectrometry, IR and, in the case of the lutetium complexes, ¹H NMR spectroscopy.     

Magnetic monopoles: Evidence since the Dirac conjecture

In the fifty-one years since its publication Dirac's magnetic monopole conjecture has stimulated a theoretical outpouring rich in variety. We review here the experimental techniques with which monopoles have been sought and we will describe the limits on monopole properties these searches have established.     

High Relaxivity Mn2+‐Based MRI Contrast Agents

Stable Mn²⁺ mono‐ and binuclear complexes containing pentadentate 6,6′‐((methylazanediyl)bis(methylene))dipicolinic acid coordinating units give remarkably high relaxivities due to the presence of two inner‐sphere water molecules. The mononuclear derivative binds human serum albumin (HSA) with an association constant of 3372 M ^?1, which results in the replacement of the coordinated water molecules by donor atoms of protein residues. The dinuclear analogue also binds HSA while leaving one of the Mn²⁺ centres exposed to the solvent with two coordinated water molecules. Thus, this complex shows remarkably high relaxivities upon protein binding (39.0 mM ^?1 s^?1 per Mn, at 20 MHz and 37 °C).