Metamorphosis of a butterfly: synthesis, structural, thermal, magnetic and DFT characterisation of a ferromagnetically coupled tetranuclear copper(II) complex

The reaction in water of Cu(OH)(2) with 2,2'-bipyridine (bipy) and (NH(4))(2)HPO(4) in a 4 : 4 : 2 molar ratio under an inert atmosphere leads to the formation of a tetranuclear copper(II) complex of formula {[(H(2)O)(2)Cu(4)(bipy)(4)(mu(4)-PO(4))(2)(mu(2)-OH)] x 0.5 HPO(4) x 15.5 H(2)O}, 1, with butterfly topology. The structure of the tetranuclear core in 1 consists of four crystallographically unique copper(II) ions in approximate square-pyramidal geometry with each coordinated to a bipy ligand and interacting through two mu(4)-O,O',O'-phosphate bridges. Additional bridging between Cu(3) and Cu(4) is provided by a hydroxide ligand, whereas two water molecules cap the Cu(1) and Cu(2) square pyramids to yield a N(2)O(3) chromophore at each copper atom. Adjacent tetranuclear units align in anti-parallel fashion where proximate metal-bound water molecules interact with each other through both intra- and inter-molecular H-bonding to link two such clusters. These pairs then further associate through pi[...]pi interactions between bipy ligands to form a 2D sheet with neighbouring sheets separated by H-bonded lattice water molecules, which form a 2D H-bonded network. Variable-temperature magnetic susceptibility measurements performed upon 1 reveal net intramolecular ferromagnetic coupling between the copper(II) ions and this is supported and rationalized by a DFT study.     

W(bipy)(CN)6]-: a suitable metalloligand in the design of heterotrimetallic complexes. The first Cu(II)Ln(III)W(V) trinuclear complexes

The first 3d-4f-5d heterotrimetallic complexes using [W(V)(bipy)(CN)(6)](-) as a metalloligand were synthesized (bipy = 2,2'-bipyridine). The structural and magnetic properties of three [Cu(II)Ln(III)W(V)] complexes (Ln = Gd, Ho, Tb) are discussed.     

On the convergence of isolated neutral oxygen vacancy and divacancy properties in metal oxides using supercell models

The properties of isolated neutral oxygen vacancies and divacancies of metal oxides of increasing complexity (MgO, CaO, alpha-Al2O3, and ZnO) have been studied by means of density-functional theory within a supercell periodic approach. Vacancy formation energies, vacancy-vacancy interactions, and geometry rearrangements around these point defects have been investigated in detail. The characterization of the electronic structure of these point defects has been established by analysis of the density of states and of the topology of the electron density and of electron localization function. It is found that the chemical character of the oxide determines the properties of the oxygen vacancies. For the covalent ZnO oxide, a more complex scheme arises in which the relaxation around the oxygen vacancy is much larger leading to the formation of Zn4-like almost metallic particles in the crystal. The relationship of these structures with the crystal shear planes is discussed. The present study shows that supercells containing approximately 200-300 atoms provide converged values for the geometric and electronic structure of oxygen vacancies of these metal oxides in the point defect low concentration limit.     

An experimental and theoretical study of competitive adsorption at the n-heptane/water interface

A model to calculate the interfacial concentration of competing surface active species in a two-phase oil/water system was developed. To enable the calculation of the surface excess of 2-hydroxy-5-nonylacetophenone oxime (HNAPO, active ingredient of LIX 84) in the presence of surfactants competing for interfacial area, an interfacial adsorption competition model was derived for noninteracting surface active species in a n-heptane/aqueous system, assuming ideal enthalpy and entropy of mixing. The model was found to be valid for HNAPO in the presence of sodium dodecyl sulfate (SDS) or dodecyldimethyl(3-sulfopropyl)ammonium (DDSA). In the case of dodecyltrimethylammonium chloride (DTAC) or octa(ethylene glycol) mono-n-dodecyl ether (C12E8) as the competing surfactants with HNAPO, the predicted surface excess values from the model fit less favorably. The difference was shown to not be due to nonideal entropy of mixing.     

Study of the retention behavior of iodinated X‐ray contrast agents in hydrophilic interaction liquid chromatography,comparing bare silica and zwitterionic stationary phases

Iodinated X‐ray contrast media are the most widely used pharmaceuticals for intravascular administration in X‐ray diagnostic procedures. The increasing concern of the fate of these compounds into the environment has led to the development of analytical methods to determine them. However, these methods present problems due to the polar character of these analytes. In this paper, hydrophilic interaction LC is presented as an alternative technique. The retention of iodinated X‐ray contrast media was studied in two bare silica phases with different particle designs (i.e. porous and Fused Core?) and a zwitterionic sulfoalkylbetaine phase. The effect of the most important parameters of the mobile phase was studied for each stationary phase. It was observed that optimal mobile phase conditions included buffers with a high buffering capacity. Additionally, the retention mechanisms involved were studied in order to provide some insight into the possible occurring interactions. The contributions of partition and adsorption and the effect of the temperature on the retention of analytes were evaluated on all of the stationary phases.     

Properties of In situ polymerized poly(3,4‐ethylenedioxythiophene)/alumina composites for energy storage applications

Composites formed by poly(3,4‐ethylenedioxythiophene) and alumina (PEDOT/Al₂O₃) have been prepared by in situ anodic polymerization. For this purpose, the stability of 1:1 and 4:1 monomer:alumina aqueous solutions has been examined as a function of the pH (2.3, 4.0, 7.0, 8.8, or 10.8). Results indicate that the monomer behaves as a dispersant that remains stable at the studied basic pHs despite they are close to the isoelectric point of alumina. Although the thermal stability of the composites is considerably affected by the pH of the reaction medium, its influence on the surface morphology is very small. Independently, of the synthetic conditions, the electrochemical properties were better for PEDOT/Al₂O₃ than for pure PEDOT, reflecting that alumina particles promote the charge mobility. The highest specific capacitance (SC; 141 F/g), which was 55% higher than that obtained for pure PEDOT, was achieved for the composite prepared at pH = 8.8 using a 4:1 monomer:alumina ratio. These conditions favor the participation of OH^– groups as secondary doping agents without degrading the polymer matrix and enhance the specific surface of the films, facilitating the ionic mobility. On the other hand, application of a multi‐step polymerization strategy has shown that interfaces originated by consecutive steps enhance the SC. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1131–1141     

X-ray absorption spectral analyses by theoretical calculations for TiO2 and Ni-doped TiO2 thin films on glass plates.

Ni L- and Ti L-edge as well as Ti K-edge X-ray absorption experiments for TiO2 thin films and Ni-doped TiO2 thin films coated on glass plates were performed using synchrotron radiation to investigate the structures around Ni and Ti ions in the films. The obtained spectra were compared with the results of theoretical calculations. It has consequently been found that the spectral features were affected by a change in the oxidizing form of Ni ions due to hydrogen reduction, by the charge variation and/or slight orbital splitting of Ti ions, and by the magnitude of the interaction between the center Ti ion and neighboring Ti ions.     

ior egf/r3: A murine monoclonal antibody for diagnostic of epithelial tumors

Monoclonal antibody ior egf/r3 is a IgG2a, recognizes the epidermal growth factor receptor. The aim of the present work was to evaluate the diagnostic efficacy of the^99mTc-labeled ior egf/r3 for the detection of epithelial tumors, its metastasis and its recurrences. The sensitivity by organs was: brain 100%, diegestive tract 90%, head and neck 89%, lung 84% and breast 79%. The overall sensitivity, specificity, accuracy, positive predictive value and negative predictive value of the immunoscintigraphic imaging were 84.1%, 100%, 86.5%, 100% and 52.4%, respectively. Immunoscintigraphy with^99mTc-ior egf/r3 is useful for the diagnosis and follow-up of epithelial tumors.