A macrocyclic ligand able to bind gallium(III) by preorganized pendant arms; coordination and kinetic studies

The equilibria and kinetics of the binding of gallium(III) to 4-(N),10-(N)-bis[2-(3-hydroxo-2-oxo-2-H-pyridine-1-y1)acetamido]-1,7-dimethyl-1,4,7,10-tetraazacyclododecane (L) were investigated in acidic medium at ionic strength 1 M (NaClO4). Spectrophotometric titrations in the UV region revealed that L is able to bind Ga3+ also at high H+ concentration. The kinetic (stopped-flow) experiments are interpreted on the basis of three parallel reaction paths (i) M3+ + H2L2+ = M(H2L)5+ where M(H2L)5+ is in a steady state, (ii) M(OH)2+ + H2L2+ = M(HL)4+ + H2O and (iii) M(OH)2+ + HL+ = ML3+ + H2O. The first-order rate constants for conversion of the outer-sphere into the inner-sphere complexes are similar to those of the Ga(III)/tropolone system which is known to react according to the dissociative Id mechanism and to the relevant rate constants for water exchange at the metal ion. The effects of pH on the UV-Vis absorption, fluorescence emission properties and NMR spectral features on the Ga(III)/L system were also investigated. Spectrophotometric titrations in the UV region reveal that, in acid medium the prevailing species is M(HL)4+ whereas the chelate ML3+ prevails for [H+] < 0.01 M. The results indicate metal coordination at the oxygen atoms of the 3-hydroxo-2-oxopyridine residues.     

A biofunctional polymeric coating for microcantilever molecular recognition

An innovative route to activate silicon microcantilevers (MCs) for label free molecular recognition is presented. The method consists in coating the underivatized MCs with a functional ter-polymer based on N,N-dimethylacrylamide (DMA) bearing N-acryloyloxysuccinimide (NAS) and 3-(trimethoxysilyl)propyl-methacrylate (MAPS), two functional monomers that confer to the polymer the ability to react with nucleophilic species on biomolecules and with glass silanols, respectively. The polymer was deposited onto MCs by dip coating. Polymer coated MCs were tested in both static and dynamic modes of actuation, featuring detection of DNA hybridization as well as protein/protein interaction. In the dynamic experiments, focused on protein detection, the MCs showed an average mass responsivity of 0.4 Hz/pg for the first resonant mode and of 2.5 Hz/pg for the second resonant mode. The results of the static experiments, dedicated to DNA hybridization detection, allowed for direct estimation of the DNA duplex formation energetics, which resulted fully consistent with the nominal expected values. These results, together with easiness and cheapness, high versatility, and excellent stability of the recognition signal, make the presented route a reliable alternative to standard SAM functionalization (for microcantilevers (MCs) and for micro-electro-mechanical systems (MEMS) in general).     

Penkvilksite‐2O: Na2TiSi4O11·2H2O

The crystal structure of synthetic penkvilksite‐2O, disodium titanium tetrasilicate dihydrate, Na₂TiSi₄O₁₁·2H₂O, a microporous titanosilicate, confirms the major features of a previous model that had been obtained by order–disorder (OD) theory from the known structure of penkvilksite‐1M. An important difference from the previous model involves the hydrogen bonding of the water molecule which, on the basis of a Raman spectrum and the finding of only one of the two H atoms, is proposed to be disordered about a fixed O–H direction. The structure of penkvilksite‐2O is based on (100) silicate layers linked by isolated TiO₆ octahedra to form a heteropolyhedral framework. The layer is strongly corrugated, based on interlaced spiral chains, and is crossed by two different channels that have an effective channel width of about 3 Å.     

Mechanistic aspects of the interaction of intercalating metal complexes with nucleic acids

Since the discovery of the intercalative binding mode, almost half a century ago, intense efforts have been devoted to design, synthesize and test new small molecules that can bind nucleic acids with improved recognition and affinity. Among them, metal bearing compounds play a principal role. Despite the plethora of different metal complexes which have been designed to react with DNA and which have been tested, the binding mechanisms have often not been analysed. This is unfortunate, considering the importance of understanding of the binding features in depth in order to optimise their biological effects. This review covers articles where an analysis of the kinetic aspects of the interaction between the target metal compound and nucleic acids has been carried out and details of the reaction mechanism are provided. Flat metal complexes (porphyrins), spherical complexes with protruding intercalating residues, azamacrocycle metallo-intercalators and intercalators with metal bearing pendant arms are the classes of molecules that have been taken into account. The limits of the SDS method, employed to measure the rates of drug dissociation from polynucleotides, are also discussed.     

Future teachers’ competence to plan a lesson: first results of a six-country study on the efficiency of teacher education

The study "Mathematics Teaching in the 21st Century (MT21)" focuses beyond others on the measurement of teachers’ general pedagogical knowledge (GPK). GPK is regarded as a latent construct embedded in a larger theory of teachers’ professional competence. It is laid out how GPK was defined and operationalized. As part of an international comparison GPK was measured with several complex vignettes. In the present paper, the results of future mathematics teachers’ knowledge from four countries (Germany, South Korea, Taiwan, and the US) with very different teacher-education systems are presented. Significant and relevant differences between the four countries as well as between future teachers at the beginning and at the end of teacher education were found. The results are discussed with reference to cultural discourses about teacher education.     

High-order finite elements in numerical electromagnetism: degrees of freedom and generators in duality

Explicit generators for high-order (r>1) scalar and vector finite element spaces generally used in numerical electromagnetism are presented and classical degrees of freedom, the so-called moments, revisited. Properties of these generators on simplicial meshes are investigated, and a general technique to restore duality between moments and generators is proposed. Algebraic and exponential optimal h- and r-error rates are numerically validated for high-order edge elements on the problem of Maxwell’s eigenvalues in a square domain.     

Spatio-Temporal Variation of the Bacterial Communities along a Salinity Gradient within a Thalassohaline Environment (Saline di Tarquinia Salterns,Italy)

The “Saline di Tarquinia” salterns have been scarcely investigated regarding their microbiological aspects. This work studied the structure and composition of their bacterial communities along the salinity gradient (from the nearby sea through different ponds). The communities showed increasing simplification of pond bacterial diversity along the gradient (particularly if compared to those of the sea). Among the 38 assigned phyla, the most represented were Proteobacteria, Actinobacteria and Bacteroidetes. Differently to other marine salterns, where at the highest salinities Bacteroidetes dominated, preponderance of Proteobacteria was observed. At the genus level the most abundant taxa were Pontimonas, Marivita, Spiribacter, Bordetella, GpVII and Lentibacter. The α-diversity analysis showed that the communities were highly uneven, and the Canonical Correspondence Analysis indicated that they were structured by various factors (sampling site, sampling year, salinity, and sampling month). Moreover, the taxa abundance variation in relation to these significant parameters were investigated by Generalized Linear Models. This work represents the first investigation of a marine saltern, carried out by a metabarcoding approach, which permitted a broad vision of the bacterial diversity, covering both a wide temporal span (two years with monthly sampling) and the entire salinity gradient (from the nearby sea up to the crystallisation ponds).     

Synthesis and characterization of cobalt(II) and copper(II) complexes with 5-amino-3,4-dimethylisoxazole

Summary Complexes of cobalt(II) and copper(II) with 5-amino-3,4-dimethylisoxazole (5-ADI) have been prepared and studied by means of magnetic susceptibility measurements, near and far i.r. spectra, electronic spectroscopy and, when possible, conductivity measurements. The 5-ADI generally behaves as bridging (N_ring-, O- or N_ring-, -NH₂) ligand. All the complexes have an octahedral sterochemistry, except Co(5-ADI)₂X₂ (X = Cl, Br), Co₂(5-ADI)₇I₄ which are tetrahedral and Cu(5-ADI)₂ (ClO₄)₂ · 4 H₂O which is square planar.