Polyoxometallates as inorganic templates for electrocatalytic network films of ultra-thin conducting polymers and platinum nanoparticles

We develop a concept of fabrication of the multilayer network films on electrodes by exploring the ability of a Keggin-type polyoxometallate, phosphododecamolybdate (PMo(12)O(40)(3-)), to form stable anionic monolayers (templates) on carbon and metals including platinum. By repeated alternate treatments in the solution of PMo(12)O(40)(3-) (or in the colloidal suspension of polyoxometallate-protected Pt-nanoparticles) and in the solution of monomer (e.g. anilinium) cations, the amount of the material can be increased systematically (layer-by-layer) to form stable three-dimensional assemblies on electrode (e.g. glassy carbon) surfaces. In the resulting hybrid (organic-inorganic) films, the layers of negatively charged polyoxometallate, or polyoxometallate-protected (stabilized) Pt-nanoparticles, are linked or electrostatically attracted by ultra-thin layers of such positively charged conducting polymers as polyaniline (PANI), polypyrrole (PPy) or poly(3,4-ethylenedioxythiophene), PEDOT. Consequently, the attractive physicochemical properties of polymers and reactivity of polyoxometallate or noble metal particles are combined. The films are functionalized and show electrocatalytic properties towards reduction of nitrite, bromate, hydrogen peroxide or oxygen. They are of importance to the chemical and biochemical sensing as well as to the biochemical and medical applications.     

Oxidation of alcohols with hydrogen peroxide catalyzed by soluble iron and osmium derivatives

Summary Osmium chloride OsCl₃ efficiently catalyzes (yields of products up to 90%, turnover numbers (TON) up to 1500) the oxidation of 2-cyanoethanol with hydrogen peroxide to produce the corresponding aldehyde and acid. Oxidation of isopropanol over OsCl₃ gave acetone in 58% yield. The reactions were carried out either in acetonitrile or without any solvent. The analogous iron compound FeCl₃ was found to be less efficient in the oxidation of 2-cyanoethanol (yields of products up to 67%, TON up to 135). Oxidation of isopropanol in this case gave acetone (yield 53%) and acetic acid (yield 11%). Some other soluble derivatives of iron or osmium exhibited noticeably lower catalytic activity in the alcohol oxidation with H₂O₂.     

PMMA: A key macromolecular component for dielectric low-κ hybrid inorganic-organic polymer films

Inorganic-organic composite and hybrid films find widespread applications for the development of functional materials. Polymer matrices with embedded inorganic fillers, nanoparticles or clusters are particularly appealing for optical, electronic, dielectric and magnetic applications. In particular, the development of hybrid layers with tailored dielectric properties represents a key issue in many technological fields.In this framework, poly(methyl methacrylate) (PMMA), due to its outstanding chemico-physical properties, represents a particularly suitable polymer component for the embedding of both microscopic and nanoscopic functional inorganic fillers. The wide use of such a matrix has to be traced back to the favourable combination of chemical and physical properties and easy processing. In this review, the main features and properties of PMMA, with a particular focus on dielectric ones, are firstly briefly described. Selected examples to illustrate the state-of-the art of its corresponding use as dielectric matrix are given and several examples are provided and surveyed.Finally, three case studies concerning PMMA-based hybrid films, produced for very different application fields, are described and discussed. The first example deals with the entrapment of micrometric zinc sulphide powders in PMMA, which acts as a host matrix for the electroluminescent particles in thick film-based Alternate Current Powder Electroluminescent Lamps (ACPELs). The second example describes the preparation of low-κ inorganic-organic hybrid dielectric films based on a PMMA-polyvinylchloride(PVC) blend and a hydrophobic silica powder functionalised on the surface with trimethylsiloxane groups (m-SiO₂). The composition of the investigated materials is [(PMMA)_x(PVC)_y]/(m-SiO₂)_z with z ranging from 0 to 38.3 wt% and x = y = (100 − z)/2. The third case concerns the use of PMMA as a matrix to embed zirconium oxoclusters through the formation of covalent bonds. The obtained material, characterised by a dielectric constant value remarkably lower (1.93 at 1 kHz and 25 °C) than in pristine PMMA (3.0 at 1 kHz and 25 °C), appears as very appealing for the development of microelectronic devices based on low dielectric constant polymer films such as, for instance, field-effect transistor (FET).These three cases are paradigms of three different approaches to composite and hybrid materials based on the embedding of particles in PMMA polymer matrix.     

Certification of a second-generation biological reference material (freeze-dried human serum) for trace element determinations

The certification of a second-generation biological reference material (freeze-dried human serum) for trace element determinations is described. The material was prepared under rigorously controlled conditions to avoid extraneous additions. Analytical data were obtained by the authors as well as by numerous other intra- and extra-mural investigators, solicited on the basis of established experience in determining selected elements. For 14 trace elements (aluminium, chromium, manganese, iron, cobalt, copper, zinc, arsenic, selenium, bromine, rubidium, molybdenum, cadmium and caesium) certified values (in ng g^?1 or μg g^?1 dry weight) are listed; for an additional element (nickel) a best estimate (in ng g^? dry weight) is added. Trace element concentrations in the material, which is available to the scientific community, closely approximate those in normal, lyophilized blood plasma or serum samples. The material thus provides the means to check the accuracy and precision of analytical procedures for quantifying low-level trace elements in the best possible conditions and to detect errors that can easily be overlooked when reference materials with higher levels of trace elements are used. In addition, and in contrast to already existing biological reference materials with high levels of trace elements, it offers the possibility of identifying unsuspected errors at the sample preparation stage.     

Biodegradable polyesters reinforced with surface-modified vegetable fibers

Flax fibers are investigated as reinforcing agents for biodegradable polyesters (Bionolle and poly(lactic acid) plasticized with 15 wt.-% of acetyltributyl citrate, p-PLLA). The composites are obtained either by high temperature compression molding fiber mats sandwiched between polymer films, or by batch mixing fibers with the molten polymer. Fibers in composites obtained by the latter method are much shorter (140-200 microm) than those of the mats (5,000 microm). Flax fibers are found to reinforce both p-PLLA and Bionolle (i.e. tensile modulus and strength increase) when composites based on fiber mats are investigated. Conversely, analogous composites obtained by batch mixing show poor mechanical properties. The observed behavior is attributed to the combined effect of fiber length and fiber-matrix adhesion. If flax fibers with a modified surface chemistry are used, the strength of short fiber composites is seen to improve significantly because the interface strengthens and load is more efficiently transferred. Appropriate surface modifications are performed by heterogeneous acylation reactions or by grafting poly(ethylene glycol) chains (PEG, molecular weight 350 and 750). The highest tensile strength of p-PLLA composites is reached when PEG-grafted flax fibers are used, whereas in the case of Bionolle the best performance is observed with acylated fibers.     

15N-NMR study of activated enamines. Structural dependence of δ (15N) and nJ(N,H) in primary,secondary and tertiary enamino-ketones,esters and amides

The pulse sequence INEPT was used to obtain proton-coupled ¹⁵N-NMR spectra in natural isotope abundance for enamines substituted in 2-position with electron-with-drawing groups. The chemical shifts and coupling constants are discussed in terms of their relationship to structural features such as multiple N-alkyl substitution, double-bond configuration, H-bonding, N-lone-pair delocalization within the conjugated system, and steric effects. It is concluded that ¹⁵N chemical shifts are a sensitive probe for local structural modifications at the N-atom and conformational changes in a remote part of a conjugated molecule, while one-bond N,H-coupling essentially reflects N-hybridization and subtle local geometric distortions. Stereospecific three-bond N,H spin coupling to olefinic protons (4.0 ± 0.2 Hz) has been found a characteristic feature of (Z)-isomers in all investigated compounds, whereas two-bond coupling to olefinic protons (²J(N,H) = 0.5 to 5 Hz) is observed in (E)-isomers. The sensitivity to solvents and steric properties of remote substituents renders geminal coupling a useful probe for studying electronic effects in the C? N bond.     

Determining PAHs and PCBs in aqueous samples: finding and evaluating sources of error

This work describes the problems that occur during routine multi-step determinations of polyaromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs), which can be present at trace levels in water, and identifies sources of analyte losses at particular steps during the analytical procedure. PAH and PCB adsorption onto the walls of the container ranged from 0 to 70%. PAH and PCB recoveries of >70% were achieved during the LLE and SPE extraction steps. During the process of enriching the dichloromethane extract with PAHs and PCBs, based on the gentle evaporation of solvent, losses were <24% and <19%, respectively. Model experiments show that neither isolation of PAHs and PCBs (performed using either LLE or SPE) nor extract enrichment reduce the reliability of PAH and PCB determination. The steps that lead to the greatest loss of analyte are the ones that involve sampling, transport and storage of the water samples.     

Thermal evidences of the interaction between plasticizers and Ca salts in cement

The interactions between an organic polymer with plasticizing activity and a model surface (CaCO₃), with a surface activity similar to the cement one, have been analysed by volumetric analysis and thermal analysis: TG/DTG and DSC. The synthesized polymer has a negative link site (carboxylate) that is able to interact with the substrate and a long ethylene oxide chain that contribute to the dispersing activity. The pattern of the adsorption isotherm suggests the occurring of a step like adsorption, initially characterised by a coil conformation of PEO chain followed by a more PEO strained, linear, conformation as the amount of polymer increases. The polymer adsorption appears to modify the crystalline phase and morphology of the CaCO₃ surface as the thermal analysis puts in evidence through the CaCO₃ decomposition temperature shifts. SEM analysis confirms the morphology changes induced by polymer adsorption.     

A semiclassical perspective on multivariate orthogonal polynomials

Differential properties for orthogonal polynomials in several variables are studied. We consider multivariate orthogonal polynomials whose gradients satisfy some quasi-orthogonality conditions. We obtain several characterizations for these polynomials including the analogues of the semiclassical Pearson differential equation, the structure relation and a differential-difference equation.