Synthesis of octahedral zirconium complex bearing [NHC?O] ligands,and its behavior as catalyst in the polymerization of olefins

The synthesis and characterization of a zirconium complex, having two alkoxide functionalized N‐heterocyclic carbene ligands, and its behavior as catalyst in the polymerization of ethylene and propylene, have been reported. NMR analysis showed that more than one species was obtained during synthesis. These data were confirmed by ethylene polymerization that gave rise to a linear polyethylene having a high Molecular weight and a polydispersity index (MDI) > 2 and often bimodal. The same catalytic system was able to produce highly isotactic polypropylene together with an atactic fraction. DFT studies on the complex stereoisomer stability gave indications on the species possibly involved in the polymerizations. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Adsorption and stability of streptavidin on cluster-assembled nanostructured TiOx films

The study of the adsorption of proteins on nanostructured surfaces is of fundamental importance to understand and control cell-surface interactions and, notably, cell adhesion and proliferation; it can also play a strategic role in the design and fabrication of nanostructured devices for postgenomic and proteomic applications. We have recently demonstrated that cluster-assembled nanostructured TiO x films produced by supersonic cluster beam deposition possess excellent biocompatibility and that these films can be functionalized with streptavidin, allowing the immobilization of biotinylated retroviral particles and the realization of living-cell microarrays for phenotype screening. Here we present a multitechnique investigation of the adsorption mechanisms of streptavidin on cluster-assembled TiO x films. We show that this nanostructured surface provides an optimal balance between adsorption efficacy and protein functionality. By using low-resolution protein arrays, we demonstrate that a layer of adsorbed streptavidin can be stably maintained on a cluster-assembled TiO x surface under cell culture conditions and that streptavidin retains its biological activity in the adsorbed layer. The adsorption mechanisms are investigated by atomic force microscopy in force spectroscopy mode and by valence-band photoemission spectroscopy, highlighting the potential role of the interaction of the exposed carboxyl groups on streptavidin with the titanium atoms of the nanostructured surface.     

Synthesis of cobalt doped silica thin film for low temperature optical gas sensor

A modified sol–gel method was used to prepare cobalt doped silica thin film with a cobalt content of 10, 20 and 30 mol% (10Co, 20Co and 30Co). The prepared films were annealed at different temperatures in the range 400–1,000 °C, and their structural evolution examined. The mixed valence cobalt oxide, Co₃O₄, crystallizes only in the sample with the higher cobalt content, while cobalt silicate is the only crystalline phase detected in the sample 10Co and 20Co. Both the cobalt content and the temperature of heat treatment resulted to affect the nature of cobalt species dispersed in the silica matrix. The 30Co was selected for further investigations by FTIR spectroscopy to follow the structural evolution of 30Co film as function of the temperature and UV–Vis to get information on the cobalt valence state. The optical gas-sensing properties of 30Co films, containing Co₃O₄ as the major cobalt phase, were studied through the measuring of the film transmittance in dry air and in presence of dry air containing variable concentrations of polluting gases, CO and NO₂. The 30Co samples resulted to be highly sensitive to CO at room temperature. An explanation for the CO sensing characteristics, at low temperature, was proposed by referring to the physisorption-related mechanics of CO.     

Surface and Structural Investigation of a MnOx Birnessite‐Type Water Oxidation Catalyst Formed under Photocatalytic Conditions

Catalytically active MnO_x species have been reported to form in situ from various Mn‐complexes during electrocatalytic and solution‐based water oxidation when employing cerium(IV) ammonium ammonium nitrate (CAN) oxidant as a sacrificial reagent. The full structural characterization of these oxides may be complicated by the presence of support material and lack of a pure bulk phase. For the first time, we show that highly active MnO_x catalysts form without supports in situ under photocatalytic conditions. Our most active ⁴MnO_x catalyst (～0.84 mmol O₂ mol Mn^?1 s^?1) forms from a Mn₄O₄ bearing a metal–organic framework. ⁴MnO_x is characterized by pair distribution function analysis (PDF), Raman spectroscopy, and HR‐TEM as a disordered, layered Mn‐oxide with high surface area (216 m²g^?1) and small regions of crystallinity and layer flexibility. In contrast, the ^SMnO_x formed from Mn²⁺ salt gives an amorphous species of lower surface area (80 m²g^?1) and lower activity (～0.15 mmol O₂ mol Mn^?1 s^?1). We compare these catalysts to crystalline hexagonal birnessite, which activates under the same conditions. Full deconvolution of the XPS Mn2p_3/2 core levels detects enriched Mn³⁺ and Mn²⁺ content on the surfaces, which indicates possible disproportionation/comproportionation surface equilibria.     

Kinetic study of the thermal degradation of PS/MMT nanocomposites preparedwith imidazolium surfactants

Styrene and montmorillonite organically modified with imidazolium surfactants (MMT) at various alkyl chain lengths (C₁₂, C₁₆ and C₁₈) were used to prepare the corresponding PS/MMT/C₁₂, PS/MMT/C₁₆ and PS/MMT/C₁₈ nanocomposites by in situ polymerization. XRD and TEM analyses evidenced the formation of both intercalated and exfoliated structures. The glass transition temperatures (T _g) of nanocomposites, as well as that of neat PS, were obtained by DSC measurements. The thermal degradations were carried out in the scanning mode, in both inert and oxidative environments, and the initial temperatures of decomposition (T _i) and the apparent activation energies of degradation (E _a) were determined. Due to an oxidative degradation mechanism, the T _i and E _a values in air atmosphere were lower than those under nitrogen. The results indicated that nanocomposites are more thermally stable than polystyrene, and suggested an increasing degree of exfoliation as a function of alkyl chain length of surfactant, associated with enhancing thermal stability.     

Peptidomic approach based on combined capillary isoelectric focusing and mass spectrometry for the characterization of the plasmin primary products from bovine and water buffalo beta-casein

The main peptides produced by hydrolysis of water buffalo beta-casein with plasmin were characterized by capillary electrophoresis and mass spectrometry and compared with their bovine homologous. A novel breakdown product arising from the hydrolysis of water buffalo beta-casein, originated by the presence of a plasmin-sensitive Lys bond at position 68 was identified, which was not present in bovine beta-casein. On the basis of this evidence, an improved procedure for the detection and the differentiation of the products of plasmin hydrolysis of bovine and water buffalo beta-casein by capillary isoelectric focusing was set-up. In the experimental conditions, the gamma-casein from the two species was efficiently separated. Comparison of the capillary electropherograms with those obtained by ultra-thin-layer isoelectric focusing, the reference method for routine analysis of plasmin digests of casein, suggests that capillary electrophoresis isoelectric focusing may constitute a successful alternative to the traditional slab gel electrophoresis analysis of plasmin digests of casein either for basic structural studies or for applications in the quality assessment of dairy products.     

Germaindacenodithiophene based low band gap polymers for organic solar cells

We report the first synthesis of a fused germaindacenodithiophene monomer and its polymerisation with 2,1,3-benzothiadiazole by Suzuki polycondensation. The resulting polymer, PGeTPTBT, is semicrystalline, despite the presence of four bulky 2-ethylhexyl groups. Blends with P(70)CBM afford solar cells with efficiencies of 5.02%.     

Swelling instability of surface-attached gels as a model of soft tissue growth under geometric constraints

The purpose of this work is to provide a theoretical analysis of the mechanical behavior of the growth of soft materials under geometrical constraints. In particular, we focus on the swelling of a gel layer clamped to a substrate, which is still the subject of many experimental tests. Because the constrained swelling process induces compressive stresses, all these experiments exhibit surface instabilities, which ultimately lead to cusp formation. Our model is based on fixing a neo-Hookean constitutive energy together with the incompressibility requirement for a volumetric, homogeneous mass addition. Our approach is developed mostly, but not uniquely, in the plane strain configuration. We show how the standard equilibrium equations from continuum mechanics have a similarity with the two-dimensional Stokes flows, and we use a nonlinear stream function for the exact treatment of the incompressibility constraint. A free energy approach allows the extension both to arbitrary hyperelastic strain energies and to additional interactions, such as surface energies. We find that, at constant volumetric growth, the threshold for a wavy instability is completely governed by the amount of growth. Nevertheless, the determination of the wavelength at threshold, which scales with the initial thickness of the gel layer, requires the coupling with a surface effect. Our findings, which are valid in proximity of the threshold, are compared to experimental results. The proposed treatment can be extended to weakly nonlinearities within the aim of the theory of bifurcations.