Spectroscopy and electrochemical properties of a homologous series of acetylacetonato and hexafluoroacetylacetonato cyclopalladated and cycloplatinated complexes

A photophysical, electrochemical and computational study has been performed on a homologous series of cyclometallated Pd(ii) () and Pt(ii) () complexes of general formula [(C,N)M(O,O)]; (H(C,N) = azobenzene, 2-phenylpyridine, benzo[h]quinoline; M = Pd, Pt; H(O,O) = acetylacetone, hexafluoroacetylacetone). Experimental and computational data have shown the strong influence exerted by electronegativity of the ancillary ligand on the frontier orbitals of the complexes, such an effect being enhanced for the Pt(ii) species.     

Macroscale time-dependent ionic liquid treatment effects on biphasic cellulose xerogels

Cellulose - The effects of variable ionic liquid (IL) treatment time (1 s–60 min) on macroscale morphology evolution in biphasic cellulose xerogels were measured using...     

Surface immobilization of fibronectin-derived PHSRN peptide on functionalized polymer films – Effects on fibroblast spreading

The Pro-His-Ser-Arg-Asn (PHSRN) sequence in fibronectin is a second cell-binding site that synergistically affects Arg-Gly-Asp (RGD). The PHSRN peptide also induces cell invasion and accelerates wound healing. We report on the surface immobilization of PHSRN by spontaneous adsorption on polysiloxane thin films which have different surface free energy characteristics. Low-surface energy (hydrophobic) polysiloxane and the corresponding high-surface energy (hydrophilic) surfaces obtained by UV–ozone treatments were used as adsorbing substrates. The peptide adsorption process was investigated by quartz crystal microbalance with dissipation monitoring and atomic force microscopy. Both adsorption kinetics and peptide rearrangement dynamics at the solid interface were significantly different on the surface-modified films compared to the untreated ones. Fibroblast cells cultures at short times and in a simplified environment, i.e., a medium-free solution, were prepared to distinguish interaction events at the interface between cell membrane and surface-immobilized peptide for the two cases. It turned out that the cell-adhesive effect of immobilized PHSRN was different for hydrophobic compared to hydrophilic ones. Early signatures of cell spreading were only observed on the hydrophilic substrates. These effects are explained in terms of different spatial arrangements of PHSRN molecules immobilized on the two types of surfaces.     

Efficient synthesis of 9H-pyrrolo[1,2-a]indol-9-one derivatives based on active manganese dioxide promoted intramolecular cyclization

A series of 9H-pyrrolo[1,2-a]indol-9-ones have been prepared via in-situ sequential oxidation of [2-(1H-pyrrol-1-yl)phenyl]methanols promoted by active manganese dioxide. The procedure led to title compounds in good yields under mild conditions, without the need to isolate the intermediate aldehydes.     

UV/Vis to NIR Photoconduction in Cyclopalladated Complexes

Funky discotics : Photoconductivity is measured in newly synthesized cyclopalladated metallomesogens exhibiting hexagonal columnar mesophases at room temperature. The tuning of the HOMO/LUMO energy levels by modification of the chain/core linkage (ester 1 vs ether 2 ) makes compound 2 photoconductive across the whole UV/Vis/NIR range.

     

Adsorption of 2-methylbenzoic acid onto MCM-41 mesoporous material: kinetics and equilibrium studies

Ordered mesoporous molecular sieves are widely studied as alternative materials in areas where sorptive and catalytic applications are required. MCM-41 type mesoporous material was tested as sorbent of 2-methylbenzoic acid (MBA), an aromatic carboxylic acid selected as model molecule for adsorption studies on mesoporous silicas. Adsorption kinetic studies of MBA on MCM-41 type materials were carried out using ethanol solutions at different MBA concentrations. Experimental results followed Langmuir isotherm model showing large adsorption capacity (3.5?g/g). Two kinetic models, the pseudo first- and second-order, were selected to describe the adsorption process and to determine the best model fitting with the experimental data. Kinetic parameters for each kinetic equation were calculated and discussed. It was shown that the MBA adsorption process onto MCM-41 material could be described by the pseudo-second-order equation and that the MCM-41 performs as a suitable adsorbent material.     

SEM-EDS investigation on PM10 data collected in Central Italy: Principal Component Analysis and Hierarchical Cluster Analysis

Background

Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA) were applied on PM10 particle data in order to: identify particle clusters that can be differentiated on the bases of their chemical composition and morphology, investigate the relationship among the chemical and morphological parameters and evaluate differences among the sampling sites. PM10 was collected in 3 different sites in central Italy characterized by different conditions: yard, urban and rural sites. The concentration of 20 chemical parameters (C, O, Na, Mg, Al, Si, P, Cd, Cl, K, Ca, Sn, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn) were determined by Scanning Electron Microscopy – Energy Dispersive X-ray Spectroscopy (SEM-EDS) and the particle images were processed by an image analysis software in order to measure: Area, Aspect Ratio, Roundness, Fractal Dimension, Box Width, Box Height and Perimeter.

Result

Results revealed the presence of different clusters of particles, differentiated on the bases of chemical composition and morphological parameters (aluminosilicates, calcium particles, biological particles, soot, cenosphere, sodium chloride, sulphates, metallic particles, iron spherical particles). Aluminosilicates and Calcium particles of rural and urban sites showed a similar nature due to a mainly natural origin, while those of the yard site showed a more heterogeneous composition mainly related to human activity. Biological particles and soot can be differentiated on the bases of the higher loads of Fractal Dimension, which characterizes soot, and content of Na, Mg, Ca, Cl and K which characterize the biological ones. The soot of the urban site showed higher loadings of Roundness and Fractal Dimension than the soot belonging to the yard and rural sites, this was due to the different life time of the particles. The metal particles, characterized mainly by the higher loading of iron, were present in two morphological forms: spherical and angular particles. The first were generated by a fusion process at high temperature, while the second one had crustal origin (those characterized by typical terrigenous elements) and also human origin.

Conclusion

In this work a protocol for the morphological-chemical characterization of single particles has been developed. SEM analysis allows to classify particles in 10 different families and PCA and HCA have provided information about the sources of PM and similarities and differences among the sites.

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Maximum-likelihood estimation of Mueller matrices

We show that the method of maximum-likelihood estimation, recently introduced in the context of quantum process tomography, can be applied to the determination of Mueller matrices characterizing the polarization properties of classical optical systems. Contrary to linear reconstruction algorithms, the proposed method yields physically acceptable Mueller matrices even in the presence of uncontrolled experimental errors. We illustrate our method with the case of an unphysical measured Mueller matrix taken from the literature.     

Thermal analysis of zeolite ZSM-5 precursors with different Si/Al ratios

The thermal analysis of crystalline zeolite ZSM-5 precurcors with different Si/Al ratios was carried out in a nitrogen atmosphere. Different interactions between tetrapropylammonium species and the zeolitic environment were evidenced, depending on the Al content of the crystalline precursors. The results support the mechanism of ZSM-5 formation through a condensation process from the liquid phase.

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Zusammenfassung Thermische Analysen kristalliner Zeolith- (ZSM-5) Vorprodukte mit unterschiedlichen Verhältnissen Si/Al wurden in Stickstoffatmosphäre ausgeführt. Verschiedene Wechselwirkungen zwischen den Tetrapropylammonium-Spezies und ihrer zeolithischen Umgebung wurden nachgewiesen, die vom Aluminiumgehalt der kristallinen Vorprodukte abhängen. Die Ergebnisse sprechen für einen Bildungsmechanismus des ZSM-5 über einen Kondensationsprozess aus der flüssigen Phase.

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ZSM-5 . . ZSM-5 .

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This work was carried out with the financial support of the Italian National Research Council Progetto Finalizzato Energetica 2.     

Contributions of different generations of recoils to sputtering by backscattered light ions

Summary Neumann's expansion of the integral form of the Boltzmann transport equation is used to estimate the contribution of different generations of recoils to sputtering. By considering the flux generated by backscattered ions it is shown that primary recoils are, in the region of low energy (few keV), the main contribution to sputtering.