Oriented orthorhombic Lead Oxide film grown by vapour phase deposition for X‐ray detector applications

Several materials are under investigations for flat panel x‐ray detector applications. Among them, PbO shows interesting properties, i.e. high sensitivity, large stopping power and high resistivity at room temperature. However, the exploitation of PbO is limited by the difficulty to obtain good quality films constituted by a single phase. In this paper, we describe a new approach for the vapour phase growth of orthorhombic PbO films. The grown layers show a single phase, good crystallinity, and preferential orientation along the c axis. Optical characterization evidenced the presence of a broad defect band. Gold contacted films showed very high electrical resistivity and appreciable response to X‐ray radiation.     

A novel base-mediated intramolecular hydroamination to build fused heteroaryl pyrazinones

Functionalized fused heteroaryl pyrazinones were built up through a novel DBU-catalyzed intramolecular hydroamination reaction of aryl(prop-2-yn-1-yl)-1H-heteroaryl-2-carboxamides. The nucleophilic addition afforded three isomers; two with an exo-cyclic double bond [cis (Z), trans (E)], and a third one with an endo-cyclic double bond. After the carboxamide deprotection, isomerization of the mixture under acidic conditions resulted in a unique isomer.     

Full rank interpolatory subdivision: A first encounter with the multivariate realm

We extend our previous work on interpolatory vector subdivision schemes to the multivariate case. As in the univariate case we show that the diagonal and off-diagonal elements of such a scheme have a significantly different structure and that under certain circumstances symmetry of the mask can increase the polynomial reproduction power of the subdivision scheme. Moreover, we briefly point out how tensor product constructions for vector subdivision schemes can be obtained.     

Assessing Green Methods for Pectin Extraction from Waste Orange Peels

In this work, we assess three different methods for the extraction of pectin from waste orange peels, using water as extracting solvent. “Hot-water”, Rapid Solid Liquid Dynamic (RSLD) and microwave-assisted extractions have been compared and evaluated in terms of amount and quality of extracted pectin, as well as embodied energy. This analysis provides useful guidelines for pectin production from food waste according to green procedures, enabling the identification of acidic “hot-water” as the most sustainable extraction route.     

Evidence for Degradation of the Chrome Yellows in Van Gogh’s Sunflowers: A Study Using Noninvasive In Situ Methods and Synchrotron‐Radiation‐Based X‐ray Techniques

This paper presents firm evidence for the chemical alteration of chrome yellow pigments in Van Gogh’s Sunflowers (Van Gogh Museum, Amsterdam). Noninvasive in situ spectroscopic analysis at several spots on the painting, combined with synchrotron‐radiation‐based X‐ray investigations of two microsamples, revealed the presence of different types of chrome yellow used by Van Gogh, including the lightfast PbCrO₄ and the sulfur‐rich PbCr_1?xS_xO₄ (x≈0.5) variety that is known for its high propensity to undergo photoinduced reduction. The products of this degradation process, i.e., Cr^III compounds, were found at the interface between the paint and the varnish. Selected locations of the painting with the highest risk of color modification by chemical deterioration of chrome yellow are identified, thus calling for careful monitoring in the future.     

Complete basis set model chemistry applied to molecules of increasing molecular complexity: Thermochemical properties of organic sulfur derivatives

To estimate the thermochemical properties, bond dissociation energies and atomization energies of sulfur organic derivatives, the complete basis set (CBS) method was employed at the lower computational level (CBS‐4) owing to the large molecular size of a number of the molecules chosen. By comparison with experimental values, calculated values of thermochemical properties are subject to error, which increases in line with the increase in molecular complexity. The main source of error affecting the calculated enthalpy of formation stems from the difference between the energy of the molecule and that of the single atoms: the greater the size of the molecule, the greater the accumulation of error. By acting on the empirical correction to the CBS energy and minimizing the error due to the contribution of the single atoms to the dissociation energy a parameter d_i for each atom i is obtained. Application of these corrections does not greatly affect the heats of formation of the small molecules included in test sets employed for previous comparisons of calculated and experimental values, while there is a great improvement in the case of large molecules, for example, diphenyl disulfide. The mean absolute deviation turns out to be 2.52, which is greater than that obtained in recent reexaminations of model chemistry methods including the G3 and G3(MP3) approaches. The improvement in the results calculated for large molecules, whose heats of formation are calculated with large errors at the CBS‐4 level, in comparison also with the CBS‐4M version, justify our approach. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 1405–1418, 2000     

Hybrid Multivalent Jack Bean α-Mannosidase Inhibitors: The First Example of Gold Nanoparticles Decorated with Deoxynojirimycin Inhitopes

Among carbohydrate-processing enzymes, Jack bean α-mannosidase (JBα-man) is the glycosidase with the best responsiveness to the multivalent presentation of iminosugar inhitopes. We report, in this work, the preparation of water dispersible gold nanoparticles simultaneously coated with the iminosugar deoxynojirimycin (DNJ) inhitope and simple monosaccharides (β-d-gluco- or α-d-mannosides). The display of DNJ at the gold surface has been modulated (i) by using an amphiphilic linker longer than the aliphatic chain used for the monosaccharides and (ii) by presenting the inhitope, not only in monomeric form, but also in a trimeric fashion through combination of a dendron approach with glyconanotechnology. The latter strategy resulted in a strong enhancement of the inhibitory activity towards JBα-man, with a K_i in the nanomolar range (K_i = 84 nM), i.e., more than three orders of magnitude higher than the monovalent reference compound.     

Trapping of Ag+ into a Perfect Six-Coordinated Environment: Structural Analysis,Quantum Chemical Calculations and Electrochemistry

Self-assembly of (Bu₄N)₄[β-Mo₈O₂₆], AgNO₃, and 2-bis[(2,6-diisopropylphenyl)-imino]acenaphthene (dpp-bian) in DMF solution resulted in the (Bu₄N)₂[β-{Ag(dpp-bian)}₂Mo₈O₂₆] (1) complex. The complex was characterized by single crystal X-ray diffraction (SCXRD), X-ray powder diffraction (XRPD), diffuse reflectance (DR), infrared spectroscopy (IR), and elemental analysis. Comprehensive SCXRD studies of the crystal structure show the presence of Ag⁺ in an uncommon coordination environment without a clear preference for Ag-N over Ag-O bonding. Quantum chemical calculations were performed to qualify the nature of the Ag-N/Ag-O interactions and to assign the electronic transitions observed in the UV–Vis absorption spectra. The electrochemical behavior of the complex combines POM and redox ligand signatures. Complex 1 demonstrates catalytic activity in the electrochemical reduction of CO₂.     

A constructive algebraic strategy for interpolatory subdivision schemes induced by bivariate box splines

This paper describes an algebraic construction of bivariate interpolatory subdivision masks induced by three-directional box spline subdivision schemes. Specifically, given a three-directional box spline, we address the problem of defining a corresponding interpolatory subdivision scheme by constructing an appropriate correction mask to convolve with the three-directional box spline mask. The proposed approach is based on the analysis of certain polynomial identities in two variables and leads to interesting new interpolatory bivariate subdivision schemes.     

Kinetic control of the direction of inclusion of nitroxide radicals into cyclodextrins

N-benzyl-tert-butyl nitroxide derivatives substituted at the aromatic ring form host-guest inclusion complexes with β-and γ-cyclodextrin. They were employed as probes to assess substituent effects on the geometry of the complex and on the kinetics of this complexation by combining EPR and (1)H NMR data.