Quantum study of Eley-Rideal reaction and collision induced desorption of hydrogen atoms on a graphite surface. I. H-chemisorbed case

Collision induced (CI) processes involving hydrogen atoms on a graphite surface are studied quantum mechanically within the rigid, flat surface approximation, using a time-dependent wave packet method. The Eley-Rideal (ER) reaction and collision induced desorption (CID) cross sections are obtained with the help of two propagations which use different sets of coordinates, a "product" and a "reagent" set. Several adsorbate-substrate initial states of the target H atom in the chemisorption well are considered, and CI processes are studied over a wide range of projectile energy. Results show that (i) the Eley-Rideal reaction is the major reactive outcome and (ii) CID cross sections do not exceed 4 A2 and present dynamic thresholds for low values of the target vibrational quantum number. ER cross sections show oscillations at high energies which cannot be reproduced by classical and quasiclassical trajectory calculations. They are related to the vibrational excitation of the reaction products, which is a rather steep decreasing function of the collision energy. This behavior causes a selective population of the low-lying vibrational states and allows the quantization of the product molecular states to manifest itself in a collisional observable. A peak structure in the CID cross section is also observed and is assigned to the selective population of metastable states of the transient molecular hydrogen.     

Mycotoxins in spices and culinary herbs from Italy and Tunisia

Abstract

Spices and aromatic herbs can be contaminated with mycotoxins, since of their preharvest, postharvest, and storage conditions. In this study, 112 samples of different spices and aromatic herbs were evaluated for their mycotoxins content by HPLC-MS/MS in order to highlight their possible risk linked with human use. The results showed that mycotoxins were occasionally detected only in samples of coriander, laurel, mint, rosemary, and verbena. In both geographical origins a different contamination was detected. Among the investigated mycotoxins, AFB2, AFG1, AFG2, T2 and HT2 were detected, whereas none of the samples contained AFB1 and FB1. The co-occurrence of two toxins were observed for some samples of rosemary and verbena. This study indicates that it is essential minimize the toxins in agriculture, industry, and food-product manufacturing for the consumer health protection.     

Crystallization of the mesomorphic form and control of the molecular structure for tailoring the mechanical properties of isotactic polypropylene

The combination of the control of the concentration of stereodefects in isotactic polypropylene using metallocene catalysts and the crystallization via the mesophase is a strategy to tailor the mechanical properties. Stiff materials, flexible materials, and thermoplastic elastomers can be produced depending only on the concentration of rr stereodefects. Modulus, ductility, and strength can be modulated through the crystallization of α and γ forms or of the mesophase. Different morphologies are observed depending on the stereoregularity and conditions of crystallization. Crystals of the mesomorphic form always exhibit a nodular morphology, accounting for the similar good deformability of all quenched samples, whatever the concentration of stereodefects. The mesophase transforms by thermal treatments into the α form preserving the nodular morphology, with increase of strength while maintaining the ductility typical of the mesophase. Annealing of the mesophase permits a precise adjustment of crystallinity and size of nodular crystals offering additional options to modify the mechanical properties. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 677–699     

Crystallographic analysis of metal-ion binding to human ubiquitin

The metal-binding ability of human ubiquitin (hUb) towards a selection of biologically relevant metal ions and complexes has been probed. Different techniques have been used to obtain crystals suitable for crystallographic analysis. In the first type of experiments, crystals of hUb have been soaked in solutions containing copper(II) acetate and two metallodrugs, Zeise salt (K[PtCl(3)(η(2)-C(2)H(4))]·H(2)O) and cisplatin (cis-[PtCl(2)(NH(3))(2)]). The Zeise salt is used in a test for hepatitis, whereas cisplatin is one of the most powerful anticancer drugs in clinical use. The Zeise salt readily reacts with hUb crystals to afford an adduct with three platinum residues per protein molecule, Pt(3)-hUb. In contrast, copper(II) acetate and cisplatin were found to be unreactive for contact times up to one hour and to cause degradation of the hUb crystals for longer times. In the second type of experiments, hUb was cocrystallized with a solution of copper(II) or zinc(II) acetate or cisplatin. Zinc(II) acetate gives, at low metal-to-protein molar ratios (8:1), crystals containing one metal ion per three molecules of protein, Zn-hUb(3) (already reported in previous work), whereas at high metal-to-protein ratios (70:1) gives crystals containing three Zn(II) ions per protein molecule, Zn(3)-hUb. In contrast, once again, copper(II) acetate and cisplatin, even at low metal-to-protein ratios, do not give crystalline material. In the soaking experiment, the Zeise anion leads to simultaneous platination of His68, Met1, and Lys6. Present and previous results of cocrystallization experiments performed with Zn(II) and other Group 12 metal ions allow a comprehensive understanding of the metal-ion binding properties of hUb with His68 as the main anchoring site, followed by Met1 and carboxylic groups of Glu16, Glu18, Glu64, Asp21, and Asp32, to be reached. In the case of platinum, Lys6 can also be a binding site. The amount of bound metal ion, with respect to that of the protein, appears to be a relevant parameter influencing crystal packing.     

Physico-chemical and anatomical characterization of residual lignocellulosic fibers

Anatomical and physico-chemical properties of residual natural fibers (sugarcane bagasse, coconut fibers and peanut hulls) were characterized in order to evaluate their potential for use in the production of particleboard. The bulk density was determined by helium pycnometer and the chemical characteristics by using an electronic pH meter (for pH determination) on fibers dissolved in acidic and neutral detergents (to determine the levels of cellulose, hemicellulose and lignin). The anatomical characteristics were established using scanning electron microscopy coupled with an X-ray detector system, as well as energy dispersive X-ray spectroscopy. Results indicated similarities and differences between physico-chemical and anatomical characteristics of the residual lignocellulosic fibers when compared with the Pinus sp. wood commercially employed in particleboard production. Bulk density and pH for residual lignocellulosic fibers and Pinus sp. wood presented analogous values. Similar amounts of cellulose and lignin were identified between waste fibers and Pinus sp. wood. The presence of silica was identified in coconut fiber, peanut hull and sugarcane bagasse waste fibers, and may affect the mechanical characteristics of panels. Coconut and sugarcane bagasse fibers show surface pores with diameters ranging from 1.2 to 2.1 μm, below the 5 μm identified for Pinus sp. wood. Both fibers present pores distributed over their entire surface, whereas peanut hull fibers have no pores on their surface. This characteristic contributes to resin dispersion among particles, reflecting positively on the physical–mechanical properties of the panels. Particleboards produced with residual lignocellulosic fibers present similar physical–mechanical properties to those of Pinus sp. wood panels.     

Inherently Chiral Macrocyclic Oligothiophenes: Easily Accessible Electrosensitive Cavities with Outstanding Enantioselection Performances

Linear conjugated oligothiophenes of variable length and different substitution pattern are ubiquitous in technologically advanced optoelectronic devices, though limitations in application derive from insolubility, scarce processability and chain‐end effects. This study describes an easy access to chiral cyclic oligothiophenes constituted by 12 and 18 fully conjugated thiophene units. Chemical oxidation of an “inherently chiral” sexithiophene monomer, synthesized in two steps from commercially available materials, induces the formation of an elliptical dimer and a triangular trimer endowed with electrosensitive cavities of different tunable sizes. Combination of chirality with electroactivity makes these molecules unique in the current oligothiophenes literature. These macrocycles, which are stable and soluble in most organic solvents, show outstanding chiroptical properties, high circularly polarized luminescence effects and an exceptional enantiorecognition ability.