Observation of a continuum-continuum interference hole in ultrafast dissociating core-excited molecules

The femtosecond dissociation of HCl after core excitation has been studied through the resonant Auger decay. The spectra contain contributions from decay occurring at both "molecular" and "atomic" internuclear distances. We have observed a new interference mechanism in these spectra: An atomic spectral line develops into a negative spectral contribution, a "hole," when detuning the excitation energy from the maximum of the Cl2p(-1)sigma(*) resonance. Resonant x-ray scattering theory quantitatively explains this behavior as due to a novel destructive continuum-continuum interference between molecular and atomic contributions to the Auger decay.     

N‐(Tri­phenyl­methyl­sulfanyl)­phthal­imide

The title compound, C₂₇H₁₉NO₂S, contains chains of fused (19) rings formed by intermolecular C—H·O=C hydrogen bonds and running along the [011] and [01] directions. These chains are linked through short intermol­ecular C—H·π contacts, giving rise to sheets. The conformation of the title compound is dominated primarily by the nearly orthogonal lone‐pair orbitals on the N and S atoms.     

95Mo NMR: a useful tool for structural studies in solution

Oxomolybdenum(VI) complexes containing diverse ligands from an electronic and topological point of view have been analysed by means of ⁹⁵Mo NMR in solution with the purpose of using this technique as a tool to study their coordination chemistry and reactivity. The relationship between the electronic density on the metal tuned by the electron‐donor ability of the coordinated ligands and the ⁹⁵Mo chemical shift has been proved for mono‐ and bimetallic complexes showing a hexa‐ or hepta‐coordination around the metal centre. The different origins of the signal broadening (associated either to the symmetry of the metallic polyhedron or to the presence of isomers or to the ligand de‐coordination) have been also considered to rationalise the obtained data. Copyright © 2009 John Wiley & Sons, Ltd.     

Theoretical study of the CO catalytic oxidation on Au/SAPO‐11 zeolite

Quantum chemistry calculations were carried out, using ONIOM2 methodology, to investigate the CO adsorption and oxidation on gold supported on Silicoaluminophospates (SAPO) molecular sieves Au/SAPO‐11 catalysts. Two models were studied, one containing one Au atom per site (Au? SAPO‐11), and the other with two Au atoms per site (Au₂? SAPO‐11). The results reveal that the CO adsorption and oxidation are exothermic on Au/SAPO11 with an ΔE of ?41.0 kcal/mol and ΔE = ?52.0 kcal/mol, for the adsorption and oxidation, respectively. On the Au₂? SAPO‐11 model, the CO adsorption and oxidation reaction occur, with a ΔE of ?29.7 kcal/mol and ?52 kcal/mol, respectively. According to our results, the oxidation reaction exhibits an Eley‐Rideal type mechanism with adsorbed CO. The theoretical calculations reveal that this type of material could be interesting to disperse Au and consequently to strengthen its catalytic use for different reactions. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110:2573–2582, 2010     

Gold adatoms and clusters on PPV: An ab initio investigation

We have performed an ab initio investigation of the energetic, structural, electronic, and vibrational properties of Au atoms and clusters adsorbed on poly-p-phenylene vinylene (PPV) chains, Au(n)/PPV (with n =?1, 2, 6, 7, 10, and 12). We find that the Au(n)/PPV systems are energetically stable by 0.5 eV, compared with the isolated systems, viz., PPV chain and Au(n) clusters, thus supporting the formation of Au(n)/PPV nanocomposites. Further support to the formation of Au(n)/PPV has been provided by examining the vibrational properties of pristine PPV and Au(n)/PPV systems. In agreement with experimental measurements, we find a reduction on the in-plane vibrational frequency of C-C bonds of Au(n)/PPV, when compared with the same vibrational modes of pristine PPV. The electronic properties of isolated Au(n) clusters are modified when adsorbed on PPV. The highest occupied states of Au(n)/PPV are mostly concentrated on the Au(n) cluster, while the lowest unoccupied states are mainly localized along the PPV chain. The HOMO-LUMO energy gap of the Au(n)/PPV systems are smaller than the energy gap of the isolated systems, Au(n) clusters, and pristime PPV chains.     

Combination of Raman, Infrared, and X-Ray Energy-Dispersion Spectroscopies and X-Ray Diffraction to Study a Fossilization Process

X-ray diffraction was combined with X-ray energy-dispersion, Fourier-transform infrared, and Raman spectroscopies to study the fossilization of a Cretaceous specimen of the plant Brachyphyllum castilhoi, a fossil from the Ipubi Formation, in the Araripe Sedimentary Basin, Northeastern Brazil. Among the possible fossilization processes, which could involve pyrite, silicon oxide, calcium oxide, or other minerals, we were able to single out pyritization as the central mechanism producing the fossil, more than 100 million years ago. In addition to expanding the knowledge of the Ipubi Formation, this study shows that, when combined with other experimental techniques, Raman spectroscopy is a valuable tool at the paleontologist’s disposal.     

Structural characterization and Curie temperature determination of a sodium strontium niobate ferroelectric nanostructured powder

The Curie temperature and its correlation with the magnitude of the displacement of the niobium atom from the center of [NbO₆] octahedra in NaSr₂Nb₅O₁₅ nanostructured powder were investigated. A single powder was prepared by high-energy ball milling. A powder with an average crystallite size of 37 nm was prepared by calcining the precursor at 1423 K. The refinement of the structural parameters was carried out by the Rietveld method. NaSr₂Nb₅O₁₅ exhibits tetragonal symmetry with the tungsten bronze structure (a=b=12.3495 (6) Å, c=3.8911 (2) Å, V=593.432 (5) Å³, and Z=2). The site occupancy of the Na⁺ and Sr²⁺ cations and the interatomic distances between the niobium and oxygen atoms were derived. The [NbO₆] octahedron undergoes both rotation and tilting depending on the crystallographic site. The Curie temperature of the powder was derived using both the impedance and infrared spectroscopy methods.     

In situ microbial fuel cell-based biosensor for organic carbon

The biological oxygen demand (BOD) may be the most used test to assess the amount of pollutant organic matter in water; however, it is time and labor consuming, and is done ex-situ. A BOD biosensor based on the microbial fuel cell principle was tested for online and in situ monitoring of biodegradable organic content of domestic wastewater. A stable current density of 282±23mA/m(2) was obtained with domestic wastewater containing a BOD(5) of 317±15mg O(2)/L at 22±2°C, 1.53±0.04mS/cm and pH 6.9±0.1. The current density showed a linear relationship with BOD(5) concentration ranging from 17±0.5mg O(2)/L to 78±7.6mg O(2)/L. The current generation from the BOD biosensor was dependent on the measurement conditions such as temperature, conductivity, and pH. Thus, a correction factor should be applied to measurements done under different environmental conditions from the ones used in the calibration. These results provide useful information for the development of a biosensor for real-time in situ monitoring of wastewater quality.     

A liquid-liquid extraction procedure followed by a low temperature purification step for the analysis of macrocyclic lactones in milk by liquid chromatography-tandem mass spectrometry and fluorescence detection

In this work a method is proposed and demonstrated for the analysis of the macrocyclic lactones abamectin, doramectin, eprinomectin, ivermectin and moxidectin in bovine milk by liquid chromatography coupled to mass spectrometry (LC-MS/MS) and liquid chromatography with fluorescence detection (LC-FL). The method is based on liquid-liquid extraction followed by a low temperature purification (LLE-LTP) step. Moreover, the proposed method was validated according to the Commission Decision 2002/657/EC, using LC-MS/MS and LC-FL for confirmatory and quantitative analysis, respectively. For LC-MS/MS the recovery rates observed ranged from 101.2 to 141.6% with coefficient of variation from 2.6 to 19.8%. For LC-FL the recovery rates observed ranged from 100.2 to 105% and coefficient of variations from 2.9 to 8.8%. Matrix effects were negligible due to the low temperature purification step. The quantification limits were far below the maximum limits established by regulations of all countries consulted. The proposed method proved to be simple, easy, and adequate for high-throughput analysis of a large number of samples per day at low cost.