Photoelectron (He(I), He(II) and X-ray) spectroscopy of γ-pyrone and its related sulphur derivatives: valence and core ionization energies and shake-up satellites

The photoelectron He(I) and He(II) spectra of 4H-pyran-4-one (1), 4H-thiopyran-4-one (2), 4H-pyran-4-thione (3) and 4H-thiopyran-4-thione (4) are reported. The assignments are based on experimental evidence, taking into account the results of theoretical calculations. The outermost orbital sequences proposed (X = O, S) are n_X (σ), 3b₁ (π), 1a₂(π) for 1, 2 and 4; and 3b₁(π), n_X(σ) and 1a₂(π) for 3. The shifts of the core-ionization energy values for 1–4 are ascribed to a drift of π-charge from the intracyclic heteroatom towards the carbonyl or thiocarbonyl group. Low-energy shake-up satellites (up to 25% with respect to the main line) are observed in the various energy regions of the XPS spectra. They are qualitatively reproduced by CNDO/2 calculations. The most important satellites derive from the transition in the ion corresponding to the 3b₁ (π) → 4b₁(π*) transition in the UV-visible spectra of the neutral molecules. Charge rearrangements accompanying this transition lead to charge depletion of the core-ionized atom.     

Activation of molecular hydrogen over a binuclear complex with Rh2S2 core: DFT calculations and NMR mechanistic studies

The dicationic complex [(triphos)Rh(mu-S)(2)Rh(triphos)](2+), 1 (modeled as 1c) [triphos = CH(3)C(CH(2)PPh(2))(3)], is known to activate two dihydrogen molecules and produce the bis(mu-hydrosulfido) product [(triphos)(H)Rh(mu-SH)(2)Rh(H)(triphos)](2+), 2 (modeled as 2b), from which 1 is reversibly obtained. The possible steps of the process have been investigated with DFT calculations. It has been found that each d(6) metal ion in 1c, with local square pyramidal geometry, is able to anchor one H(2) molecule in the side-on coordination. The step is followed by heterolytic splitting of the H-H bond over one adjacent and polarized Rh-S linkage. The process may be completed before the second H(2) molecule is added. Alternatively, both H(2) molecules are trapped by the Rh(2)S(2) core before being split in two distinct steps. Since the ambiguity could not be solved by calculations, (31)P and (1)H NMR experiments, including para-hydrogen techniques, have been performed to identify the actual pathway. In no case is there experimental evidence for any Rh-(eta(2)-H(2)) adduct, probably due to its very short lifetime. Conversely, (1)H NMR analysis of the hydride region indicates only one reaction intermediate which corresponds to the monohydride-mu-hydrosulfide complex [(triphos)Rh(H)(mu-SH)(mu-S)Rh(triphos)](2+) (3) (model 5a). This excludes the second hypothesized pathway. From an energetic viewpoint the computational results support the feasibility of the whole process. In fact, the highest energy for H(2) activation is 8.6 kcal mol(-1), while a larger but still surmountable barrier of 34.6 kcal mol(-1) is in line with the reversibility of the process.     

First comparative emission assay of single-wall carbon nanotubes--solutions and dispersions

A variety of single-wall carbon nanotube samples were tested in steady-state and time-resolved emission experiments, where it was found that chemical functionalization and different degrees of oxidation affect the emission behavior.     

Local coordination geometry around Cu and Cu ions in silicate glasses: an X-ray absorption near edge structure investigation

We present an X-ray absorption near edge structure (XANES) study on Cu⁺ and Cu²⁺ ions in silicate glasses at the Cu K-edge, aimed to determine the geometry of the local structure around the metal. This study is based on the comparison between experimental data and theoretical calculations made in the framework of multiple scattering theory. The XANES signals relative to several clusters are simulated on the basis of known crystalline structures involving Cu⁺ and Cu²⁺ ions in silicate matrices. Concerning the Cu²⁺ in glass, the simulations suggest the presence of a square coordination of oxygen atoms around the absorber, with a possible presence of metal ions in the second shell. As for the Cu⁺ ions, the metal clustering is excluded and a linear O-Cu-O coordination is evidenced. Received 30 April 1999     

Electrochemically Driven Swinging of a Nitrobenzyl Pendant Arm in a Nickel Scorpionand Complex

A radical anion −NO₂^.− is formed upon an electrochemically reversible one-electron reduction of the square-planar Ni^II complex of N-nitrobenzylcyclam. The −NO₂^.− group goes to occupy an axial position of the metal ion, thus establishing a significant electronic interaction with the metal center. In particular, the ESR spectrum supports the occurrence of an electron transfer from −NO₂^.− to the metal, which therefore presents a significant Ni^I character. On re-oxidation, the nitrobenzyl side chain detaches and the Ni^II complex is restored, providing an example of a fully reversible redox driven intramolecular motion.     

Influence of Pore Size in Benzoin Condensation of Furfural Using Heterogenized Benzimidazole Organocatalysts

A designed N-heterocyclic carbene (NHC) catalyst was covalently anchored on a range of mesoporous and hierarchical supports, to study the influence of pore size in the benzoin condensation of furfural. The structural and spectroscopic characteristics of the anchored catalysts were investigated, also with the help of molecular dynamics simulations, in order to rationalize the degree of stability and recyclability of the heterogenized organocatalysts. Quantitative yields (99 %) and complete recyclability were maintained after several cycles, vindicating the design rationale.     

On the incompressible flow in axial turbomachinery with several closely packed blade rows

Summary The velocity field in an axial multistage turbomachinery is easily investigated, ignoring the fluid viscosity and compressibility, by means of the actuator disc theory. By developing this theory, general expressions of fluid velocity in such a machine are obtained, these in turn yield the approximate expressions usually given in the literature.

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Sommario Lo studio del campo di moto in una turbomacchina a più stadi puramente assiale per fluido inviscido ed incomprimibile viene sviluppato in modo agevole mediante la teoria del disco attuatore. Nella presente nota vengono ricavate, sviluppando tale teoria, le espressioni generali delle velocità del fluido in una tale macchina e da queste vengono derivate successivamente le espressioni approssimate comunemente riportate nella bibliografia a proposito.

     

Influence of gravity and lift on particle velocity statistics and transfer rates in turbulent vertical channel flow

The present study reports detailed statistics for velocity and transfer rates of heavy particles dispersed in turbulent boundary layers. Statistics have been extracted from a homogeneous source of data covering a large target parameter space and are used here to analyze the effects of gravity and lift on particle dispersion and deposition in a systematic way. Datasets were obtained performing Direct Numerical Simulation (DNS) of particle-laden turbulent upward/downward flow in a vertical channel. Six values for the particle timescale (the particle Stokes number, St) ranging three orders of magnitude were considered to analyze the deposition process as the controlling mechanism was shifting from turbulent diffusion to inertia-moderated crossing trajectories. For the particle timescales examined, gravity and lift do not influence the qualitative behavior of particles even though velocity profiles and deposition coefficients are modified in a non-monotonic fashion, reaching an optimum for St ? 15. Physical mechanisms for the different behavior are discussed. Raw data and statistics obtained from the present DNS are made available at http://cfd.cineca.it (mirror site: http://158.110.32.35/download/database) and can be used to test simple models and closure equations for multiphase RANS and Large Eddy simulations.     

Reflection of bounded acoustic beams on a fluid-solid interface

The reflection of an acoustic beam onto a fluid-solid interface is studied under the assumption that the solid medium is viscoelastic. The incident beam is represented as a superposition of plane monochromatic homogeneous waves and its profile is assumed to be Gaussian shaped. The outcoming wave field at the interface, and away from it in the fluid, is numerically calculated for different values of the frequency and of the beam width.

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Sommario Si studia la riflessione di un fascio di onde acustiche sulla superficie di separazione fra un liquido ed un solido nell'ipotesi che il mezzo solido sia viscoelastico. Il fascio incidente ha un profilo gaussiano e viene rappresentato mediante la sovrapposizione di onde piane monocromatiche omogenee. Si calcola numericamente il profilo del fascio riflesso sia sull'interfaccia, sia lontano da essa nel fluido, per diversi valori della frequenza e della larghezza del fascio.

     

Pulsed amperometric detection at glassy carbon electrodes: A new waveform for sensitive and reproducible determination of electroactive compounds

In this work, the application of a new pulsed amperometric detection (PAD) waveform at a glassy carbon electrode, operating in typical chromatographic mobile phases, is proposed for the sensitive and reproducible determination of arylethanolaminic and phenolic moiety based compounds (e.g. beta-agonists and polyphenols). Preliminary experiments by cyclic voltammetry were carried out to investigate the electrochemical behaviour and to select the detection and cleaning electrode potentials. The proposed potential-time profile was designed to prevent the carbon electrode fouling under repeated analyses, thus ensuring a reproducible and sensitive quantitative determination, without the need of any mechanical or chemical electrode cleaning procedure. The waveform electrochemical parameters, including detection and delay times, were optimized in terms of sensitivity, limit of detection and response stability. The optimized waveform allowed the sensitive and stable detection of model compounds, such as clenbuterol and caffeic acid, that showed detection limits of 0.1 μg L⁻¹ and 14 μg L⁻¹, quantification limits of 0.4 μg L⁻¹ and 46 μg L⁻¹, and linearity up to 100 μg L⁻¹ (r = 0.9993) and 10 mg L⁻¹ (r = 0.9998), respectively. Similar results were obtained for other compounds of the same classes, with precision values under repeatability conditions ranging from 3.0 to 5.9%. The proposed method can be then considered as an excellent alternative to the post-column detection of beta-agonists, phenols and polyphenols.