Formation of PAHs and soot platelets: multiconfiguration theoretical study of the key step in the ring closure–radical breeding polyyne‐based mechanism

Polyynes of general formula H? (C?C? )_nH are known to play a significant role in combustion and pyrolysis, possibly being intermediates in the formation of polycyclic aromatic hydrocarbons (PAHs) and soot. They have also been detected in astrophysical investigations. The key step in the polyyne‐based radical breeding mechanism for PAH growth is a cyclization, put forward by Krestinin, which implies disruption of electron couples, plausibly expected to be energy demanding. We explore the electronic features and energy requirements of such a process by quantum mechanical multiconfiguration methods (CASSCF and CASPT2). The features of the wavefunction are analyzed, and the free energy barriers are estimated over a wide range of temperatures, for three molecular models. The initial radical adduct A, generated by H ^. , HC?C ^. (ethynyl), or HC?C? C ^. H₂ ( propargyl ) addition to butadiyne (BD, HC?C? C?CH), undergoes a cyclization with the generation of two new radical centers. However, in most of the cases, one of these new singly occupied sp² orbitals has some overlap with the unpaired electron lobe already existent in A: some sort of bonding builds up and consequently the triradical character cannot be large. Only one model suggests a possible role of the radical breeding mechanism during combustion. Copyright © 2009 John Wiley & Sons, Ltd.     

Synergic approach to XAFS analysis for the identification of most probable binding motifs for mononuclear zinc sites in metalloproteins

In the present work a data analysis approach, based on XAFS data, is proposed for the identification of most probable binding motifs of unknown mononuclear zinc sites in metalloproteins. This approach combines multiple‐scattering EXAFS analysis performed within the rigid‐body refinement scheme, non‐muffin‐tin ab initio XANES simulations, average structural information on amino acids and metal binding clusters provided by the Protein Data Bank, and Debye–Waller factor calculations based on density functional theory. The efficiency of the method is tested by using three reference zinc proteins for which the local structure around the metal is already known from protein crystallography. To show the applicability of the present analysis to structures not deposited in the Protein Data Bank, the XAFS spectra of six mononuclear zinc binding sites present in diverse membrane proteins, for which we have previously proposed the coordinating amino acids by applying a similar approach, is also reported. By comparing the Zn K‐edge XAFS features exhibited by these proteins with those pertaining to the reference structures, key spectral characteristics, related to specific binding motifs, are observed. These case studies exemplify the combined data analysis proposed and further support its validity.     

Magnetic measurement of transport AC losses in Bi-2223/Ag tapes

Magnetic nature of the losses in superconducting wire carrying AC current implies that it should be possible to determine these losses in a contactless way. Ribbon-like samples are quite favorable for such an experiment, because a notable portion of magnetic flux related to losses ‘escapes' the sample volume and can be detected by an appropriate pick-up coil. In this case, a model describing the AC current penetration into the tape, based, e.g., on the critical state model, allows one to derive the losses from the pick-up coil signal. Because this signal is proportional to the number of coil turns, extension of the accessible range of measured voltages (and losses) can be achieved. We demonstrate the data obtained on a 1 cm long portion of a low-loss multifilamentary tape carrying AC current with frequency 35 Hz. The pick-up coil technique allowed us to reach loss level more than one order below the experimental limit for direct measurements.     

Stable colloidal suspensions of nanostructured zirconium oxide synthesized by hydrothermal process

Nanocrystalline zirconium oxide was synthesized by hydrothermal treatment of ZrO(NO₃)₂ and ZrOCl₂ aqueous solutions at different temperatures and time in presence of hydrogen peroxide. Hydrothermal treatment of zirconium salts (0.25 and 0.50 mol L^?1) produced nanocrystalline monoclinic ZrO₂ powders with narrow size distribution, which were formed by the attachment of the smaller particles with crystallites size of 3.5 nm, estimated by means of the Scherrer’s equation and confirmed by transmission electronic microscopy. Typical monoclinic zirconium oxide X-ray powder diffraction patterns and Raman spectra were obtained for all the crystalline powders. It was observed that the crystallization depends strongly on the temperature, resulting in amorphous material when the synthesis was realized at 100 °C, and crystalline with monoclinic phase when synthesized at 110 °C, independently of the salt used. Zirconium oxide colloidal nanoparticles were formed only at hydrothermal treatments longer than 24 h. The stability of the colloids was successfully characterized of zeta potential, showing an initial value of + 59.2 mV in acid media and isoelectric point at pH = 5.2, in good agreement with previous studies.     

Geometric dynamic recrystallization of austenitic stainless steel through linear plane-strain machining

ABSTRACT

Type 316L austenitic stainless steel was severely plastically deformed at room temperature using linear plane-strain machining in a single pass that imparted shear strains up to 2.2 at strain rates up to 2?×?10³ s^?1. The resulting microstructures exhibited significant grain size refinement and improved mechanical strength where geometric dynamic recrystallization was identified as the primary microstructural recrystallization mechanism active at high strain rates. This mechanism is rarely observed in low to medium stacking fault energy materials. The critical stress required for twin initiation is raised by the combined effects of refined grain size and the increase in stacking fault energy due to the adiabatic heating of the chip, thus permitting geometric dynamic recrystallization. The suppression of martensite formation was observed and is correlated to the significant adiabatic heating and mechanical stabilisation of the austenitic stainless steel. A gradient of the amount of strain induced martensite formed from the surface towards the interior of the chip. As the strain rate is increased from 4?×?10² s^?1–2?×?10³ s^?1, a grain morphology change was observed from a population of grains with a high fraction of irregular shaped grains to one dominated by elongated grain shapes with a microstructure characterised by an enhanced density of intragranular sub-cell structure, serrated grain boundaries, and no observable twins. As strain rates were increased, the combination of reduction in strain induced martensite and non-uniform intragranular strain led to grain softening where a Hall-Petch relationship was observed with a negative strengthening coefficient of ?0.08?MPa m^1/2.     

Modeling Transverse Relative Locality

We investigate some aspects of relativistic classical theories with “relative locality”, in which pairs of events established to be coincident by nearby observers may be described as non-coincident by distant observers. While previous studies focused mainly on the case of longitudinal relative locality, where the effect occurs along the direction connecting the distant observer to the events, we here focus on transverse relative locality, in which instead the effect is found in a direction orthogonal to the one connecting the distant observer to the events. Our findings suggest that, at least for theories of free particles, transverse relative locality is as significant as longitudinal relative locality both conceptually and quantitatively. And we observe that “dual gravity lensing” can be viewed as one of two components of transverse relative locality. We also speculate about a type of spacetime noncommutativity for which transverse relative locality could be particularly significant.     

The Suzuki homocoupling reaction under high-intensity ultrasound

The Pd-catalysed Suzuki homocoupling of boronic acids was successfully carried out in water under high-intensity ultrasound (HIU). Heterogeneous catalysis with Pd/C, facilitating work up and purification, could be used without adding phosphine ligands. Reaction rates and yields were strongly influenced by the oxidant employed; excellent results were obtained using either molecular oxygen or 3-bromo-4-hydroxycoumarin. 3-Arylation of the latter with the Suzuki procedure had failed, exclusively affording the homocoupling products, symmetric biaryls. Besides offering a number of operational advantages, the use of HIU broadens the field of application for the Suzuki reaction.