State-specific reactions and autoionization dynamics of Ar produced by synchrotron radiation

The long-lived excited states of doubly charged rare gases can markedly affect their reactivity. In this paper we demonstrate the presence of strong state-specific effects in the charge exchange of Ar²⁺ (³P, ¹D and ¹S) with several neutral targets (He, Ne, Kr, Xe, D₂, and CH₄). State sensitive measurements have been performed by producing the different Ar²⁺ electronic states via tunable synchrotron radiation (Elettra-Trieste, Italy and SuperACO-Orsay, France). From the product ion yield data of charge transfer, state-selected total cross-sections have been deduced. Using the state-specific reactivity of Ar²⁺ towards different neutral targets, it has been possible to extract the photon-energy-dependent production branching of the three doubly charged states and to investigate the autoionization dynamics of neutral or singly charged Ar in the vicinity of the double ionization threshold.     

Yield criteria for quasibrittle and frictional materials: A generalization to surfaces with corners

Convexity of a yield function (or phase-transformation function) and its relations to convexity of the corresponding yield surface (or phase-transformation surface) is essential to the invention, definition and comparison with experiments of new yield (or phase-transformation) criteria. This issue was previously addressed only under the hypothesis of smoothness of the surface, but yield surfaces with corners (for instance, the Hill, Tresca or Coulomb–Mohr yield criteria) are known to be of fundamental importance in plasticity theory. The generalization of a proposition relating convexity of the function and the corresponding surface to nonsmooth yield and phase-transformation surfaces is provided in this paper, together with the (necessary to the proof) extension of a theorem on nonsmooth elastic potential functions. While the former of these generalizations is crucial for yield and phase-transformation functions, the latter may find applications for potential energy functions describing phase-transforming materials, or materials with discontinuous locking in tension, or contact of a body with a discrete elastic/frictional support.     

A novel hydroxy functionalized polyester obtained by ring opening copolymerization of L‐lactide with a pyrolysis product of cellulose

A hydroxylactone ((1R,5S)‐1‐hydroxy‐3,6‐dioxabicyclo [3.2.1] octan‐2‐one, abbreviated as LAC) obtained from catalytic pyrolysis of cellulose was investigated as a monomer in the synthesis of polyesters by ring‐opening polymerization (ROP) with L ‐lactide. Although stannous octoate resulted inactive, ROP initiated by zirconium (IV) acetylacetonate afforded novel copolyesters from LAC and lactide mixtures in the bulk at 110 °C. Copolymers were obtained with different LAC content (from 19 to 45%) with a random microstructure as established by detailed NMR analysis. FTIR spectrometry confirmed the presence in the polymer chain of the OH groups originally present in LAC, which do not react during polymerization due to steric hindrance and inter/intramolecular hydrogen bonding. Reaction with trichloroacetylisocyanide proved that OH groups of the polyesters can be readily derivatized. The application of LAC as a comonomer enables the insertion of the alcohol functionality in polylactide avoiding protection/deprotection steps and potentially expanding the realm of biomaterials affordable from carbohydrate feedstock. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 247–257, 2009     

Rationality in families of threefolds

We prove that in a family of projective threefolds defined over an algebraically closed field, the locus of rational fibers is a countable union of closed subsets of the locus of separably rationally connected fibers. When the ground field has characteristic zero, this implies that the locus of rational fibers in a smooth family of projective threefolds is the union of at most countably many closed subfamilies.     

Chemically stable anode-supported solid oxide fuel cells based on Y-doped barium zirconate thin films having improved performance

Anode-supported solid oxide fuel cells (SOFCs) based on thin BaZr_0.8Y_0.2O_3 ? δ (BZY) electrolyte films were fabricated by pulsed laser deposition (PLD) on sintered NiO–BZY composite anodes. After in situ reduction of NiO to Ni, the anode substrates became porous, while retaining good adhesion with the electrolyte. A slurry-coated composite cathode made of La_0.6Sr_0.4Co_0.2Fe_0.8O_3 ? δ (LSCF) and BaCe_0.9Yb_0.1O_3 ? δ (BCYb), specifically developed for proton conducting electrolytes, was used to assemble fuel cell prototypes. Depositing by PLD 100 nm thick LSCF porous films onto the BZY thin films was essential to improve the cathode/electrolyte adhesion. A power density output of 110 mW/cm² at 600 °C, the largest reported value for an anode-supported fuel cell based on BZY at this temperature, was achieved. Electrochemical impedance spectroscopy (EIS) measurements were used to investigate the different contributions to the total polarization losses.     

CAESAR models for developmental toxicity

Background

The new REACH legislation requires assessment of a large number of chemicals in the European market for several endpoints. Developmental toxicity is one of the most difficult endpoints to assess, on account of the complexity, length and costs of experiments. Following the encouragement of QSAR (in silico) methods provided in the REACH itself, the CAESAR project has developed several models.

Results

Two QSAR models for developmental toxicity have been developed, using different statistical/mathematical methods. Both models performed well. The first makes a classification based on a random forest algorithm, while the second is based on an adaptive fuzzy partition algorithm. The first model has been implemented and inserted into the CAESAR on-line application, which is java-based software that allows everyone to freely use the models.

Conclusions

The CAESAR QSAR models have been developed with the aim to minimize false negatives in order to make them more usable for REACH. The CAESAR on-line application ensures that both industry and regulators can easily access and use the developmental toxicity model (as well as the models for the other four endpoints).

     

A new on-line solid phase extraction high performance liquid chromatography tandem mass spectrometry method to study the sun light photodegradation of mono-chloroanilines in river water

The study investigates the natural photodegradation pathway of mono-chloroanilines in river waters, with the aim to identify the predominant photoproducts formed. At this purpose a new sensitive on-line SPE HPLC–MS/MS method has been developed with LOQ values equal or lower than the legal threshold concentration levels allowed for mono-chloroanilines in waters. The degradation processes of o-, m- and p-chloroaniline have been investigated subjecting their solutions, prepared both in ultrapure and in river water, to sun light irradiation simulated by a solar box system. The SPE HPLC–MS/MS methodology allowed to evaluate the degradation kinetics, to identify the predominant photodegradation products and to propose the chemical structures. Two photoproducts (aniline and 3-aminophenol), for which standards are available, have also been quantified.     

Triggering rogue waves in opposing currents

We show that rogue waves can be triggered naturally when a stable wave train enters a region of an opposing current flow. We demonstrate that the maximum amplitude of the rogue wave depends on the ratio between the current velocity U(0) and the wave group velocity c(g). We also reveal that an opposing current can force the development of rogue waves in random wave fields, resulting in a substantial change of the statistical properties of the surface elevation. The present results can be directly adopted in any field of physics in which the focusing nonlinear Schr?dinger equation with nonconstant coefficient is applicable. In particular, nonlinear optics laboratory experiments are natural candidates for verifying experimentally our results.     

Proposed search for a fourth neutrino with a PBq antineutrino source

Several observed anomalies in neutrino oscillation data can be explained by a hypothetical fourth neutrino separated from the three standard neutrinos by a squared mass difference of a few eV(2). We show that this hypothesis can be tested with a PBq (ten kilocurie scale) (144)Ce or (106)Ru antineutrino beta source deployed at the center of a large low background liquid scintillator detector. In particular, the compact size of such a source could yield an energy-dependent oscillating pattern in event spatial distribution that would unambiguously determine neutrino mass differences and mixing angles.