Cathode thickness-dependent tolerance to Cr-poisoning in solid oxide fuel cells

This work aimed to set new guidelines for the quantification of Cr accumulation in solid oxide fuel cell cathodes after operation, and enabled to pinpoint a diffusion-controlled tolerance to Cr-poisoning for increased cathode thickness; the additional cathode material decreases the deposition rate from Cr vapor species in the active layer.These experimentally based findings were obtained by direct comparison of cathode performances measured on a segmented test arrangement enabling the independent control of four cathodes, with different thicknesses, on an anode-support. The cathode thickness-dependent performance degradation was correlated to deliberate poisoning by volatile Cr species stemming from the test arrangement.     

Recent developments on Reactivity: Theoretical conceptualization and empirical verification

This paper seeks to enrich the literature of operations and supply chain management through the development of the concept of Reactivity and the introduction of related performance indicators. Reactivity explains the capability to perform operationally and economically under unexpected conditions. A qualitative investigation has aimed to identify useful managerial practices to be adopted to properly perform Reactivity, while an empirical analysis has tested the relevance of each practice as well as the economic benefits that Reactivity provides. The findings suggest that managers and practitioners should develop a Reactivity orientation because it benefits firms’ economic performance when an unexpected event occurs; in addition, several recommended managerial practices should be undertaken to ensure its correct implementation.     

Structural discrimination of isomeric tetrahydrofuran lignan glucosides by tandem mass spectrometry

Due to the possible role in human health, the number of analytical studies on lignans aimed at their quali‐ and quantitative analysis in plant extracts, biological fluids and foods is continuously increasing. However, helpful systematic mass spectrometric investigations on these compounds are few and rather limited to specific lignan sub‐classes. To increase the comprehension of the previously outlined picture of the gas‐phase properties of furofuran lignans, we extended the study to tetrahydrofuran lignans and here we reported the collision‐activated dissociation (CAD) fragmentation patterns of the alkali metal cation adducts, [M+Alk]⁺, and [M–H]^? ions of three isomeric tetrahydrofuran lignans, (+)‐8′‐hydroxylariciresinol 4′‐O‐β‐D ‐glucopyranoside (1), (+)‐7′‐hydroxylariciresinol 7′‐O‐β‐D ‐glucopyranoside (2) and 4‐O‐β‐D ‐glucopyranosyloxy‐3,3′‐dimethoxy‐7,9′‐epoxylignan‐5′,8′,9‐triol (3) investigated by electrospray ionization triple quadrupole mass spectrometry (ESI‐TQMS). Hydrogen/deuterium (H/D) solution exchange experiments, allowing the selective H/D exchange of all the acidic hydrogen atoms, proved to be a very effective tool to obtain information on the nature of fragments generated during TQ/CAD processes. The [M+Na]⁺ CAD mass spectra of the three isomeric tetrahydrofurans revealed four different pathways involving the loss of the glucose moiety, which allowed the assignment of the glycosylation site. In the negative ion mode, the main fragmentation channel of the [M–H]^? ions of O‐glucosylated lignans at the phenolic oxygen atoms is represented by the loss of 162 Da. When the sugar is bound to a benzylic OH group the loss of the sugar as a 180 Da unit occurs eventually following the loss of a water molecule involving both the C(9)H₂OH chain and the sugar. Copyright © 2010 John Wiley & Sons, Ltd.     

Micro‐Raman innovative methodology to identify Ag–Cu mixed sulphides as tarnishing corrosion products

Mixed Cu–Ag alloys with different compositions have been produced and subjected to an accelerated sulphidation process which causes the development of a mixed sulphide‐rich corroded film on their surface. It was called tarnishing, that is, the formation of a blue‐brownish patina when Cu–Ag alloys are exposed in a sulfur‐containing atmosphere. The structures of the pristine alloys have been determined by the combined analytical techniques as scanning electron microscopy energy dispersive X‐ray microanalysis and X‐ray diffraction. The experimental conclusions confirmed the occurrence of micro phase separation with the formation of different dendritic domains of about 10 µm in width. The sulphidized samples were firstly investigated by optical microscopy and X‐ray diffraction in order to verify the homogeneity of the patina and to identify the different AgCuS phases appearing on the alloy surfaces. It was observed that, despite the inherent micro‐heterogeneity of the alloys, the sulphide layer was throughout uniform in composition at the micro‐scale. The complex scenario of the relative stability of all the various mixed sulphides involved was then explored by micro‐Raman spectroscopy (μ‐RS), pointing out that the Cu‐for‐Ag substitution in the crystal lattice of the mixed Ag–Cu sulphides caused a monotonous blue shift of the vibrational wavenumbers in Raman spectra. This study has unveiled microscopic details of the tarnishing process, furnishing an innovative, cheap and non‐destructive methodology based on μ‐Raman spectroscopy for the evaluation of the silver‐copper artefacts via the compositions of their corroded products. Copyright © 2016 John Wiley & Sons, Ltd.     

A non-squeezing theorem for convex symplectic images of the Hilbert ball

We prove that the non-squeezing theorem of Gromov holds for symplectomorphisms on an infinite-dimensional symplectic Hilbert space, under the assumption that the image of the ball is convex. The proof is based on the construction by duality methods of a symplectic capacity for bounded convex neighbourhoods of the origin. We also discuss the role of infinite-dimensional non-squeezing results in the study of Hamiltonian PDEs and show some examples of symplectomorphisms on infinite-dimensional spaces exhibiting behaviours which would be impossible in finite dimensions.     

Fluxional rearrangement in congested ruthenium(II) complexes containing pyrimidine- and/or pyridine-based dithioether ligands

The solvento species obtained by the treatment of cis-RuCl₂(N,N-L)₂ [L = di-2-pyridyl sulfide (dps), di-2-pyrimidyl sulfide (dprs)] with AgPF₆, reacted with dithioethers L′ [L′ = 2,6-bis(2-pyridylthiomethyl)pyridine (pytmp), 2,6-bis(2-pyrimidylthiomethyl)pyridine (prtmp) and 2,6-bis{2-(4-methyl)pyrimidylthiomethyl} pyridine (mprtmp)] to afford the compounds [Ru(N,N-L)₂(N,S-L′)][PF₆]₂. The ¹H NMR spectra indicate that L′ is chelated through S and N atoms with the formation of a four-membered ring. As a consequence, the ruthenium and sulfur atoms are stereogenic centers with ∆ and Λ and (R) and (S) configurations, respectively. NMR spectra, at low temperatures, show that two invertomers, of similar abundance, as enantiomeric couples ∆S, ΛR and ∆R, ΛS are present. In the methylene region, four AB systems are observed that in both the species contain two non-equivalent methylene groups. Variable-temperature NMR spectra and EXSY experiments show that the sulfur inversion produces an exchange between the invertomers. The one-dimensional band-shape analysis of the exchanging methylene signals showed that the energy barriers for the process are in the 43–52 kJ mol⁻¹ range. The possible mechanisms of the sulfur inversion are discussed.     

Structural and Optical Properties of Novel Surfactant Coated TiO<Subscript>2</Subscript>–Ag Based Nanoparticles

Stable dispersions of surfactant-coated TiO₂–Ag based nanoparticles in apolar medium have been prepared by performing sequentially the hydrolysis of titanium(IV) isopropoxide and the reduction of Ag⁺ in the confined space of sodium bis(2-ethylhexyl)sulfosuccinate (NaAOT) reverse micelles. Depending on the sequence length, this novel procedure allowed the synthesis of semiconductor–metal nanoparticles, nominally indicated as TiO₂/Ag, TiO₂/Ag/TiO₂, and TiO₂/Ag/TiO₂/Ag, stabilized by a monolayer of oriented surfactant molecules. The structural characterization of these nanoparticles has been performed by High Resolution Transmission Electron Microscopy (HR-TEM), while optical properties were investigated by UV–Vis absorption and fluorescence spectroscopies. TEM investigation showed the presence of globular nanoparticles with an average diameter of about 10 nm composed by distinct amorphous TiO₂ and crystalline Ag glued domains whose structure depends on the sequence length. UV–Vis absorption measurements highlighted the mutual metal–semiconductor influence on the TiO₂ energy band gap and on the Ag plasmon resonance. Steady-state fluorescence spectra analysis allowed to reveal the strong inhibition of the electron–hole radiative recombination in the TiO₂ domains due to the Ag and the appearance of a new emission band centred in the 484–545 nm range. Possible attributions of the involved electronic transition of this last emission are discussed.     

Compression of digital holograms via adaptive-sparse representation

Efficient storage and transmission of digital holograms (DHs) requires the development of appropriate compression techniques for such a special class of images. In this Letter, we investigate a method to compress DHs using a sparse matrix representation. Using digital holography to numerically manage complex wave fields, we are able to apply an adaptive mask, based on a threshold filter, to the object wave field. From there, we store the result of this filtering by sparse representation. In this Letter, we demonstrate that using sparse representation allows for a high compression factor with minimal loss in the quality of the reconstructed image. This technique is efficient for storage and transmission of DHs.