Dielectric studies of a laterally-linked siloxane ester dimer

This paper reports measurements of the dielectric response over the frequency range 10² to 10⁹ Hz of a liquid crystal dimer consisting of two ester mesogens laterally linked by an alkoxy chain containing a siloxane group. The synthesis and phase behaviour of the siloxane dimer are also reported. Results show that there are two relaxations in the isotropic phase and four in the nematic phase of the material. The possible molecular origins for these modes are given. It is found that there is a coupling between internal and external modes which gives rise to a cooperative mode as the temperature in the nematic phase is lowered towards a glass transition.     

Thorough Investigation of the Phenolic Profile of Reputable Greek Honey Varieties: Varietal Discrimination and Floral Markers Identification Using Liquid Chromatography–High-Resolution Mass Spectrometry

Honey is a highly consumed commodity due to its potential health benefits upon certain consumption, resulting in a high market price. This fact indicates the need to protect honey from fraudulent acts by delivering comprehensive analytical methodologies. In this study, targeted, suspect and non-targeted metabolomic workflows were applied to identify botanical origin markers of Greek honey. Blossom honey samples (n = 62) and the unifloral fir (n = 10), oak (n = 24), pine (n = 39) and thyme (n = 34) honeys were analyzed using an ultra-high-performance liquid chromatography hybrid quadrupole time-of-flight mass spectrometry (UHPLC-q-TOF-MS) system. Several potential authenticity markers were revealed from the application of different metabolomic workflows. In detail, based on quantitative targeted analysis, three blossom honey markers were found, namely, galangin, pinocembrin and chrysin, while gallic acid concentration was found to be significantly higher in oak honey. Using suspect screening workflow, 12 additional bioactive compounds were identified and semi-quantified, achieving comprehensive metabolomic honey characterization. Lastly, by combining non-targeted screening with advanced chemometrics, it was possible to discriminate thyme from blossom honey and develop binary discriminatory models with high predictive power. In conclusion, a holistic approach to assessing the botanical origin of Greek honey is presented, highlighting the complementarity of the three applied metabolomic approaches.     

Monotonicity properties of harmonic maps into NPC spaces

In this paper, we study monotonicity properties of harmonic maps into general NPC spaces. In addition, we introduce the notion of Alexandrov tangent maps and state a criterion for uniqueness.     

The use of model probes for assessing in depth modifications induced during laser cleaning of modern paintings

The cleaning of over-paint layers is a usual requirement to be met in the conservation of modern paintings. In most cases, acrylics or other related compounds must be removed without affecting the original painting. The elucidation of the extent of any photochemical or structural modification induced to the substrate following laser irradiation is a crucial challenge for the broader implementation of such laser cleaning strategies into the conservation practice. To achieve this, a methodology based on the use of a sensitive photochemical and photomechanical model system is introduced. A probe consisting of a polymeric material (e.g., Paraloid B72) doped with aromatic photo-sensitizers (e.g., POPOP) of known photochemistry and coated with uniform acrylic layer effectively simulates the real case scenario. Following laser irradiation, a variety of spectroscopic techniques including single or multiphoton laser-induced fluorescence and third-harmonic generation are employed for the assessment of any photochemical and structural modification induced in the bulk material. Practical issues related to the laser parameters employed will be presented, and the potential for a more general applicability of this methodology in the laser cleaning of modern paintings will be discussed.     

A multicriteria decision support tool for modelling bank credit ratings

We introduce an application of the SMAA-Fuzzy-FlowSort approach to the case of modelling bank credit ratings. Its stochastic nature allows for imprecisions and uncertainty that naturally surround a decision-making exercise to be embedded into the proposed framework, whilst its output complements the ordinal nature of a crisp classification with cardinal information that shows the degree of membership to each rating category. Combined with the SMAA variant of GAIA that offers a visual of a bank’s judgmental analysis, both recent approaches provide a holistic multicriteria decision support tool in the hands of a credit analyst and enable a rich inferential procedure to be conducted. To illustrate the assets of this framework, we provide a case study evaluating the credit risk of 55 EU banks according to their financial fundamentals.

     

Interfacial Impregnation Chemistry in the Synthesis of Cobalt Catalysts Supported on Titania

The interfacial chemistry of the impregnation step involved in the synthesis of cobalt catalysts supported on titania was investigated with regard to the mode of interfacial deposition of the aqua complex [Co(H₂O)₆]²⁺ on the “titania/electrolyte solution” interface, the structure of the inner‐sphere complexes formed, and their relative interfacial concentrations. Several methodologies based on the application of deposition experiments and electrochemical techniques were used in conjunction with diffuse‐reflectance spectroscopy and EPR spectroscopy. These suggested the formation of mononuclear/oligonuclear inner‐sphere complexes on deposition of the [Co(H₂O)₆]²⁺ ions at the “titania/electrolyte solution” interface. The joint application of semiempirical quantum‐mechanical calculations, stereochemical considerations, and modeling of the deposition data revealed the exact structure of these complexes and allowed their relative concentrations at various Co^II surface concentrations to be determined. It was found that the interface speciation depends on the Co^II surface concentration. Mononuclear complexes are formed at the compact layer of the “titania/electrolyte solution” interface for low and medium Co^II surface concentrations. Formation of mono‐hydrolyzed Ti₂O–TiO and the dihydrolyzed TiO–TiO disubstituted configurations is very probable. In the first configuration one water ligand of the [Co(H₂O)₆]²⁺ ion is substituted by a bridging surface oxygen atom and another by a terminal surface oxygen atom. In the second configuration two water ligands of the [Co(H₂O)₆]²⁺ ion are substituted by two terminal surface oxygen atoms. Binuclear and trinuclear inner‐sphere complexes are formed, in addition to the mononuclear ones, at relatively high Co^II surface concentrations.     

The design of a continuous reactor for fluorous biphasic reactions under pressure and its use in alkene hydroformylation

A reactor, into which all reagents can be fed continuously and from which the reaction mixture can be continuously removed to a gravity separator, where product can be continuously removed and the catalyst phase recycled to the reactor, has been constructed and used for the hydroformylation of alkenes in fluorocarbon solvents.     

Mechanical behaviour of a poydimethylsiloxane elastomer after outdoor weathering in two different weathering locations

The degradation of maxillofacial prosthetic elastomers that occur during physical weathering is usually responsible for the replacement of the prosthesis. In this study the mechanical behaviour of a polydimethylsiloxane (PDMS) elastomer was investigated, after 1 year outdoor weathering in two different weathering locations in Greece (Thessaloniki, Athens). The hypothesis investigated was that irradiation time did not affect the measured properties. Specimens (Elastomer 42) were prepared according to manufacturer’s instructions and exposed to solar radiation for 1 year. Compression, tensile and nanoindentation tests were performed before and after the exposure. Compression and tensile data were also subjected to analysis of variance (ANOVA) and Tukey Post hoc tests at a level of α = .05. These properties were selected due to their clinical significance for fabrication and maintenance of a facial prosthesis. According to statistical analysis all the measured properties changed significantly after outdoor weathering. More specifically, most of the properties presented significant changes after six months of weathering. The observed changes also depended on the weathering locations. The hypothesis investigated was rejected. Material A became harder and the observed differences in the mechanical behaviour resulted from photo-degradation and hydrolysis that might occur due to weathering. The study also provides new information about maxillofacial prosthetics serviceability obtained from nanoindentation tests.     

Superrigidity of Hyperbolic Buildings

In this paper, we study the behavior of harmonic maps into complexes with branching differentiable manifold structure. The main examples of such target spaces are Euclidean and hyperbolic buildings. We show that a harmonic map from an irreducible symmetric space of noncompact type other than real or complex hyperbolic into these complexes are non-branching. As an application, we prove rank-one and higher-rank superrigidity for the isometry groups of a class of complexes which includes hyperbolic buildings as a special case.