Sputtered tungsten-based ternary and quaternary layers for nanocrystalline diamond deposition

Many of today's demanding applications require thin-film coatings with high hardness, toughness, and thermal stability. In many cases, coating thickness in the range 2-20 microm and low surface roughness are required. Diamond films meet many of the stated requirements, but their crystalline nature leads to a high surface roughness. Nanocrystalline diamond offers a smoother surface, but significant surface modification of the substrate is necessary for successful nanocrystalline diamond deposition and adhesion. A hybrid hard and tough material may be required for either the desired applications, or as a basis for nanocrystalline diamond film growth. One possibility is a composite system based on carbides or nitrides. Many binary carbides and nitrides offer one or more mentioned properties. By combining these binary compounds in a ternary or quaternary nanocrystalline system, we can tailor the material for a desired combination of properties. Here, we describe the results on the structural and mechanical properties of the coating systems composed of tungsten-chromium-carbide and/or nitride. These WC-Cr-(N) coatings are deposited using magnetron sputtering. The growth of adherent nanocrystalline diamond films by microwave plasma chemical vapor deposition has been demonstrated on these coatings. The WC-Cr-(N) and WC-Cr-(N)-NCD coatings are characterized with atomic force microscopy and SEM, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, and nanoindentation.     

Ruthenium‐Catalyzed One‐Pot Tandem Isomerization–Transfer Hydrogenation Reactions of γ‐Trifluoromethylated Allylic Alcohols and β‐Trifluoromethylated Enones

The ruthenium–2‐propanol combination was found to transform γ‐trifluoromethylated allylic alcohols and β‐trifluoromethylated enones into the corresponding saturated alcohols in excellent yields via a one‐pot tandem process involving isomerization and transfer hydrogenation(s). High stereospecificity was demonstrated and evidence for two mechanistic pathways is provided. The method was applied to a rapid synthesis of trifluoromethylated citronellol.     

Charge‐recombination processes in oligomer‐ and polymer‐based light‐emitting diodes: A molecular picture

Abstract— An overview of our recent work on the mechanisms of singlet and triplet exciton formation in electroluminescent π‐conjugated materials will be presented. According to simple spin statistics, only one‐fourth of the excitons are formed as singlets. However, deviations from that statistics can occur if the initially formed triplet charge‐transfer (CT) excited states are amenable to intersystem crossing or dissociation. Although the electronic couplings between the CT states and the neutral exciton states are expected to be largest for the lowest singlet and triplet excitons (S¹ and T¹, respectively), the possibility for direct recombination into T¹ is always very small due to the large exchange energy. In small molecules, spin statistics is expected to be observed because both singlet and triplet exciton formations proceed via higher‐lying S_n/T_n states with similar electronic couplings and fast formation rates. In extended conjugated chains, however, that the ¹CT → S¹ pathway is faster while the ³CT → ^Tn channels become much slower, opening the route to intersystem crossing or dissociation among the ³CT states.     

Impact of toxic cyanobacteria on gastropods and microcystin accumulation in a eutrophic lake (Grand-Lieu, France) with special reference to Physa (= Physella) acuta

Hepatotoxic microcystins (MCs) produced by cyanobacteria are known to accumulate in gastropods following grazing of toxic cyanobacteria and/or absorption of MCs dissolved in water, with adverse effects on life history traits demonstrated in the laboratory. In the field, such effects may vary depending on species, according to their relative sensitivity and ecology. The aims of this study were to i) establish how various intensities of MC-producing cyanobacteria proliferations alter the structure of gastropod community and ii) compare MC tissue concentration in gastropods in the field with those obtained in our previous laboratory experiments on the prosobranch Potamopyrgus antipodarum and the pulmonate Lymnaea stagnalis. We explored these questions through a one-year field study at three stations at Grand-Lieu Lake (France) affected by different intensities of cyanobacteria proliferations. A survey of the community structure and MC content of both cyanobacteria and gastropods was associated with a caging experiment involving P. antipodarum and L. stagnalis. In total, 2592 gastropods belonging to 7 prosobranch and 16 pulmonate species were collected. However, distribution among the stations was unequal with 62% vs 2% of gastropods sampled respectively at the stations with the lowest vs highest concentrations of MC. Irrespective of the station, pulmonates were always more diverse, more abundant and occurred at higher frequencies than prosobranchs. Only the pulmonate Physa acuta occurred at all stations, with abundance and MC tissue concentration (≤ 4.32 µg g DW^− 1) depending on the degrees of MC-producing cyanobacteria proliferations in the stations; therefore, P. acuta is proposed as a potential sentinel species. The caging experiment demonstrated a higher MC accumulation in L. stagnalis (≤ 0.36 µg g DW^− 1 for 71% of individuals) than in P. antipodarum (≤ 0.02 µg g DW^− 1 for 12%), corroborating previous laboratory observations. Results are discussed in terms of differential gastropod sensitivity and MC transfer through the food web.     

A Multi-Disciplinary Contribution to the Provenance Determination of Ancient Greek and Roman Marble Artifacts

The problem of determining the provenance of the white marble used for antique artifacts has been tackled in different ways. During the past decade it became clear that a multimethod approach is required to solve the problem. In addition, reliable reference material, i.e., samples collected at the ancient quarry sites in an archaeologically and geologically justified manner, turned out to be a prerequisite for reliable provenance determination. A multimethod approach based on petrography, stable isotope analysis of O and C, and trace element analysis yields complementary information. These methods were applied to the same set of 225 quarry samples. When processed with powerful statistical methods, the data thus obtained allowed all major types of marble used in antiquity to be distinguished. Thus, most problems concerning the provenance of artifacts can be solved. This approach was successfully applied to the provenance determination of about 75 artifacts from different museums in Europe and the USA.     

Effect of pre rigor stretching on beef tenderness development

The objective of this study was to determine effects of pre rigor stretching on beef tenderness development. Beef loins (M. longissimus dorsi; n=24) were assigned to either stretching or non-stretching treatments and aged for 14days at -1.5°C. Sarcomere length, shear force, water-holding capacity and proteolysis were determined for the loins at 1, 7 and 14days of ageing. Stretching increased the length of the loins by 33% resulting in a trend of increasing sarcomere length (P=0.19). However, no significant differences for shear force values, purge, drip and cooking losses between treatments were found. Shear force values decreased with ageing times (P<0.05). Western blot assay found that stretching did not affect the extent of desmin degradation. The findings from the present study suggest that pre rigor stretching with the current increase in length will not contribute to tenderness improvement of the beef loins.     

EDUCA: A web 2.0 authoring tool for developing adaptive and intelligent tutoring systems using a Kohonen network

This paper presents a Web 2.0 Learning Environment, for a systematic creation of adaptive and intelligent tutoring systems. Authoring contents is made by a community of users including teachers and students. The tutoring systems adapt the contents according to the best learning style using self-organizing maps (SOMs). The SOM was trained for classifying Felder–Silverman learning styles. The most important advantage of these unsupervised neural networks is that they do not require an external teacher for presenting a training set. The approach was implemented under an authoring tool that allows the production of personalized learning material to be used under collaborative and mobile learning environments. The tutoring systems together with the neural network can also be exported to mobile devices. We present different results to the approach working under the authoring tool.     

Selectivity of Supercritical CO<Subscript>2 </Subscript>in the Fractionation of Hake Liver Oil Ethyl Esters

The solubility of different ethyl esters derivatized from hake liver oil in supercritical carbon dioxide was studied. A selectivity factor was used to determine optimal conditions to fractionate the ethyl ester mixture. A strong influence of solvent pressure and temperature was observed within 8.63–18.04 MPa and 40–70 °C. The lowest total solubility of the ethyl ester mixture was obtained when using supercritical carbon dioxide at the lowest density (the lowest pressure and the highest temperatures value tested). The highest discrimination against long-chain polyunsaturated fatty acids (e.g. EPA and DHA) was also obtained at these above conditions. Conversely, higher solubility and lower selectivity were obtained when solvent density increased. Considering this inverse correlation between selectivity and solubility, a single-step batch-fractionation process was designed to increase the 22:6 ethyl ester content from an initial value of 17.5% in the starting material to 55% in the final extract.