Electrical double layer in solid electrolytes—theory: oxide electrolytes

The surface structure model of ionic crystal and the equivalent circuit of electrical double layer on the interface of solid electrolyte/vacuum or solid electrolyte/blocking electrode is suggested, taking into account intrinsic disorder of surface layer. In terms of this model the expressions are obtained for surface capacity as a function of potential, temperature and defect concentrations in solid electrolyte.In oxide solid electrolytes from ZrO₂ doped by Y₂O₃, CaO, Yb₂O₃ on the liquid metal droplet (Ag, Sn and CuSn, AuSn, AuCu alloys) near parabolic dependence of double layer capacitance on potential has been established. The minimum capacitance increases exponentially with temperature and decreases in inverse proportion to charge carrier concentration. The minimum capacitance potential coincides within error limits with zero charge potential, which does not depend on temperature; its position is determined by the electrode nature and does not depend on the electrolyte composition. All of these peculiarities agree well with the theoretical conclusions.     

Switching Ion Binding Selectivity of Thiacalix[4]arene Monocrowns at Liquid–Liquid and 2D-Confined Interfaces

Understanding the interaction of ions with organic receptors in confined space is of fundamental importance and could advance nanoelectronics and sensor design. In this work, metal ion complexation of conformationally varied thiacalix[4]monocrowns bearing lower-rim hydroxy (type I), dodecyloxy (type II), or methoxy (type III) fragments was evaluated. At the liquid–liquid interface, alkylated thiacalixcrowns-5(6) selectively extract alkali metal ions according to the induced-fit concept, whereas crown-4 receptors were ineffective due to distortion of the crown-ether cavity, as predicted by quantum-chemical calculations. In type-I ligands, alkali-metal ion extraction by the solvent-accessible crown-ether cavity was prevented, which resulted in competitive Ag⁺ extraction by sulfide bridges. Surprisingly, amphiphilic type-I/II conjugates moderately extracted other metal ions, which was attributed to calixarene aggregation in salt aqueous phase and supported by dynamic light scattering measurements. Cation–monolayer interactions at the air–water interface were monitored by surface pressure/potential measurements and UV/visible reflection–absorption spectroscopy. Topology-varied selectivity was evidenced, towards Sr²⁺ (crown-4), K⁺ (crown-5), and Ag⁺ (crown-6) in type-I receptors and Na⁺ (crown-4), Ca²⁺ (crown-5), and Cs⁺ (crown-6) in type-II receptors. Nuclear magnetic resonance and electronic absorption spectroscopy revealed exocyclic coordination in type-I ligands and cation–π interactions in type-II ligands.     

Highly Oxygen-Permeable NiV<Subscript>2</Subscript>O<Subscript>6</Subscript>–25 wt % V<Subscript>2</Subscript>O<Subscript>5</Subscript> Molten-Oxide Membrane Material

A NiV₂O₆–25 wt % V₂O₅ molten-oxide material has been prepared and characterized, and its transport properties (electrical conductivity, oxygen ion transport number, and oxygen permeability) have been studied in the temperature range 680–700°C. The results demonstrate that the molten-oxide membrane material obtained possesses high selective oxygen permeability (KO₂ = (2.5–5.6) × 10^–10 mol/(cm s) in the range 680–740°C and \(\frac{{{j_{{O_2}}}}}{{{j_{{N_2}}}}}\) ~ 1500) and can be used in separators for the preparation of extrapure oxygen from air.     

Evaluation of a participatory ergonomic intervention process in kitchen work

We evaluated a participatory ergonomic intervention process applied in 59 municipal kitchens. In groups of three to five kitchens, the workers participated in eight workshops, and generated and evaluated solutions to optimize musculoskeletal load in their work. An ergonomist initiated and supported the process. By the end, 402 changes were implemented. Evaluative data were collected using research diaries, questionnaires, and focus group interviews. The intervention model proved feasible and the participatory approach was mostly experienced as motivating. The workers’ knowledge and awareness of ergonomics increased, which improved their ability to tackle ergonomic problems by themselves. The changes in ergonomics were perceived to decrease physical load and improve musculoskeletal health. As hindering factors for implementation, lack of time and motivation, and insufficient financial resources were mentioned. In addition, the workers expressed a wish for more support from the management, technical staff, and ergonomists.     

Unusual Cytochrome c552 from Thioalkalivibrio paradoxus: Solution NMR Structure and Interaction with Thiocyanate Dehydrogenase

The search of a putative physiological electron acceptor for thiocyanate dehydrogenase (TcDH) newly discovered in the thiocyanate-oxidizing bacteria Thioalkalivibrio paradoxus revealed an unusually large, single-heme cytochrome c (CytC552), which was co-purified with TcDH from the periplasm. Recombinant CytC552, produced in Escherichia coli as a mature protein without a signal peptide, has spectral properties similar to the endogenous protein and serves as an in vitro electron acceptor in the TcDH-catalyzed reaction. The CytC552 structure determined by NMR spectroscopy reveals significant differences compared to those of the typical class I bacterial cytochromes c: a high solvent accessible surface area for the heme group and so-called “intrinsically disordered” nature of the histidine-rich N- and C-terminal regions. Comparison of the signal splitting in the heteronuclear NMR spectra of oxidized, reduced, and TcDH-bound CytC552 reveals the heme axial methionine fluxionality. The TcDH binding site on the CytC552 surface was mapped using NMR chemical shift perturbations. Putative TcDH-CytC552 complexes were reconstructed by the information-driven docking approach and used for the analysis of effective electron transfer pathways. The best pathway includes the electron hopping through His528 and Tyr164 of TcDH, and His83 of CytC552 to the heme group in accordance with pH-dependence of TcDH activity with CytC552.     

Variation in work tasks in relation to pinch grip strength among middle-aged female dentists

Objectives

We aimed to investigate the relationship of task variation during dental work history with pinch grip strength among dentists.

Methods

We measured pinch grip strength among 295 female Finnish dentists aged 45–63 years. Variation in dental work tasks during work history was empirically defined by cluster analysis. Three clusters of task variation emerged: low (most work time in restoration treatment/endodontics), moderate (about 50% in the former and 50% in prosthodontics/periodontics/surgery), and high (variable tasks including administrative duties). Hand radiographs were examined for the presence of OA in the wrist and each joint of the 1–3rd fingers. Information on hand-loading leisure-time activities, and joint pain was obtained by questionnaire. Glove size was used as a proxy for hand size. BMI (kg/m2) was based on measured weight and self-reported height.

Results

Dentists with low variation of work task history had an increased risk of low pinch grip strength in the right hand (OR 2.3, 95% CI 1.2–4.3), but not in the left (1.13, 0.62–2.08), compared to dentists with high task variation, independent of age, hand size, hand-loading leisure-time activities, BMI and symptomatic hand OA.

Conclusion

The dentists with the most hand-loading tasks were at an increased risk of low pinch grip strength, independent of e.g. symptomatic hand OA. It is advisable among dentists to perform as diverse work tasks as possible to reduce the risk of decreased pinch grip strength.     

Growth and characterization of Yb doped garnet crystals for scintillator application

Several concentration of Yb-doped Lu₃Al₅O₁₂ (Yb:LuAG) and Lu₃Ga₅O₁₂ (Yb:LGG) single crystals were grown by the micro-pulling-down method. The crystals were seeded-grown in the 1 1 1 direction and transparent and crack free crystals were obtained. Photoluminescence spectra and decay kinetics of these crystals were studied. Charge transfer luminescence of Yb³⁺ was observed in both crystals. Mean decay time of about 25 ns at 90 K and strong thermal quenching at room temperature was measured for Yb 5%:LuAG. Radioluminescence intensity was compared to the standard BGO sample.     

Synthesis,Structure and Magnetic Properties of Mn2Tb2 Tetranuclear Complex with p-tert-Butylthiacalix[4]arene

A new tert-buthylthiacalix[4]arene-based tetranuclear 3d-4f metal complex with the Mn₂Tb₂ core has been synthesized and its molecular and crystal structures have been studied by X-ray diffraction. The complex geometry is similar to that of the earlier synthesized tert-buthylthiacalix[4]arene-based M₂Ln₂ complexes with M=Mn(II), Co(II), and Ln=Gd, Pr, Eu, but unlike those systems, it exhibits intricated cooperative low-temperature magnetic properties arising from the presence of intercluster interactions. At T<8.5 K the complex shows weak spin-canted ferromagnetism and field induced metamagnetic phase transition. The paramagnetic behavior observed at temperatures higher than 8.5 K is similar to that previously reported for the Mn₂Gd₂ complex, this being indicative of the existence of competitive ferro- and antiferromagnetic intracluster interactions.     

Calix[4]arene Polyamine Triazoles: Synthesis,Aggregation and DNA Binding

Artificial gene delivery systems are in great demand from both scientific and practical biomedical points of view. In this paper, we present the synthesis of a new click chemistry calix[4]arene precursor with free lower rim and new water-soluble calixarene triazoles with 12 amino-groups on the upper rim (one with free phenol hydroxyl groups and two another containing four butyl or tetradecyl fragments). Aggregation in the series of amino-triazole calixarenes of different lipophilicity (calixarene with free phenol hydroxyl groups or butyl and tetradecyl fragments on the lower rim) was studied using dynamic light scattering and fluorescent pyrene probe. It was found that calix[4]arene with a free lower rim, like alkyl-substituted butyl calix[4]arene, forms stable submicron aggregates 150–200 nm in size, while the more lipophilic tetradecyl –substituted calix[4]arene forms micellar aggregates19 nm in size. Using UV-Vis spectroscopy, fluorimetry and CD, it was shown that amino-triazole calix[4]arenes bind to calf thymus DNA by classical intercalation. According to DLS and TEM data, all studied macrocycles cause significant DNA compaction, forming stable nanoparticles 50–20 nm in size. Among all studied calix[4]arenes the most lipophilic tetradecyl one proved to be the best for both binding and compaction of DNA.