Single atom hot-spots at Au-Pd nanoalloys for electrocatalytic H2O2 production

A novel strategy to direct the oxygen reduction reaction to preferentially produce H(2)O(2) is formulated and evaluated. The approach combines the inertness of Au nanoparticles toward oxidation, with the improved O(2) sticking probability of isolated transition metal "guest" atoms embedded in the Au "host". DFT modeling was employed to screen for the best alloy candidates. Modeling indicates that isolated alloying atoms of Pd, Pt, or Rh placed within the Au surface should enhance the H(2)O(2) production relative to pure Au. Consequently, Au(1-x)Pd(x) nanoalloys with variable Pd content supported on Vulcan XC-72 were prepared to investigate the predicted selectivity toward H(2)O(2) production for Au alloyed with Pd. It is demonstrated that increasing the Pd concentration to 8% leads to an increase of the electrocatalytic H(2)O(2) production selectivity up to nearly 95%, when the nanoparticles are placed in an environment compatible with that of a proton exchange membrane. Further increase of Pd content leads to a drop in H(2)O(2) selectivity, to below 10% for x = 0.5. It is proposed that the enhancement in H(2)O(2) selectivity is caused by the presence of individual surface Pd atoms surrounded by gold, whereas surface ensembles of contiguous Pd atoms support H(2)O formation. The results are discussed in the context of exergonic electrocatalytic H(2)O(2) synthesis in Polymer Electrolyte Fuel Cells for the simultaneous cogeneration of chemicals and electricity, the latter a credit to production costs.     

Molecular mechanisms of signalling specificity via phosphorelay pathways in Arabidopsis

Multistep phosphorelay (MSP) pathways mediate a wide spectrum of adaptive responses in plants, including hormonal and abiotic stress regulations. Recent genetic evidence suggests both partial redundancy and possible functional cross-talk on the one hand and a certain level of specificity on the other. Here, we discuss recent achievements improving our understanding of possible molecular mechanisms of specificity in MSP. We consider a certain evolutionary conservation of ancestral two-component signalling systems from bacteria in a process of molecular recognition that, as we have recently shown, could be applied also to a certain extent in the case of plant MSP. Furthermore, we discuss possible roles of kinase and phosphatase activities, kinetics of both these enzymatic reactions, and phosphorylation lifetime. We include also recent findings on the expression specificity of individual members of MSP pathways and, finally, based on our recent findings, we speculate about a possible role of magnesium in regulation of MSP pathways in plants. All these mechanisms could significantly influence specificity and signalling output of the MSP pathways.     

Phase transformation in shape memory alloys: a numerical approach for thermomechanical modeling via peridynamics

Meccanica - The work is devoted to the numerical aspects of the modeling tool elaborated to simulate the phenomenon of solid phase transformation in shape memory alloys. Particularly, a nonlocal...     

Assessing Similarity of Random sets via Skeletons

Methodology and Computing in Applied Probability - The paper concerns a method for assessing similarity of realisations of random sets based on a construction of their morphological skeletons and a...     

Electron spin polarisation in laser induced autoionisation

The electron spin polarisation in the strong laser light induced autoionisation is discussed in the simple model. It is shown that confluence of coherences manifests itself in the dependence of polarisation on the laser detuning as a field strength dependent resonance, which enables verification of the phenomenon by means of the spin polarisation measurement. The separation of the confluence of coherences point and the point at which the maximal slowing down of the ionisation process (population trapping) occurs is showed.     

Spektrophotometrische Untersuchungen von 5-Hydroxy-, 5-Amino- und 5-Anilino-11-methylbenzo(a)phenoxazonen-(9) und über deren Verwendung als acidobasische Indikatoren

Zusammenfassung Die Absorption im ultravioletten und sichtbaren Spektralgebiet sowie in Abhängigkeit vom p_H wurde bei den folgenden Benzo(a)phenoxazonfarbstoffen vermessen: 5-Anilino-11-methylbenzo(a)phenoxazon-(9) (I), 5-Amino-11-methylbenzo(a)phenoxazon-(9) (II) und 5-Hydroxy-11-methylbenzo(a)phenoxazon-(9) (III). Außerdem wurde deren schrittweise Protonosierung in konz. Schwefelsäure vermessen. In äthanolischem Medium lassen sich gegen alle drei Indikatoren starke Säuren und Basen, indirekt auch Ammoniak, gegen III auch Essigsäure titrieren. Die Resultate aller Titrationen wurden mit Methylorange, Kongorot und Phenolphthalein kontrolliert. Der relative Fehler gegenüber potentiometrisch ermittelten Werten hat ±1% nicht überschritten.

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Summary The absorption in the ultraviolet and visible spectral region as well as in dependence on p_H was measured in the case of the following benzo(a)-phenoxazone dyestuffs: 5-anilino-11-methylbenzo(a)phenoxazone-(9), (I); 5-amino-11-methylbenzo(a)phenoxazone-(9) (II); and 5-hydroxy-11-methyl-benzo(a)phenoxazone-(9) (III). In addition their stepwise protonation was measured in conc, sulfuric acid. Strong acids and bases can be titrated in the presence of all three indicators in ethanol solution, also ammonia indirectly in the presence of III; likewise acetic acid. The results of all titrations were checked with methyl orange, phenophthalein and Congo red. The relative error as compared with values determined potentiometrically did not exceed ±1%.

     

The first member of the eleven-vertex azadicarbaborane series, 1,6,9-NC2B8H13, and its N-alkyl derivatives

Reactions between closo-1,2-C(2)B(8)H(10) (1) and amines of general formulation R(1)R(2)NH (where R(1), R(2) = H, H; Me, H; t-Bu, H and Et, Et) resulted in a straightforward cluster expansion and formation of the 11-vertex arachno-azadicarbaboranes of the 1,1-R(1),R(2-)1,6,9-NC(2)B(8)H(11) (2) cluster constitution (where R(1), R(2) = H, H 2a; Me, H 2b; t-Bu, H 2c and Et, Et 2d) in yields 10-75%, depending on the nature of the amine used. The reactions are the first example of a direct closo to arachno transformation in the area of cluster-boron compounds. Compounds 2b and 2c were isolated in two isomeric forms anti- and syn- that differ in the positioning of the t-Bu substituent with respect to the bridging hydrogen site. Deprotonation of compounds 2 generally leads to removal of the bridging proton and formation of the [1,1-R(1),R(2-)1,6,9-NC(2)B(8)H(11)](-) (2-) anions that, in the case of the monoalkylated Me and t-Bu derivatives, adopt only an anti configuration. The structure of anti-2c was determined by X-ray diffraction analysis and the geometries of the parent compound and the corresponding syn and anti isomers were optimised at the RMP2/6-31G* level. The composition of all compounds is consistent with the results of mass spectrometry and multinuclear ((1)H and (11)B) spectroscopy complemented by two-dimensional [(11)B-(11)B]-COSY and (1)H{(11)B(selective)} NMR measurements. Experimental (11)B chemical shifts generally show acceptable agreement with theoretical values calculated by GIAO methods, in particular at GIAO-MP2/II, where possible.     

Gas chromatographic determination of the interconversion energy barrier for dimethyl-2,3-pentadienedioate enantiomers

The enantiomers of dimethyl-2,3-pentadienedioate undergo interconversion during gas chromatographic separation on 2,6-di-O-methyl-3-O-pentyl-beta-, 2,6-di-O-methyl-3-O-pentyl-gamma-, and 2,3-di-O-methyl-6-O-tert butyldimethylsilyl-beta-CD chiral stationary phases. The combination of a deconvolution method with an internal standard was used to determine individual enantiomer peak areas and retention times needed for the calculation of the interconversion rate constants and the energy barrier for dimethyl-2,3-pentadienedioate enantiomers. The kinetic and thermodynamic data obtained for the interconversion data (rate constants, energy barriers, enthalpies, and entropies) were in good agreement with the published data (Trapp, O., Schurig, V., Chirality 2002, 14, 465-470) using permethylated-beta-CD (Chirasil-beta-Dex).     

Size determination of Acipenser ruthenus spermatozoa in different types of electron microscopy

In this study three types of scanning electron microscopes were used for the size determination of spermatozoa of sterlet Acipenser ruthenus – high vacuum scanning electron microscope (SEM, JEOL 6300), environmental scanning electron microscope (ESEM, Quanta 200 FEG), field emission scanning electron microscope (FESEM, JEOL 7401F) with cryoattachment Alto 2500 (Gatan) and transmission electron microscope (TEM, JEOL 1010). The use of particular microscopes was tied with different specimen preparation techniques. The aim of this study was to evaluate to what degree the type of used electron microscope can influence the size of different parts of spermatozoa. For high vacuum SEM the specimen was prepared using two slightly different procedures. After chemical fixation with 2.5% glutaraldehyde in 0.1 M phosphate buffer and post-fixation by 1% osmium tetroxide, the specimen was dehydrated by acetone series and dried either by critical point method or by means of t-butylalcohol. For ESEM fresh, unfixed material was used, which was dropped on microscopic copper grids. In FESEM working in cryo-mode the specimen was observed in a frozen state. Ultrathin sections from chemically fixed and Epon embedded specimens were prepared for TEM observation. Distinct parts of sterlet spermatozoa were measured in each microscope and the data obtained was statistically processed. Results confirmed that the classical chemical procedure of specimen preparation for SEM including critical point drying method led to a significant contraction of all measured values, which could deviate up to 30% in comparison with values measured on the fresh chemically untreated specimen in ESEM. Surprisingly sperm dimensions determinated on ultrathin sections by TEM are comparable with values obtained in ESEM or FESEM.     

The lattice of congruence lattices of algebras on a finite set

The congruence lattices of all algebras defined on a fixed finite set A ordered by inclusion form a finite atomistic lattice \(\mathcal {E}\). We describe the atoms and coatoms. Each meet-irreducible element of \(\mathcal {E}\) being determined by a single unary mapping on A, we characterize completely those which are determined by a permutation or by an acyclic mapping on the set A. Using these characterisations we deduce several properties of the lattice \(\mathcal {E}\); in particular, we prove that \(\mathcal {E}\) is tolerance-simple whenever \(|A|\ge 4\).