Facile method to synthesize platelet SBA-15 silica with highly ordered large mesopores

Highly ordered mesoporous SBA-15 silica with large pore diameter of 18 nm (nominal BJH pore diameter ~22 nm) and short pore length (~500 nm) was synthesized using a micelle expander 1,3,5-triisopropylbenzene in the absence of ammonium fluoride by employing short initial stirring time at 17 °C followed by static aging at low temperature. Scanning and transmission electron microscopies revealed that the material comprised of platelet particles in which large mesopores were nearly flawlessly arranged within uniform domains up to 3 μm in size. The platelet SBA-15 had the (100) interplanar spacing of 17 nm, high surface area (~470 m(2) g(-1)) and large pore volume (~1.6 cm(3) g(-1)). The hydrothermal treatment at 130 °C for 2 days was employed to eliminate constrictions from the pore channels. The control experiment showed that a sample prepared with prolonged stirring had very similar mesoporous properties, but the particle size was smaller and the domains were irregular, proving that the static conditions facilitate the formation of SBA-15 with platelet particle morphology. The absence of ammonium fluoride was also critical in attaining the platelet particle shape.     

Low-dimensional compounds containing cyanido groups. XXI. Crystal structure, spectroscopic, thermal and magnetic properties of two polymorphous modifications of [Cu(men)2Pt(CN)4]n complex (men = N-methyl-1,2-diaminoethane)

Violet (1) and blue (2) polymorphous modifications of [Cu(men)₂Pt(CN)₄]_n (men = N-methyl-1,2-diaminoethane) have been prepared and investigated by IR and UV-vis spectroscopy, thermal analysis, measurement of magnetic data and X-ray structural analysis. Both modifications are formed by similar but differently packed zigzag chains, which consist of [Cu(men)₂]²⁺ moieties bridged by two trans arranged cyanido groups of [Pt(CN)₄]²⁻ units. The Cu(II) atoms in both structures are hexacoordinated by four nitrogen atoms in the equatorial plane from two molecules of bidentate men ligands with the average Cu-N(Me) and Cu-N(H₂) bond lengths of 2.046(8) and 2.008(8) Å, respectively, and by two nitrogen atoms from bridging cyanido groups in the axial positions at average distance of 2.50(7) Å. Broad nearly symmetric bands observed in the UV-vis spectra of 1 and 2 of ²B_1g → ²E_g transitions are consistent with a deformed octahedral coordination of the CuN₆ chromophoric groups. One and two ν(CN) absorption bands observed in the IR spectra of 1 and 2, respectively, are in agreement with different local symmetries of [Pt(CN)₄]²⁻ units and different Cu-N(cyanido) bond lengths in these polymorphs and are subject of discussion on the spectral-structural correlations in 1D compounds. The complexes are stable up to 238 °C when their two-stage thermal decompositions start and ending up with a mixture of CuO and metallic Pt as the most probable final thermal decomposition products. The temperature dependence of the magnetic susceptibility suggests the presence of a weak antiferromagnetic exchange coupling between Cu(II) atoms in 1, J/hc = −0.17 cm⁻¹ and in 2, J/hc = −1.3 cm⁻¹.     

A modular approach to aryl-C-ribonucleosides via the allylic substitution and ring-closing metathesis sequence. a stereocontrolled synthesis of all four α-/β- and D-/L-C-nucleoside stereoisomers

Iridium(I)-catalyzed allylation of the enantiopure monoprotected copper(I) alkoxide, generated from (S)-5a, with the enantiopure allylic carbonates (R)-9a,b has been developed as the key step in a new approach to C-nucleoside analogues. The anomeric center was thus constructed via a stereocontrolled formation of the C-O rather than C-C bond with retention of configuration. The resulting bisallyl ethers 15a,b (≥90% de and >99% ee) were converted into C-ribosides 29a,b via the Ru-catalyzed ring-closing metathesis, followed by a diastereoselective dihydroxylation catalyzed by OsO(4) or RuO(4) and deprotection. Variation of the absolute configuration of the starting segments 5a and 9a,b allowed a stereocontrolled synthesis of all four α/β-D/L-combinations.     

Congestion games with failures

We introduce a new class of games, congestion games with failures (CGFs), which allows for resource failures in congestion games. In a CGF, players share a common set of resources (service providers), where each service provider (SP) may fail with some known probability (that may be constant or depend on the congestion on the resource). For reliability reasons, a player may choose a subset of the SPs in order to try and perform his task. The cost of a player for utilizing any SP is a function of the total number of players using this SP. A main feature of this setting is that the cost for a player for successful completion of his task is the minimum of the costs of his successful attempts. We show that although CGFs do not, in general, admit a (generalized ordinal) potential function and the finite improvement property (and thus are not isomorphic to congestion games), they always possess a pure strategy Nash equilibrium. Moreover, every best reply dynamics converges to an equilibrium in any given CGF, and the SPs’ congestion experienced in different equilibria is (almost) unique. Furthermore, we provide an efficient procedure for computing a pure strategy equilibrium in CGFs and show that every best equilibrium (one minimizing the sum of the players’ disutilities) is semi-strong. Finally, for the subclass of symmetric CGFs we give a constructive characterization of best and worst equilibria.     

Absorption bleaching by stimulated emission in erbium-doped silicon-rich silicon nitride waveguides

Stimulated emission from sensitized erbium ions in silicon-rich silicon nitride is demonstrated by pump-probe measurements carried out in waveguides. A decrease in the photoinduced absorption of the probe at the wavelength of erbium emission is observed and is attributed to stimulated emission from erbium excited indirectly via localized states in the silicon nitride matrix.     

A contact angle and ToF-SIMS study of SAM-thiol interactions on polycrystalline gold

A process of chemical differentiation of neighboring Au features on a substrate (for biosensing applications) involves a step, where after electrochemical removal of a self-assembled monolayer (SAM) from one feature, another SAM is deposited onto it by incubation with a different thiol. During this incubation step, other undesorbed features are also exposed to this thiol which may lead to a partial SAM-thiol exhange, the extent of which is a function of time. Here, such surface reactions were followed on polystalline Au in both directions using contact angle measurements and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The thiols involved were dodecanethiol (DDT) which forms SAM promoting adsorption of proteins and 11-mercaptoundecyl)tri(ethylene glycol) (TPEG) whose SAM prevents such adsorption. The surface reactions in both directions cannot be described by a simple pseudo-first-order kinetics. It was found that while the DDT SAM interaction with a TPEG solution leads eventually to a total replacement, the reverse process, TPEG SAM interaction with DDT, leads to no noticeable exchange over the first 3 h and then asymptotically approaches ∼50% replacement.     

Negative Binomial Distribution and the multiplicity moments at the LHC

In this work we show that the latest LHC data on multiplicity moments C₂-C₅ are well described by a two-step model in the form of a convolution of the Poisson distribution with energy-dependent source function. For the source function we take Γ Negative Binomial Distribution. No unexpected behavior of Negative Binomial Distribution parameter k is found. We give also predictions for the higher energies of 10 and 14 TeV.     

Nucleobase modification as redox DNA labelling for electrochemical detection

Basic aspects of DNA electrochemistry with a strong focus on the use of modified nucleobases as redox probes for electrochemical bioanalysis are reviewed. Intrinsic electrochemical properties of nucleobases in combination with artificial redox-active nucleobase modifications are frequently applied in this field. Synthetic approaches (both chemical and enzymatic) to base-modified nucleic acids are briefly summarized and their applications in redox labelling are discussed. Finally, analytical applications including DNA hybridization, primer extension, PCR, SNP typing, DNA damage and DNA-protein interaction analysis are presented (critical review, 91 references).     

Influence of recycling and temperature on the swelling ability of paper

Hornification is the loss of fiber wall swelling which is detrimental to subsequent recycling resulting from drying. It is known that dried fibers lose their conformability and swelling capacity. The effect of recycling treatment on the swelling ability of hardwood bleached kraft pulp fibers was determined. Modelling paper recycling, sheets were recycled using heat treatment (23°C, 60°C, 100°C). The results were compared with those for natural fibers from bleached kraft pulp. Swelling kinetics of sheets was measured by a modified method monitoring interactions of pulp with water. Swelling ability decreased during the recycling in comparison with never-recycled pulp at all temperatures. Recycling of sheets caused only small changes in the cupri-ethylene-diamine viscosity, however, the water retention value decreased considerably.     

Comparative model studies of gastric toxicity of nonsteroidal anti-inflammatory drugs

A high percentage of people treated with a long-term nonsteroidal anti-inflammatory drug (NSAID) therapy suffer NSAID-induced gastrointestinal-tract-related side effects. A current hypothesis states that the side effects are related to the topical action of NSAID molecules on gastric mucus that lowers its resistance to luminal acid. The main lipids in human mucus are palmitoyloleoylphosphatidylcholine (POPC) and cholesterol (Chol). In this study, both X-ray diffraction and molecular dynamics (MD) simulation methods were employed to investigate the effects of selected NSAIDs in protonated and deprotonated states on the structural parameters of a POPC-Chol bilayer. The drugs were three commonly used NSAIDs with apparently different gastric toxicity: ketoprofen (KET), aspirin (ASP), and piroxicam (PXM). Both methods revealed that the effects of the NSAIDs on the POPC-Chol bilayer parameters were moderate and only slightly differentiated among the drugs. Much larger differences among the drugs were noticed in their interactions with interfacial water and Na(+) as well as with the polar groups of POPC and Chol, mainly via H-bonds. Of the three NSAIDs, KET interacted with POPC and water the most extensively, whereas ASP interacted with Chol and Na(+) more than did the other two. Interactions of PXM with POPC and Chol polar groups as well as with water and Na(+) were limited.