Double Yielding in a Styrene/Butadiene Star Block Copolymer

Summary: The morphology and tensile deformation behaviour of a highly asymmetric styrene/butadiene star block copolymer (polystyrene (PS) content = 74%) containing random PS‐co‐PB (polybutadiene) copolymer as a rubbery phase were investigated. The existence of double yielding, similar to that observed in some semicrystalline polymers, was detected in this nanostructured amorphous polymer. The observed phenomenon may be correlated with two different micromechanical processes taking place at the initial stage of deformation.

The stress‐strain curve of the star block copolymer prepared here (each curve represents a different method). The two yield points are clearly visible (labelled I and II).     

Simulation of a mixed-conducting membrane-based gas turbine power plant for CO<Subscript>2</Subscript> capture: system level analysis of operation stability and individual process unit degradation

A gas turbine power plant for CO₂ capture, based on oxygen-permeable membranes with mixed ionic-electronic conductivity, was analysed with respect to long-term stability by means of numerical simulation. Due to the attractive transport and physicochemical properties of mixed-conducting La₂NiO_4+δ, this nickelate was selected as a prototype membrane material for this application. Experiments showed very slow degradation of La₂NiO_4+δ membranes at oxygen chemical potentials close to atmospheric conditions, which are associated with kinetic demixing and other microstructure-related factors. Interaction with CO₂ in the intermediate temperature range also leads to lower oxygen permeation, whilst increasing oxygen pressure may cause partial phase decomposition and microstructural changes, thus again limiting the range of possible operation conditions. The relevant operational constraints were included in a detailed membrane-based gas turbine power plant model. The membrane performance degradation with time was approximated by a linear function with average rate of 3.3% per 1,000 operation hours. Furthermore, performance deterioration of the gas turbine compressor and turbine were also considered. Simulations revealed that the power plant is substantially affected by degradation of the ceramic membranes and turbomachinery components. The already rather small operating window was further narrowed when compared with a conventional gas turbine power plant. Two different designs of the membrane-based power plant were analysed: (1) with and (2) without additional combustors (afterburners) between the membrane reactor and the gas turbine. Afterburners increase thermal efficiency as well as power output, but also lead to non-negligible CO₂ emissions. In order to have a frame of comparison, results for a conventional gas turbine power plant with degradation of turbomachinery components are also presented. Simulations representing changes in ambient temperature and fuel composition as well as failure incidents were executed to analyse the susceptibility of the gas turbine power plant to external and internal changes.     

Microdroplet growth mechanism during water condensation on superhydrophobic surfaces

By promoting dropwise condensation of water, nanostructured superhydrophobic coatings have the potential to dramatically increase the heat transfer rate during this phase change process. As a consequence, these coatings may be a facile method of enhancing the efficiency of power generation and water desalination systems. However, the microdroplet growth mechanism on surfaces which evince superhydrophobic characteristics during condensation is not well understood. In this work, the sub-10 μm dynamics of droplet formation on nanostructured superhydrophobic surfaces are studied experimentally and theoretically. A quantitative model for droplet growth in the constant base (CB) area mode is developed. The model is validated using optimized environmental scanning electron microscopy (ESEM) imaging of microdroplet growth on a superhydrophobic surface consisting of immobilized alumina nanoparticles modified with a hydrophobic promoter. The optimized ESEM imaging procedure increases the image acquisition rate by a factor of 10-50 as compared to previous research. With the improved imaging temporal resolution, it is demonstrated that nucleating nanodroplets coalesce to create a wetted flat spot with a diameter of a few micrometers from which the microdroplet emerges in purely CB mode. After the droplet reaches a contact angle of 130-150°, its base diameter increases in a discrete steplike fashion. The droplet height does not change appreciably during this steplike base diameter increase, leading to a small decrease of the contact angle. Subsequently, the drop grows in CB mode until it again reaches the maximum contact angle and increases its base diameter in a steplike fashion. This microscopic stick-and-slip motion can occur up to four times prior to the droplet coalescence with neighboring drops. Lastly, the constant contact angle (CCA) and the CB growth models are used to show that modeling formation of a droplet with a 150° contact angle in the CCA mode rather than in the CB mode severely underpredicts both the drop formation time and the average heat transfer rate through the drop.     

Modulating Properties of Piroxicam,Meloxicam and Oxicam Analogues against Macrophage-Associated Chemokines in Colorectal Cancer

The mechanisms underlying the antineoplastic effects of oxicams have not been fully elucidated. We aimed to assess the effect of classic and novel oxicams on the expression/secretion of macrophage-associated chemokines (RTqPCR/Luminex xMAP) in colorectal adenocarcinoma cells, and on the expression of upstream the non-steroidal anti-inflammatory drug (NSAID)-activated genes NAG1, NFKBIA, MYD88, and RELA, as well as at the chemokine profiling in colorectal tumors. Meloxicam downregulated CCL4 9.9-fold, but otherwise the classic oxicams had a negligible/non-significant effect. Novel analogues with a thiazine ring substituted with arylpiperazine and benzoyl moieties significantly modulated chemokine expression to varying degree, upregulated NAG1 and NFKBIA, and downregulated MYD88. They inhibited CCL3 and CCL4, and their effect on CCL2 and CXCL2 depended on the dose and exposure. The propylene linker between thiazine and piperazine nitrogens and one arylpiperazine fluorine substituent characterized the most effective analogue. Only CCL19 and CXCL2 were not upregulated in tumors, nor was CXCL2 in tumor-adjacent tissue compared to normal mucosa. Compared to adjacent tissue, CCL4 and CXCL2 were upregulated, while CCL2, CCL8, and CCL19 were downregulated in tumors. Tumor CCL2 and CCL7 increased along with advancing T and CCL3, and CCL4 along with the N stage. The introduction of arylpiperazine and benzoyl moieties into the oxicam scaffold yields effective modulators of chemokine expression, which act by upregulating NAG1 and interfering with NF-κB signaling.     

Free Glycine Accelerates the Autoproteolytic Activation of Human Asparaginase

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Highlights? Increased expression of hASNase3 was observed in several tumors, but the relevance is unclear ? Cancer cells have increased glycolytic flux and thus have more glycine but less aspartate ? Glycine activates the asparaginase activity of hASNase3 by promoting self-cleavage ? Thus, glycine may act as a sensor that regulates cellular aspartate concentrations     

Reactions of Bromine Fluoride Dioxide,BrO2F,for the Generation of the Mixed‐Valent Bromine Oxygen Cations Br3O4+ and Br3O6+

A reliable synthesis of unstable and highly reactive BrO₂F is reported. This compound can be converted into BrO₂⁺SbF₆^?, BrO₂⁺AsF₆^?_, and BrO₂⁺AsF₆^??2 BrO₂F. The latter decomposes into mixed‐valent Br₃O₄?Br₂⁺AsF₆^? with five‐, three‐, one‐, and zero‐valent bromine. BrO₂⁺ H(SO₃CF₃)₂^? is formed with HSO₃CF₃. Excess BrO₂F yields mixed‐valent Br₃O₆⁺OSO₃CF₃^? with five‐ and three‐valent bromine. Reactions of BrO₂F and MoF₅ in SO₂ClF or CH₂ClF result in Cl₂BrO₆⁺Mo₃O₃F₁₃^?. The reaction of BrO₂F with (CF₃CO)₂O and NO₂ produces O₂Br‐O‐CO‐CF₃ and the known NO₂⁺Br(ONO₂)₂^?. All of these compounds are thermodynamically unstable.     

Synthesis of CuCorePtShell Nanoparticles as Model Structures for Core–Shell Electrocatalysts by Direct Platinum Electrodeposition on Copper

The synthesis of Cu(core)Pt(shell) model catalysts by the direct electrochemical deposition of Pt on Cu particles is presented. Cu particles with an average diameter of 200 nm have been deposited on glassy‐carbon electrodes by double pulse electrodeposition from a copper sulfate solution. Subsequent deposition from a platinum nitrate solution under potential control allows for a high selectivity of the Pt deposition towards Cu. Using a combination of cyclic voltammetry, XPS and sputtering, the structure of the generated particles has been analyzed and their core–shell configuration proven. It is shown that the electrocatalytic activity for the oxygen reduction is similar to that of other PtCu catalyst systems. The synthesized structures could allow for the analysis of structure–activity relations of core–shell catalysts on the way to the simple and controlled synthesis of supported Cu(core)Pt(shell) nanoparticles as oxygen reduction catalysts.     

Modification of the Cp′ ring in the ferrocifen precursor and its influence on the recognition by the estrogen receptor

A synthetic pathway giving access to diphenyl ethylene organometallic derivatives possessing the ferrocifen precursor skeleton modified in the Cp′ ring is described. It relies on reaction of the (η⁵-propionylcyclopentadienyl) (η⁶-benzene)iron(II) salt 7 with substituted cyclopentadienyl anions or their heteroanalogs followed by the McMurry coupling reaction with 4,4′-dihydroxybenzophenone. Using this approach pentamethylcyclopentadienyl and 3,4-dimethylphospholyl analogs of ferrocifen precursor (10 and 11) have been synthesized. Even with the presence of the bulky and containing phosphorus η⁵-ligands these compounds are still recognized by the two subtypes of estrogen receptor(ERα and ERβ).