SciCombinator

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Concept: Chemical equilibrium

167

Background and the purpose of the study: Rizatriptan is used effectively for the treatment of migraine headache. In this study, a simple, rapid and low cost spectrophotometric method based on the ion-pair complexation is proposed for the determination of rizatriptan in raw material and dosage forms. METHODS: The ion-pair complexation using bromocresol green as reagent was performed in a buffer solution and the absorbance was measured by a spectrophotometer. The ion-pair formation conditions were optimized and the accuracy and precision of the method were calculated.Results and major conclusion: Best results were achieved by using 6 ml of the bromocresol green reagent in the presence of phosphate buffer (pH 3.0). The stoichiometry of the resulted complex was 1:1. The within-day and between-day precision values were lower than 2.9 and 1.8 percent for the calibration range of 0.5–50 and 10–100 mug/ml, respectively. The proposed method was successfully used for the determination of rizatriptan in dosage forms without any interference.

Concepts: Spectroscopy, Chemical equilibrium, PH, Phosphate buffered saline, Accuracy and precision, Buffer solution, Equilibrium chemistry, Spectrophotometry

156

A study was undertaken to determine activity concentrations for (134)Caesium, (137)Caesium and (210)Polonium in New Zealand seafood, and establish if activity concentrations varied with respect to species/ecological niche and coastal region. Thirty seafood samples were obtained from six fishing regions of New Zealand along with a further six samples of two commercially important species (hoki and arrow squid) with well-defined fisheries. (134)Caesium was not detected in any sample. (137)Caesium was detected in 47% of samples, predominantly in pelagic fish species, with most activities at a trace level. Detections of (137)Caesium were evenly distributed across all regions. Activity concentrations were consistent with those expected from the oceanic inventory representing residual fallout from global nuclear testing. (210)Polonium was detected above the minimum detectable concentration in 33 (92%) of the analysed samples. Molluscs displayed significantly elevated activity concentrations relative to all other species groups. No significant regional variation in activity concentrations were determined. Two dose assessment models for high seafood consumers were undertaken. Dose contribution from (137)Caesium was minimal and far below the dose exemption limit of 1 mSv/year. Exposure to (210)Polonium was significant in high seafood consumers at 0.44-0.77 mSv/year (5th-95th percentile). (137)Caesium is concluded to be a valuable sentinel radionuclide for monitoring anthropogenic releases, such as global fallout and reactor releases, in the marine environment. (210)Polonium is of importance as a natural radionuclide sentinel due to its high contribution to dietary committed dose in seafood consumers.

Concepts: Species, Fish, Concentration, Chemical equilibrium, New Zealand, Radioactive contamination, Region, Pelagic fish

148

This study is dedicated to the environmental monitoring of radionuclides released in the course of the Fukushima nuclear accident. The activity concentrations of β(-) -emitting (90)Sr and β(-)/γ-emitting (134)Cs and (137)Cs from several hot spots in Japan were determined in soil and vegetation samples. The (90)Sr contamination levels of the samples were relatively low and did not exceed the Bq⋅g(-1) range. They were up four orders of magnitude lower than the respective (137)Cs levels. This study, therefore, experimentally confirms previous predictions indicating a low release of (90)Sr from the Fukushima reactors, due to its low volatility. The radiocesium contamination could be clearly attributed to the Fukushima nuclear accident via its activity ratio fingerprint ((134)Cs/(137)Cs). Although the correlation between (90)Sr and (137)Cs is relatively weak, the data set suggests an intrinsic coexistence of both radionuclides in the contaminations caused by the Fukushima nuclear accident. This observation is of great importance not only for remediation campaigns but also for the current food monitoring campaigns, which currently rely on the assumption that the activity concentrations of β(-)-emitting (90)Sr (which is relatively laborious to determine) is not higher than 10% of the level of γ-emitting (137)Cs (which can be measured quickly). This assumption could be confirmed for the samples investigated herein.

Concepts: Chernobyl disaster, Nuclear medicine, Concentration, Chemical equilibrium, HotSpot, Radioactive contamination, Lists of nuclear disasters and radioactive incidents, Assumption of Mary

29

Industrially, the artificial fixation of atmospheric nitrogen to ammonia is carried out using the Haber-Bosch process, but this process requires high temperatures and pressures, and consumes more than 1% of the world’s power production. Therefore the search is on for a more environmentally benign process that occurs under milder conditions. Here, we report that a Ru-loaded electride [Ca(24)Al(28)O(64)](4+)(e(-))(4) (Ru/C12A7:e(-)), which has high electron-donating power and chemical stability, works as an efficient catalyst for ammonia synthesis. Highly efficient ammonia synthesis is achieved with a catalytic activity that is an order of magnitude greater than those of other previously reported Ru-loaded catalysts and with almost half the reaction activation energy. Kinetic analysis with infrared spectroscopy reveals that C12A7:e(-) markedly enhances N(2) dissociation on Ru by the back donation of electrons and that the poisoning of ruthenium surfaces by hydrogen adatoms can be suppressed effectively because of the ability of C12A7:e(-) to store hydrogen reversibly.

Concepts: Ammonia, Metabolism, Chemical reaction, Hydrogen, Catalysis, Nitrogen, Haber process, Chemical equilibrium

28

Novel ruthenium(ii) complexes were obtained as a result of a stoichiometric reaction of Grubbs' benzylidene second generation catalysts with 3-nitropropene. These stable complexes, formally ruthenaisoxazole N-oxide derivatives, display activity in both metathesis and non-metathetic processes such as cycloisomerisation, isomerisation and transfer hydrogenation.

Concepts: Chemical reaction, Hydrogen, Catalysis, Hydrogenation, Chemical equilibrium, Olefin metathesis, Alkene, Richard R. Schrock

27

A chemical mixture that continually absorbs work from its environment may exhibit steady-state chemical concentrations that deviate from their equilibrium values. Such behavior is particularly interesting in a scenario where the environmental work sources are relatively difficult to access, so that only the proper orchestration of many distinct catalytic actors can power the dissipative flux required to maintain a stable, far-from-equilibrium steady state. In this article, we study the dynamics of an in silico chemical network with random connectivity in an environment that makes strong thermodynamic forcing available only to rare combinations of chemical concentrations. We find that the long-time dynamics of such systems are biased toward states that exhibit a fine-tuned extremization of environmental forcing.

Concepts: Energy, Chemical reaction, Chemistry, Chemical equilibrium, Thermodynamics, Systems theory, Steady state, Dynamic equilibrium

27

Elicitation of plant in vitro cultures represents a biotechnological tool to improve the production of secondary metabolites. In this study, the effect of AgNO3 and CdCl2 on the sanguinarine production by the suspension culture of Eschscholtzia californica CHAM. was investigated. Elicitors were added to the cultures at the 14th day of subcultivation and their effect on the sanguinarine production was evaluated after a 48 h exposure. AgNO3 at the concentration of 0.075 mmol.l-1 and CdCl2 at the concentration of 4 mmol.l-1 induced a ca. 5.2- and 5.6-multiple increase in sanguinarine synthesis, respectively. This amount represents probably the maximal production, because a further increase in the elicitors concentrations did not increase sanguinarine production. Both abiotic elicitors induced a polyphenol oxidase specific activity increase. Polyphenol oxidase is probably involved in the biosynthesis of sanguinarine at the level of dopamine formation. Dopamine is a precursor of (S)-norcoclaurine, the first intermediate with the benzylisoquinoline structure. Keywords: Eschscholtzia californica CHAM. suspension cultures abiotic elicitation sanguinarine polyphenol oxidase.

Concepts: Metabolism, Concentration, Chemical equilibrium, Culture, In vitro, Solution, Polyphenol, Polyphenol oxidase

27

OTUB1 is a Lys48-specific deubiquitinating enzyme that forms a complex in vivo with E2 ubiquitin (Ub)-conjugating enzymes including UBC13 and UBCH5. OTUB1 binds E2~Ub thioester intermediates and prevents ubiquitin transfer, thereby noncatalytically inhibiting accumulation of polyubiquitin. We report here that a second role of OTUB1-E2 interactions is to stimulate OTUB1 cleavage of Lys48 polyubiquitin. This stimulation is regulated by the ratio of charged to uncharged E2 and by the concentration of Lys48-linked polyubiquitin and free ubiquitin. Structural and biochemical studies of human and worm OTUB1 and UBCH5B show that the E2 enzyme stimulates binding of the Lys48 polyubiquitin substrate by stabilizing folding of the OTUB1 N-terminal ubiquitin-binding helix. Our results suggest that OTUB1-E2 complexes in the cell are poised to regulate polyubiquitin chain elongation or degradation in response to changing levels of E2 charging and available free ubiquitin.

Concepts: Protein, Cell, Enzyme, Glucose, Enzyme substrate, Product, Chemical equilibrium, Ratio

27

We have developed heterogeneous polymer-incarcerated nickel nanoparticles, which catalyzed cross-coupling reactions. The matrix structure of these catalysts incorporates both N-heterocycle carbenes (NHCs) as ligands and nickel nanoparticles, thanks to a new design of cross-linking agents in polymer supports. These embedded NHCs were detected by Field Gradient Swollen-Resin Magic Angle Spinning (FGSR-MAS) NMR analysis. They were successfully applied to Corriu-Kumada-Tamao reactions with a broad substrate scope and could be recovered and reused several times without loss of activity.

Concepts: Enzyme, Chemical reaction, Hydrogen, Nuclear magnetic resonance, Chemical equilibrium, The Matrix, Magic angle spinning, Magic angle

27

Thin porous alumina sheets have been synthesized using a lysine-assisted hydrothermal approach resulting in an extraordinary catalyst support that can stabilize Au nanoparticles at annealing temperatures up to 900 °C. Remarkably, the unique architecture of such an alumina with thin sheets (the average thickness ~15 nm and length 680 nm) and rough surface is beneficial to prevent gold nanoparticles from sintering. HRTEM observations clearly showed that the epitaxial growth between Au nanoparticles and alumina support was due to strong interfacial interactions, further explaining the high sinter-stability of the obtained Au/Al2O3 catalyst. Consequently, despite calcination at 700 oC, the catalyst maintains its gold nanoparticles of size predominantly 20.8 nm. Surprisingly, catalyst annealed at 900 oC retained the highly dispersed small gold nanoparticles. It was also observed that a few gold particles (625 nm) were encapsulated by an alumina layer (thickness less than 1 nm) to minimize the surface energy, revealing a surface restructuring of the gold/support interface. As a typical and size-dependent reaction, CO oxidation is used to evaluate the performance of Au/Al2O3 catalysts. The results obtained demonstrated Au/Al2O3 catalyst calcined at 700 oC exhibited excellent activity with a complete CO conversion at ~30 oC (T100%=30 oC), and even after calcination at 900 °C, the catalyst still achieved its T50% at 158 °C. In sharp contrast, Au catalyst prepared using conventional alumina support shows almost no activity under the same preparation and catalytic test conditions.

Concepts: Nanoparticle, Chemical reaction, Hydrogen, Catalysis, Chemical equilibrium, Adsorption, Gold, Colloidal gold