Optimized Biocatalytic Synthesis of 2-Selenopyrimidine Nucleosides by Transglycosylation**

Selenium-modified nucleosides are powerful tools to study the structure and function of nucleic acids and their protein interactions. The widespread application of 2-selenopyrimidine nucleosides is currently limited by low yields in established synthetic routes. Herein, we describe the optimization of the synthesis of 2-Se-uridine and 2-Se-thymidine derivatives by thermostable nucleoside phosphorylases in transglycosylation reactions using natural uridine or thymidine as sugar donors. Reactions were performed at 60 or 80 °C and at pH 9 under hypoxic conditions to improve the solubility and stability of the 2-Se-nucleobases in aqueous media. To optimize the conversion, the reaction equilibria in analytical transglycosylation reactions were studied. The equilibrium constants of phosphorolysis of the 2-Se-pyrimidines were between 5 and 10, and therefore differ by an order of magnitude from the equilibrium constants of any other known case. Hence, the thermodynamic properties of the target nucleosides are inherently unfavorable, and this complicates their synthesis significantly. A tenfold excess of sugar donor was needed to achieve 40−48 % conversion to the target nucleoside. Scale-up of the optimized conditions provided four Se-containing nucleosides in 6–40 % isolated yield, which compares favorably to established chemical routes.     

Noninvasive assessment of hepatobiliary and renal elimination of cysteinyl leukotrienes by positron emission tomography

N-Acetyl-leukotriene E4 has been identified as an endogenous, biologically less active cysteinyl leukotriene metabolite in rodents and humans. To evaluate the ratio of hepatobiliary to renal elimination of leukotrienes noninvasively by positron emission tomography (PET), we synthesized N-[11C]acetyl-leukotriene E4 by chemical N-acetylation of leukotriene E4. After the intravenous injection of N-[11C]acetyl-leukotriene E4 in normal rats and monkey, uptake by the liver and subsequent excretion into bile were largely responsible for its rapid elimination from blood. In the Cynomolgus monkey, renal excretion of the leukotriene into urine was of additional quantitative importance. Kinetic modeling indicated a mean transit time through the liver of 17 minutes and 34 minutes in rat and monkey, respectively; the corresponding hepatic excretion half-times amounted to 8.5 minutes and 16 minutes. In a mutant rat strain deficient in the hepatobiliary excretion of cysteinyl leukotrienes across the canalicular membrane, the apparent mean liver transit time was 54 minutes, and the hepatic excretion half-time was 29 minutes, indicating prolonged organ storage and metabolism. After transport from the liver back into the circulating blood of omega-oxidized and beta-oxidized metabolites of N-[11C]acetyl-leukotriene E4, renal excretion compensated for the impairment of hepatobiliary elimination in the transport mutant. Metabolite analyses in urine after intravenous injection of N-[3H]acetyl-leukotriene E4 indicated the extensive inactivation of N-acetyl-leukotriene E4 by beta-oxidation from the omega-end in the mutants. A similar shift from hepatobiliary to renal cysteinyl leukotriene elimination was monitored in rats with cholestasis due to bile duct obstruction.(ABSTRACT TRUNCATED AT 250 WORDS)     

Dynamic light scattering and ultrasonic investigations during the cure reaction of an epoxy resin

Brillouin scattering (BS), photon correlation spectroscopy (PCS), and ultrasonic (US) measurements were conducted to study the curing process of diglycidyl ether of bisphenol A with butane-1,4-diol at a curing temperature of 100°C. The experimental techniques probe the primary glass-rubber transition during the curing reaction. The primary relaxation time τ obtained from the BS and US velocity and absorption increases with curing time and hence the BS experiment measures τ at earlier stages of cure than the US experiment. The relaxation times at a different extent of reaction and for different measuring temperatures are consistent with BS, US, PCS, and DSC measurements and conform to a single reduced Vogel–Fulcher–Hesse–Tamann equation. Furthermore, the US experiments show evidence of secondary relaxations in the epoxy system.     

Influence of Molybdenum Silicide Additions on High-Temperature Oxidation Resistance of Silicon Nitride Materials

The influence of additions of molybdenum disilicide (MoSi₂) on the microstructure and the mechanical properties of a silicon nitride (Si₃N₄) material, with neodymium oxide (Nd₂O₃) and aluminum nitride (AIN) as sintering aids, was studied. The composites, containing 5, 10, and 17.6 wt% MoSi₂, were fabricated by hot pressing. All materials exhibited a similar phase composition, detected by X-ray diffractometry. Up to MoSi₂ additions of 10 wt%, mechanical properties such as strength, fracture toughness, or creep at 1400°C were not affected significantly, in comparison to that of monolithic Si₃N₄. The oxidation resistance of the composites, in terms of weight gain, degraded. After 1000 h of oxidation at 1400° and 1450°C in air, a greater weight gain (by a factor of approximately three) was obtained, in comparison to that of the material without MoSi₂. Nevertheless, after 1000 h of oxidation, the degradation in strength of the composites was considerably less severe than that of the material without MoSi₂. An additional layer was formed, caused by processes at the surface of the Si₃N₄ material, preventing the formation of pores, cracks, or glassy-phase-rich areas, which are common features of oxidation damage in Si₃N₄ materials. This surface layer, containing Mo₅Si₃ and silicon oxynitride (Si₂ON₂), was the result of reactions between MoSi₂, Si₃N₄, and the oxygen penetrating by diffusion into the material during the hightemperature treatment.     

Effect of steel microfibers on corrosion of steel reinforcing bars

Steel microfiber reinforcement was previously found to be successful in mitigating alkali silica reaction in concrete, an expansive phenomenon. The use of steel microfibers to mitigate rebar corrosion, another expansive reaction, was investigated. Mortar specimens with and without steel microfiber reinforcement were exposed to a corrosive environment. All specimens were prepared with water/cement ratios of both 0.40 and 0.55, cured for 28 days, and then submerged in aerated 3.5% NaCl solution. The corrosion behavior of the specimens was monitored via electrochemical measurements. Three types of electrochemical tests were performed: corrosion potential measurements, potentiodynamic polarization, and electrochemical impedance spectroscopy. Chloride concentration measurements and microscopic analysis were performed as well. The polarization curves, Tafel, and polarization resistance measurements indicate that the steel rebar in the microfiber-reinforced mortars are more resistant to corrosion than the rebar in the control mortars, despite higher chloride concentrations. Furthermore, the steel microfiber-reinforced cement based materials have a lower electrolytic resistance. This is not indicative of a higher corrosion rate, which would be the case if it had been observed in standard mortar specimens.     

Sustainability in Web server systems

The exponential growth of Internet during the last decade leads us to make more efforts in the researching and developing of sustainable Web servers in order to decrease the global energy demand. In this paper, we cover, as a first step, a proper review of the literature related to the energy efficiency research in Web server systems to depict the state of the art to plan further contributions as more research in sustainable Web systems. We also propose and implement an energy metric that permits to establish a relation between the Quality of Service (QoS) obtained by the system and the power it consumes.     

Data and models for metonymy resolution

We describe the first shared task for figurative language resolution, which was organised within SemEval-2007 and focused on metonymy. The paper motivates the linguistic principles of data sampling and annotation and shows the task’s feasibility via human agreement. The five participating systems mainly used supervised approaches exploiting a variety of features, of which grammatical relations proved to be the most useful. We compare the systems’ performance to automatic baselines as well as to a manually simulated approach based on selectional restriction violations, showing some limitations of this more traditional approach to metonymy recognition. The main problem supervised systems encountered is data sparseness, since metonymies in general tend to occur more rarely than literal uses. Also, within metonymies, the reading distribution is skewed towards a few frequent metonymy types. Future task developments should focus on addressing this issue.