Thermodynamic assessment of systems of actinide or rare earth with Cd

A pyrometallurgical process is being developed for recycling nuclear reactor fuels. Thermodynamic information on multicomponent systems of actinides and rare earths (REs) with liquid Cd is very useful in the design of a process in which a liquid Cd electrode is used for the selective recovery of Pu and U, and a reductive extraction process using a molten salt/liquid Cd system for the recovery of minor actinides, such as Np, Pu, etc. A key issue in the design of these processes is a variation in solubility or activity of actinides or REs in multielement systems. In the present study, phase diagrams of U-Cd, Pu-Cd, Np-Cd, Y-Cd, La-Cd, Ce-Cd, Pr-Nd, Nd-Cd, and Gd-Cd were optimized by the CALPHAD method. For these systems, thermodynamic data, such as the activity of solutes in liquid Cd and the Gibbs energies of formation of the intermetallic compounds as well as the phase diagram data were available for the optimization. For optimization, the calculated primary results were entered into a database. Then, some ternary systems were preliminarily assessed through the use of the optimized data for the binary systems. Two extreme conditions were assumed: one condition was complete miscibility between the compounds that have the same mole ratio between solutes and Cd; the other condition was no solid solubility between the compounds. The results indicated the tendencies toward solubility and activity of actinides and REs in multielement systems.     

Nitrogen-15 Kinetic Isotope Effects in the Menschutkin-Type Reaction of Benzyl Benzenesulfonates with N,N-Dimethylanilines

Nitrogen-15 kinetic isotope effects were measured for the Menschutkin-type reaction of Z-substituted benzyl X-substituted benzenesulfonates with Y-substituted N,N-dimethylanilines (Eq. 1) in acetone at 35°C. The values of ¹⁴k/¹⁵k for six combinations of X, Y, and Z fell in the range of 1.002–1.004. These small and almost constant nitrogen isotope effects are in contrast to the large and extensively varying carbon-14 and small but distinctly changing α-tritium isotope effects observed for this reaction series. The results are discussed in connection with the reactivity–selectivity relationships.     

Aqueous humor dynamics in beagle dogs with caffeine-induced ocular hypertension

In order to investigate the possible mechanisms for caffeine-induced ocular hypertension, the intraocular pressure (IOP) and the outflow through the trabecular meshwork were measured in beagle dog eyes after dosing with intravenous caffeine (30 mg/kg) alone or in combination with the topical beta-blocker befunolol [applied as 100 microliters of a 1% (w/v) solution] which inhibits aqueous humor formation in the ciliary body. Intravenous injections of caffeine significantly increased the IOP at 0.25 and 1 hr after a single dose. The ocular hypertension recovered within 2 hr following dosing. Over time, there were no differences in the outflow between the caffeine and control groups. The instillation of befunolol lowered outflow and produced ocular hypotension. The levels of the IOP and outflow in dogs treated with caffeine and befunolol in combination were almost the same as those in dogs treated with befunolol alone. Single-dose and combination-dose studies demonstrate that intravenous caffeine increases the IOP in normal beagle dogs possibly by increasing aqueous humor formation and not by the inhibition of aqueous humor drainage through the trabecular meshwork.     

Characterization of elevated neutrophil-associated IgG in various autoimmune disorders: not anti-neutrophil autoantibodies, but possibly immune complexes, bind to neutrophils

Resistance to toxicants is a convenient model for investigating whether adaptive changes are associated with pleiotropic fitness costs. Despite the voluminous literature devoted to this subject, intraspecific comparisons among toxicant resistance genes are rare. We report here results on the pleiotropic effect on adult survival of Culex pipiens mutants involved in the same adaptation: the resistance to organophosphorus insecticides. This field study was performed in southern France where four resistance genes sequentially appeared and increased in frequency in response to intense insecticide control. By repeated sampling of overwintering females through winter, we analysed the impact of each of three resistance genes on adult survival. We showed that (i) the most recent gene seems to be of no disadvantage during winter, (ii) the oldest affects survival in some environmental conditions, and (iii) the third induces a constant, severe and dominant survival cost. Such variability is discussed in relation to the physiological changes involved in resistance.     

Alternate activity in the synergistic muscles during prolonged low-level contractions

The purpose of this study was to investigate the functional interrelationship between synergistic muscle activities during low-level fatiguing contractions. Six human subjects performed static and dynamic contractions at an ankle joint angle of 110 degrees plantar flexion and within the range of 90-110 degrees (anatomic position = 90 degrees) under constant load (10% maximal voluntary contraction) for 210 min. Surface electromyogram records from lateral gastrocnemius (LG), medial gastrocnemius (MG), and soleus (Sol) muscles showed high and silent activities alternately in the three muscles and a complementary and alternate activity between muscles in the time course. In the second half of all exercise times, the number of changes in activity increased significantly (P < 0.05) in each muscle. The ratios of active to silent periods of electromyogram activity were significantly higher (P < 0.05) in MG (4.5 +/- 2.2) and Sol (4.3 +/- 2.8) than in the LG (0.4 +/- 0.1), but no significant differences were observed between MG and Sol. These results suggest that the relative activation of synergistic motor pools are not constant during a low-level fatiguing task.     

PredNTS: Improved and Robust Prediction of Nitrotyrosine Sites by Integrating Multiple Sequence Features

Nitrotyrosine, which is generated by numerous reactive nitrogen species, is a type of protein post-translational modification. Identification of site-specific nitration modification on tyrosine is a prerequisite to understanding the molecular function of nitrated proteins. Thanks to the progress of machine learning, computational prediction can play a vital role before the biological experimentation. Herein, we developed a computational predictor PredNTS by integrating multiple sequence features including K-mer, composition of k-spaced amino acid pairs (CKSAAP), AAindex, and binary encoding schemes. The important features were selected by the recursive feature elimination approach using a random forest classifier. Finally, we linearly combined the successive random forest (RF) probability scores generated by the different, single encoding-employing RF models. The resultant PredNTS predictor achieved an area under a curve (AUC) of 0.910 using five-fold cross validation. It outperformed the existing predictors on a comprehensive and independent dataset. Furthermore, we investigated several machine learning algorithms to demonstrate the superiority of the employed RF algorithm. The PredNTS is a useful computational resource for the prediction of nitrotyrosine sites. The web-application with the curated datasets of the PredNTS is publicly available.     

Improvement of gas barrier property of polyolefins by diamond‐like carbon deposition and photografting polymerization

The gas barrier properties of isotactic polypropylene (iPP) and high‐density polyethylene (HDPE) are both significantly improved by diamond‐like carbon (DLC) deposition and photografting polymerization using acrylic acid (AA) monomers. In fact, the gas barrier properties can be highly improved just by DLC or by AA‐photografting polymerization. The improvement observed by AA‐photografting polymerization is more pronounced than that by DLC deposition in our general experimental condition. In more detail, the oxygen barrier property of DLC‐deposited and AA‐grafted iPP is considerably improved by ～10 times when compared with that of neat iPP. As for HDPE, the oxygen barrier property is enhanced by nearly six times through DLC deposition and photografting polymerization. By observing the surfaces, 30 nm layer of DLC and 1.0 μm of AA‐grafted layer are firmly constructed on the polyolefins, which should contribute to the enhancement of the oxygen barrier property. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Adsorptive Recovery of Palladium(II) and Platinum(IV) on the Chemically Modified-Microalgal Residue

A biomass waste of microalgae was chemically modified by immobilizing the functional group of polyethyleneimine to prepare a new type of adsorbent. The adsorption test revealed that this adsorbent exhibited remarkably high selectivity for Pd(II) and Pt(IV) over base metal ions in HCl solution. From the adsorption isotherm, its maximum adsorption capacity for Pd(II) and Pt(IV) was evaluated as 2.0 and 0.8 mmol/g, respectively. This adsorbent also exhibited high affinity and selectivity for Pd(II) and Pt(IV) even in the presence of high concentrations of base metals in actual leach liquor.     

Electrochemical oxidation of ethylene glycol on Pt-based catalysts in alkaline solutions and quantitative analysis of intermediate products

Electrocatalytic activities of Pt/C, Pt-Ru/C, and Pt-Ni/C for the oxidation of ethylene glycol in a basic solution are evaluated by cyclic voltammetry and quasi-steady state polarization. Based on the results of Tafel slopes from quasi-steady state polarization, the catalytic activities for ethylene glycol oxidation are in the order of Pt-Ru/C > Pt-Ni/C > Pt/C. The analysis of intermediate products for ethylene glycol oxidation by higher performance liquid chromatograph (HPLC) demonstrates that the degree of ethylene glycol oxidation is dependent on catalysts. Pt-Ru/C shows the highest current densities for ethylene glycol oxidation, but shows lower fuel utilization. On the other hand, Pt-Ni/C shows higher ability to cleavage C–C bonds, but is suffered from catalyst poisoning. To improve the tolerance for catalyst poisoning, we construct a novel Pt-Ni-SnO₂/C catalyst, compare its catalytic activities, and evaluate the intermediates. Pt-Ni-SnO₂/C shows superior catalytic activities for ethylene glycol oxidation, resulting in the highest degree of complete electro-oxidation of ethylene glycol to CO₂.     

Selective recovery of gold by simultaneous adsorption–reduction using microalgal residues generated from biofuel conversion processes

BACKGROUND: This research provides a new approach to the effective use of microalgal biomass waste generated by biofuel conversion processes. In this study, a novel adsorbent for Au(III) recovery was prepared by treating microalgal residues with concentrated sulfuric acid. RESULTS: The prepared adsorbent, crosslinked microalgae, exhibited high affinity and selectivity for Au(III) over other precious and base metal ions in a hydrochloric acid medium. From the adsorption isotherms, the maximum adsorption capacity of the crosslinked microalgae for Au(III) was estimated to be 3.25 mol kg^?1 (640 g kg^?1), which was about eight times higher than the adsorption capacity of the microalgal residue. Microphotographs, scanning electron microscopy, and X‐ray diffraction confirmed the formation of metallic Au, suggesting that a redox reaction had taken place between the adsorbent and Au(III) ions during adsorption. Comparison of Fourier‐transform infrared spectra before and after adsorption indicated that hydroxyl groups as well as ether oxygen atoms in the crosslinked microalgae participated in the Au(III) uptake mechanism. It also suggested that the reduction of Au(III) to Au(0) was facilitated by hydroxyl groups in the crosslinked microalgae. CONCLUSION: The results presented in this paper are very promising for the practical use of microalgal residues for the recovery of Au(III) because of good selectivity and favorable adsorption capacity for Au(III). Copyright © 2011 Society of Chemical Industry