Extraction of Trivalent Rare Earths and Minor Actinides from Nitric Acid with N,N,N’,N’-Tetradodecyldiglycolamide (TDdDGA) by Using Mixer-Settler Extractors in a Hot Cell

Single-stage batch experiments to reveal the extraction properties of N,N,N’,N’-tetradodecyldiglycolamide (TDdDGA) for Y, La, Eu, Nd, and Am in nitric acid were carried out. The distribution ratios of Y, Eu, Nd, and Am exceeded 10 when the nitric acid concentration was 1–2 mol/dm³ (M), and the distribution ratio of La was 5.5 when the nitric acid concentration was 2 M. A continuous counter-current experiment using 0.1 M TDdDGA diluted with n-dodecane was performed using mixer-settler extractors installed in a hot cell. Nitric acid with a concentration of 2.1 M containing minor actinides (MAs: Am and Cm), rare earths (REs: Y, La, Nd, and Eu), and other fission products (Sr, Cs, Zr, Mo, Ru, Rh, and Pd) was fed to the extractor. TDdDGA effectively extracted MAs and REs from the feed, while other fission products were barely extracted. The extracted MAs and REs were back-extracted by bringing them in contact with 0.02 M nitric acid, and they were collected as the MA–RE fraction. The results indicated that more than 98% of Am and Cm in the feed were recovered in the MA–RE fraction. The proportions of Y, La, Nd, and Eu in the MA–RE fraction were 94.0%, 99.9%, 99.9%, and 86.9%, respectively.     

Stabilizing effect of the cyclodextrins additive to spray-dried particles of curcumin/polyvinylpyrrolidone on the supersaturated state of curcumin

Although curcumin is considered to have various therapeutic effects, its use as a functional food or supplement is restricted owing to its low water solubility and bioavailability. To increase the solubility of curcumin in water, the use of polyvinylpyrrolidone (PVP) and vinylpyrrolidone-vinyl acetate copolymers with a pyrrolidone skeleton was noted to be promising. In particular, the bi-component formulations of curcumin/PVP prepared through spray drying exhibited an amorphous state in powder X-ray diffraction observations and temporally increased the apparent solubility of curcumin to over 5000 times that of untreated curcumin; nevertheless, after 24 h, the solubility decreased owing to the unstable supersaturated state of curcumin. The addition of α-cyclodextrin (α-CyD) in the bi-component curcumin/PVP formulation helped maintain the supersaturated state of curcumin, whereas the addition of β- and γ-CyD led to the collapse of the supersaturated state. The addition of α-CyD can likely help inhibit the nucleation and crystal growth of curcumin, through the interaction among the solubilized units of curcumin/PVP and α-CyD.     

Effects of supercritical carbon dioxide treatment on the morphology of poly(l‐lactide)

Synthetic l ‐lactide random copolymers can be employed as controlled release materials when prepared using supercritical carbon dioxide (scCO₂), since they are biodegradable via hydrolysis. To determine the effects of thermal properties on polymer performance following scCO₂ processing, three types of poly(l ‐lactide) having different properties were assessed. The T_m of one poly(l ‐lactide) sample (H‐100) was found to be approximately 170 °C over the processing pressure range from 8 to 18 MPa, while a second sample (H‐440) also showed a constant value of approximately 152 °C. In contrast, the poly(l ‐lactide) REVODE exhibited a T_m of 146 °C prior to processing but a higher value of 147 °C following treatment at 8 MPa. Unlike the H‐100 and H‐440, the T_m value of the REVODE tended to decrease with increasing pressure. The T_g values increased greatly under mild conditions of 8 MPa pressure and a temperature of 40 °C. In particular, the T_g values for the H‐440 and REVODE increased by 4 °C and 5 °C, respectively. All T_g values were lowest at 12 MPa and increased with increasing processing pressure, although the effect of processing temperature was minimal. The Χ_{c DSC} of the H‐100 was 18% initially but increased to 20% upon scCO₂ processing at 40 °C and 14 MPa, and showed further increases at higher processing temperatures. Although the relationship between processing temperature and Χ_{c DSC} values for the H‐440 showed the same trend as observed with the H‐100, a different trend was seen for the REVODE. The Χ_{c XRD} values obtained from the XRD analyses differed from the values generated by DSC analysis, and showed a maximum degree of crystallinity following processing at 80 °C both with and without scCO₂ treatment. ATR FT‐IR analyses identified peaks due to semicrystalline regions in poly(l ‐lactide) samples treated with scCO₂, even when applying low temperatures. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44006.     

Serum Amyloid A3 Promoter-Driven Luciferase Activity Enables Visualization of Diabetic Kidney Disease

The early detection of diabetic nephropathy (DN) in mice is necessary for the development of drugs and functional foods. The purpose of this study was to identify genes that are significantly upregulated in the early stage of DN progression and develop a novel model to non-invasively monitor disease progression within living animals using in vivo imaging technology. Streptozotocin (STZ) treatment has been widely used as a DN model; however, it also exhibits direct cytotoxicity to the kidneys. As it is important to distinguish between DN-related and STZ-induced nephropathy, in this study, we compared renal responses induced by the diabetic milieu with two types of STZ models: multiple low-dose STZ injections with a high-fat diet and two moderate-dose STZ injections to induce DN. We found 221 genes whose expression was significantly altered during DN development in both models and identified serum amyloid A3 (Saa3) as a candidate gene. Next, we applied the Saa3 promoter-driven luciferase reporter (Saa3-promoter luc mice) to these two STZ models and performed in vivo bioluminescent imaging to monitor the progression of renal pathology. In this study, to further exclude the possibility that the in vivo bioluminescence signal is related to renal cytotoxicity by STZ treatment, we injected insulin into Saa3-promoter luc mice and showed that insulin treatment could downregulate renal inflammatory responses with a decreased signal intensity of in vivo bioluminescence imaging. These results strongly suggest that Saa3 promoter activity is a potent non-invasive indicator that can be used to monitor DN progression and explore therapeutic agents and functional foods.     

Effects of fatty acid and emulsifier on the complex formation and in vitro digestibility of gelatinized potato starch

The effects of fatty acid, monoacylglycerol, and polyglycerol fatty acid ester with varying chain length in their acyl chains on the extent of complex formation (complex index) and in vitro enzymatic digestibility of gelatinized potato starch were investigated. The complex index increased with increase in the concentration of the ligands (fatty acid, monoacylglycerol, and polyglycerol fatty acid ester), with the plateau in the complex index value depending on the type of ligands. In comparison of complex index among fatty acid-samples, the complex index maximum increased as the chain length increased up to octanoic acid and then decreased. In comparison of complex index among fatty acid-, monoacylglycerol-, and polyglycerol fatty acid ester-samples at each acyl chain, the complex index maximum followed the order polyglycerol fatty acid ester > monoacylglycerol > fatty acid. Fatty acid, monoacylglycerol, and polyglycerol fatty acid ester with long acyl chains greatly reduced the enzymatic hydrolysis of starch. Polyglycerol fatty acid ester with palmitic acid chains was the strongest inhibitor of starch hydrolysis, suggesting that further complex formation may occur during the hydrolysis of gelatinized starch (enzyme-annealing).     

Effects of energetic heavy ion irradiation on the structure and magnetic properties of FeRh thin films

Fe-54at.%Rh thin films were irradiated with 10 MeV iodine ions at room temperature. Before and after the irradiations, the changes in magnetic properties and the lattice structure of the samples were studied by means of a SQUID magnetometer and X-ray diffraction. For the low fluence irradiation, the SQUID measurement at 20 K shows that the anti-ferromagnetic region of the thin film is changed into ferromagnetic region by the irradiation. As the film thickness is much smaller than the ion range, we can discuss the relationship between the density of energy deposited by ions and the change in magnetization quantitatively. For the high fluence irradiation, the magnetization of the film is strongly decreased by the irradiation, which can be explained as due to the change in lattice structure from B2 into A1 structure by the irradiation.     

On Robust Stability And Sensitivity Of Circadian Rhythms

We develop an approach to robustness analysis of circadian rhythms from the viewpoints of (local) robust stability of periodic trajectories and their period‐sensitivity, based on mathematical models. Our attention is directed to the core molecular model generating circadian rhythms in Drosophila, proposed by Goldbeter [1], for our approach to be illustrated. We consider two cases when the circadian rhythms are subjected to periodic forcing by light/dark (LD) cycles and when the circadian rhythms are under continuous darkness (DD). First, we propose conditions/algorithms for (local) robust stability, and show that the circadian rhythms generated by the core molecular model are (locally) robustly stable, in both LD and DD cases. Second, in DD case, we derive a formula of period sensitivity, and assess effects of (infinitesimal) parameter‐variations on the period of the circadian rhythms.     

Degradation of a Victorian brown coal in sub-critical water

Conversion characteristics of a Victorian brown coal in sub-critical water were investigated. Pulverized brown coal was heated up to 623 K in flowing sub-critical water pressurized at 25 MPa. The total conversion of the coal into extract and non-condensable gas reached over 70 wt%-daf, which was appreciably higher than the maximum conversion (50 wt%-daf) with a sub-critical non-hydrogen donor solvent, 1-methylnaphthalene (MN). Laser-ionization-desorption mass spectrometry showed that the sub-critical water extract was richer in lower-molecular-mass compounds than the sub-critical MN one. Thus, degradation of the coal occurred more extensively in sub-critical water than in MN. Along with the conversion in sub-critical water, both the total contents of hydrogen and phenolic hydroxyls in the whole products remained nearly unchanged. This suggests comparable and simultaneous formation and decomposition of hydroxyls through hydrolysis of ethers/esters and dehydration condensation between hydroxyls/carboxyls, respectively. For detecting the hydroxyl formation, the coal was first heated at 623 K under an inert gas atmosphere until the formation of water and the other volatiles was completed. Then, the heat-treated coal (LY-H) was exposed to flowing sub-critical water. As expected, the net formation of phenolic hydroxyls from LY-H was detected as 0.8 mmol-OH/g-LY-H while that of hydrogen as 2.3 mmol-H/g-LY-H. Approximately a half of the hydrogen gain was explained as phenolic hydroxyls gain, suggesting the importance of hydrolysis of esters and ethers that formed carboxyls and alcoholic hydroxyls as well as phenolic hydroxyls.