Hydrothermal Synthesis and Formation Mechanisms of Lanthanum Tin Pyrochlore Oxide

Well-defined La₂Sn₂O₇ with a phase-pure pyrochlore structure was produced by hydrothermal synthesis at temperatures as low as 200°C. Production of phase-pure La₂Sn₂O₇ requires a pH above 10, and higher pH accelerates the crystallization process. The synthesis produced spherical particles of average particle size ∼0.59 μm (±0.12) and surface area ∼14.1 m²/g. SEM and TEM observation for morphologic evolution and kinetic analysis during crystallization indicated that La₂Sn₂O₇ formation probably proceeds via a two-step reaction. First a transient dissolution–precipitation occurs. Then the primary crystallites aggregate because of their colloidal instability, and heterocoagulation with the lanthanum hydrous oxide precursor particles also occurs. The sluggish reaction rate at the later stage of reaction is characterized by an in situ transformation, where the soluble tin species is diffused through the porous La₂Sn₂O₇ aggregates to react with entrapped lanthanum precursors.     

Separation of C6H6 and C6H12 from H2 using ionic liquid/PVDF composite membrane

Ionic liquid/polyvinylidene fluoride composite membrane was successfully prepared by impregnation method and used for the separation on organic chemical hydride process. The separation factors of C₆H₆/H₂ and C₆H₁₂/H₂ in the ternary mixture system were 7500 and 300, respectively. The ionic liquid membrane showed an excellent possibility as a technology of H₂ purification in the organic chemical hydride process by removing aromatic hydrocarbon and cycloalkane simultaneously from the ternary system. © 2015 American Institute of Chemical Engineers AIChE J, 62: 624–628, 2016     

Synthesis of thermoresponsive block and graft copolymers via the combination of living cationic polymerization and RAFT polymerization using a vinyl ether-type RAFT agent

A novel vinyl ether-type RAFT agent, benzyl 2-(vinyloxy)ethyl carbonotrithioate (BVCT) was synthesized for various block copolymers via the combination of living cationic polymerization of vinyl ethers and reversible addition−fragmentation chain transfer (RAFT) polymerization. The novel BVCT–trifluoroacetic acid adduct play an important role to produce well-defined block copolymers, which is both as a cationogen under EtAlCl₂ initiation system in the presence of ethyl acetate for living cationic polymerization and a RAFT agent for blocks by RAFT polymerization. The resulting polymer, poly(vinyl ether)s, by living cationic polymerization had a high number average α-end functionality (≥0.9) as determined by both ¹H NMR and MALDI-TOF-MS spectrometry. In addition, this poly(vinyl ether)s worked well as a macromolecular chain transfer agent for RAFT polymerization. The RAFT polymerization of radically polymerizable monomers was conducted in toluene using 2,2′-azobis(isobutyronitrile) at 70 °C. For example, a double thermoresponsive block copolymer (MOVE₆₁-b-NIPAM₁₅₀) consisting of 2-methoxyethyl vinyl ether (MOVE) and N-isopropylacrylamide (NIPAM) was prepared via the combination of living cationic polymerization and RAFT polymerization. The block copolymer reversibly formed and deformed micellar assemblies above the phase separation temperature (T_ps) of poly(NIPAM) block in water. This BVCT is not only functioned as an initiator, but also acted as a monomer. When BVCT was copolymerized with MOVE by living cationic polymerization, followed by graft copolymerization with NIPAM via RAFT polymerization, well-defined graft copolymers (MOVE_n-co-BVCT_m)-g-NIPAM_x (n = 62–73, m = 1–9, x = 19–214) were successfully obtained. However, no micelle formed in water above T_ps of poly(NIPAM) graft chain unlike the case of block copolymers.     

Runx1 Messenger RNA Delivered by Polyplex Nanomicelles Alleviate Spinal Disc Hydration Loss in a Rat Disc Degeneration Model

Vertebral disc degenerative disease (DDD) affects millions of people worldwide and is a critical factor leading to low back and neck pain and consequent disability. Currently, no strategy has addressed curing DDD from fundamental aspects, because the pathological mechanism leading to DDD is still controversial. One possible mechanism points to the homeostatic status of extracellular matrix (ECM) anabolism, and catabolism in the disc may play a vital role in the disease’s progression. If the damaged disc receives an abundant amount of cartilage, anabolic factors may stimulate the residual cells in the damaged disc to secrete the ECM and mitigate the degeneration process. To examine this hypothesis, a cartilage anabolic factor, Runx1, was expressed by mRNA through a sophisticated polyamine-based PEG-polyplex nanomicelle delivery system in the damaged disc in a rat model. The mRNA medicine and polyamine carrier have favorable safety characteristics and biocompatibility for regenerative medicine. The endocytosis of mRNA-loaded polyplex nanomicelles in vitro, mRNA delivery efficacy, hydration content, disc shrinkage, and ECM in the disc in vivo were also examined. The data revealed that the mRNA-loaded polyplex nanomicelle was promptly engulfed by cellular late endosome, then spread into the cytosol homogeneously at a rate of less than 20 min post-administration of the mRNA medicine. The mRNA expression persisted for at least 6-days post-injection in vivo. Furthermore, the Runx1 mRNA delivered by polyplex nanomicelles increased hydration content by ≈43% in the punctured disc at 4-weeks post-injection (wpi) compared with naked Runx1 mRNA administration. Meanwhile, the disc space and ECM production were also significantly ameliorated in the polyplex nanomicelle group. This study demonstrated that anabolic factor administration by polyplex nanomicelle-protected mRNA medicine, such as Runx1, plays a key role in alleviating the progress of DDD, which is an imbalance scenario of disc metabolism. This platform could be further developed as a promising strategy applied to regenerative medicine.     

Direct Observation of Pure Cu and Cu-Ag Anode Passivation in H2SO4-CuSO4 Aqueous Solution by Channel Flow Double Electrode and Optical Microscopy

Metallurgical and Materials Transactions B - The dissolution and passivation of pure Cu and Cu-5 wt pct Ag anodes in H2SO4-CuSO4 electrolyte were investigated by a direct...     

Sonochemical decomposition of perfluorooctane sulfonate and perfluorooctanoic acid

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are shown to be globally distributed, environmentally persistent, and bioaccumulative. Although the toxicities of these compounds were reported, the cleanup procedure from the environment is not developed because of their inertness. In this report the sonochemical degradations of PFOS and PFOA to the products through the fission of the perfluorocarbon chains were observed and the half-life times of the PFOS and PFOA degradations under an argon atmosphere determined to be 43 and 22 min, respectively. The shortening of perfluorocarbon chain of PFOS and PFOA leads to the lowering of the toxicity in view of the decrease of the persistence, and the technique would contribute to the remediation of the environmental pollution by these compounds.     

Direct Formation of Crystalline Gadolinium-Doped Ceria Powder via Polymerized Precursor Solution

Synthesis of Ce_0.9Gd_0.1O_1.95 (CGO) powder from a polymeric precursor solution containing a mixture of nitrates, nitric acid, and ethylene glycol was investigated with emphasis on the effect of polymerization of the precursor solution on the crystallization and morphology of the derived solid intermediate and the final oxide powder. It is shown for the first time in this work that the solid intermediate derived from the polymerized solution is present in the form of well-crystallized cerium-gadolinium formate solid solution, Ce_{1− x} Gd _x (HCOO)₃, exhibiting anisotropic growth. Further polymerization of the precursor solution resulted in the direct formation of loosely agglomerated nanoscaled CGO oxide powder from the polymerized solution at temperatures as low as 130°C.     

Probability distributions of gas hydrate formation

Induction time distributions for gas hydrate formation were measured for gas mixtures of methane + propane at pressures up to 11.3 MPa using a high‐pressure automated lag time apparatus (HP‐ALTA). Measurements were made at subcooling temperatures between 4.3 and 13.5 K and, while isothermal induction times between 0 and 15,000 s were observed, the median isothermal induction times for the distributions ranged from 100 to 4000 s. A hyperbolic relationship between median induction time and subcooling was used to correlate the data. A graphical interpretation is presented that relates the two types of data that can be acquired by using the HP‐ALTA in one of two modes to study hydrate formation: induction time distributions at constant subcooling and formation temperature distributions observed during linear cooling ramps. The equivalence of these two modes provides a robust method for studying the variation of formation phenomena in different hydrate systems. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2640–2646, 2013     

Short-term irradiation behavior of minor actinide doped uranium plutonium mixed oxide fuels irradiated in an experimental fast reactor

A fuel irradiation program is being conducted using the experimental fast reactor ‘Joyo’. Two short-term irradiation tests in the program were completed in 2006 using a uranium and plutonium mixed oxide fuel which contains minor actinides (MA-MOX fuel). The objective of the tests is the investigation of early thermal behavior of MA-MOX fuel such as fuel restructuring and redistribution of minor actinides. Three fuel pins which contained MA-MOX: 2% neptunium and 2% americium doped uranium plutonium mixed oxide (Am,Pu,Np,U)O_2−x fuel were supplied for testing. The first test was conducted with high-linear heating rate of approximately 430 W cm⁻¹ for only 10 min. After the first test, one fuel pin was removed for examinations. Then the second test was conducted with the remaining two pins at nearly the same linear power for 24 h. In these tests, two oxygen-to-metal molar ratios were used for fuel pellets as a test parameter. Non-destructive and destructive post-irradiation examinations results are discussed with early on the behavior of the fuel during irradiation.