Globular pattern formation of hierarchical ceria nanoarchitectures.

Dissipative structures often appear as an unstable counterpart of ordered structures owing to fluctuations that do not form a homogeneous phase. Even a multiphase mixture may simultaneously undergo one chemical reaction near equilibrium and another one that is far from equilibrium. Here, we observed in real time crystal seed formation and simultaneous nanocrystal aggregation proceeding from CeIV complexes to CeO2 nanoparticles in an acidic aqueous solution, and investigated the resultant hierarchical nanoarchitecture. The formed particles exhibited two very different size ranges, resulting in further pattern formation with opalescence. The hierarchically assembled structures in solutions were CeO2 colloids, viz. primary core clusters (1-3 nm) of crystalline ceria and secondary clusters (20-30 nm) assembled through surface ions. Such self-assembly is widespread in multi-component complex fluids, paradoxically moderating hierarchical reactions. Stability and instability are not only critical but also complementary for co-optimisation around the nearby free energy landscape prior to bifurcation.

Ion Tracks and Nanohillocks Created in Natural Zirconia Irradiated with Swift Heavy Ions.

Natural monoclinic zirconia (baddeleyite) was irradiated with 340 MeV Au ions, and the irradiation-induced nanostructures (i.e., ion tracks and nanohillocks) were observed using transmission electron microscopy. The diameter of the nanohillocks was approximately 10 nm, which was similar to the maximum molten region size calculated using the analytical thermal spike model. Ion tracks were imaged as strained regions that maintained their crystalline structure. The cross-sections of most of the ion tracks were imaged as rectangular contrasts as large as 10 nm. These results strongly indicated that the molten region was recrystallized anisotropically, reflecting the lattice structure. Furthermore, low-density track cores were formed in the center of the ion tracks. The formation of low-density track cores can be attributed to the ejection of molten matter toward the surface. A comparison of the ion tracks in the synthetic zirconia nanoparticles and those in larger natural zirconia samples showed that the interface between the strained track contrast and the matrix was less clear in the former than in the latter. These findings suggest that the recrystallization process was affected by the size of the irradiated samples.

A Reliable Hybrid Adsorbent for Efficient Radioactive Cesium Accumulation from Contaminated Wastewater.

Cesium (Cs) removal from nuclear liquid wastewater has become an emerging issue for safeguarding public health after the accident at the Fukushima Daiichi Nuclear Power Plant. A novel macrocyclic ligand of o-benzo-p-xylyl-22-crown-6-ether (OBPX22C6) was developed and successfully immobilized onto mesoporous silica for the preparation of hybrid adsorbent. The benzene ring π electron is the part of crown ether of OBPX22C6 for easy orientation of the macrocyclic compound for making the π electron donation with Cs complexation. The potential and feasibility of the hybrid adsorbent as being Cs selective was evaluated in terms of sensitivity, selectivity and reusability. The results clarified that the Cs removal process was rapid and reached saturation within a short time. Considering the effect of competitive ions, sodium (Na) did not markedly affect the Cs adsorption whereas potassium (K) was slightly affected due to the similar ionic radii. However, the oxygen in long ethylene glycol chain in OBPX22C6 was expected to show strong coordination, including Cs-π interaction with Cs even in the presence of the high amount of K and Na. Due to its high selectivity and reusability, significant volume reduction is expected as this promising hybrid adsorbent is used for Cs removal in Fukushima wastewater.

Selective cesium removal from radioactive liquid waste by crown ether immobilized new class conjugate adsorbent.

Conjugate materials can provide chemical functionality, enabling an assembly of the ligand complexation ability to metal ions that are important for applications, such as separation and removal devices. In this study, we developed ligand immobilized conjugate adsorbent for selective cesium (Cs) removal from wastewater. The adsorbent was synthesized by direct immobilization of dibenzo-24-crown-8 ether onto inorganic mesoporous silica. The effective parameters such as solution pH, contact time, initial Cs concentration and ionic strength of Na and K ion concentrations were evaluated and optimized systematically. This adsorbent was exhibited the high surface area-to-volume ratios and uniformly shaped pores in case cavities, and its active sites kept open functionality to taking up Cs. The obtained results revealed that adsorbent had higher selectivity toward Cs even in the presence of a high concentration of Na and K and this is probably due to the Cs-π interaction of the benzene ring. The proposed adsorbent was successfully applied for radioactive Cs removal to be used as the potential candidate in Fukushima nuclear wastewater treatment. The adsorbed Cs was eluted with suitable eluent and simultaneously regenerated into the initial form for the next removal operation after rinsing with water. The adsorbent retained functionality despite several cycles during sorption-elution-regeneration operations.

Deposition of hydroxyapatite on SiC nanotubes in simulated body fluid.

SiC nanotubes can become candidate reinforcement materials for dental and orthopedic implants due to their light weight and excellent mechanical properties. However, the development of bioactive SiC materials has not been reported. In this study, hydroxyapatites were found on SiC nanotubes treated with NaOH and subsequently HCl solution after soaking in simulated body fluid. On the other hand, hydroxyapatites did not deposit on as-received SiC nanotubes, the SiC nanotubes with NH4OH solution treatment and SiC bulk materials with NaOH and subsequently HCl solution treatment. Therefore, we succeeded in the development of bioactive SiC nanotubes by downsizing SiC materials to nanometer size and treating with NaOH and subsequently HCl solutions for the first time.

Facile, rapid and efficient biofabrication of gold nanoparticles decorated with functional proteins.

We report a one-pot biological approach to fabricate gold nanoparticle (AuNP)-ZZ domain conjugates using peptide-functionalized proteins that can simultaneously direct both biomineralization and surface modification of AuNPs. In addition, immuno-AuNPs are readily prepared through the specific binding of antibodies to the ZZ domain on the AuNPs.

Finite size effects of nanoparticles on the atomic pair distribution functions.

The finite size effects of nanoparticles on the atomic pair distribution functions (PDF) are discussed by calculating the radial distribution functions (RDF) on nanoparticles with various shapes, such as sheet, belt, rod, tube and sphere, assuming continua. Their characteristics are shown depending on the shapes and the sizes of the nanoparticles. The formulas of a PDF analysis which take account of such effects are presented and are found to reproduce the experimental data.