Ryo Ishihara

Removal of Cesium Using Cobalt-Ferrocyanide-Impregnated Polymer-Chain-Grafted Fibers

Radioisotopes are currently being released by Fukushima Daiichi nuclear power plant, which was damaged by the magnitude 9.0 earthquake and the tsunami that followed. Cesium-137, cesium-134, and iodine-131 produced by the fission of nuclear fuels are expected to seriously contaminate the sea and ground. Cesium and iodine dissolve in water and seawater in ionic forms of Csþ and I or IO3 , respectively. Cesium-137, with a longer half-life (30 years) than iodine131 (8 days), should be removed and confined. Adsorption is a feasible method of removing radioactive species from water contaminated with radioisotopes. Zeolites and insoluble metal ferrocyanides are known as adsorbents capable of specifically capturing cesium-137 ions. Moreover, the insoluble metal ferrocyanides are loaded onto solid supports in bead or granule form such as porous anionexchange resins, silica gels, and zeolites. However, fibrous adsorbents are effective for easy operation at sites for processing water contaminated with radioisotopes. Here, we propose a novel fiber that can immobilize metal ferrocyanides for the removal of cesium ions using a commercially available 6-nylon fiber as a starting material. Precipitates of metal ferrocyanide (M-FC) were formed among the polymer chains grafted onto the 6-nylon fiber. Therefore, the M-FC-impregnated fibers with a small diameter enhance the mass transfer of cesium ions from the bulk of liquid to the M-FC particles, leading to the rapid removal of cesium ions. In addition, the M-FC-impregnated fibers can be fabricated into various fiber modules for easy operation at the sites. In this study, the cobalt ion was used as a metal ion that precipitates with potassium ferrocyanide. II. Experimental

Multiplex MicroRNA Detection on a Power-free Microfluidic Chip with Laminar Flow-assisted Dendritic Amplification

MicroRNA (miRNA) profile-based point-of-care (POC) diagnostic methods have attracted considerable attention. In our laboratory, singleplex miRNA detection on a power-free poly(dimethylsiloxane) (PDMS) microfluidic chip with laminar flow-assisted dendritic amplification (LFDA) has been developed. In this study, to obtain the miRNA profile and to improve the reliability of the diagnosis, multiplex miRNA detection on the same system is demonstrated without compromising any advantages of the singleplex miRNA detection. The limit of detection (LOD) was at the femto- to picomolar level and the assay time was 20 min. The sensitivity, rapidity, and portability of the microfluidic chip are adequate for POC diagnosis.

Dependence of Lanthanide-Ion Binding Performance on HDEHP Concentration in HDEHP Impregnation to Porous Sheet

An octadecylamino-group-introduced polymer chain grafted onto a porous sheet was impregnated with bis(2-ethylhexyl)hydrogen phosphate (HDEHP). A mixture of HDEHP and ethanol of various HDEHP concentrations was used for the impregnation. The porous sheet into which a C18H37NH group was introduced was immersed in HDEHP/ethanol solution before ethanol evaporation. The liquid permeability of a cartridge charged with the HDEHP-impregnated porous sheet in disk form prepared in 50 (v/v)% HDEHP/ethanol solution was 96% that of the starting-porous-disk-packed cartridge. The equilibrium binding capacity of the HDEHP-impregnated porous disk for yttrium ions was 0.32 mol per kg of the disk. In addition, the HDEHP-impregnated-porous-disc-packed cartridge was found to be applicable to the preconcentration of trace amounts of lanthanides in a multielement solution prior to their measurement by inductively coupled plasma mass spectrometry.

Preparation of Microvolume Anion-Exchange Cartridge for Inductively Coupled Plasma Mass Spectrometry-Based Determination of 237Np Content in Spent Nuclear Fuel

Microvolume anion-exchange porous polymer disk-packed cartridges were prepared for Am/Np separation, which is required prior to the measurement of Neptunium-237 ((237)Np) with inductively coupled plasma mass spectrometry (ICPMS). Disks with a volume of 0.08 cm(3) were cut out from porous sheets having anion-exchange-group-containing polymer chains densely attached on the pore surface. Four different amine-based groups, N,N-dimethylaminoethyl methacrylate, trimethylammonium, diethylamine, and triethylenediamine (TEDA), were selected as the anion-exchange groups to be introduced into the porous sheets. The separation performances of Am/Np were evaluated using a standard solution of (243)Am, which had the same activity as its daughter nuclide (239)Np in secular equilibrium. (239)Np recovery of close to 100% with practically no contamination of (243)Am was achieved using the TEDA-introduced disk-packed cartridge. The time to elute (239)Np from the cartridge was approximately 40 s. The TEDA-introduced disk-packed cartridge was applied to the separation of Np from a spent nuclear fuel sample to confirm its separation performance. A known amount of (243)Am ((239)Np) was added to the spent nuclear fuel sample solution to monitor the chemical yield of Np. The chemical yield of Np calculated from a measured concentration of (239)Np was 90.4%. Am leakage in the Np-eluted solution was less than 1 ppt, corresponding to 0.001% of the original Am concentration in the sample. This indicates that no additional (239)Np was produced by the decay of the (243)Am remaining in the Np-eluted solution, thus providing a reliable chemical yield. U, which can cause a serious spectral interference involving the peak tail from the mass spectrum of (238)U, was thoroughly removed with the TEDA cartridge, providing interference-free measurement of (237)Np. The concentration of (237)Np obtained by ICPMS was 718 ± 12 ng/mg-U, which agrees well with the theoretically calculated value. Compared with the conventional separation technique using commercially available anion-exchange resin columns, the time required to adsorb, wash, and elute Np using the TEDA- introduced disk-packed cartridge was reduced by 75%.

Crosslinked-Chelating Porous Sheet with High Dynamic Binding Capacity of Metal Ions

A crosslinked chelating porous sheet was prepared by cografting ethylene glycol dimethacrylate (EGDMA) with glycidyl methacrylate onto an electron-beam-irradiated porous polyethylene sheet, followed by the introduction of an iminodiacetate group. At a molar percentage of EGDMA of 1.0 mol%, the sheet exhibited a maximum dynamic binding capacity for copper ions of 0.93 mmol/g, while the equilibrium binding capacity remained the same (1.2 mmol/g) as that of a non-crosslinked chelating porous sheet. The crosslinking of the grafted chain causes copper ions to lower their diffusion rate along the sheet thickness driven by the gradient of the amount of copper ions adsorbed.

Simple Method for High-Density Impregnation of Aliquat 336 onto Porous Sheet and Binding Performance of Resulting Sheet for Palladium Ions

Aliquat 336 was impregnated onto the polymer chain grafted onto a 2.0-mm-thick porous sheet with a porosity of 75% and a pore size of 1.2 µm via the graft polymerization of glycidyl methacrylate and the subsequent reaction of the epoxy group with mercaptoundecanoic acid. In a 2:1 ethanol/4M NaOH (v/v) mixture, Aliquat 336 was impregnated at a density of 0.85 mmol/g, which was comparable to that of conventional Aliquat-336-impregnated polymeric beads. The dynamic binding capacity for palladium was 0.60 mmol/g when 100 mg-Pd/L palladium chloride solution was forced to permeate at a space velocity of 3700 h−1.

Preparation of a Surface-functionalized Power-free PDMS Microchip for MicroRNA Detection Utilizing Electron Beam-induced Graft Polymerization

We propose an easy microchannel surface functionalization method for a poly(dimethylsiloxane) (PDMS) microchip that utilizes electron beam-induced graft polymerization (EIGP) as a platform for microchip-based biomarker analysis. Unlike other grafting techniques, EIGP enables rapid surface modification of PDMS without initiator immobilization. The grafted microchip is preservable, and can be easily functionalized for versatile applications. In this study, the surface-functionalized power-free microchip (SF-PF microchip) was used for the detection of microRNA (miRNA), which is a biomarker for many serious diseases. The EIGP enables high-density three-dimensional probe DNA immobilization, resulting in rapid and sensitive miRNA detection on the portable SF-PF microchip. The limit of detection was 0.8 pM, the required sample volume was 0.5 μL, and the analysis time was 15 min. The SF-PF microchip will be a versatile platform for microchip-based point-of-care diagnosis.

Rapid separation of zirconium using microvolume anion-exchange cartridge for 93 Zr determination with isotope dilution ICP-MS

Estimating the risks associated with radiation from long-lived fission products (LLFP) in radioactive waste is essential to ensure the long-term safety of potential disposal sites. In this study, the amount of 93Zr, a LLFP, was determined by ICP-MS after separating Zr from a spent nuclear fuel solution using a microvolume anion-exchange cartridge (TEDA cartridge). Zirconium in 9.4 M HCl was stably retained on the TEDA cartridge and readily eluted with 0.75 mL of a mixed solution of 9.4 M HCl and 0.01 M HF. The time taken to complete the Zr separation was 1.2 min. Almost all the other elements initially present in the spent nuclear fuel sample were removed, leading to accurate measurement of all six Zr isotopes (90Zr, 91Zr, 92Zr, 93Zr, 94Zr, and 96Zr). This demonstrated that the TEDA cartridge allowed highly selective separation of Zr regardless of its small bed volume of 0.08 cm3. The concentrations of these isotopes were determined by an isotope-dilution method using a natural Zr standard that has a different isotopic composition from that of the spent nuclear fuel sample. The amount of 93Zr in an initial spent nuclear fuel pellet was 1081 ± 79 ng per mg of 238U. The measured concentrations of all Zr isotopes, as well as the isotopic composition, were consistent with values predicted using a burnup calculation code.

Fabrication of Hybrid Capsules via CaCO3 Crystallization on Degradable Coacervate Droplets

Organic-inorganic CaCO3 capsules were prepared by crystallization of CaCO3 on Pickering emulsion prepared using coacervate droplets made from thermoresponsive and degradable poly(2-methylene-1,3-dioxepane- co-2-hydroxyethyl acrylate) (poly(MDO- co-HEA)) in sole aqueous medium. The diameters of CaCO3-based Pickering emulsion could be controlled by varying several parameters: diameter of CaCO3 powders, initial polymer concentration, and copolymer composition. The CaCO3 Pickering emulsion was able to load low-molecular-weight hydrophobic substances at temperatures above the lower critical solution temperature (LCST) due to formation of polymer-concentrated phases, i.e., coacervate droplets. The diameter of CaCO3 capsules prepared by crystallization also depended on the diameter of the CaCO3 Pickering emulsion. The CaCO3 shell was composed of calcite-type crystals, the most stable polymorph among known CaCO3 crystals. The facially prepared CaCO3 capsules are valuable for use in functional biomaterials, such as drug delivery carriers and cell culture scaffolds for noninvasive bone-regenerative medicine.

High-resolution separation of neodymium and dysprosium ions utilizing extractant-impregnated graft-type particles

An efficient method for rare metal recovery from environmental water and urban mines is in high demand. Toward rapid and high-resolution rare metal ion separation, a novel bis(2-ethylhexyl) phosphate (HDEHP)-impregnated graft-type particle as a filler for a chromatography column is proposed. To achieve rapid and high-resolution separation, a convection-flow-aided elution mode is required. The combination of 35 μm non-porous particles and a polymer-brush-rich particle structure minimizes the distance from metal ion binding sites to the convection flow in the column, resulting in minimized diffusional mass transfer resistance and the convection-flow-aided elution mode. The HDEHP-impregnated graft-type non-porous-particle-packed cartridge developed in this study exhibited a higher separation performance for model rare metals, neodymium (III) and dysprosium (III) ions, and a narrower peak at a higher linear velocity, than those of previous HDEHP-impregnated fiber-packed and commercially available Lewatit® VP OC 1026-packed cartridges.