Language：English   Publishing type：Research paper (scientific journal)  

Phosphate (PO43-) is an essential nutrient in agriculture; however, it is hazardous to the environment if discharged in excess as in wastewater discharge and runoff from agriculture. Moreover, the stability of chitosan under acidic conditions remains a concern. To address these problems, CS-ZL/ZrO/Fe3O4 was synthesized using a crosslinking method as a novel adsorbent for the removal of phosphate (PO43-) from water and to increase the stability of chitosan. The response surface methodology (RSM) with a Box-Behnken design (BBD)-based analysis of variance (ANOVA) was implemented. The ANOVA results clearly showed that the adsorption of PO43- onto CS-ZL/ZrO/Fe3O4 was significant (p ≤ 0.05), with good mechanical stability. pH, dosage, and time were the three most important factors for the removal of PO43-. Freundlich isotherm and pseudo-second-order kinetic models generated the best equivalents for PO43- adsorption. The presence of coexisting ions for PO43- removal was also studied. The results indicated no significant effect on PO43- removal (p ≤ 0.05). After adsorption, PO43- was easily released by 1 M NaOH, reaching 95.77% and exhibiting a good capability over three cycles. Thus, this concept is effective for increasing the stability of chitosan and is an alternative adsorbent for the removal of PO43- from water.

DOI： 10.3390/ijms24119754

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Authorship：Lead author   Language：Japanese   Publisher：東京 : 畑地農業振興会  

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Other Link： https://ndlsearch.ndl.go.jp/books/R000000004-I032905231

Language：English   Publishing type：Research paper (scientific journal)  

To address Cu(II) and Cr(VI) water pollution, a carbonized zeolite/chitosan (C-ZLCH) composite adsorbent was produced via pyrolysis at 500 °C for two hours. C-ZLCH was characterized using scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), dynamic light scattering (DLS), and zeta potential measurements. The batch experiments were performed by varying the initial pH, concentration, and contact time. The optimal pH values for Cu(II) and Cr(VI) were 8.1 and 9.6, respectively. The highest adsorption capacities for Cu(II) and Cr(VI) were 111.35 mg/g at 60 min and 104.75 mg/g at 90 min, respectively. The effects of chemicals such as sodium (Na+), glucose, ammonium (NH4+), and acid red 88 (AR88) were also studied. Statistical analysis showed that sodium had no significant effect on Cu(II) removal, in contrast to Cr(VI) removal. However, there was a significant effect of the presence of glucose, ammonium, and AR88 on both Cu(II) and Cr(VI) removal. The adsorption isotherm and kinetic models were fitted using Langmuir and pseudo-second-order models for Cu(II) and Cr(VI), respectively.

DOI： 10.3390/ma16062532

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Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Elsevier BV  

Soil contamination by PCBs is still known as a serious problem across the world, and the development of new technologies or the improvement of existing ones (e.g. higher efficiency, shorter processing time, lower input energy) are more and more important. Moreover, understanding the chemistry of the entire process, from a mechanistic point of view, can accelerate the process of improvement. In these circumstances, we attempted a clarification of the highly efficient degradation of PCBs by nano-sized particle of metallic Ca in CaO ("nCa") at 250 °C in dry solid state conditions. The reaction involved the hydrodechlorination, simple reduction, reductive coupling and hydroxylation processes. The detoxification efficiency reached over 99%. A tentative pathway and mechanism is proposed for explaining the final reactions products. Finally, the process was applied to real PCBs-contaminated soil, containing various amounts of PCBs, with a total success in completely eliminating the toxic polychlorinated compounds.

DOI： 10.1016/j.chemosphere.2022.137197

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In the present study, alkaline-treated zeolite/chitosan/Fe3+ (ZLCH-Fe) composites were prepared and analyzed using scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR) and pH of zero point of charge (pHzpc) to remove nitrates from water. The process was carried out using an adsorption method with a varied initial pH, adsorbent dosage, initial nitrate concentration and contact time. The pHzpc demonstrated that the ZLCH-Fe surface had a positive charge between 2 and 10, making it easier to capture the negative charge of nitrate. However, the optimal pH value is 7. After 270 min, the maximum adsorption capacity and percent removal reached 498 mg/g and 99.64%, respectively. Freundlich and pseudo-second-order were fitted to the adsorption isotherm and kinetic models, respectively. An evaluation was conducted on the effects of anions-SO42- and PO43--and dyes-methylene blue (MB) and acid red 88 (AR88)-upon nitrate removal. The results indicated that the effect of the anion could be inhibited, in contrast to dye effects. However, the optimal pH values were changed to 10 for MB and 2 for AR88, resulting in a hydrogel formation. This might be indicated by the protonation of hydroxyl and amino groups resulting from a chitosan nitrate reaction in the AR88 solution.

DOI： 10.3390/gels8120782

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Hindawi Limited  

Developing innovative technology for removing methylene blue (MB) from water is essential since the widespread discharge of MB from industrial effluents causes problems for humans and the environment. In this study, we conducted the adsorption method, a simple technique that utilizes an adsorbent. Chitosan is cross-linked with zeolite as a promising adsorbent material and environmentally friendly. For the characterization, FTIR, SEM-EDS, DLS, and pHzpc were analyzed. It was discovered that the removal percentage reached 97% with an adsorption capacity of 242.51 mg/g for 60 minutes at pH 10. The adsorption isotherm and kinetic model were investigated. As a result, the Freundlich model and pseudo-second-order model were fitted to the adsorption process. Moreover, the effect of other ions was investigated for 5 minutes of mixing time. The results showed that the removal percentage increased in the presence of H2O2 ion. Contrary to sodium chloride, glucose, and citric acid ions, the effectiveness of H2SO4 as a desorbing agent was 99.65% for 30 minutes at 45°C.

DOI： 10.1155/2022/1853758

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Other Link： http://downloads.hindawi.com/journals/ast/2022/1853758.xml

Language：English   Publishing type：Research paper (scientific journal)   Publisher：MDPI AG  

In the present study, we developed a new adsorbent product with zeolite crosslinked chitosan (ZL–CH hydrogel) to remove acid red 88 (AR88) in an aqueous solution. The effects of several factors, such as the comparison of ZL–CH hydrogel and the absence of chitosan, pH, adsorbent dosage, initial AR88 concentration, contact time, and ion strength, were determined. Obtained results showed that ZL–CH hydrogel improved AR88 removal compared to the absence of chitosan, with an adsorption capacity of 332.48 mg/g in equilibrium time of 1 min, and adding ionic strength had no significant effect. However, with optimal conditions at pH 2.0, dry ZL–CH became hydrogel due to protonation of amino and hydroxyl groups through hydrogen bonds in the AR88 solution. Volume fraction and interaction force decreased with increasing porosity, leading to an increase in adsorption capacity and swelling ratio. Experimental data of the adsorption process showed the Freundlich isotherm model. The equilibrium for adsorption and swelling kinetics studies showed and fitted a pseudo-second-order model. NaOH was successful as a desorbing agent with 93.8%, and it followed the pseudo-second-order kinetics model. The recycling process indicates great potential for AR88 removal.

DOI： 10.3390/polym14050893

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Authorship：Corresponding author   Language：Japanese  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Scientific Research Publishing, Inc.  

DOI： 10.4236/gsc.2021.113009

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Scientific Research Publishing, Inc.  

DOI： 10.4236/msce.2021.95004

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Scientific Research Publishing, Inc.  

DOI： 10.4236/jacen.2021.101007

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Authorship：Corresponding author   Language：Japanese  

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Publishing type：Research paper (scientific journal)   Publisher：The Materials Research Society of Japan  

DOI： 10.14723/tmrsj.45.179

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：AIP Publishing  

Fertilization on plants is normally performed by spreading fertilizer directly to the soil, which can pollute the environment since not all the fertilizers are instantaneously absorbed by the plants. One method being developed to overcome this problem is by using a matrix for controlled release fertilizers (CRF). CRF that is commonly used is hydrogel composite based. In this study, hydrogel composite was synthesized from local arrowroot starch with co -monomer (acrylic acid-co-acrylamide), zeolite, and urea-KH2PO4 through a radical polymerization process. The hydrogel and hydrogel composite were characterized by using FT-IR spectroscopy, SEM, and EDS. The swelling capabilities test and release rate of nitrogen, potassium, and phosphorus were measured at buffered pH of 5 and 7, and in distilled water. The results of FT-IR, SEM, and EDS show that zeolite and fertilizers were dispersed evenly in the hydrogel composite. Results from the swelling capabilities test showed the highest value when performed in distilled water, followed by results in pH 5, and pH 7. Measuring the concentration of nitrogen, phosphorus, and potassium released in the buffer pH 5, pH 7 and in water over a period of 0 to 100 hours shows that they are released gradually. Therefore, hydrogel composites synthesized from local arrowroot starch, monomers (acrylic-acrylamide), zeolite, and urea-KH2PO4 show promising results as controlled release fertilizers of Nitrogen, Phosphorous and Potassium.

DOI： 10.1063/5.0015312

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Springer Science and Business Media LLC  

In this study, we cloned the ATP-binding cassette (ABC) subfamily G member 2 gene (Abcg2gene; breast cancer resistance protein) from the liver of the marine pufferfishTakifugu rubripes, and examined its tissue distribution and gene structure. The full-length complementary DNA (cDNA) was 1977 base pairs (bp), comprising 15 exons in chromosome 17, and was assigned to the teleostAbcg2bparalogue. The open reading frame was 1839 bp in length, and encodes 612 amino acids constituting Walker A, Q-loop, C motif, Walker B, D-loop, and H-loop sequences in the first half and six transmembrane domains in the second half. Gene expression ofAbcg2was predominantly found in the intestines, followed by the liver and kidneys. The Kozak motif and the polyadenylation signal sequences were at respective ends of the transcript. The putative core promoter sequences including the transcription factor II B recognition elements, the TATA box, the initiator element, and the downstream core promoter element were found in the transcript and its upstream genomic DNA sequence. The hypoxia response element and the estrogen response element were located in the upstream genomic DNA sequence, suggesting that the pufferfishAbcg2gene possesses the same regulation mechanism of transcription as the humanABCG2gene.

DOI： 10.1007/s12562-020-01451-z

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Other Link： https://link.springer.com/article/10.1007/s12562-020-01451-z/fulltext.html

Publishing type：Research paper (international conference proceedings)  

The aim for this research is to make black compost from spent coffee grounds (SCG). The content of hemicellulose and lignin from SCG were 37.28% and 22.45%. For mineral content, Potassium (3 g/kg) is the most abundant element in spent coffee ground, followed by calcium (1.23 g/kg), magnesium (1.11 g/kg), phosphorus (0.89 g/kg) and natrium (0.7 g/kg). SCG also contains Carbon and Nitrogen ratios 1:19.5 which approaches the C/N ratio of the soil 1: 20. Composting process in aerobic condition for 2 months using Fungi, Bacillus and Lactic Acid Bacteria activator, produce black compost with good characteristic for plant and soil, such as C/N ratio under 1:10 and pH around 6 to 9.

DOI： 10.1051/e3sconf/202014204002

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Romanian Academy - Revue Roumaine De Chimie  

The treatment of alpha,beta-unsaturated carbonyl compounds and 1,3-diketones with Raney Ni-Al alloy in aqueous media yielded as major reaction products the corresponding saturated alcohols and/or the corresponding hydrocarbons, in a complete transformation of the starting material.

DOI： 10.33224/rrch/2020.65.1.05

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Publisher：Springer Singapore  

DOI： 10.1007/978-981-15-7190-9_6

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Authorship：Last author   Language：Japanese   Publishing type：Research paper (scientific journal)  

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Language：Japanese   Publishing type：Research paper (bulletin of university, research institution)   Publisher：八戸工業大学  

identifier:120006560771

DOI： 10.32127/00003871

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Treatment of p-cresol and other substituted phenols in aqueous media with Fe as electron donor, an acid as proton provider and a reduction catalyst was carried out as to mimic the treatment of phenolic wastewaters, in a first attempt of a reductive decontamination. From the various combinations tested, best results were obtained with a mixture of 7 mmol Fe, 9 mL 0.8 M H 2 SO 4 and 0.1 g Rh/C. The parent cyclohexanols were obtained quantitatively after only 50 minutes of shaking, at room temperature, at pH ~ 0.1. The effect of weight ratio phenol: reagents as well as the influence of the reaction time were studied. A reaction pathway was also proposed. © 2018 American Institute of Chemical Engineers Environ Prog, 38: 483–488, 2019.

DOI： 10.1002/ep.13001

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Language：Japanese   Publishing type：Research paper (scientific journal)  

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Publishing type：Research paper (scientific journal)   Publisher：一般社団法人 日本機械学会  

DOI： 10.1299/jsmemecj.2019.S08113

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：{Journal of Materials Science and Chemical Engineering}  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Elsevier Ltd  

It is hereby reported a simple, effective and sustainable method for the recovery of precious metals from end-of-life vehicle shredder residue and/or automobile shredder residue based on a hybrid ball-milling and microbubble froth flotation process. A ball-milling treatment of automobile shredder residue along a mixture of Fe/Ca/CaO nanoparticles had as main result the entrapment of precious metals and in subsidiary an improvement of the floatability of the various size fraction particles (1.0, 0.425, and 0.25 mm, respectively). Therefore, a separation of the settled fraction (poor in precious metals) and the floating fraction yielded a recovery of approximately 83–89% precious metals in the latter. Scanning electron microscopy-energy dispersive X-ray spectroscopy maps of gold (Au), silver (Ag), platinum (Pt), palladium (Pd), Iridium (Ir), and copper (Cu) confirmed that result.

DOI： 10.1016/j.jclepro.2017.09.279

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Language：Japanese  

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Publisher：InTech  

DOI： 10.5772/intechopen.79083

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：MDPI AG  

This study examined the urinary excretion of tetrodotoxin (TTX) modeled in a porcine renal proximal tubule epithelial cell line, LLC-PK₁. Time course profiles of TTX excretion and reabsorption across the cell monolayers at 37 °C showed that the amount of TTX transported increased linearly for 60 min. However, at 4 °C, the amount of TTX transported was approximately 20% of the value at 37 °C. These results indicate that TTX transport is both a transcellular and carrier-mediated process. Using a transport inhibition assay in which cell monolayers were incubated with 50 µM TTX and 5 mM of a transport inhibitor at 37 °C for 30 min, urinary excretion was significantly reduced by probenecid, tetraethylammonium (TEA), l-carnitine, and cimetidine, slightly reduced by p-aminohippuric acid (PAH), and unaffected by 1-methyl-4-phenylpyridinium (MPP+), oxaliplatin, and cefalexin. Renal reabsorption was significantly reduced by PAH, but was unaffected by probenecid, TEA and l-carnitine. These findings indicate that TTX is primarily excreted by organic cation transporters (OCTs) and organic cation/carnitine transporters (OCTNs), partially transported by organic anion transporters (OATs) and multidrug resistance-associated proteins (MRPs), and negligibly transported by multidrug and toxic compound extrusion transporters (MATEs).

DOI： 10.3390/md15070225

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Authorship：Corresponding author   Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：Springer Science and Business Media LLC  

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Other Link： http://link.springer.com/article/10.1007/s11356-016-7785-8/fulltext.html

Language：English   Publishing type：Research paper (scientific journal)   Publisher：SPRINGER HEIDELBERG  

One method of weakening the inherently hydrophobic surface of plastics relevant to flotation separation is heterogeneous nano-Fe/Ca/CaO catalytic ozonation. Nano-Fe/Ca/CaO-catalyzed ozonation for 15 min efficiently decreases the surface hydrophobicity of brominated and chlorinated flame retardant (B/CFR)-containing plastics (such as acrylonitrile-butadienestyrene (ABS), high-impact polystyrene (HIPS), and polyvinyl chloride (PVC)) in automobile shredder residue (ASR) to such an extent that their flotation ability is entirely depressed. Such a hydrophilization treatment also stimulates the ABS, HIPS, and PVC surface roughness, wetting of the surface, and the thermodynamic equilibrium conditions at the surface and ultimately changes surface polarity. SEM-EDS, AFM, and XPS analyses of the PVC and ABS surfaces demonstrated a marked decrease in [Cl/Br] and a significant increase in the number of hydrophilic groups, such as C-O, C=O, and (C=O)-O. Under froth flotation conditions at 50 rpm, about 99.5 % of ABS and 99.5 % of HIPS in ASR samples settled out, resulting in a purity of 98 and 98.5 % for ABS and HIPS in ASR samples, respectively. Furthermore, at 150 rpm, we also obtained 100 % PVC separation in the settled fraction, with 98 % purity in ASR. Total recovery of non-B/CFR-containing plastics reached nearly 100 % in the floating fraction. The amount of nano-Fe/Ca/CaO reagent employed during ozonation is very small, and additional removal of surface contaminants from the recycled ASR plastic surfaces by ozonation makes the developed process simpler, greener, and more effective.

DOI： 10.1007/s11356-016-8074-2

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

The separation of plastics containing brominated flame retardants (BFR) like (acrylonitrile-butadiene-styrene (ABS), high-impact polystyrene (HIPS), and polyvinyl chloride (PVC)) from automobile and electronic waste shredder residue (ASR/ESR) are a major concern for thermal recycling. In laboratory scale tests using a hybrid nano-Fe/Ca/CaO assisted ozonation treatment has been found to selectively hydrophilize the surface of ABS/HIPS and PVC plastics, enhancing ABS wettability and thereby promoting its separation from ASR/ESR by means of froth flotation. The water contact angles, of ABS/HIPS and PVC decreased, about 18.7°, 18.3°, and 17.9° in ASR and about 21.2°, 20.7°, and 20.0° in ESR respectively. SEM-EDS, FT-IR, and XPS analyses demonstrated a marked decrease in [Cl] and a significant increase in the number of hydrophilic groups, such as CO, CO, and (CO)O, on the PVC or ABS surface. Under froth flotation conditions at 50rpm, about 99.1% of combined fraction of ABS/HIPS in ASR samples and 99.6% of ABS/HIPS in ESR samples were separated as settled fraction. After separation, the purity of the recovered combined ABS/HIPS fraction was 96.5% and 97.6% in ASR and ESR samples respectively. Furthermore, at 150rpm a 100% PVC separation in the settled fraction, with 98% and 99% purity in ASR and ESR plastics, respectively. Total recovery of non-ABS/HIPS and PVC plastics reached nearly 100% in the floating fraction. Further, this process improved the quality of recycled ASR/ESR plastics by removing surface contaminants or impurities.

DOI： 10.1016/j.wasman.2017.01.003

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SPRINGER HEIDELBERG  

Both hexachlorobenzene and hexabromobenzene were successfully hydrodehalogenated to the monohalogenated derivative and ultimately to benzene (which was subsequently reduced to cyclohexane) using a mixture of metallic Ca, ethanol, and Rh/C, by simple stirring in diethyl ether, at room or mild temperature (60 °C). Various experiments were performed in order to assess the role of the solvent and Rh/C catalyst, as well as for elucidating the reaction pathway.

DOI： 10.1007/s11356-016-7785-8

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DOI： 10.4236/jep.2017.811086

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

In order to elucidate the metal-alcohol hydrodechlorination reaction mechanism, several experiments using chloroanisoles as substrates were performed. Thus, chloroanisoles were stirred at 60 °C for 2 h with a mixture of Ca, methanol and various reduction catalysts. The use of deuterated methanol and zeta potential experiments offered supplementary informations, pointing toward a probable radicalic mechanism that occurs on Ca and Pd/C surfaces.

DOI： 10.1016/j.chemosphere.2016.08.088

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-BLACKWELL  

This study was conducted to examine the dry synthesis and application of novel nano-size calcium/iron-based composite material as a separation/immobilization treatment of heavy metals (As, Cd, Cr, and Pb) in fly ash from municipal solid waste incinerator. After grinding with nano-Fe/Ca/CaO and with nano-Fe/Ca/CaO/[PO4], approximately 30 wt % and 25 wt % of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lighter, magnetically-separated fly ash fraction (i.e. 91% heavy metals in 25% treated fly ash). Immobilization rate of heavy metals in the magnetic or non-magnetic fly ash fractions were about 98% and 100%, respectively. SEM-EDS observations indicate that the main fraction of enclosed/bound materials on treated fly ash includes Ca/PO4-associated crystalline complexes. After nano-Fe/Ca/CaO/[PO4] treatment, the heavy metal concentrations in the fly ash leachate were much lower than the Japan standard regulatory limit for hazardous waste landfills. The addition of a nano-Fe/Ca/CaO/PO4 mixture with simple grinding technique is potentially applicable for the remediation and volume reduction of fly ash contaminated by heavy metals. (C) 2016 American Institute of Chemical Engineers Environ Prog, 35: 1693-1698, 2016

DOI： 10.1002/ep.12418

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Simultaneous immobilization of heavy metals and decomposition of halogenated organic compounds in different fractions of automobile shredder residue (ASR) were achieved with a nano-sized metallic calcium through a 60-min ball milling treatment. Heavy metal (HM) immobilization and chlorinated/brominated compound (CBC) decomposition efficiencies both reached 90-100 %, after ball milling with nanometallic calcium/calcium oxide (Ca/CaO) dispersion, regardless of ASR particle size (1.0, 0.45-1.0, and 0.250 mm). Concentrations of leachable HMs substantially decreased to a level lower than the regulatory standard limits (Co and Cd 0.3 mg L-1; Cr 1.5 mg L-1; Fe, Pb, and Zn 3.0 mg L-1; Mn and Ni 1 mg L-1) proposed by the Korean hazardous waste elution standard regulatory threshold. Scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS) element maps/spectra showed that while the amounts of HMs and CBCs detectable in ASR significantly decreased, the calcium mass percentage increased. X-ray powder diffraction (XRD) patterns indicate that the main fraction of enclosed/bound materials on ASR includes Ca-associated crystalline complexes that remarkably inhibit HM desorption and simultaneously transform dangerous CBCs into harmless compounds. The use of a nanometallic Ca/CaO mixture in a mechanochemical process to treat hazardous ASR (dry conditions) is an innovative approach to remediate cross-contaminated residues with heavy metals and halogenated compounds.

DOI： 10.1007/s11356-016-7458-7

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Recently, point of care testing (POCT) used for diagnosis of influenza infection has a problem showing false negative diagnosis because of the low sensitivity. We would like to report detection of influenza virus A (H1N1) by an immunosensor based on electrochemiluminescence (ECL) that uses an immunoliposome encapsulating tris(2,2'-bipyridyl)ruthenium(II) complex. By using the sensor, we could detect the virus that competed with hemagglutinin (HA) peptide immobilized on self-assembled monolayers (SAMs) in immunoreaction of the antibody bound on the surface of liposome. The HA peptide was 19 mer (TGLRNGITNKVNSVIEKAA). We demonstrated great improvement of sensitivity and accuracy by introducing binary SAMs instead of mono SAMs. The binary SAMs was prepared from 3,3'-dithiodipropionic acid and 1-hexanethiol. Use of the binary SAMs enabled to increase the SAMs coverage on Au electrode; the fact was confirmed by observation of the cathodic desorption currents. By using such an electrode, first the detection method of BSA was optimized to lower ECL background signal. Then we applied the method to the detection of influenza virus. We could successfully detect the virus with higher sensitivity compared with that by POCT and ELISA. The detection range was from a concentration of 2.7 × 10(2) to 2.7 × 10(3) PFU/mL.

DOI： 10.1007/s00216-016-9587-8

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-BLACKWELL  

PCDDs, PCDFs, and PCBs present in soil can be hydrodechlorinated without a preliminary separation (extraction) step using a nano-size dispersed mixture of metallic Ca and CaO (206 nm average particle size). The treatment is quite simple: grinding in an electric mortar (100 rpm) at room temperature in open atmosphere for 24 h, producing up to 91, 99 and 97% hydrodechlorination yield for PCDDs, PCDFs and PCBs, respectively. The method is sensitive to soil moisture content, but because of its simplicity and low-cost, it can accommodate larger-scale adaptation. (c) 2015 American Institute of Chemical Engineers Environ Prog, 35: 34-40, 2016

DOI： 10.1002/ep.12183

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DOI： 10.5772/65335

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

This study assessed the synthesis and application of nano-Fe/Ca/CaO-based composite material for use as a separation and immobilizing treatment of dry soil contaminated by stable ((133)Cs) and radioactive cesium species ((134)Cs and (137)Cs). After grinding with nano-Fe/CaO, nano-Fe/Ca/CaO, and nano-Fe/Ca/CaO/[PO4], approximately 31, 25, and 22 wt% of magnetic fraction soil was separated. Their resultant (133)Cs immobilization values were about 78, 81, and 100%, respectively. When real radioactive cesium contaminated soil obtained from Fukushima was treated with nano-Fe/Ca/CaO/[PO4], approximately 27.3 wt% of magnetic and 72.75% of non-magnetic soil fractions were separated. The highest amount of entrapped (134)Cs and (137)Cs was found in the lowest weight of the magnetically separated soil fraction (i.e., 80% in 27.3% of treated soil). Results show that (134)Cs and (137)Cs either in the magnetic or non-magnetic soil fractions was 100% immobilized. The morphology and mineral phases of the nano-Fe/Ca/CaO/[PO4] treated soil were characterized using SEM-EDS, EPMA, and XRD analysis. The EPMA and XRD patterns indicate that the main fraction of enclosed/bound materials on treated soil included Ca/PO4 associated crystalline complexes. These results suggest that simple grinding treatment with nano-Fe/Ca/CaO/[PO4] under dry conditions might be an extremely efficient separation and immobilization method for radioactive cesium contaminated soil.

DOI： 10.1016/j.jhazmat.2015.04.071

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

This study was conducted to synthesize and apply a nano-size calcium dispersed reagent as an immobilization material for heavy metal-contaminated automobile shredder residues (ASR) dust/thermal residues in dry condition. Simple mixing with a nanometallic Ca/CaO/PO4 dispersion mixture immobilized 95-100% of heavy metals in ASR dust/thermal residues (including bottom ash, cavity ash, boiler and bag filter ash). The quantity of heavy metals leached from thermal residues after treatment by nanometallic Ca/CaO/PO4 was lower than the Korean standard regulatory limit for hazardous waste landfills. The morphology and elemental composition of the nanometallic Ca/CaO-treated ASR residue were characterized by field emission scanning election microscopy combined with electron dispersive spectroscopy (FE-SEM/EDS). The results indicated that the amounts of heavy metals detectable on the ASR thermal residue surface decreased and the Ca/PO4 mass percent increased. X-ray diffraction (XRD) pattern analysis indicated that the main fraction of enclosed/bound materials on ASR residue included Ca/PO4- associated crystalline complexes, and that immobile Ca/PO4 salts remarkably inhibited the desorption of heavy metals from ASR residues. These results support the potential use of nanometallic Ca/CaO/PO4 as a simple, suitable and highly efficient material for the gentle immobilization of heavy metals in hazardous ASR thermal residue in dry condition.

DOI： 10.1016/j.jhazmat.2015.04.039

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UNLABELLED: This study was conducted to examine the synthesis and application of novel nano-size calcium/iron-based composite material as an immobilizing and separation treatment of the heavy metals in fly ash from municipal solid waste incineration. After grinding with nano-Fe/Ca/CaO and with nano-Fe/Ca/CaO/[PO₄], approximately 30 wt% and 25 wt% of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lowest weight of the magnetically separated fly ash fraction (i.e., 91% in 25% of treated fly ash). Heavy metals in the magnetic or nonmagnetic fly ash fractions were about 98% and 100% immobilized, respectively. Additionally, scanning electron microscopy combined with energy-dispersive X-ray spectrometry (SEM-EDS) observations indicate that the main fraction of enclosed/bound materials on treated fly ash includes Ca/PO₄-associated crystalline complexes. After nano-Fe/Ca/CaO/[PO₄] treatment, the heavy metal concentrations in the fly ash leachate were much lower than the Japan standard regulatory limit for hazardous waste landfills. These results appear to be extremely promising. The addition of a nano-Fe/Ca/CaO/PO₄mixture with simple grinding technique is potentially applicable for the remediation and volume reduction of fly ash contaminated by heavy metals. IMPLICATIONS: After grinding with nano-Fe/Ca/CaO and nano-Fe/Ca/CaO/[PO₄], approximately 30 wt% and 25 wt% of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lowest weight of the magnetically separated fly ash fraction (i.e., 91% in 25% of treated fly ash), whereas heavy metals either in the magnetic or nonmagnetic fly ash fractions were about 98% and 100% immobilized. These results appear to be very promising, and the addition of nano-Fe/Ca/CaO/PO₄mixture with simple grinding technique may be considered potentially applicable for the remediation and volume reduction of contaminated fly ash by heavy metals.

DOI： 10.1080/10962247.2015.1077175

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Although direct radiation induced health impacts were considered benign, soil contamination with (137)Cs, due to its long-term radiological impact (30 years half-life) and its high biological availability is of a major concern in Japan in the aftermath of the Fukushima nuclear power plant disaster. Therefore (137)Cs reduction and immobilization in contaminated soil are recognized as important problems to be solved using suitable and effective technologies. One such thermal treatment/vitrification with nanometallic Ca/CaO amendments is a promising treatment for the ultimate immobilization of simulated radionuclide (133)Cs in soil, showing low leachability and zero evaporation. Immobilization efficiencies were 88%, 95% and 96% when the (133)Cs soil was treated at 1200 °C with activated carbon, fly ash and nanometallic Ca/CaO additives. In addition, the combination of nanometallic Ca/CaO and fly ash (1:1) enhanced the immobilization efficiency to 99%, while no evaporation of (133)Cs was observed. At lower temperatures (800 °C) the leachable fraction of Cs was only 6% (94% immobilization). Through the SEM-EDS analysis, decrease in the amount of Cs mass percent detectable on soil particle surface was observed after soil vitrified with nCa/CaO + FA. The (133)Cs soil was subjected to vitrified with nCa/CaO + FA peaks related to Ca, crystalline phases (CaCO3/Ca(OH)2), wollastonite, pollucite and hematite appeared in addition to quartz, kaolinite and bentonite, which probably indicates that the main fraction of enclosed/bound materials includes Ca-associated complexes. Thus, the thermal treatment with the addition of nanometallic Ca/CaO and fly ash may be considered potentially applicable for the remediation of radioactive Cs contaminated soil at zero evaporation, relatively at low temperature.

DOI： 10.1016/j.jenvrad.2014.10.006

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Phosphorus (P) ore is an expensive and limited resource that will be depleted in a few decades if the current global consumption rate continues. Japan, one of the most developed countries in the world, relies completely on imported phosphate rock for P. Potassium (K) ore, which is equally important for continuous development, is also becoming increasingly expensive. The recovery of P and K is therefore important for continuous and sustainable development. In this study, concentrated P (obtained from eluent) and K (obtained through alkali leaching of rice straw charcoal) were recovered as potassium magnesium phosphate (PMP) through the controlled addition of magnesium (Mg). A PMP crystal was produced when an equimolar (with respect to P) Mg solution was added to the leaching solution (rich in P and K) at a pH range of 11–12. Thus, the production of PMP in a crystalline form demonstrates the huge scope for the recycling of limited resources.

DOI： 10.1007/s40093-015-0086-2

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In this work, the capability of nanometallic Ca/CaO methanol suspension in removing and/or immobilizing stable ((133)Cs) and radioactive cesium species ((134)Cs and (137)Cs) in contaminated fly ash was investigated. After a first methanol and second water washing yielded only 45% of (133)Cs removal. While, after a first methanol washing, the second solvent with nanometallic Ca/CaO methanol suspension yielded simultaneous enhanced removal and immobilization about 99% of (133)Cs. SEM-EDS analysis revealed that the mass percent of detectable (133)Cs on the fly ash surface recorded a 100% decrease. When real radioactive cesium contaminated fly ash (containing an initial 14,040Bqkg(-1)(134)Cs and (137)Cs cumulated concentration) obtained from burning wastes from Fukushima were reduced to 3583Bqkg(-1) after treatment with nanometallic Ca/CaO methanol suspension. Elution test conducted on the treated fly ash gave 100BqL(-1) total (134)Cs and (137)Cs concentrations in eluted solution. Furthermore, both ash content and eluted solution concentrations of (134)Cs and (137)Cs were much lower than the Japanese Ministry of the Environment regulatory limit of 8000Bqkg(-1) and 150BqL(-1) respectively. The results of this study suggest that the nanometallic Ca/CaO methanol suspension is a highly potential amendment for the remediation of radioactive cesium-contaminated fly ash.

DOI： 10.1016/j.jhazmat.2014.06.044

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Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Springer Science and Business Media LLC  

In the present work, we investigated the use of nano-metallic calcium (Ca) and calcium oxide (CaO) dispersion mixture for the simultaneous remediation of contaminated soils with both heavy metals (As, Cd, Cr, and Pb) and polychlorinated biphenyls (PCBs). Regardless of soil moisture content, nano-metallic Ca/CaO dispersion mixture achieved about 95-99% of heavy metal immobilization by a simple grinding process. During the same treatment, reasonable PCB hydrodechlorination efficiencies were obtained (up to 97%), though higher hydrodechlorination efficiency by preliminary drying of soil was observed.

DOI： 10.1007/s11356-014-2830-y

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Publisher：Japan Society of Material Cycles and Waste Management  

DOI： 10.14912/jsmcwm.25.0_531

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Livestock water drainage after secondary treatment contains potassium and phosphorus is influenced by the efficiency of the processing method. In this study, we examined the effect of ammonium ion concentration on the simultaneous recovery of coexisting potassium and phosphorus. The ammonium nitrogen, potassium, and phosphorus concentrations were 0.3-8.3 mM, 0.0-25.6 mM, and 7.6 mM, respectively. Magnesium chloride at a concentration of 3 mM was added to a synthetic wastewater bubble column with a draught tube, and the pH was maintained at around 10 using a pH controller. The hydraulic retention time was 2.3 h. When the ammonium nitrogen concentration was less than 1.1 mM, the decreases in the molar ratios of magnesium, potassium, and phosphorus in the liquid almost corresponded to the production of magnesium potassium phosphate (MPP). Also, MPP was confirmed to be the main component of crystals obtained at low ammonia nitrogen concentrations, using various analytical methods. © 2013 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.jece.2013.08.032

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Authorship：Corresponding author   Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：EDP Sciences  

Present study, first time we developed a nano-Fe/Ca/CaO dispersion mixture based remediation and volume reduction method of real radioactive cesium contaminated soils. After soil samples treated with 10wt% of nano-Fe/Ca/CaO dispersion mixtures, emitting radiation intensity was reduced from 4.00 mu Sv/h to 0.95 mu Sv/h in non-magnetic fraction soils. While, after treatment, about 30wt% magnetic and 70wt% nonmagnetic fraction soils were separated, and it's condensed radioactive cesium concentration was about 80% and 20%, respectively. By this way, cesium contaminated soil volume can be reduced. These preliminary results appear to be very promising and the simple mixing with the addition of nano-Fe/Ca/CaO may be considered potentially applicable for the remediation and separation of radioactive Cs contaminated soil in dry conditions.

DOI： 10.1051/e3sconf/20130108003

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This report shows that soil heavy metals can be totally immobilized by grinding with nano-Fe/Ca/CaO. Remediation of soils contaminated by heavy metals is a critical issue in Japan. Indeed, contaminated soils are notoriously difficult to remediate using available technologies. Major setbacks in typical immobilization techniques for heavy metals are wet conditions, forming secondary effluents and further treatment for effluents. Solidification with nano-Fe/Ca/CaO dispersion mixture is a promising treatment for the total immobilization of soil heavy metals As, Cd, Cr, Pb, and separation in dry conditions. Here, we studied the heavy metal immobilization by simple grinding with the addition of three mixtures: nano-Fe/CaO, nano-Fe/Ca/CaO, and nano-Fe/Ca/CaO/PO4. Samples were analyzed by inductively coupled plasma optical emission spectrometry (ICP-OES) and scanning electron microscopy combined with electron dispersive spectroscopy (SEM-EDS). Results show that the addition of nano-Fe/Ca/CaO immobilized 95-99 % of heavy metals, versus 65-80 % by simple grinding. After treatment, 36-45 wt% of magnetic and 64-55 wt% of nonmagnetic fractions of soil were separated. Their condensed heavy metal concentration was 85-95 % and 10-20 %, respectively. Nano-Fe/Ca/CaO treatment reduced the concentration of leachates heavy metals to values lower than the Japan soil elution standard regulatory threshold of 0.01 mg/l for As, Cd, and Pb
and 0.05 mg/l for Cr. This technology can therefore immobilize totally soil heavy metals and reduce heavy metal by separation. © 2012 Springer-Verlag.

DOI： 10.1007/s10311-012-0384-0

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In the present work, the use of nano-metallic calcium (Ca) and calcium oxide (CaO) dispersion mixture for the immobilization of heavy metals (As, Cd, Cr and Pb) in soil was investigated. With simple grinding, 85-90% of heavy metals immobilization could be achieved, while it could be enhanced to 98-100% by grinding with the addition of nano-metallic Ca/CaO dispersion mixture. By SEM-EDS elemental maps as well as semi-quantitative analysis observed that the amount of As, Cd, Cr and Pb measurable on soil particle surface decreases after nano-metallic Ca/CaO treatment. The leachable heavy metals concentrations were reduced, to the concentration lower than the Japan soil elution standard regulatory threshold, i. e., &lt
0.01 mg/l for As, Cd and Pb and 0.05mg/l for Cr. Whereas, the effect of soil moisture and pH on heavy metals immobilization was not much influenced. The results suggest that nano-metallic Ca/CaO mixture is suitable to be used for the gentle immobilization of heavy metals contaminated soil at normal moisture conditions.

DOI： 10.1051/e3sconf/20130135002

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Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Springer Science and Business Media LLC  

This study describes the decomposition of polychlorinated biphenyls (PCBs) in soil with dispersion mixtures of metallic calcium (Ca) and calcium oxide (CaO) at different temperatures. In these experiments, naturally moisturized and contaminated soil (1.0 g [31 ppm PCBs]), CaO (dried 2.0 wt%), and metallic Ca (0.01 g [0.25 mmol]) were introduced into a stainless steel pressure reactor under 0.1 MPa N(2) gas. The mixtures were stirred magnetically and heated at 260, 280, and 300 °C, respectively. Soil treatment with metallic Ca and CaO under various temperature conditions is extremely effective for degrading existing PCBs. Decomposition resulted from dechlorination (DC). Initial moisture in soil acted as a hydrogen source during stirring. Soil moisture can be beneficial for hydrodechlorination in the presence of metallic Ca and CaO. Furthermore, metallic Ca and CaO can greatly increase the number of collisions and mutual refinement. Treatment at 260, 280, and 300 °C combined with metallic Ca and CaO is effective for the decomposition (approximately 95 % DC) of PCBs in soil under natural moisture conditions.

DOI： 10.1007/s00244-012-9829-5

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

Transformer oil can be directly decontaminated from PCB residues by direct treatment with metallic Ca and an alcoholic mixture, offering the possibility to recycle this product. The procedure, consisting in mixing, stirring and separating, is simple and effective. The hydrodechlorination yield is 99.6%, the remaining chlorobiphenyl belonging to the almost non-toxic family of ortho-monochloro- and ortho-dichlorobiphenyl. Low miscibility problems were overcome, using a mixture of ethanol and isopropanol. (C) 2012 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.seppur.2012.10.026

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This work assessed ball-milling treatment for remediation of cesium (Cs)-contaminated soil. The immobilization efficiency increases from 56.4% in the absence of treatment to 89.9, 91.5, 97.7, and 96.4% when the soil is ball milled for 30, 60, and 120 min, respectively. However, the addition of nanometallic Ca/CaO and NaH2PO4 increased the immobilization efficiency to approximately 96.4% compared with ball milling alone, even when the milling time was decreased to 60 min. Actually, with the addition of Ca/CaO and NaH2PO4, the leachable fraction of Cs was reduced in the soil after a short milling time. These promising results suggest that ball milling can be regarded as applicable for the remediation of cesium-contaminated soil in dry and water-free conditions. This treatment method requires no expensive reagent and does not generate exhaust gases. It requires only electricity with cheap and commercially available reagents. This treatment process is an environmentally friendly depollution technique ©2013 American Society of Civil Engineers.

DOI： 10.1061/(ASCE)HZ.2153-5515.0000151

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Other Link： https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-25550058/

Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

This study investigated the use of a nanometallic Ca and CaO dispersion mixture for the immobilization of heavy metals (As, Cd, Cr and Pb) in contaminated soil. Simple grinding achieved 85-90% heavy metal immobilization, but it can be enhanced further to 98-100% by addition of a nanometallic Ca/CaO dispersion mixture produced by grinding. Observations using SEM-EDS elemental maps and semi-quantitative analysis showed that the amounts of As, Cd, Cr, and Pb measurable on the soil particle surface decrease after nanometallic Ca/CaO treatment. The leachable heavy metal concentrations were reduced after nanometallic Ca/CaO treatment to concentrations lower than the Japan soil elution standard regulatory threshold: <0.01 mg L(-1) for As, Cd, and Pb; and 0.05 mg L(-1) for Cr. Effects of soil moisture and pH on heavy metal immobilization were not strongly influenced. The most probable mechanisms for the enhancement of heavy metal immobilization capacity with nanometallic Ca/CaO treatment might be due to adsorption and entrapment of heavy metals into newly formed aggregates, thereby prompting aggregation of soil particles and enclosure/binding with Ca/CaO-associated immobile salts. Results suggest that the nanometallic Ca/CaO mixture is suitable for use in immobilization of heavy-metal-contaminated soil under normal moisture conditions.

DOI： 10.1016/j.chemosphere.2012.06.030

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：VERSITA  

We report hereby the first method of direct treatment of a wet soil containing toxic polychloroderivatives. Using a system with metallic Ca and 5% Rh fixed on charcoal in methanol, soil samples artificially polluted with fly ash containing polychloro-dibenzodioxins (PCDDs), polychloro-dibenzofurans (PCDFs) and coplanar polychlorinated biphenyls (co-PCBs), and having 69.2% to 84.6% moisture content, were successfully treated and decontaminated. This treatment afforded excellent hydrodechlorination yields for the 29 most toxic congeners of PCDDs, PCDFs and PCBs (98.3% degradation yield based on toxic equivalent quotient - or TEQ) after a 24 h treatment, at room temperature.

DOI： 10.2478/s11532-012-0066-6

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SPRINGER HEIDELBERG  

This report shows that cesium can be immobilized in soils with an efficiency of 96.4% by ball milling with nano-metallic Ca/PO4. In Japan, the major concern on Cs-137 deposition and soil contamination due to the emission from the Fukushima Daiichi nuclear power plant showed up after a massive quake on March 11, 2011. The accident rated 7, the highest possible on the international nuclear event scale, released 160 petabecquerels (PBq) of iodine I-131 and 15 PBq of Cs-137 according to the Japanese Nuclear and Industrial Safety Agency. Both Cs-137 and I-131 radioactive nuclides are increasing cancer risk. Nonetheless, Cs-137, with a half-life of about 30 years compared with 8 days for I-131, is a major threat for agriculture and stock farming and, in turn, human life for decades. Therefore, in Japan, the Cs-137 fixation and immobilization in contaminated soil is the most important problem, which should be solved by suitable technologies. Ball milling treatment is a promising treatment for the remediation of cesium-contaminated soil in dry conditions. Here, we studied the effect, factors and mechanisms of soil Cs immobilization by ball milling with the addition of nano-metallic Ca/CaO/NaH2PO4, termed "nano-metallic Ca/PO4." We used scanning electron microscopy combined with electron dispersive spectroscopy (SEM/EDS) and X-ray diffraction. Results show that immobilization efficiency increases from 56.4% in the absence of treatment to 89.9, 91.5, and 97.7 when the soil is ball-milled for 30, 60 and 120 min, respectively. The addition of nano-metallic Ca/PO4 increased the immobilization efficiency to about 96.4% and decreased the ball milling time. SEM/EDS analysis allows us to observe that the amount of Cs decreased on soil particle surface. Use of nano-metallic Ca/PO4 over a short milling time also decreases Cs leaching. Therefore, ball milling with nano-metallic Ca/PO4 treatment may be potentially applicable for the remediation of radioactive Cs-contaminated soil in dry conditions.

DOI： 10.1007/s10311-012-0357-3

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Language：Japanese   Publisher：産業と環境  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：TAYLOR & FRANCIS INC  

Esterification of several types of mono- and disubstituted phenols with various mono- and dialkanoyl chlorides was performed in phase-transfer catalysis conditions, using tetrabutylammonium chloride in a mixture of aqueous NaOH and dichloromethane. The process is particularly efficient (almost quantitative yields) as well as rapid (only 5 min reaction time, at a temperature of 0 degrees C).

DOI： 10.1080/00397911.2011.584007

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

This report presents our results in a low-temperature mechanochemical hydrodechlorination process applied to fly ash coming from a municipal waste incinerator in order to efficiently remove all traces of PCDDs, PCDFs and PCBs. We found that the most suitable degradation agent is a mixture of metallic calcium and calcium oxide. A sample of fly ash presenting a TEQ of 5200 pg g(-1) was completely detoxified (no traces of PCDDs, PCDFs and PCBs detected) after ball-milling at 400 rpm over night.

DOI： 10.1016/j.chemosphere.2011.04.015

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：JAPAN SOC ANALYTICAL CHEMISTRY  

Cultivation of rice plants (Koshihikari, IR4595 and IR28) in 250 mmol/L NaCl over 16 days provided interesting profiles of responses on a flow-through electrochemiluminescence (ECL) system with tris(2,2'-bipyridine)ruthenium complex. Although some time lags were noted among these rice plants, the increment in the ECL responses was clearly observed on the 11th day. The obtained ECL response profiles were consistent with the proline profiles obtained by HPLC. Such consistency demonstrated that the present ECL system would find a utility as a useful sensor for salt stress on rice plants.

DOI： 10.2116/analsci.26.371

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Various thioesters were obtained through an efficient phase-transfer catalysis method, by treating several thiophenols with different acyl chlorides, in a biphasic system composed of 10% aqueous NaOH and dichloromethane in the presence of tetrabutylammonium chloride. The thiolation reaction was complete in only 5 minutes, at 0 degrees C.

DOI： 10.1080/10426501003713072

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DOI： 10.1002/chin.200121239

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DOI： 10.1002/chin.200221265

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DOI： 10.1002/chin.200202066

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We investigated the reduction of some substituted mono- and poly chlorobenzenes bearing functional groups such as methyl, methoxy, hydroxyl, and amino, under mild conditions (80 degrees C and magnetic stirring, for 2 h) using a system consisting of metallic calcium and methanol (as hydrogen donor system) and 5% wt. Rh/C (as hydrodechlorination/ring reduction catalyst). Hydrodechlorination easily took place for methoxy- and alkyl-chlorobenzenes, yielding the corresponding hydrodechlorinated compounds (57-76%) and affording as secondary reaction products the ring-reduced compounds (16-43%). Treatment of hydroxy- and amino-chlorobenzenes under the same conditions, respectively, gave corresponding hydrodechlorinated compounds (over 60%) along with the ring-reduced compounds. Results show that the reaction of substituted polychlorinated benzenes needs a longer reaction time (6 h), the transformation being nevertheless complete.

DOI： 10.1021/es9004587

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Treatment of PCBs in soil using metallic calcium and alcohol ultimately reduced 1300 x 10(-3)mgkg(-1) PCB concentration to 1.8 x 10(-3)mg kg(-1). Moreover, using the metallic calcium catalyst method to promote the effective use of hydrogen gas in the presence of a specific reducing catalyst such as Rh/C, the decomposition efficiency of PCBs was notably increased despite mild reaction conditions. The total PCB concentration of treated soils decreased from 1300 x 10(-3)mg kg(-1) to 0.62 x 10(-3)mg kg(-1) (decomp. avg.=99.95%). Treatment of soils with metallic calcium and a Rh/C catalyst in alcohol under mild conditions such as 0.15-0.26 MPa at room temperature is extremely effective for degradation of existing PCBs.

DOI： 10.1016/j.chemosphere.2008.10.034

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DOI： 10.1002/chin.200914093

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An immunoliposome (80 nm in diameter) encapsulating a Ru complex with two aminobutyl moieties was prepared to detect the presence of hemagglutinin molecules, which play an important role in influenza virus infection. The highly sensitive detection was accomplished by electrochemiluminescence (ECL) from the Ru complex adsorbed onto Au electrodes after competitive immunoreactions. This method clarified that the adsorption of the Ru complex onto the electrode was an important factor in obtaining high sensitivity. Optimization of the analytical conditions enabled determination of the hemagglutinin molecules of the influenza virus in the concentration range of 3 x 10(-14) (6 x 10(-19) mol/50 microL sample) to 2 x 10(-12) g/mL. The sensitivity was far superior to that obtained by conventional ELISA as well as to that obtained by biosensors and reported thus far.

DOI： 10.1021/ac702625d

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An immunoliposome encapsulating a Ru complex with two aminopropyl moieties was prepared to rapidly detect the hemagglutinin (HA) protein of influenza virus. Under optimal conditions, the electrochemiluminescence method using the liposome gave a calibration curve that enabled to detect 3 × 10-13 g/mL of the HA. Alternatively, the method using Ru complex-labeled antibody can detect 1 × 10-8 g/mL HA and the sensitivity was far lower than that of the above method. ©The Electrochemical Society.

DOI： 10.1149/1.2981111

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Pinacol-type coupling reaction products presenting a high meso-diastereoselectivity (the ratio dl/meso was 4/96 up to 1/99) were obtained in fair to good yields (24-69%) using several aromatic aldehydes as starting materials and aluminium powder/copper sulfate as catalysts, in water, under reflux conditions.

DOI： 10.1080/00397910802110198

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The reduction of imines using metallic calcium in alcohol rapidly gave the corresponding secondary amines, in good yields.

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Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：CSIRO PUBLISHING  

Effective hydrodechlorination of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like compounds such as coplanar polychlorinated biphenyls in fly ash was achieved in 24 h using a simple stirring operation in a sealed tube with metallic calcium and Rh/C catalyst in an alcohol solution at room temperature with 0.15 MPa of increasing internal pressure. The initial 7806 pg dioxin toxic equivalent (TEQ) ( g of ash)(-1) of dioxins in fly ash, which had adsorbed inside the solid phase, was finally degraded to 23.6 pg of TEQ ( g of ash)(-1), according to estimation using gas chromatography-mass spectrometry analysis.

DOI： 10.1071/EN06002

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Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

The authors achieved highly efficient degradation of polychlorinated aromatic compounds, including polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like compounds such as coplanar polychlorinated biphenyls (co-PCBs), which are known as persistent organic pollutants. Degradation was accomplished in 24 h through a simple stirring operation using safe and high workability metallic calcium, which acts as both a scavenger and a reducing agent, and Rh/C catalyst in an alcohol solution under mild conditions in a sealed tube at 25 degrees C without a temperature increase within 0.15 MPa of increasing internal pressure during the reaction. In this system, reductive dechlorination by metallic calcium and catalytic reduction by Rh/C and generated hydrogen gas, without any external addition of hydrogen, exert a synergistic effect on the degradation of chlorinated compounds. Alcohol was used as a proton source and hydrogen, which was generated by a side reaction, causes an increase in the activity of Rh/C catalyst. Through the degradation of 4-chloroanisole in ethyl alcohol, anisole and cyclohexyl methyl ether were obtained in good conversions. Using ethyl alcohol as a solvent, treatment of dioxins and co-PCBs in a solution was markedly effective for degradation to reduce 2806 pg TEQ/ml of initial concentration to 31.8 pg TEQ/ml; its yield was 98.5%. Moreover, degradation in methyl alcohol took place in a 993% yield. That concentration ultimately reached 20.3 pg TEG/ml under a mild wet process. All congeners of dioxins and co-PCBs were degraded in high conversions. In this degradation, lower aliphatic alcohol, such as methyl alcohol, is effective for making a new calcium surface as compared to alcohol with more methylene chains. In addition, it seemed that a higher pressure of hydrogen was easily generated in methyl alcohol, and then catalytic degradation was effectivley influenced.

DOI： 10.1021/es051976k

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Language：English   Publishing type：Research paper (scientific journal)  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

An advanced flow-through electrochemiluminescence (ECL) detector was applied to determination of resulting amino acids and oligopeptides in hydrolysis of four peptides by leucine aminopeptidase. For 20mer polypeptide PRGPDRPEGIEEEGGERDRD, the ECL intensity due to the polypeptide and produced proline was analyzed to give the dissociation contant K-m (1.2 x 10(-4)M) and the catalytic reaction constant k(cat), (3.7 s(-1)), which were good agreement with those obtained by HPLC. The enzymatic parameters were similarly obtained for the other peptides.

DOI： 10.1002/elan.200302944

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Language：English   Publishing type：Research paper (international conference proceedings)  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society (ACS)  

Detoxification of highly toxic polychlorinated aromatic compounds such as polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and dioxin-like compounds such as coplanar polychlorinated biphenyls (co-PCBs) under mild conditions(atmospheric pressure and room temperature) was achieved by a simple stirring operation for 24 h using metallic calcium in ethanol, without any tedious decomposition procedures and harsh conditions such as high temperature and/or high pressure. Metallic calcium can be kept stable under atmospheric conditions for a long period as compared to metallic sodium since the surface is coated with CaCO3, which is formed in the contact with air. Moreover, ethanol, which is one of the safest solvents for humans, acts not only as a solvent but also as an accelerator due to its ablility to remove the carbonated coating. This decomposition method for PCDDs, PCDFs, and co-PCBs therefore is one of the most economical and environmentally friendly detoxification methods with respect to the input energy and safety of reagents used. Concentration for each isomer of PCDDs, PCDFs, and co-PCBs was reduced in 98.32-100% conversions by treatment in ethanol at room temperature. The toxicity equivalency quantity (TEQ), which was measured by the HRGC-HRMS analysis, for the total residues of isomers was reduced from 22 000 to 210 pg TEQ/mL of hexane (conversion: 99.05%) at room temperature. By refluxing over 24 h, the conversion increased up to 99.45%.

DOI： 10.1021/es034379b

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：EDITURA ACADEMIEI ROMANE  

The phenolic ester synthesis between equimolecular amounts of phenols and various alkanoyl chlorides in the presence of aqueous sodium hydroxide solution in a two-phase system (20 mL of each 10% NaOH and dicloromethane, respectively) was reinvestigated under PTC conditions (10 mmol of tetrabutyl ammonium chloride, BNC). The esterification was complete within several minutes and the obtained ester was in high purity. For example, phenyl acetate was obtained quantitatively at 0degreesC in 5 minutes using a stoichiometric amount of BNC. This acylation procedure is technically simple and does not require anhydrous conditions. A bimolecular electrophilic attack of alkanoyl chloride against the ion-pair in the organic phase, which was formed between the quaternary ammonium cation and the phenoxide anion, must be a rate-determining step, because a plot of the logarithm of relative rate constants of various alkanoyl chlorides vs Taft's polar substituents constants (taking into account the steric constants, Es) gave a good linear relationship. We have found a simple, rapid, convenient, easily separating and efficient PTC technique to synthesize phenolic esters.

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Language：English   Publishing type：Research paper (scientific journal)  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry (RSC)  

The reduction of carbonyl compounds 1a-h using Ni-Al alloy in water under reflux proceeded to give the corresponding methylene compounds 2a-h within 2 h in 89.0-99.8% relative yields.

DOI： 10.1039/b211571a

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：The Japan Society for Analytical Chemistry  

Two novel ruthenium (II) complexes (Ru^II) having four positive charges were prepared so as to be strongly incorporated into a Nafion film. Complex A is a bis-Ru^II complex bound with a long alkyl chain and Complex B is a Ru^II having two pyridinium pendants. A flow-through detector using Ru^II/Nafion-coated Au electrdodes was applied for the determination of amino acids. The Complex A electrode more strongly responded to proline than did the Ru (bpy)₃²⁺ electrode, and showed a more stable response than did the Ru (bpy)₃²⁺ electrode. On the other hand, the Complex B electrode showed almost the same response profile for amino acids as did the Ru (bpy)₃²⁺ electrode. The response intensity was 1/60-times less strong than that of the Complex A electrode, perhaps due to the consumption of a strong reducing agent which may have been generated from oxidation of amino acids.

DOI： 10.2116/bunsekikagaku.51.1187

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Other Link： http://dl.ndl.go.jp/info:ndljp/pid/10895389

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society (ACS)  

The scope and limitations of the dehalogenation of aromatic halides 1 and 4a-p using metallic calcium in ethanol at room temperature were revealed. The cleavage of the carbon-chlorine bond on the aromatic ring bearing electron-donating group was difficult compared to the one bearing electron-withdrawing group. Moreover, we applied this method to the dechlorination of polychlorinated biphenyls (PCBs) in transformer oil. It was also found that the dechlorination took place easily under mild conditions. The existence of PCBs residue in the reaction at room temperature was less than 0.04% according to the GC-MS analysis. The chlorine was identified as calcium chloride.

DOI： 10.1021/es010716+

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

Although it is recognized that the presence of water is disadvantageous for imine synthesis, we demonstrate that such synthesis can be effective in completely aqueous media, without any catalyst and under mild conditions. Thus, aryl-aryl, aryl-alkyl., alkyl-aryl and alkyl-alkyl monoimines as well as a large variety of diimines are obtained by direct condensation of the corresponding carbonyl compounds and amines, in water. The same process is used to synthesize macrocyclic diimines starting from methylene, ethylene, trimethylene and tetramethylene glycol bis(2-formylphenyl ether) and ethylene-, trimethylene- and tetramethylene-diamine, some of these macrocycles being known for their chelating properties.

DOI： 10.1039/b102749m

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

The synthesis of title compounds (1a-f) by intramolecular reductive coupling is presented. The reaction is carried out in water solution, in the presence of Zn or Al powder, in basic media.

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Authorship：Lead author   Language：English   Publishing type：Research paper (international conference proceedings)  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry  

Reductive coupling of aromatic imines is performed by the use of zinc powder and additives such as NH4Cl and L-tyrosine in water without any organic solvents under mild conditions to give the corresponding vicinal diamines in good yields
cross-coupling of N-benzylideneaniline and benzaldehyde similarly proceeds in aqueous media to afford the corresponding 2-aminoalcohol.

DOI： 10.1039/b001533o

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Authorship：Lead author   Language：English   Publishing type：Research paper (international conference proceedings)  

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Authorship：Lead author   Language：English   Publishing type：Research paper (international conference proceedings)  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：The Chemical Society of Japan  

Dibenzo[3.3]orthocyclophanes ([3.3]OCPs) with a bicyclo[4.4.1]undecane substructure form charge-transfer (C-T) complexes with tetracyanoethylene (TCNE). 3,4: 8,9-Dibenzobicyclo[4.4.1]undecane (9) and its 11-methylene derivative 8 are flexible molecules and take a chair-boat conformation. Complexes 8- and 9-TCNE exhibit the absorption maximum at ca. 420 nm, which coincides with the value for the TCNE complex of o-xylene. On the other hand, acetal 5, methylcarbinol 6, and dimethylmethylene derivative 7 are rigid, layered [3.3]OCPs with stacked benzene rings. Compounds 5, 6, and 7 form a 1 : 1 complex with TCNE in solution. The absorption maxima of the complexes at ca. 500 nm suggest an enhanced C-T complexation due to a pi-pi through-space interaction in 5, 6, and 7. A 2 : 1 complex of rigid [3.3]OCP 7 with TCNE crystallized from dichloromethane, while OCP 8 gave a red crystalline 2:3 complex with TCNE. X-ray crystallographic analyses of these two complexes is given.

DOI： 10.1246/bcsj.71.2661

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Reduction of imines was performed with zinc powder in 5% aq NaOH solution without any organic solvents under mild conditions, and the corresponding amines were obtained in good yields. (C) 1998 Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S0040-4039(98)01904-2

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Elsevier BV  

Use of a Raney Ni-Al alloy in dilute aqueous alkaline solution gave rise to strong reducing power and chlorobiphenyls were reduced easily to biphenyl and/or phenylcyclohexane, respectively, without any organic solvents. (C) 1998 Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/s0040-4039(98)01230-1

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Anti-Benzo[1,2-h;4,5-h']bis(benzo[1,2-c]bicyclo[4.4.1]undeca-3,8-diene-11-one) (7a) and bis(naphtho[2,3-c]bicyclo[4.4.1]undeca-3,8-diene-11-one) derivative 7b reacted with Grignard reagents (MeMgI and PhMgBr) to give bis(alcohol)s 10-12 or monoalcohols 13 and 14, depending upon the amount of the reagent used. Similarly, syn-bis(alcohol)s 15-17 and syn-monnalcohols 18 and 19 were obtained in the reaction of syn-benzo[ 1,2-h;4,5-h']bis(benzo[1,2-c]bicyclo[4.4.1]undeca-3,8-diene-11-one) (9) with tie Grignard reagents. The alcohols 10-19 were produced as a mixture of configurational isomers and each isomer was isolated by HPLC. The structures were determined by H-1 and C-13 NMR spectra, NOE study, and X-ray crystallographic analyses of 12a, 13, and 17a. The triple-layered [3.3][3.3]orthocyclophanes 10-12 take the (twin-chair)/(twin-chair) arrangement and in the structure, tie top and the bottom aromatic rings sandwich a central benzo ring. syn-Cyclophanes 15-17 exist as an equilibrium mixture of two equivalent (twin-chair)/(chair-boat)- and (chair-boat)/(twin-chair)-conformers in solution. In the solid, the conformation is fixed, as clarified by X-ray crystallographic analysis of 17a. Because of steric congestion, the central benzene ring in 17a is not planar. Monoalcohols 13-14 and 18-19 have a rigid and layered twin-chair substructure and a flexible chair-boat pat L. The existence of a through-space interaction between the three slacked aromatic rings of [3.3][3.3]orthocyclophanes 10-12 was determined on the basis of a long wavelength shift in UV spectra, as compared to the spectra of 13-19 having a double-layered [3.3]orthocyclophane-substructure. (C) 1998 Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S0040-4020(98)00217-8

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

DOI： 10.1002/(SICI)1521-3773(19981002)37:18<2532::AID-ANIE2532>3.0.CO;2-R

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Publishing type：Research paper (scientific journal)   Publisher：日本ソノケミストリー学会  

DOI： 10.20577/pamjss.7.0_27

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Tetraesters anti-9a,b and syn-9a,b, which have three aromatic rings, were prepared by the reaction of benzocycloheptenediester 7 with 1,2,4,5-tetrakis(bromomethyl)benzene. Subsequent hydrolysis and pyrolysis gave diketones anti-11a,b and syn-11a,b, which were acetalized to yield bisacetals anti-5a,b and syn-5a,b. X-Ray crystallographic analyses indicate a symmetric (twin-chair)/(twin-chair)-conformation of anti-5a,b, in which two naphtho or benzo rings sandwich one benzene ring. Anti-5a and anti-5b(9b)) are rigid structures. The protons of their central aromatic rings show an up-field shift, due to an anisotropic effect of the facing outer aromatic units. In contrast, syn-5a,b are flexible structures. The UV-spectra of anti-5a,b show a long wavelength shift, as compared to syn-5a,b, suggesting a through-space interaction among the aromatic rings. (C) 1997 Elsevier Science Ltd.

DOI： 10.1016/S0040-4020(97)00042-2

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

Conformational behaviour of dibenzo[c,h]bicyclo[4.4.1]undecanes having a dichloro- and a dibromo-cyclopropane ring, together with an oxirane ring on the methylene bridge, has been studied by H-1 NMR spectroscopy and X-ray crystallography.

DOI： 10.1039/a604939g

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Triple-layered [3.3][3.3]orthocyclophane of the anti-type was prepared for the first Lime, and its structure, in which two naphthalene rings sandwitch one benzene ring, was established by X-ny crystallographic analysis.

DOI： 10.1016/0040-4039(95)02103-5

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Language：English   Book type：Scholarly book

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Total pages：ix, 131p   Language：Japanese  

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Publisher：Springer Nature Singapore  

DOI： 10.1007/978-981-16-9001-3_38

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Publisher：Springer Nature Singapore  

DOI： 10.1007/978-981-16-9001-3_33

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Publisher：Book Publisher International (a part of SCIENCEDOMAIN International)  

DOI： 10.9734/bpi/cras/v11/10544d

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Publisher：Elsevier  

DOI： 10.1016/B978-0-12-821881-5.00007-6

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Language：Japanese   Publisher：京都 : 京都大学環境衛生工学研究会  

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