Ryo Kanzaki

A new proton conductive liquid with no ions: pseudo-protic ionic liquids.

Liquids with no ions! Raman analysis and quantum calculations suggest that electrically neutral molecular species predominantly exist in an N-methylimidazole and acetic acid equimolar mixture, and that ionic species are rather minor. Nevertheless, the mixture has significant ionic conductivity, and shows good ionic or superionic behavior (see figure). It may be suitable to call such liquids pseudo-ionic liquids rather than ionic liquids.

A pH Scale for the Protic Ionic Liquid Ethylammonium Nitrate

To quantify the properties of protic ionic liquids (PILs) as acid-base reaction media, potentiometric titrations were carried out in a neat PIL, ethylammonium nitrate (EAN). A linear relationship was found between the 14 pKa u2005values of 12u2005compounds in EAN and in water. In other words, the pKa u2005value in EAN was found to be roughly one unit greater than that in water regardless of the charge and hydrophobicity of the compounds. It is possible that this could be explained by the stronger acidity of HNO3 in EAN than that of H3 O(+) in water and not by the difference in the solvation state of the ions. The pHu2005value in EAN ranges from -1 to 9 on the pHu2005scale based on the pHu2005value in water.

Rapid method for monitoring N-nitrosodimethylamine in drinking water at the ng/L level without pre-concentration using high-performance liquid chromatography-chemiluminescence detection

As a contaminant in drinking water, N-nitrosodimethylamine (NDMA) is of great concern because of its carcinogenicity; it has been limited to levels of ng/L by regulatory bodies worldwide. Consequently, a rapid and sensitive method for monitoring NDMA in drinking water is urgently required. In this study, we report an improvement of our previously proposed HPLC-based system for NDMA determination. The approach consists of the HPLC separation of NDMA, followed by NDMA photolysis to form peroxynitrite and detection with a luminol chemiluminescence reaction. The detection limit for the improved HPLC method was 0.2ng/L, which is 10 times more sensitive than our previously reported system. For tap water measurements, only the addition of an ascorbic acid solution to eliminate residual chlorine and passage through an Oasis MAX solid-phase extraction cartridge are needed. The proposed NDMA determination method requires a sample volume of less than 2mL and a complete analysis time of less than 15min per sample. The method was utilized for the long-term monitoring of NDMA in tap water. The NDMA level measured in the municipal water survey was 4.9ng/L, and a seasonal change of the NDMA concentration in tap water was confirmed. The proposed method should constitute a useful NDMA monitoring method for protecting drinking water quality.

Determination of Organic and Inorganic Mercury Species as Emetine Dithiocarbamate Complexes by High-Performance Liquid Chromatography with Electrogenerated Tris(2,2′-bipyridine)ruthenium(III) Chemiluminescence Detection

A sensitive method for simultaneous determination of organic and inorganic mercury species has been developed and is presented in this study. The method is based on complex formation of mercury species with the emetine dithiocarbamate (emetine-CS2) ligand, HPLC separation, and tris(2,2′-bipyridine)ruthenium(III) chemiluminescence detection. The complexation reactions of the mercury species and emetine-CS2 ligand occurred instantaneously upon the addition of emetine-CS2 solution to the solution containing the mercury species. The complete separation of these complexes was achieved using an ODS column with 20 mM NaH2PO4-acetonitrile (52:48, v/v) containing 30 mM NaClO4 as an ion-pair reagent. The calibration graphs of these complexes were linear in the range from 1–100 µg/L. The detection limits were 0.27 µg/L, 0.33 µg/L, 0.39 µg/L, and 0.17 µg/L for methylmercury, ethylmercury, phenylmercury, and the mercury ion, respectively, at a signal-to-noise ratio of 3. The developed technique was validated by analyzing certified reference materials, CRM7402-a (cod fish, NMIJ) and CE464 (tuna fish, ERM), in combination with sonication-assisted acid leaching and liquid-liquid extraction. The emetine-CS2 ligand has been used for extraction, separation, and detection of mercury species. The results determined using the proposed method were in good agreement with the values of the certified reference materials. The MeHg+ and EtHg+ recoveries for the spiked samples were found to be almost 100%.

The influence of sample drying and storage conditions on methylmercury determination in soils and sediments

The separate influences of drying and storage conditions on methylmercury (MeHg) concentrations in soil and sediment samples were investigated. Concentrations of MeHg and total Hg were determined in various soil and sediment samples that had been stored or dried under differing conditions. The influence of drying conditions (oven-drying (40xa0°C) versus freeze-drying) on MeHg concentrations in marine sediments, river sediments, soils, and paddy field soils was investigated (nxa0=xa043). The ratio of the MeHg concentration in oven-dried sub-samples divided by the concentration in freeze-dried sub-samples ranged from 0 to 336%. In order to confirm the production of MeHg during storage in some samples, Hg2+ was added at 15xa0mgxa0kg-1 to a paddy soil, and the sample was then stored at 30xa0°C. The concentrations of MeHg at 1-h, 1-day, 4-days and 7-days after Hg2+ spiking were 2.0xa0±xa00.1, 13.8xa0±xa01.0, 36.0xa0±xa05.0, and 24.9xa0±xa01.6xa0μgxa0kg-1 (nxa0=xa03), respectively. The concentration of MeHg at 4-days after Hg spiking and sterilizing (121xa0°C, 30xa0min) was 1.8xa0μgxa0kg-1, similar to the original value. These results indicate that bacterial Hg methylation and MeHg demethylation occurred within days in the soil. In addition, tests of the stability of MeHg in wet and dry samples during storage were also performed. Overall, our results indicate that the best way to preserve MeHg in soil and sediment samples is to freeze the samples immediately after collection, followed subsequently by freeze-drying, grinding, homogenization, and storage of the dry material in cool, dark conditions until analysis.

Ultra-sensitive HPLC-photochemical reaction-luminol chemiluminescence method for the measurement of secondary amines after nitrosation.

A novel method for the determination of secondary amines at the nanomolar level was developed. The method is based on the nitrosation reaction of secondary amines, with the generated N-nitrosamines being measured using an HPLC separation, photochemical reaction, and chemiluminescence detection system. The efficient nitrosation of secondary amines was performed using sodium nitrite (200xa0mM) and acetic acid (0.8xa0M) at 80xa0°C over 60xa0min. Although compounds bearing OH and SH functional groups also underwent the nitrosation reaction, the sensitivity of these compounds was 1000 times lower than that of the secondary amines. Our method was applied to the determination of low molecular weight secondary amines, including dimethylamine, morpholine, pyrrolidine, diethylamine, and piperidine, giving method detection limits of 0.7xa0nM, 0.2xa0nM, 0.4xa0nM, 0.7xa0nM, and 1.5xa0nM, respectively. The calibration curves were linear in the range of 5-100xa0nM. We then applied this method for the detection and quantification of these secondary amines in samples of tap water, river water, treated wastewater, and sea water. Dimethylamine was detected at concentrations up to 15.4xa0nM, <0.7xa0nM, and 48.5xa0nM in tap water, river water, and treated wastewater samples, respectively, with recoveries ranging from 94 to 103%. Other amines were also detected at nanomolar levels. These results indicate that our proposed method can be applied to the analysis of secondary amines in various environmental water samples. To the best of our knowledge, the proposed method is one of the most sensitive and selective methods for the determination of secondary amines without pre-concentration steps.

Dispersion mechanism of polyacrylic acid-coated nanoparticle in protic ionic liquid, N,N-diethylethanolammonium trifluoromethanesulfonate

HYPOTHESISnIonic liquids (ILs) are extremely concentrated electrolyte solutions. The ubiquitous presence of ions induces specific behaviors for chemical reactions compared to reactions in water solutions. This is also the case for the stability of colloidal dispersions, for which the DLVO model cannot be applied as the ionic strength is out of the model range. In a previous work, in the protic IL ethylammonium nitrate (doi: https://doi.org//10.1016/j.jcis.2015.04.059), we observed an unexpected influence of the pH on the stability of dispersion of maghemite nanoparticles coated with poly(acrylic acid) (pAA).nnnEXPERIMENTSnTo clarify and generalize these observations, we investigated here the pH response of the dispersion in a second protic ionic liquid with a different acid-base nature, diethylethanolammonium trifluoromethanesulfonate. pH titrations of the dispersions were achieved with an IS-FET electrode and the associated thermodynamic constants determined. The colloid structural properties were examined by small angle X-ray scattering.nnnFINDINGSnUnder acidic or mildly basic condition, a stable dispersion was obtained, i.e., when the degree of dissociation of pAA, α, was αu202f<u202f0.1 or αu202f>u202f0.7. Dispersions form quite dense but reversible aggregates in the intermediate α range. A model for the solvation layer around the particles is proposed and generalizes the former findings.

Role of water in complexation of 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6) with Li+ and K+ in hydrophobic 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ionic liquid

Complexation characteristics of 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6, 18C6) with Li+ and K+ in a hydrophobic ionic liquid of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide under dry and humid conditions at 298.2xa0K were studied by 1H and 13C NMR chemical shifts. The comparison of the 1H and 13C chemical shifts of 18C6 molecule between the dry and humid IL solutions without the alkali metal ions showed that uncomplexed 18C6 molecules are solvated by water molecules in the humid ionic liquid solution. The changes in the 1H and 13C chemical shifts of 18C6 ligand molecule with the increases in the Li+ and K+ concentrations revealed that in both dry and humid ionic liquid solutions 18C6 molecule forms 1:1 complexes with Li+ and K+. The 1H NMR data of water molecules in the humid ionic liquid solutions demonstrated that water molecules interact with Li+-18C6 complexes and free Li+, but do not with K+-18C6 complexes and free K+. The mechanisms of the formation of the Li+ and K+ complexes in the humid ionic liquid solution are different from each other due to the differences in the complex-water interactions.

Behavior of mercury from the fumarolic activity of Mt. Myoko, Japan: production of methylmercury and ethylmercury in forest soil

The behavior of mercury (Hg) in water, sediments, air, dwarf bamboo leaves, and soils around the fumarolic area of Mt. Myoko, Japan, was investigated. Although some of the hot spring water samples contained over 1 µg/L total-Hg, overall, the total-Hg concentrations in the water samples decreased rapidly as the water flowed into a river. The total-Hg concentrations decreased not only due to simple dilution, but also to co-precipitation of Hg2+ with Fe(OH)3. The highest atmospheric Hg concentration, 91.7xa0ng/m3, was detected near the fumarole, and the concentrations decreased with distance from the fumarolic area. This tendency was also confirmed in the total-Hg concentrations of plant leaf samples. Total-Hg, methylmercury (MeHg), and ethylmercury (EtHg) concentrations in the soil surface layer (nu2009=u200913) ranged from 0.19 to 21.7xa0mg/kg, 0.3 to 9.3 µg/kg, and undetected to 7.7 µg/kg, respectively. The total-Hg concentrations in the surface layer soil samples decreased with distance from the fumarolic area, while the vertical distribution of total-Hg concentrations in the core and outcrop samples showed no clear trends. However, the MeHg and EtHg concentrations had no relationship with the total-Hg concentrations and were higher in the upper layer soils. The results suggest that MeHg and EtHg not only migrate with other Hg species from the volcanic gases, but are also generated on site. It was also confirmed that EtHg occurs in soil at the same level as MeHg in the study area.