Updated on 2024/10/11

写真a

 
Ryo Kanzaki
 
Organization
Research Field in Science, Science and Engineering Area Graduate School of Science and Engineering (Science) Department of Science Chemistry Program Associate Professor
Title
Associate Professor

Degree

  • 博士(理学) ( 2002.3   九州大学 )

Research Interests

  • Solution Chemistry

  • Chemical Thermodynamics

  • Coordination Chemistry

  • Ionic Liquid

  • Reaction Thermodynamics

  • Solution Chemistry

  • 分析化学

  • 溶液化学

  • 溶液錯体化学

  • Coordination Chemistry

Research Areas

  • Others / Others  / 溶液反応化学

  • Nanotechnology/Materials / Inorganic/coordination chemistry

  • Nanotechnology/Materials / Fundamental physical chemistry

  • Environmental Science/Agriculture Science / Environmental dynamic analysis

  • Nanotechnology/Materials / Analytical chemistry

Education

  • Kyushu University

    - 2002

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    Country: Japan

Research History

  • Kagoshima University   Research Field in Science, Science and Engineering Area Graduate School of Science and Engineering (Science) Department of Science Chemistry Program   Associate Professor

    2020.4

  • Université Pierre-et-Marie-Curie   Laboratoire PHENIX, UMR 8234   Visiting Researcher

    2014.8 - 2015.3

  • Kagoshima University   Graduate School of Science and Engineering   Associate Professor

    2009.4

  • Kagoshima University   Research Field in Science, Science and Engineering Area Graduate School of Science and Engineering (Science) Earth and Environmental Sciences Course   Associate Professor

    2009.4 - 2020.3

  • Kyushu University   Faculty of Sciences   Assistant Professor

    2007.4 - 2009.3

  • Kyushu University   Faculty of Sciences   Assistant Professor

    2003.6 - 2007.3

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Professional Memberships

  • 日本熱測定学会

    2015.10

  • 日本化学会

    2015.10

  • 日本分析化学会

    2015.10

  • THE CHEMICAL SOCIETY OF JAPAN

  • THE ELECTROCHEMICAL SOCIETY OF JAPAN

  • THE JAPAN ASSOCIATION OF SOLUTION CHEMISTRY

  • THE JAPAN SOCIETY FOR ANALYTICAL CHEMISTRY

  • THE JAPAN SOCIETY OF CALORIMETRY AND THERMAL ANALYSIS

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Committee Memberships

  • The Japan Society of Calorimetry and Thermal Analysis   Editor of Netsu Sokutei  

    2023.8   

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    Committee type:Academic society

  • The Japan Society for Analytical Chemistry   Analytical Sciences Associate Editor  

    2022.2   

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    Committee type:Academic society

  • 第13回イオン液体討論会   実行委員  

    2023.11   

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    Committee type:Academic society

  • The Japan Society of Calorimetry and Thermal Analysis   Editor in Chief (netsu sokutei)  

    2023.10   

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    Committee type:Academic society

  • 日本分析化学会第72年会   実行委員  

    2023.9   

  • ICCT-2023   Session Organizer  

    2023.7 - 2023.8   

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    Committee type:Academic society

  • 第44回溶液化学シンポジウム   実行委員長  

    2022.10   

  • ICFPM 2022   National Committee  

    2022.9   

  • The Japan Society of Analytical Chemistry   Associate Editor (Analytical Sciences)  

    2022.2   

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    Committee type:Academic society

  • 日本熱測定学会   庶務幹事  

    2018 - 2019   

  • 日本熱測定学会   委員  

    2018 - 2019   

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    Committee type:Academic society

  • 第30回九州分析化学若手の会夏季セミナー   世話人  

    2012.7   

  • 第72回分析化学討論会   実行委員  

    2012.5   

  • 日本分析化学会   「分析化学」編集委員  

    2012   

  • 日本熱測定学会   委員  

    2011 - 2012   

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    Committee type:Academic society

  • 日本分析化学会九州支部   副支部長  

    2011   

  • 日本分析化学会第57年会   実行委員  

    2008.9   

  • 日本熱測定学会   「熱測定」編集委員  

    2008 - 2009   

  • 日本熱測定学会   委員  

    2007 - 2008   

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    Committee type:Academic society

  • 第41回熱測定討論会   実行委員  

    2005.10   

  • 日本分析化学会九州支部   幹事  

    2005   

  • 日本分析化学会九州支部   会計幹事  

    2005   

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Studying abroad experiences

  • 2014.8 - 2015.3   université Paris VI, Université Pierre-et-Marie-Curie  

 

Papers

  • Kanzaki R., Hidaka T., Tokuda Y., Kodamatani H., Tomiyasu T. .  Brønsted acidity of bis(trifluoromethanesulfonyl)amide and trifluoromethanesulfonic acid in ionic liquids of ternary ammonium .  Journal of Molecular Liquids409   2024.9

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    Language:Japanese   Publisher:Journal of Molecular Liquids  

    Bis(trifluoromethanesulfonyl)amide (Tf2N−) and triflate (TfO−) are commonly used anions of protic ionic liquids (PILs). They are the conjugate anions of strong acids, Tf2NH and TfOH, whose Brønsted acidities crucially influence the performance of the PILs. In this study, the Brønsted acidity of Tf2NH and TfOH was compared directly through potentiometric titrations carried out in the ionic liquids of ternary ammonium salts. As a result, Tf2NH exhibits stronger Brønsted acidity than TfOH by approximately 2 pH units. Furthermore, calorimetric titrations revealed that this difference originates from differences in their entropy states. This suggests that the solvation state, rather than the properties in their isolated state, has a more significant impact on the acidities of Tf2NH and TfOH. Besides, ionization thermodynamics turned out to be governed by both the constituent cations and anions of the PILs. Therefore, once the acid-base natures of the constituent ions are characterized, the overall acid-base behavior of the PIL may become predictable.

    DOI: 10.1016/j.molliq.2024.125433

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  • Takashi Tomiyasu, Chihiro Nozoe, Wilder Leonardo Gamboa Ruiz, Hitoshi Kodamatani, Ryo Kanzaki .  Distribution of selenium and mercury concentrations in sediments of Kagoshima Bay: can submarine volcanic activity affect the distribution of selenium in sediments? .  Environmental Earth Sciences82 ( 20 )   2023.10Reviewed

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

    DOI: 10.1007/s12665-023-11159-9

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    Other Link: https://link.springer.com/article/10.1007/s12665-023-11159-9/fulltext.html

  • Takashi Tomiyasu, Hideaki Matsuki, Masanori Oda, Hitoshi Kodamatani, Ryo Kanzaki, Toru Kobari .  Impact of mercury discharged from submarine volcano on inner bay ecosystems .  Chemosphere339   139748   2023.10Reviewed

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

    Organic mercury, inorganic mercury and total mercury concentrations in phytoplankton (<0.1 mm) and zooplankton (>0.1 mm) collected in Kagoshima Bay, Japan were measured from 2017 to 2019 to estimate the impact of mercury discharged from submarine volcanoes on ecosystems; submarine volcanic activity continues at a depth of 200 m in the inner part of Kagoshima Bay. The total mercury concentrations in phyto- and zooplankton collected by vertical hauling at 0–200 m at just above the submarine volcano were in the range of 0.11–2.0 mg kg−1 (avg. 0.67 mg kg−1) and 0.090–0.56 mg kg−1 (avg. 0.21 mg kg−1), respectively. These values were one order of magnitude higher than the values in plankton collected in the central part of Kagoshima Bay. Organic mercury concentrations in phyto- and zooplankton were <0.010–0.071 mg kg−1 (avg. 0.028 mg kg−1) and 0.012–0.25 mg kg−1 (avg. 0.10 mg kg−1), respectively, for the inner part, and <0.010–0.040 mg kg−1 (avg. 0.010 mg kg−1) and <0.010–0.025 mg kg−1 (avg. 0.012 mg kg−1), respectively, for the central part. The values obtained in the inner part of the bay increased in summer and decreased in winter, which was consistent with changes in seawater mercury concentrations affected by volcanic activity. The organic mercury concentration in zooplankton collected just above the submarine volcano showed a size dependency, and a higher value was observed in the larger size, which suggested that the discharged mercury from the volcano was absorbed and concentrated through the ecosystem.

    DOI: 10.1016/j.chemosphere.2023.139748

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  • Ryo Kanzaki, Tomoya Hidaka, Hitoshi Kodamatani, Takashi Tomiyasu .  Determination of autoprotolysis (autoionization) constant according to gran's procedure on potentiometric titrations .  Journal of Molecular Liquids384   2023.8Reviewed

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

    Gran's plot is an ingenious tool to find endpoints in potentiometric neutralization titrations. It can also be utilized for determining the formal potential of the electrodes, which is required in the case of obtaining the hydrogen ion concentration with pH sensor electrodes involving glass electrodes. Furthermore, autoprotolysis constants can be determined through Gran's plots with high accuracy, even those containing impurities. Gran's plot is thus a fundamental technique for investigating the properties of novel solvents such as protic ionic liquids as acid-base media. However, there are limitations in the autoprotolysis constants of the solvents and the ionization constants of the impurities, and so on, where Gran's plots work well. Hence, we have clarified the reliable range of these constants to be determined through Gran's plot by calculating the titration curves under various conditions and simulating these determination processes.

    DOI: 10.1016/j.molliq.2023.122180

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  • Ryo kanzaki .  Deep eutectic solvents for liquid–liquid extraction .  Analytical Sciences39 ( 7 ) 1021 - 1022   2023.6Invited

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

    DOI: 10.1007/s44211-023-00362-0

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    Other Link: https://link.springer.com/article/10.1007/s44211-023-00362-0/fulltext.html

  • Takashi Tomiyasu, Ryohei Shitauchi, Daigo Kasai, Toshiki Kitagawa, Hitoshi Kodamatani, Ryo Kanzaki .  The distribution and dynamics of residual mercury from the Chisso chemical plant in sediments of the Yatsushiro Sea, western Kyushu, Japan: have recent sedimentations lowered surface mercury concentrations? .  Environmental science and pollution research international30 ( 28 ) 72769 - 72781   2023.6Reviewed International journal

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

    To determine the long-term dynamics of mercury discharged from Chisso chemical plant between 1932 and 1968, the vertical variation in mercury concentrations in Yatsushiro Sea sediments was studied from 2013 to 2020 at 31 locations and compared to the mercury concentration distribution obtained in 1996. The results suggest that new sedimentation occurred after 1996, but the mercury concentrations at the surface ranged from 0.2 to 1.9 mg kg-1, which did not decrease significantly over a 20-year period. It was estimated that approximately 17 t of mercury remained in the southern Yatsushiro Sea sediment, which is equivalent to 10-20% of the total mercury discharged between 1932 and 1968. From results of WD-XRF and TOC measurement, it was suggested that mercury in sediment had been transported with suspended particles derived from sludges from the chemical plant and further suggests that the suspended particles derived from the sediment surface layer are still slowly diffusing.

    DOI: 10.1007/s11356-023-27505-0

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  • Hitoshi Kodamatani, Shotaro Kubo, Akinori Takeuchi, Ryo Kanzaki, Takashi Tomiyasu .  Sensitive Detection of Nitrite and Nitrate in Seawater by 222 nm UV-Irradiated Photochemical Conversion to Peroxynitrite and Ion Chromatography-Luminol Chemiluminescence System. .  Environmental science & technology57 ( 14 ) 5924 - 5933   2023.4International journal

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

    Sensitive detection methods for nitrite (NO2-) and nitrate (NO3-) ions are essential to understand the nitrogen cycle and for environmental protection and public health. Herein, we report a detection method that combines ion-chromatographic separation of NO2- and NO3-, on-line photochemical conversion of these ions to peroxynitrite (ONOO-) by irradiation with a 222 nm excimer lamp, and chemiluminescence from the reaction between luminol and ONOO-. The detection limits for NO2- and NO3- were 0.01 and 0.03 μM, respectively, with linear ranges of 0.010-2.0 and 0.10-3.0 μM, respectively, at an injection volume of 1 μL. The results obtained by the proposed method for seawater analysis corresponded with those of a reference method (AutoAnalyzer based on the Griess reaction). As luminol chemiluminescence can measure ONOO- at picomolar concentrations, our method is expected to be able to detect NO2- and NO3- at picomolar concentrations owing to the high conversion ratio to ONOO- (>60%), assuming that contamination and background chemiluminescence issues can be resolved. This method has the potential to emerge as an innovative technology for NO2- and NO3- detection in various samples.

    DOI: 10.1021/acs.est.3c00273

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  • Takashi Tomiyasu, Sora Yasumatsu, Hitoshi Kodamatani, Ryo Kanzaki, Chisato Takenaka, Satoshi Murao, Shuichi Miyagawa, Kenichi Nonaka, Akiko Ikeguchi, Ian A Navarrete .  The dynamics of mercury around an artisanal and small-scale gold mining area, Camarines Norte, Philippines. .  Environmental science and pollution research international30 ( 8 ) 20052 - 20064   2023.2Reviewed International journal

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

    To elucidate the dynamics of mercury emitted and released by artisanal and small-scale gold mining (ASGM) activity and to estimate its impact on the ecosystems of the bay, the distribution of mercury in the atmosphere, soil, water, and sediment around Mambulao Bay, Camarines Norte, Philippines, was investigated. The ASGM operations use mercury to extract gold from ore and are located on the east shore side of the bay. Samplings were conducted in August 2017 and September 2018. The samples were used for determination of total mercury (T-Hg) and organic mercury (org-Hg) concentrations, total organic carbon (TOC) content, and chemical composition. The atmospheric mercury concentration on the east shore side, 6.1-25.8 ng m-3, was significantly higher than the value of 1.4-9.9 ng m-3 observed on the west shore side. The average concentrations of T-Hg in the forest soils of the west shore side and those of the east shore side were 0.081 ± 0.028 mg kg-1 and 0.496 ± 0.439 mg kg-1, respectively. In the vertical distribution of T-Hg in the soil of the east shore side, a higher concentration was observed near the surface. For the vertical variations in T-Hg in the marine sediment, higher values were observed near the estuary, and the vertical variations in core samples showed an increase in mercury concentration toward the surface. The highest concentration of T-Hg in sediment, 9.5 mg kg-1, which was 2 orders of magnitude higher than the background levels of this area, was found near the river mouth. The T-Hg, org-Hg, and TOC levels showed a positive correlation, suggesting that the rivers are the main sources of T-Hg and org-Hg in the bay. Although the fish sample containing a mercury content higher than the regulatory level for fish and shellfish of 0.4 mg kg-1 in Japan was only one of 42 samples, the percentage of org-Hg in fish samples was 91 ± 18%. Mercury released into the surroundings by the ASGM activities can be converted into methylmercury and affect the bay's ecosystem.

    DOI: 10.1007/s11356-022-23497-5

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  • Hitoshi Kodamatani, Karin Kubozono, Ryo Kanzaki, Takashi Tomiyasu, Takahiro Fujioka .  Reverse osmosis membrane-based pretreatment for the quantification of N-nitrosodimethylamine concentrations in high-matrix water samples .  Environmental Science: Water Research and Technology9 ( 10 ) 2553 - 2560   2023Reviewed

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

    N-Nitrosodimethylamine (NDMA) is a carcinogenic constituent commonly found in recycled water and pharmaceuticals. Developing an analytical method to continuously monitor changes in NDMA concentrations during water recycling and pharmaceutical manufacturing can mitigate accidents caused by NDMA formation. However, NDMA analysis in high-matrix water samples, such as beverages, wastewater, and pharmaceutical ingredients, is difficult. In this study, we adapted reverse osmosis (RO) membrane treatment as a pretreatment for NDMA analysis by isolating NDMA from interfering substances in high-matrix water samples. Subsequently, high-performance liquid chromatography-chemiluminescence detection was used for NDMA analysis. In a pure water matrix, 95% of NDMA can pass through at a low permeate flux of 1 L m−2 h−1. The method was then validated using beer, which is known to contain high concentrations of NDMA, as a representative high-matrix water sample. We found that RO pretreatment leads to clean chromatograms in which NDMA peaks are clearly visible while other peaks are mostly absent. Analysis of six different beer samples showed a maximum NDMA concentration of 315 ng L−1, and an average NDMA concentration of 138 ± 83 ng L−1 (n = 6), which fall within the regulation limits for NDMA in beer in the United States of America. The proposed pretreatment method has the potential to provide a platform for developing technologies for continuous monitoring of NDMA in aqueous solutions.

    DOI: 10.1039/d3ew00222e

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  • Takashi Tomiyasu, Akihiro Mitsui, Mai Mitarai, Hitoshi Kodamatani, Ryo Kanzaki .  Seasonal variation in mercury species in seawater of Kagoshima Bay, southern Kyushu, Japan: The impact of active submarine volcanos on the inner bay .  Marine Chemistry244   2022.7Reviewed

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

    Wakamiko Proto-Caldera, a submarine volcano, is located at the bottom of the sea in the bay head area of Kagoshima Bay. In Kagoshima Bay, several species of fish with total mercury exceeding the provisional regulation value of 0.40 mg kg−1 were found in the 1970s. The effects of mercury released from submarine volcanoes are suspected. However, the path from volcanic mercury to the broader ecosystem has not yet been clarified. In this study, as the first step to elucidate the impact of volcanic activity on the ecosystems of Kagoshima Bay, seasonal changes in the concentrations of dissolved gaseous mercury (DGM), Hg(II), filtered total mercury (FT-Hg), particulate mercury (P-Hg), and mercury in suspended particulate matter (Hg in SPM) in seawater of Kagoshima Bay were tracked every two months from Feb. 2014 to Dec. 2017. The dissolved total mercury (DT-Hg) concentration was calculated by summing the DGM and FT-Hg concentrations. The DT-Hg at the location in the caldera ranged from 0.09 to 6.83 ng L−1 showing higher values in summer compared to winter, that is, in the stratified period. The P-Hg showed similar periodic variation as DT-Hg, and the highest Hg in SPM was 2.15 mg kg−1, which is one order of magnitude higher than that observed at the reference site. The high mercury concentration in SPM suggests the accumulation of dissolved mercury discharged from volcanic activity on SPM. Since mercury loaded on SPM can be taken up by suspension feeders and enter the food chain, the Hg in SPM may be a key factor affecting Hg in fishes in Kagoshima Bay.

    DOI: 10.1016/j.marchem.2022.104133

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  • Hitoshi Kodamatani, Azusa Shigetomi, Junna Akama, Ryo Kanzaki, Takashi Tomiyasu .  Distribution, alkylation, and migration of mercury in soil discharged from the Itomuka mercury mine. .  The Science of the total environment815   152492 - 152492   2022.4Reviewed International journal

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

    The purpose of this study was to investigate the behavior of previously discharged mercury (Hg) released from the Itomuka Hg mine into the surrounding environment, especially into soil. Total-Hg (T-Hg), methylmercury (MeHg), and ethylmercury (EtHg) concentrations in the surface soil at eight sample sites around the mine were 3.8-64.2 mg/kg, 6.0-54.7 μg/kg, and undetected to 4.5 μg/kg, respectively. Core samples collected from seven of the eight sample sites showed that the vertical distribution of T-Hg was the highest in the surface soil layer and decreased rapidly in the lower layers. A strong positive correlation was observed between T-Hg and MeHg concentrations in the core samples; however, the slope of the regression line varied considerably for each core. This suggests that Hg and MeHg were not supplied from the atmosphere simultaneously, but rather that MeHg was produced on-site. Further, the formation of MeHg and EtHg in soil was considered in terms of the total organic carbon/total nitrogen ratio, which is a decomposition index of soil organic matter. The strong positive correlation between T-Hg and MeHg can be attributed to the migration of organic matter containing Hg species to the lower layers. There was no relationship between T-Hg and MeHg at the riverbed sample site because of the high T-Hg in the lower soil layers, suggesting that Hg was supplied by ore at this sample site. These assumptions of the formation change and migration of Hg in soil were supported by the results of the fractionation experiment and the elution test. To understand the current conditions in this area, measurements of Hg in the water, sediment, atmosphere, and plants were also conducted.

    DOI: 10.1016/j.scitotenv.2021.152492

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  • Ryo Kanzaki, Mika Sako, Hitoshi Kodamatani, Takashi Tomiyasu, Clément Guibert, Jérôme Fresnais, Véronique Peyre .  Enthalpy profile of pH-induced flocculation and redispersion of polyacrylic acid-coated nanoparticles in protic ionic liquid, N,N-diethylethanolammonium trifluoromethanesulfonate .  Journal of Molecular Liquids349   2022.3Reviewed

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

    Maghemite nanoparticles coated with polyacrylic acid (pAA) were dispersed in the protic ionic liquid, diethylethanolammonium trifluoromethanesulfonate (DEEAH+⋅TfO−), and the thermodynamics of particle dispersion was studied by means of potentiometric and calorimetric titrations over the entire accessible pH range. As previously reported, the domain of colloidal stability is divided into two pH regions, mildly acidic and basic, separated by a flocculation domain at an intermediate pH. In this study, solvent DEEAH+⋅TfO− was first characterized in terms of the thermodynamic parameters of two reference reactions: autoprotolysis and ionization of acetic acid. A negative autoprotolysis entropy is obtained due to hydrogen-bond formation between the neutralized solvent cation, DEEA, and the neighboring cation DEEAH+. This suggests that the solvent structure is reinforced by the formation of neutral species, being an opposite trend to both ethylammonium nitrate and water. Second, the ionization and flocculation of pAA-coated nanoparticles (CNps) in the ionic liquid were examined. The potentiometric results could be modeled using a simple pAA ionization, independent of the aggregation state over the entire pH range. However, the calorimetric titration detected extra heat generation in an acidic condition prior to flocculation, in addition to an ionization enthalpy of pAA of 30 kJ/mol. This exothermic contribution is attributed to a change in the solvation process of CNps in the ionic liquid. Herein, we propose a model in which different types of solvation in the acidic and basic domains are sufficient to ensure colloidal stability, while aggregation unfolds between the switching pH.

    DOI: 10.1016/j.molliq.2021.118146

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  • Hitoshi Kodamatani, Daisuke Yoshimine, Takahiro Fujioka, Ryo Kanzaki, Takashi Tomiyasu .  A novel luminol chemiluminescence induced by photoexcited ketones: A selective determination method for acetone in wastewater .  Talanta open3   100035 - 100035   2021.8Reviewed

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:Elsevier {BV}  

    DOI: 10.1016/j.talo.2021.100035

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  • Hitoshi Kodamatani, Taketo Tanisue, Takahiro Fujioka, Ryo Kanzaki, Takashi Tomiyasu .  Inhibitory effect of alkyl groups on N-nitrosamine formation from secondary and tertiary alkylamines with monochloramine .  Environmental Technology and Innovation22   2021.5Reviewed

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

    N-nitrosamines are contaminants of emerging concern, and controlling these chemicals in potable water and recycled water for potable reuse has become important for protecting public health. This study aimed to evaluate the influence of the alkyl chain lengths of N-nitrosamine precursors (secondary and tertiary amines) on the formation of N-nitrosamines via chloramination. The molar conversion efficiency from dimethylamine, an N-nitrosodimethylamine (NDMA) precursor, to NDMA (0.67%) was greater than that from diethylamine, an N-nitrosodiethylamine (NDEA) precursor, to NDEA (0.38%). Similarly, the molar conversion efficiency from trimethylamine to NDMA (0.92%) was greater than from triethylamine to NDEA (0.33%). Interestingly, a considerable difference in molar conversion efficiencies were observed for tertiary amines with the N,N-dialkyl-α-arylamine structure: the molar conversion efficiencies from N,N-dimethylbenzylamine and N,N-diethylbenzylamine to NDMA and NDEA were 50.2% and 1.7%, respectively. These results indicate that amines with ethyl groups have lower potentials for producing the corresponding N-nitrosamines than those with methyl groups. These differences in yields between amines with methyl and ethyl groups can be explained by the difference in electron density in the nitrogen atom of the amine, which influences the protonation of the amine and stabilization of intermediate species. These findings could be useful for enhancing source control of water and wastewater by regulating runoff or industrial wastewater containing high concentrations of specific N-nitrosamine precursors.

    DOI: 10.1016/j.eti.2021.101520

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  • Takashi Tomiyasu, Misato Nakagawa, Hitoshi Kodamatani, Ryo Kanzaki .  The influence of submarine volcano on seasonal changes in arsenic in the waters of Kagoshima Bay, southwestern Japan .  ENVIRONMENTAL EARTH SCIENCES80 ( 8 )   2021.4Reviewed

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

    Volcanic activity is one of the primary sources of arsenic in nature, and chemical forms of arsenic discharged by volcanic activity are inorganic. Kagoshima Bay has active submarine volcano located in the 200 m deep basin of its northern part. Since dissolved inorganic arsenic is more toxic than organic arsenic it is important to understand the dispersion of discharged arsenic in seawater. To estimate the influence of arsenic emitted from the bottom vents seasonal changes in As(III) and As(V) concentrations in seawater were studied. There are few studies on the impact of arsenic discharged by submarine volcanos in the inner bay. The total concentrations of As(III) and As(V) (T-As) in seawater at the background site in Kagoshima Bay was 1.71 +/- 0.35 mu g L-1 (av. +/- s.d.), similar to the world average value of 1.7 mu g L-1. The highest T-As value at the nearest point to the submarine volcano, 3.48 mu g L-1, was observed in summer. Since the vertical mixing of seawater cannot occur in summer due to the formation of the thermocline, the deep water is strongly affected by volcanic activity. The increase in T-As was caused by the increase in As(III) concentration suggesting the discharge of As(III) from the vents.

    DOI: 10.1007/s12665-021-09619-1

    Web of Science

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  • Hitoshi Kodamatani, Kenta Sugihara, Taketo Tanisue, Ryo Kanzaki, Takashi Tomiyasu .  Contamination, Decomposition, and Formation of N-Nitrosodimethylamine in Water Samples at the ng/L Level of Determination .  ANALYTICAL SCIENCES36 ( 11 ) 1393 - 1399   2020.11Reviewed

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

    An ultra-sensitive analytical system that can determine the concentration of N-nitrosamines at the ng/L level without preconcentration was used to investigate the contamination, decomposition, and formation of N-nitrosodimethylamine (NDMA) and other N-nitrosamines in water samples during general analytical procedures. A preliminary experiment was performed to estimate the NDMA concentrations in ambient air. Since the air samples contained NDMA at concentrations in the range of 2.0 - 10.7 ng/m(3), ambient air was identified as the source of NDMA contamination in water samples. We directly confirmed that the concentration of aqueous 10-ng/L NDMA samples stored in clear glass bottles decreased upon exposure to sunlight. Thus, to maintain the N-nitrosamine concentration, such samples must always be protected from sunlight during sampling. The existence of N-nitrosamines in experimental reagents, such as ranitidine and sodium hypochlorite solutions, was also confirmed, as was the formation of NDMA on an activated carbon solid-phase extraction cartridge.

    DOI: 10.2116/analsci.20P162

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  • Takashi Tomiyasu, Christine Baransano, Yuriko Kono Hamada, Hitoshi Kodamatani, Ryo Kanzaki, Nuril Hidayati, Joeni Setijo Rahajoe .  Distribution of total and organic mercury in soils around an artisanal and small-scale gold mining area in West Java, Indonesia .  SN APPLIED SCIENCES2 ( 7 )   2020.7Reviewed

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    This study was conducted to understand the environmental behavior of mercury released by artisanal and small-scale gold mining (ASGM) activities. For this purpose, we attempted to assess the effect of diffused mercury on mercury concentrations in soil, demonstrate the presence of methylmercury in soil affected by the deposited mercury and determine the reactions associated with methylmercury production. The vertical profiles of mercury were obtained from two sites in the forest of the ASGM village in Pongkor (West Java, Indonesia) and from two sites in Mount Halimun-Salak National Park, which is approximately 12 km from the ASGM village. The highest total mercury concentration, 8.9 mg kg(-1), was observed for soil samples collected at the ASGM village. The mercury was concentrated at the surface or in the subsurface layers, and the concentrations were several times to more than ten times higher than the lowest values observed in the deeper layers at each site. Even in the national park, the highest concentration of 1.9 mg kg(-1) was observed in the upper soil layer. These results suggest that the primary source of mercury in the forest soil is atmospheric deposition; fallen plant leaves also deliver accumulated mercury to the soil surface. The organic mercury percentages of the total mercury were 0.2 +/- 0.1% for the national park and 0.3 +/- 0.2% for ASGM sites. The vertical variation in organic mercury concentration did not always match that in total mercury concentration, which suggested that the formation of methylmercury in soil was closely related to the decomposition of organic matter near the surface. The soil surface is an important reaction field for methylmercury production in forested areas.

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  • Hitoshi Kodamatani, Yuri Daiba, Shintarou Morisaki, Katsuyuki Ichitani, Ryo Kanzaki, Takashi Tomiyasu .  Detailed investigation of methylmercury accumulation in rice grain from Hg<sup>2+</sup>-spiked non-contaminated paddy field soils .  Chemosphere247   125827   2020.5Reviewed

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    © 2020 Elsevier Ltd Total-Hg (T-Hg) and methylmercury (MeHg) concentrations in rice grains were measured to understand the MeHg accumulation process. Rice plants were cultivated in Hg2+-spiked non-contaminated soils in experimental pots at three different places. Although soil MeHg concentrations in the pots changed significantly and individually during the rice-growing season, T-Hg concentration of brown rice grain was high at high soil MeHg concentration. In addition, there was no significant variation in T-Hg concentration in brown rice grains from individual panicles or among panicles obtained from the same pot, although the period of growth for each panicle was different. The highest T-Hg concentration of brown rice grains recorded for a panicle was 1.4 ± 0.1 mg kg−1 (n = 8), and the corresponding MeHg ratio was 76%. In addition, the T-Hg and MeHg concentrations in various parts of the brown rice grain—white rice (endosperm), bran, and embryo—were measured. Among the parts of the brown rice grain, the embryo had the highest Hg concentration. Furthermore, Hg concentration in the grain was constant during grain filling. These findings suggest that MeHg formed in soil accumulates in the rice plant during growth and is supplied to the rice grains continuously for the entire duration of the grain development period.

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  • Yuji Kamiyama, Masayuki Shibata, Ryo Kanzaki, Kenta Fujii .  Lithium-Ion Coordination-Induced Conformational Change of PEG Chains in Ionic-Liquid-Based Electrolytes .  Physical Chemistry Chemical Physics22 ( 10 ) 5561 - 5567   2020.3

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  • Kanzaki Ryo .  Chemical Thermodynamics for Analytical Chemist .  Netsu Sokutei46 ( 4 ) 195 - 201   2019.10Chemical Thermodynamics for Analytical ChemistInvited Reviewed

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    One of the fundamental roles of analytical chemistry is to provide the information of chemical species distributing in solutions, where chemical equilibria of acid dissociation, dissolving of salts, complex formation, electrode reaction, etc., are considered. This extensively owes to chemical thermodynamics, however, the relationship is rarely taught in detail in the class of physical chemistry nor analytical chemistry. It will be a great loss in both fields. In this article, with beginning from the usual equilibria in analytical chemistry, its groundwork of chemical thermodynamics will be explained. First, chemical potential is introduced as the determining factor of equilibrium constant, then Gibbs energy is defined. Although this is inverted from the ordinary way of instruction, possibly more convenient for the field of analytical chemistry. Then, activity coefficient and the standard state are explained, followed by the derivation of chemical potential from the work for changing concentration of solute in solution for clarifying its physical meaning. Turning to the solvent, the solvent transfer is considered by both transfer Gibbs energy and transfer activity coefficient. Finally, electrochemical potential is outlined. They are described within the word of analytical chemistry. Hopefully, this article will help establishing the energy-based perspective on the chemical equilibria in solutions.

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  • Kanzaki Ryo, Kodamatani Hitoshi, Tomiyasu Takashi .  Proton Thermodynamics in a Protic Ionic Liquid, Ethylammonium Nitrate .  CHEMISTRY-A EUROPEAN JOURNAL25 ( 59 ) 13500 - 13503   2019Reviewed

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  • Kitagawa Toshiki, Kasai Daigo, Shitauchi Ryouhei, Kodamatani Hitoshi, Kanzaki Ryo, Tomiyasu Takashi .  The distribution of residual mercury in sediment around Minamata Bay ,and the chemical composition of the sediment. .  Abstracts of Annual Meeting of the Geochemical Society of Japan66 ( 0 ) 259   2019

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  • Nozoe Chihiro, Kodamatani Hitoshi, Kanzaki Ryo, Tomiyasu Takashi .  Distribution of mercury and selenium in sediments from Kagoshima Bay, and impact of submarine fumaroles .  Abstracts of Annual Meeting of the Geochemical Society of Japan66 ( 0 ) 126   2019

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  • Kanzaki Ryo, Daiba Hikaru, Kodamatani Hitoshi, Tomiyasu Takashi .  Validation of pH Standards and Estimation of the Activity Coefficients of Hydrogen and Chloride Ions in an Ionic Liquid, Ethylammonium Nitrate .  JOURNAL OF PHYSICAL CHEMISTRY B122 ( 46 ) 10593 - 10599   2018.11Reviewed

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    DOI: 10.1021/acs.jpcb.8b08870

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  • Kodamatani Hitoshi, Katsuma Souta, Shigetomi Azusa, Hokazono Toshimune, Imura Ryusuke, Kanzaki Ryo, Tomiyasu Takashi .  Behavior of mercury from the fumarolic activity of Mt. Myoko, Japan: production of methylmercury and ethylmercury in forest soil .  ENVIRONMENTAL EARTH SCIENCES77 ( 13 )   2018.7Reviewed

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  • Ryo Kanzaki, Clément Guibert, Jérôme Fresnais, Véronique Peyre .  Dispersion mechanism of polyacrylic acid-coated nanoparticle in protic ionic liquid, N,N-diethylethanolammonium trifluoromethanesulfonate .  Journal of Colloid and Interface Science516   248 - 253   2018.4Reviewed

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    Hypothesis: Ionic 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). Experiments: To 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. Findings: Under acidic or mildly basic condition, a stable dispersion was obtained, i.e., when the degree of dissociation of pAA, α was α &lt
    0.1 or α &gt
    0.7. 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.

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  • Ryo Kanzaki, Shuma Uchida, Hitoshi Kodamatani, Takashi Tomiyasu .  Copper(II) Chloro Complex Formation Thermodynamics and Structure in Ionic Liquid, 1-Butyl-3-Methylimidazolium Trifluoromethanesulfonate .  JOURNAL OF PHYSICAL CHEMISTRY B121 ( 41 ) 9659 - 9665   2017.10

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    Metal ions in ionic liquids are laid under an unprecedented reaction field. In order to assess the reaction thermodynamics of metal ions in such a situation, Cu2+-chloro complex formation was examined with spectroscopic and calorimetric titrations in an ionic liquid, 1-buthy1-3-methylimidazolium trifluoromethanesulfonate (C(4)mimTfO). In addition, the effect of the structure of the solvated complexes on the complexation mechanism was investigated with the aid of DFT calculations. Chloro complexation successively proceeded and finally provided a [CuCl4](2-) species, which is also the final product in conventional molecular solvents. Their stability constants were comparable to those in molecular solvents. Interestingly, in spite of the charged solvent in the ionic liquid, the entropy profile of the complexation resembled that in the conventional molecular liquids. This indicates that the entropy gain of the released solvent species from the complexes is the main driving force of the chloro complexation in the ionic liquid. In contrast, unlike the major molecular solvents, the total coordination number of Cu2+ is saturated to 4 in the ionic liquid, and the Cl- complexation tends to be accompanied by a 1:1 exchange of the solvent TfO- from the complex. In addition, this ligand exchange was almost athermal. This possibly indicates that the coordination number is dominated by the electrostatic hindrance among the ligands including the solvent ions in the primary coordination sphere.

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  • Hitoshi Kodamatani, Chihiro Maeda, Steven J. Balogh, Yabing H. Nollet, Ryo Kanzaki, Takashi Tomiyasu .  The influence of sample drying and storage conditions on methylmercury determination in soils and sediments .  CHEMOSPHERE173   380 - 386   2017.4Reviewed

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    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 (40 degrees C) versus freeze-drying) on MeHg concentrations in marine sediments, river sediments, soils, and paddy field soils was investigated (n = 43). 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 15 mg kg(-1) to a paddy soil, and the sample was then stored at 30 degrees C. The concentrations of MeHg at 1-h, 1-day, 4-days and 7-days after Hg2+ spiking were 2.0 +/- 0.1, 13.8 +/- 1.0, 36.0 +/- 5.0, and 24.9 +/- 1.6 mu g kg(-1) (n = 3), respectively. The concentration of MeHg at 4-days after Hg spiking and sterilizing (121 degrees C, 30 min) was 1.8 mu g kg(-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.

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  • Hitoshi Kodamatani, Yoshimi Iwaya, Makoto Saga, Keiitsu Saito, Takahiro Fujioka, Shigeo Yamazaki, Ryo Kanzaki, Takashi Tomiyasu .  Ultra-sensitive HPLC-photochemical reaction-luminol chemiluminescence method for the measurement of secondary amines after nitrosation .  ANALYTICA CHIMICA ACTA952   50 - 58   2017.2Reviewed

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    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 (200 mM) and acetic acid (0.8 M) at 80 degrees C over 60 min. 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 0.7 nM, 0.2 nM, 0.4 nM, 0.7 nM, and 1.5 nM, respectively. The calibration curves were linear in the range of 5-100 nM. 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 15.4 nM, &lt;0.7 nM, and 48.5 nM 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. (C) 2016 Elsevier B.V. All rights reserved.

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  • Hitoshi Kodamatani, Hitomi Yamasaki, Takeru Sakaguchi, Shinya Itoh, Yoshimi Iwaya, Makoto Saga, Keiitsu Saito, Ryo Kanzaki, Takashi Tomiyasu .  Rapid method for monitoring N-nitrosodimethylamine in drinking water at the ng/L level without pre-concentration using high-performance liquid chromatography-chemiluminescence detection .  JOURNAL OF CHROMATOGRAPHY A1460   202 - 206   2016.8Reviewed

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    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 0.2 ng/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 2 mL and a complete analysis time of less than 15 min 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 4.9 ng/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. (C) 2016 Elsevier B.V. All rights reserved.

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  • Hikari Watanabe, Hiroyuki Doi, Soshi Saito, Masaru Matsugami, Kenta Fujii, Ryo Kanzaki, Yasuo Kameda, Yasuhiro Umebayashi .  Hydrogen bond in imidazolium based protic and aprotic ionic liquids .  JOURNAL OF MOLECULAR LIQUIDS217   35 - 42   2016Reviewed

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    Liquid structure of bis-(trifluoromethanesulfonyl)amide TFSA(-) based protic and aprotic ionic liquids composed of imidazolium [h(2)Im(+)], N-methylimidazolium [C(1)hIm(+)] and N,N'-dimethylimidazolium [C(1)mIm(+)] were investigated by high-energy total scattering (NETS) experiments. The nearest neighboring cation-anon orientation variations by the N-methyl groups substitution to proton were suggested based on the peaks at around 6 and 9 angstrom in the differential radial distribution functions as the form of r(2){G(x-ray)(r)-1) for these ionic liquids. It was supposed that the NH center dot center dot center dot O hydrogen bond causes the cation-anion orientation variations. To obtain further insight into the hydrogen bond in the PIL, MD simulations performed and agreed well with the experiments. According to spatial distribution functions (SDF) for the three ionic liquids, the O atom of TFSA(-) prefers the NH hydrogen of the imidazolium that has the most positive partial atomic charge in the cation, while the F atom locates right above and right below the imidazolium ring plane. In addition, the NH center dot center dot center dot O hydrogen bond has short bond lengths and linear bond angles, while the C2H center dot center dot O interaction is long and bent. The NH center dot center dot center dot O hydrogen bond in the PIL was discussed based on structural aspect accompanied by a thermodynamic viewpoint. (C) 2015 Elsevier B.V. All rights reserved.

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  • Ryo Kanzaki, Hitoshi Kodamatani, Takashi Tomiyasu, Hikari Watanabe, Yasuhiro Umebayashi .  A pH Scale for the Protic Ionic Liquid Ethylammonium Nitrate .  ANGEWANDTE CHEMIE-INTERNATIONAL EDITION2016 ( 21 ) 6266 - 6269   2016Reviewed

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    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 pK(a) values of 12 compounds in EAN and in water. In other words, the pK(a) value 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 H3O+ in water and not by the difference in the solvation state of the ions. The pH value in EAN ranges from -1 to 9 on the pH scale based on the pH value in water.

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  • Hikari Watanabe, Hiroyuki Doi, Soshi Saito, Koichiro Sadakane, Kenta Fujii, Ryo Kanzaki, Yasuo Kameda, Yasuhiro Umebayashi .  Raman Spectroscopic Speciation Analyses and Liquid Structures by High-Energy X-ray Total Scattering and Molecular Dynamics Simulations for N-methylimidazolium-Based Protic Ionic Liquids .  BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN89 ( 8 ) 965 - 972   2016Reviewed

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    Recently, we revealed N-methylimidazole C(1)Im equimolar mixtures with superacids and strong acids such as trifluoromethanesulfonic acid HTfO (Tf: CF3SO2-), bis-(trifluoromethanesulfonyl)amide acid HTf2N or trifluoroacetic acid CF3COOH are essentially protic ionic liquids by means of potentiometry of direct pH measurement in such liquids. Here, we demonstrated Raman spectroscopic speciation analysis of [C(1)hIm(+)][TfO-] and [C(1)hIm(+)][Tf2N-] (C(1)hIm(+): N-methylimidazolium) to elucidate both liquids are spectroscopically protic ionic liquids; much excess ionic species exist in these liquids and the amount of electrically neutral molecular species are practically negligible. In addition, to further insight into the hydrogen bond in the imidazolium-based protic ionic liquids, liquid structure of [C(1)hIm(+)][TfO-] were studied by high-energy X-ray total scattering HEXTS experiments with the aid of molecular dynamics simulations. Comparing with the hydrogen bond in [C(1)hIm(+)][Tf2N-] previously reported, the hydrogen bond in [C(1)hIm][TfO-] is stronger probably due to the narrower negative charge de-localization.

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  • Takashi Tomiyasu, Takuya Minato, Wilder Leonardo Gamboa Ruiz, Hitoshi Kodamatani, Yuriko Kono, Masayasu Hidaka, Kimihiko Oki, Ryo Kanzaki, Yoko Taniguchi, Akito Matsuyama .  Influence of submarine fumaroles on the seasonal changes in mercury species in the waters of Kagoshima Bay, Japan .  MARINE CHEMISTRY177   763 - 771   2015.12Reviewed

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    Submarine fumaroles are located in the 200-m deep basin of the northern part of Kagoshima Bay. To estimate the influence of mercury emitted from these fumaroles, the seasonal changes in total mercury (T-Hg), reactive mercury (RM), dissolved gaseous mercury (DGM), and monomethylmercury (MMHg) in water were studied. Seawater samples were collected from five separate locations in the northern part from May, 2011 to May, 2012 using a CTD-Rosette water sampler; the samples were taken every 50 m, starting from the surface. T-Hg, DGM, RM, and MMHg in the seawater columns (n = 132) were in the range of 0.05-3.04 ng L-1, 0.003-1.08 ng L-1, 0.006-1.47 ng L-1, 0.02-0.69 ng L-1 for an entire sample. Although the average T-Hg values at the surface and middle layers (0-100 m) for each sample showed no significant seasonal variation throughout the year, those at the deeper layer (150-200 m) were high from summer to autumn and low in winter. The seasonal changes and vertical distributions of DGM, RM, and MMHg concentrations were similar to those of T-Hg. A thermodine was observed from spring to autumn and ceased in winter. Because the thermocline prohibits vertical circulation of seawater, the fumarole impact may increase during those months. (C) 2015 Elsevier B.V. All rights reserved.

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  • Ryo Kanzaki .  Acid-base Property and pH of Protic Ionic Liquids .  BUNSEKI KAGAKU64 ( 3 ) 189 - 196   2015.3Invited Reviewed

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    A certain type of onium salt whose melting point is near an arbitrary temperature is a so-called a protic ionic liquid (PIL). PILs are expected to be the 'third solvents' that follow water and organic solvents for many techniques in analytical chemistry, such as separation, purification, and extraction, because of its ability for being an acid-base reaction medium. In this article, some ideas for understanding the acid-base reactions in PILs are briefly introduced with comparing with those in water and conventional non-aqueous solvents (i.e., organic solvents). Then, recent results of the autoprotolysis constants and acid dissociation constants in PILs are summarized to show quantitatively that PILs exhibit their acid-base property, depending on the constituting anion and cation. The relationship between the pH and the reactivity of hydrogen ion in a typical PIL, ethylammonium nitrate, is compared with that in water.

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  • Takashi Tomiyasu, Shinya Takenaka, Yukiko Noguchi, Hitoshi Kodamatani, Akito Matsuyamab, Kimihiko Oki, Yuriko Kono, Ryo Kanzaki, Hirokatsu Akagi .  Estimation of the residual total mercury in marine sediments of Minamata Bay after a pollution prevention project .  MARINE CHEMISTRY159   19 - 24   2014.2Reviewed

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    To estimate the current contamination levels in Minamata Bay, the vertical and horizontal distributions of mercury in the sediment were investigated. Sediment core samples were collected in 2002, 2006, 2008, and 2010 at 12 locations by gravity core sampling in Minamata Bay and Fukuro Bay, which is located in the southern part of Minamata Bay. The average total mercury concentrations during each year in the surface sediment were 2.47-3.34 and 3.50-4.66 mg kg(-1) for Minamata Bay and Fukuro Bay, respectively; significant variation in the values was not observed during the study period. The total mercury concentration in Fukuro Bay increased with increasing depth and reached a maximum at 8-14 cm from the surface and decreased with increasing depth in the deeper layer. In Minamata Bay, the total mercury concentration did not change significantly from the surface to a depth of 10 cm and the values were considerably higher than the background level. In the lower layers of the long cores taken from both areas, the total mercury concentration decreased with depth, and the deepest layers exhibited relatively uniform low values. These values can be considered to represent the background concentration in the absence of anthropogenic influence. The depth of the sediment affected by the effluent was estimated to be 20 +/- 7 cm and 33 +/- 4 cm for Minamata Bay and Fukuro Bay, respectively. Furthermore, it was estimated from the average concentration and volume of the contaminated layer that approximately 1 ton of discharged mercury remained in the sediment of the two bays. (C) 2014 Elsevier B.V. All rights reserved.

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  • Tatsuya Umecky, Toshiyuki Takamuku, Ryo Kanzaki, Masaya Takagi, Eiji Kawai, Tomoya Matsumoto, Toshitaka Funazukuri .  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 .  JOURNAL OF INCLUSION PHENOMENA AND MACROCYCLIC CHEMISTRY80 ( 3-4 ) 401 - 407   2014Reviewed

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    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 298.2 K were studied by H-1 and C-13 NMR chemical shifts. The comparison of the H-1 and C-13 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 H-1 and C-13 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 H-1 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.

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  • Hiroyuki Doi, Xuedan Song, Babak Minofar, Ryo Kanzaki, Toshiyuki Takamuku, Yasuhiro Umebayashi .  A New Proton Conductive Liquid with No Ions: Pseudo-Protic Ionic Liquids .  CHEMISTRY-A EUROPEAN JOURNAL19 ( 35 ) 11522 - 11526   2013.8Reviewed

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  • Hitoshi Kodamatani, Akito Matsuyama, Keiitsu Saito, Yuriko Kono, Ryo Kanzaki, Takashi Tomiyasu .  Sensitive Determination Method for Mercury Ion, Methyl-, Ethyl-, and Phenyl-mercury in Water and Biological Samples Using High-Performance Liquid Chromatography with Chemiluminescence Detection .  ANALYTICAL SCIENCES28 ( 10 ) 959 - 965   2012.10Reviewed

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    A sensitive determination method for mercury speciation analysis was developed. Four mercury species, mercury ion, methylmercury, ethylmercury, and phenylmercury, were complexed with emetine-dithiocarbamate (emetine-CS2), and then injected onto a HPLC instrument coupled with a tris(2,2'-bipyridine)ruthenium(III) chemiluminescence detection system. The emetine-CS2 complexing agent was effectively used to measure the concentration in addition to serving as a separation and detection reagent. The calibration curves for these mercury complexes were linear in the range of 0.050 - 10 mu g L-1 (as Hg). The limit of detection for (emetine-CS2)(2)Hg, emetine-CS2-methylmercury, emetine-CS2-ethylmercury, and emetine-CS2-phenylmercury were 30, 17, 21, and 22 ng L-1, respectively. The sensitivity of this method enables the determination of mercury species in water samples at sub-ppb levels. Furthermore, the method was applied to biological samples in combination with acid leaching and liquid-liquid extraction using emetine-CS2 as an extraction reagent. The determination results were in good agreement with the values of the certified reference materials.

    DOI: 10.2116/analsci.28.959

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  • Takashi Tomiyasu, Masato Hirose, Hitoshi Kodamatani, Katsuro Anazawa, Ryo Kanzaki, Yuriko Kono, Yoshihide Shiga .  The Distribution of Arsenic Concentration around Gejiu Tin Mine, Yunnan, China .  BUNSEKI KAGAKU61 ( 1 ) 21 - 29   2012.1Reviewed

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    In order to estimate the dispersion of arsenic released thorough mining activity, a total of 39 soil samples were taken around the Gejiu tin mine, Yunnan, China. The highest total arsenic concentration, 1.1 x 10(4) mg kg(-1), was observed in the tailing. Although the concentration in soil samples was slightly lower than that in the tailings, higher than 5.1 x 10(2) mg kg(-1) of arsenic was still observed. A linear relation was observed between SiO(2) and Fe(2)O(3), which can be used for estimating the dispersion of the tailings. A trend was observed that the higher the chemical index of alteration, the lower the arsenic concentration, which suggests the elution of arsenic from tailings through weathering.

    DOI: 10.2116/bunsekikagaku.61.21

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  • Ryo Kanzaki, Hiroyuki Doi, Xuedan Song, Shota Hara, Shin-ichi Ishiguro, Yasuhiro Umebayashi .  Acid-Base Property of N-Methylimidazolium-Based Protic Ionic Liquids Depending on Anion .  The Journal of Physical Chemistry B 116   14146 - 14152   2012Acid-Base Property of N-Methylimidazolium-Based Protic Ionic Liquids Depending on AnionReviewed

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  • Toshiyuki Takamuku, Hiroshi Wada, Chiemi Kawatoko, Takuya Shimomura, Ryo Kanzaki, Munetaka Takeuchi .  Amide-induced phase separation of hexafluoroisopropanol-water mixtures depending on the hydrophobicity of amides .  Physical Chemistry and Chemical Physics14   8335 - 8347   2012Amide-induced phase separation of hexafluoroisopropanol-water mixtures depending on the hydrophobicity of amidesReviewed

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  • Xuedan SONG, Ryo KANZAKI, Shin-ichi ISHIGURO, Yasuhiro UMEBAYASHI .  Physicochemical and Acid-base Properties of a Series of 2-Hydroxyethylammonium-based Protic Ionic Liquids .  Analytical Sciences28   469 - 474   2012Physicochemical and Acid-base Properties of a Series of 2-Hydroxyethylammonium-based Protic Ionic LiquidsReviewed

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  • Xuedan Song, Hiroshi Hamano, Babak Minofar, Ryo Kanzaki, Kenta Fujii, Yasuo Kameda, Shinji Kohara, Masayoshi Watanabe, Shin-ichi Ishiguro, Yasuhiro Umebayashi .  Structural Heterogeneity and Unique Distorted Hydrogen Bonding in Primary Ammonium Nitrate Ionic Liquids Studied by High-Energy X-ray Diffraction Experiments and MD Simulations .  The Journal of Physical Chemistry B116   2801 - 2813   2012Structural Heterogeneity and Unique Distorted Hydrogen Bonding in Primary Ammonium Nitrate Ionic Liquids Studied by High-Energy X-ray Diffraction Experiments and MD SimulationsReviewed

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  • Kenta Fujii, Ryo Kanzaki, Toshiyuki Takamuku, Yasuo Kameda, Shinji Kohara, Mitsuhiro Kanakubo, Mitsuhiro Shibayama, Shin-ichi Ishiguro, Yasuhiro Umebayashi .  Experimental evidences for molecular origin of low-Q peak in neutron X-ray scattering of 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl) amide ionic liquids .  JOURNAL OF CHEMICAL PHYSICS135 ( 24 ) 244502   2011.12Reviewed

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    Short- and long-range liquid structures of [C(n)mIm(+)][TFSA(-)] with n = 2, 4, 6, 8, 10, and 12 have been studied by high-energy x-ray diffraction (HEXRD) and small-angle neutron scattering (SANS) experiments with the aid of MD simulations. Observed x-ray structure factor, S(Q), for the ionic liquids with the alkyl-chain length n &gt; 6 exhibited a characteristic peak in the low-Q range of 0.2-0.4 angstrom (-1), indicating the heterogeneity of their ionic liquids. SANS profiles I-H(Q) and I-D(Q) for the normal and the alkyl group deuterated ionic liquids, respectively, showed significant peaks for n = 10 and 12 without no form factor component for large spherical or spheroidal aggregates like micelles in solution. The peaks for n = 10 and 12 evidently disappeared in the difference SANS profiles Delta I(Q) [= I-D(Q) - I-H(Q)], although that for n = 12 slightly remained. This suggests that the long-range correlations originated from the alkyl groups hardly contribute to the low-Q peak intensity in SANS. To reveal molecular origin of the low-Q peak, we introduce here a new function; x-ray structure factor intensity at a given Q as a function of r, S-Qpeak(r). The S-Qpeak(r) function suggests that the observed low-Q peak intensity depending on n is originated from liquid structures at two r-region of 5-8 and 8-15 angstrom for all ionic liquids examined except for n = 12. Atomistic MD simulations are consistent with the HEXRD and SANS experiments, and then we discussed the relationship between both variations of low-Q peak and real-space structure with lengthening the alkyl group of the C(n)mIm. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3672097]

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  • Toshiyuki Takamuku, Takuya Shimomura, Mai Tachikawa, Ryo Kanzaki .  N,N-Dimethylformamideinduced phase separation of hexafluoroisopropanol- water mixtures .  Physical Chemistry and Chemical Physics13   11222 - 11232   2011N,N-Dimethylformamideinduced phase separation of hexafluoroisopropanol- water mixturesReviewed

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  • Hitoshi Kodamatani, Ryo Kanzaki, Takashi Tomiyasu, Keiitsu Saito, Yuriko Kono .  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 .  ANALYTICAL LETTERS44 ( 17 ) 2769 - 2779   2011Reviewed

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    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-CS(2)) ligand, HPLC separation, and tris(2,2'-bipyridine) ruthenium(III) chemiluminescence detection. The complexation reactions of the mercury species and emetine-CS(2) ligand occurred instantaneously upon the addition of emetine-CS(2) solution to the solution containing the mercury species. The complete separation of these complexes was achieved using an ODS column with 20mM NaH(2)PO(4)-acetonitrile (52:48, v/v) containing 30mM NaClO(4) as an ion-pair reagent. The calibration graphs of these complexes were linear in the range from 1-100 mu g/L. The detection limits were 0.27 mu g/L, 0.33 mu g/L, 0.39 mu g/L, and 0.17 mu g/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%.

    DOI: 10.1080/00032719.2011.565442

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  • Shin-ichi Ishiguro, Yasuhiro Umebayashi, Ryo Kanzaki, Kenta Fujii .  Structure, solvation, and acid-base property in ionic liquids .  PURE AND APPLIED CHEMISTRY82 ( 10 ) 1927 - 1941   2010.10Reviewed

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:INT UNION PURE APPLIED CHEMISTRY  

    Ionic liquids (ILs) are expected to have specific properties as solvents for chemical reactions in view of solution chemistry. Among physicochemical properties, liquid structure, acid-base, and electron-pair donating and accepting abilities of solvent play a crucial role in ion-solvation and acid-base, metal-ion complexation, and electrochemical reactions. Various types of ILs have been developed, and among others, the bis(trifluoromethanesulfonyl)amide (TFSA-)-based ILs are extensively used. TFSA- is a flexible molecule to give two stable conformers, cis (C1) and trans (C2), which are present in equilibrium in the liquid state. The conformational equilibrium shifts upon solvation to the metal ion. This is quantitatively studied to obtain thermodynamic parameters of conformational change from C2 to Cl in the bulk and in the solvation sphere of the lithium ion. On the other hand, with ethylammonium nitrate (EAN), a typical protic IL, it is revealed that the ammonium group is hydrogen-bonded with three nitrate ions to form a heterogeneous liquid structure. The solvent acid-base property of EAN and acid dissociation reaction in EAN have been quantitatively revealed, and the results will be discussed in comparison with those in normal molecular solvents.

    DOI: 10.1351/PAC-CON-09-10-28

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  • 神﨑 亮 .  イオン液体の酸塩基性とpH測定 .  Electrochemistry78 ( 8 ) 687 - 692   2010.8Invited Reviewed

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    DOI: 10.5796/electrochemistry.78.687

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    Other Link: https://jlc.jst.go.jp/DN/JALC/00354999630?from=CiNii

  • Ryo Kanzaki, Xuedan Song, Yasuhiro Umebayashi, Shin-ichi Ishiguro .  Thermodynamic Study of the Solvation States of Acid and Base in a Protic Ionic Liquid, Ethylammonium Nitrate, and Its Aqueous Mixtures .  CHEMISTRY LETTERS39 ( 6 ) 578 - 579   2010.6Reviewed

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    Ethylammonium nitrate (EAN) is a typical protic ionic liquid (PIL) known for a long time. In order to investigate acid-base reaction mechanisms in PIL, thermodynamic quantities of a reaction, which corresponds to autoprotolysis in amphoteric solvents, has been determined in neat EAN. Unlike H3O+ and OH- in water, proton donor and acceptor species in EAN are both neutral; this makes acid-base reaction mechanisms in EAN distinct from that in water. EAN-water mixtures have also been studied.

    DOI: 10.1246/cl.2010.578

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  • Toshiyuki Takamuku, Miho Tanaka, Takunosuke Sako, Takuya Shimomura, Kenta Fujii, Ryo Kanzaki, Munetaka Takeuchi .  Solvation of the Amphiphilic Diol Molecule in Aliphatic Alcohol-Water and Fluorinated Alcohol-Water Solutions .  JOURNAL OF PHYSICAL CHEMISTRY B114 ( 12 ) 4252 - 4260   2010.3

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    We investigated the solvation properties of aqueous Solutions of aliphatic alcohols and fluorinated alcohols. These included ethanol (EtOH), 2-propanol (2-PrOH), 2,2,2-trifluoroethanol (TFE), and 1, 1, 1,3,3,3-hexafluoro-2-propanol (HFIP). The amphiphilic diol, 1,4-pentanediol (1,4-PD), was used as the solute to probe solvation properties at the molecular level. Small-angle neutron scattering (SANS) experiments revealed that the inherent microheterogeneity or HFIP-water binary Solutions was significantly enhanced by addition of 1,4-PD. In contrast, the addition of 1,4-PD to EtOH-, 2-PrOH-, and TFE-water solutions hardly changed the mixing state. Molecular dynamics simulations were used to obtain the spatial distribution functions for the oxygen atom of water molecules and the carbon and fluorine atoms of alcohol molecules around 1,4-PD. Of the alcohols studied, these spatial distributions illustrated that HFIP molecules formed the strongest hydrophobic solvation shell around the hydrocarbons of 1,4-PD. This preferential solvation of 1,4-PD by HFIP leads to enhancement of HFIP Clusters ill the Solutions. (13)C NMR and infrared spectroscopic measurements on 1,4-PD ill the different alcohol-water Solutions suggested that the number of water molecules around the hydrocarbons of 1,4-PD decreased in aliphatic alcohol-water solutions. Additionally, HFIP Molecules are thought to strongly interact with the hydrocarbons of 1,4-PD in HFIP-water solutions.

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  • Ryo Kanzaki, Takushi Mitsugi, Shuhei Fukuda, Kenta Fujii, Munetaka Takeuchi, Yasufumi Soejima, Toshiyuki Takamuku, Toshio Yamaguchi, Yasuhiro Umebayashi, Shin-ichi Ishiguro .  Ion-ion interaction in Room Temperature Ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate studied by large angle X-ray scattering experiment and molecular dynamics simulations .  Journal of Molecular Liquids147   77 - 82   2009Ion-ion interaction in Room Temperature Ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate studied by large angle X-ray scattering experiment and molecular dynamics simulationsReviewed

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  • Yasuhiro Umebayashi, Takushi Mitsugi, Kenta Fujii, Shiro Seki, Kazumi Chiba, Hideo Yamamoto, Jpse N. Canongia Lopes, Agilio A. H. Padua, Munetaka Takeuchi, Ryo Kanzaki, Shin-ichi Ishiguro .  Raman Spectroscopic Study, DFT Calculations and MD Simulations on the Conformational Isomerism of N-Alkyl-N-methylpyrrolidinium Bis-(trifluoromethanesulfonyl) Amide Ionic Liquids .  The Journal of Physical Chemistry B113   4338 - 4346   2009Raman Spectroscopic Study, DFT Calculations and MD Simulations on the Conformational Isomerism of N-Alkyl-N-methylpyrrolidinium Bis-(trifluoromethanesulfonyl) Amide Ionic LiquidsReviewed

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  • Yasuhiro Umebayashi, Wan-Lin Chung, Takushi Mitsugi, Shuhei Fukuda, Munetaka Takeuchi, Kenta Fujii, Toshiyuki Takamuku, Ryo Kanzaki, Shin-ichi Ishiguro .  Liquid Structure and the Ion-Ion Interactions of Ethylammonium Nitrate Ionic Liquid Studied by Large Angle X-Ray Scattering and Molecular Dynamics Simulations .  Journal of Computer Chemistry, Japan7   125 - 134   2008.11Liquid Structure and the Ion-Ion Interactions of Ethylammonium Nitrate Ionic Liquid Studied by Large Angle X-Ray Scattering and Molecular Dynamics SimulationsReviewed

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  • Ryo Kanzaki, Kuniaki Uchida, Xuedan Song, Yasuhiro Umebayashi, Shin-ichi Ishiguro .  Acidity and Basicity of Aqueous Mixtures of a Protic Ionic Liquid, Ethylammonium Nitrate .  ANALYTICAL SCIENCES24 ( 10 ) 1347 - 1349   2008.10Reviewed

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

    Ethylammonium nitrate (EAN) is composed of C2H5NH3+ and NO3- ions, which behave as an acid and a base, respectively. The ionic liquid thus involves small amounts of C2H5NH2 and HNO3 molecules owing to proton transfer from C2H5NH3+ to NO3-. The equilibrium constant K-s (= [C2H5NH2][HNO3]), which corresponds to the autoprotolysis constant of water, was obtained to be ca. 10(-10) mol(2) dm(-6) by potentiometry using an ion-selective field-effect transistor and hydrogen electrodes at 298 K. The value indicates that C2H5NH2 and HNO3 molecules of ca. 10(-5) mol dm(-3) are involved in neat EAN. On the other hand, in an EAN-water mixture, a water molecule behaves as a base. The apparent pK(s) value was determined in EAN-water mixtures of various solvent compositions. Interestingly, the pK(s) value is remained at 10.5 in mixtures over the range of an EAN mole fraction of 0.05 - 0.9. The value is close to the pKa of C2H5NH2, or the acid-dissociation constant of C2H5NH3+, in aqueous solution. This implies that the reaction C2H5NH3+ + H2O -&gt; C2H5NH2 + H3O+ is responsible for the pK(s) over a wide range of solvent composition. The pK(s) value in neat EAN is thus slightly smaller than that in the mixtures, implying that H3O+ is a stronger acid than HNO3 in an EAN solution, unlike water.

    DOI: 10.2116/analsci.24.1347

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  • Shuhei Fukuda, Munetaka Takeuchi, Kenta Fujii, Ryo Kanzaki, Toshiyuki Takamuku, Kazumi Chiba, Hideo Yamamoto, Yasuhiro Umebayashi, Shin-ichi Ishiguro .  Liquid structure of N-butyl-N-methylpyrrolidinium bis-(trifluoromethanesulfonyl) amide ionic liquid studied by large angle X-ray scattering and molecular dynamics simulations .  JOURNAL OF MOLECULAR LIQUIDS143 ( 1 ) 2 - 7   2008.9Reviewed

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    Large angle X-ray scattering of the N-butyl-N-methylpyrrolidinium bis-(trifluoromethanesulfony) amide (P-14*TFSA(-)) ionic liquid was measured at 298 K. The total interference function i(LAXS)(s) and the total pair correlation function G(LAXS)(r) were successfully obtained. The i(LAXS)(s) was analyzed in terms of the intramolecular geometries of the conformational isomers of the P-14* and TFSA(-) ions based on the crystal structures, s the inter-molecular correlation function G(inter)(LAXS)(r) and the inter-molecular radial distribution function as the form D-inter(LAXS)(r)-4 pi r(2)rho(0) were evaluated. With G(inter)(LAXS)(r)-4 pi r(2)rho(0). the inter-molecular correlation peaks at 3.5. 4.5 and 5-6 angstrom evidently appeared as the short range interaction, while considerable long range interactions were found as the broad peaks at 10 and 15 angstrom. Molecular dynamics simulations of the ionic liquid based on the effective pairwise potentials were carried out. The X-ray total interference function derived from the MD simulations i(MD)(S) was in agreement with the experimental one. According to the inter-molecular partial atom-atom correlation functions from MD simulations, the observed peaks at 3.5, 4.5 and 5-6 angstrom can be predominantly ascribed to the closest atom-atom correlations between the P-14* and TFSA(-) ions such as C...O and C...F In the inter-molecular partial atom-atom correlation function between terminal methyl carbons of the butyl chain in the P-14* ion. a peak at 4.0 angstrom was found as the inter-molecular correlation, suggesting that the ionic liquid shows an alkyl chain aggregation, which is similar to that observed for 1-alkyl-3-methylmidazolium ionic liquids. (C) 2008 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.molliq.2008.02.012

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  • Kenta Fujii, Yasufumi Soejima, Yasuhiro Kyoshoin, Shuhei Fukuda, Ryo Kanzaki, Yasuhiro Umebayashi, Toshio Yamaguchi, Shin-ichi Ishiguro, Toshiyuki Takamuku .  Liquid structure of room-temperature ionic liquid, 1-ethyl-3-methylimidazolium bis-(trifluoromethanesulfonyl) imide .  JOURNAL OF PHYSICAL CHEMISTRY B112 ( 14 ) 4329 - 4336   2008.4Reviewed

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    The liquid structure of 1-ethyl-3-methylimidazolium bis-(trifluoromethanesulfonyl) imide (EMI+TFSI-) has been studied by means of large-angle X-ray scattering (LAXS), H-1, C-13, and F-19 NMR, and molecular dynamics (MD) simulations. LAXS measurements show that the ionic liquid is highly structured with intermolecular interactions at around 6, 9, and 15 angstrom. The intermolecular interactions at around 6, 9, and 15 angstrom are ascribed, on the basis of the MD simulation, to the nearest neighbor EMI+...TFSI- interaction, the EMI+...EMI+ and TFSI-...TFSI- interactions, and the second neighbor EMI+...TFSI- interaction, respectively. The ionic liquid involves two conformers, C-1 (cis) and C-2 (trans), for TFSI-, and two conformers, planar cis and nonplanar staggered, for EMI+, and thus the system involves four types of the EMI+...TFSI- interactions in the liquid state by taking into account the conformers. However, the EMI+...TFSI- interaction is not largely different for all combinations of the conformers. The same applies also to the EMI+...EMI+ and TFSI-...TFSI- interactions. It is suggested from the C-13 NMR that the imidazolium C-2 proton of EMI+ strongly interacts with the O atom of the -SO2(CF3) group of TFSI-. The interaction is not ascribed to hydrogen-bonding, according to the MD simulation. It is shown that the liquid structure is significantly different from the layered crystal structure that involves only the nonplanar staggered EMI+ and C-1 TFSI- conformers.

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  • Kenta Fujii, Shiro Seki, Shuhei Fukuda, Ryo Kanzaki, Toshiyuki Takamuku, Yasuhiro Ulmebayashi, Shin-ichi Ishiguro .  Anion conformation of low-viscosity room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(fluorosulfonyl) imide .  JOURNAL OF PHYSICAL CHEMISTRY B111 ( 44 ) 12829 - 12833   2007.11Reviewed

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    Anion conformation of a low-viscosity room-temperature ionic liquid 1-ethyl-3-methylimidazolium his(fluorosulfonyl) imide (EMI+FSI-) has been studied by Raman spectra and theoretical DFT calculations. Three strong Raman bands were found at 293, 328, and 360 cm(-1), which are ascribed to the FSI- ion. These Raman bands show significant temperature dependence, implying that two FSI- conformers coexist in equilibrium. This is supported by theoretical calculations that the FSI- ion is present as either C-2 (trans) or C-1 (cis) conformer; the former gives the global minimum, and the latter has a higher SCF energy of about 4 W mol(-1). Full geometry optimizations followed by normal frequency analyses show that the observed bands at 293, 328, and 360 cm(-1) are ascribed to the Q, conformer. The corresponding vibrations at 305, 320, and 353 cm(-1) were extracted according to deconvolution of the observed Raman bands in the range 280-400 cm(-1) and are ascribed to the C-2 conformer. The enthalpy Delta H degrees of conformational change from C-2 to C-1 was experimentally evaluated to be ca. 4.5 W mol(-1), which is in good agreement with the predicted value by theoretical calculations. The bis(ti-ifluoromethanesulfonyl) imide anion (TFSI-) shows a conformational equilibrium between C-1 and C-2 analogues (Delta H degrees = 3.5 kJ mol(-1)). However, the profile of the potential energy surface of the conformational change for FSI- (the F-S-N-S dihedral angle) is significantly different from that for TFSI- (the C-S-N-S dihedral angle).

    DOI: 10.1021/jp074325e

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  • Yasuhiro Umebayashi, Takushi Mitsugi, Shuhei Fukuda, Takao Fujimori, Kenta Fujii, Ryo Kanzaki, Munetaka Takeuchi, Shin-Ichi Ishiguro .  Lithium ion solvation in room-temperature ionic liquids involving bis(trifluoromethanesulfonyl) imide anion studied by Raman Spectroscopy and DFT calculations .  JOURNAL OF PHYSICAL CHEMISTRY B111 ( 45 ) 13028 - 13032   2007.11Reviewed

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

    The solvation structure of the lithium ion in room-temperature ionic liquids 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide (EMI+TFSI-) and N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (BMP+TFSI-) has been studied by Raman spectroscopy and DFT calculations. Raman spectra of EMI+TFSI- and BMP+TFSI- containing Li+TFSI- over the range 0.144-0.589 and 0.076-0.633 mol dm(-3), respectively, were measured at 298 K. A strong 744 cm(-1) band of the free TFSI- ion in the bulk weakens with increasing concentration of the lithium ion, and it revealed by analyzing the intensity decrease that the two TFSI- ions bind to the metal ion. The lithium ion may be four-coordinated through the 0 atoms of two bidentate TFSI- ions. It has been established in our previous work that the TFSI- ion involves two conformers of C-1 (cis) and C-2 (trans) symmetries in equilibrium, and the dipole moment of the C-1 conformer is significantly larger than that of the C-2 conformer. On the basis of these facts, the geometries and SCF energies of possible solvate ion clusters [Li(C-1-TFSI-)(2)](-), [Li(C-1-TFSI-)(C-2-TFSI-)](-))]-, and [Li(C-2-TFS)(-))(2)](-) were examined using the theoretical DFT calculations. It is concluded that the C-1 conformer is more preferred to the C, conformer in the vicinity of the lithium ion.

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  • Mitsunori Asada, Takushi Mitsugi, Kenta Fujii, Ryo Kanzaki, Yasuhiro Umebayashi, Shin-Ichi Ishiguro .  Vibrational spectroscopy and molecular orbital calculations of N,N-dimethylacrylamide and N,N-dimethylpropionamide - Conformational equilibrium in the liquid state .  JOURNAL OF MOLECULAR LIQUIDS136 ( 1-2 ) 138 - 146   2007.11Reviewed

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    Molecular vibrations of N,N-dimethylacrylamide (DMAA) and N,N-dimethylpropionamide (DMPA) in the liquid state were studied by means of Raman and IR spectra over the wide frequency range. It has been established in our previous work that DMPA involves two rotational isomers within its propionyl CH3-CH2-C(=O)- group. In the present work, it is revealed that, like DMPA, DMAA also involves two rotational isomers, the planar cis and nonplanar staggered ones, within its acryl CH2=CH-C(=O)- group. The terminal methylene carbon of the acryl group locates cis to the 0 atom within the amide O=C-N plane (the planar cis conformer) or above the amide plane (the nonplanar staggered conformer). This is well supported by theoretical MO calculations. Torsion potential energy surfaces (PES) for the C-C-C-O dihedral angle 0 of the acryl group show that a global minimum appears at ca. theta=0 degrees (the planar cis conformer) and a local minimum at ca. theta=130 degrees (the nonplanar staggered conformer). The geometry optimization followed by normal frequency analyses showed that theoretical Raman and IR bands for the conformers satisfactorily reproduce the observed ones. The enthalpy for the conformational change from the planar cis conformer to the nonplanar staggered one was experimentally evaluated by analyzing the integrated intensity changes of the bands in the range 700-800 cm(-1). The value thus obtained for the acryl group of DMAA is ca. 9 kJ mol(-1), which is significantly higher than the corresponding value for the propionyl group of DMPA (5 kJ mol(-1)). (c) 2007 Elsevier B.V. All rights reserved.

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  • Tetsuya Sukizaki, Shuhei Fukuda, Taishi Yamaguchi, Kenta Fujii, Ryo Kanzaki, Kazumi Chiba, Hideo Yamamoto, Yasuhiro Umebayashi, Shin-ichi Ishiguro .  Raman spectroscopic study and DFT calculations on the conformation of 5-azonia-spiro[4.4]nonane cation in crystal and dimethyl carbonate solution .  ELECTROCHEMISTRY75 ( 8 ) 628 - 634   2007.8Reviewed

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    5-Azonia-spiro[4.4]nonane tetrafluoroborate [(CH2)(4)N(CH2)(4)](+) BF4- is dissolved in dimethyl carbonate (DMC) to yield two liquid phases, DMC and salt-rich DMC solutions. The molecular structure of the [(CH2)(4)N(CH2)(4)](+) ion in the crystalline state and in the salt-rich DMC solution was studied by means of Raman spectroscopy at 298 K and theoretical DFT calculations. The [(CH2)(4)N(CH2)(4)](+) ion involves two pyrrolidinium (CH2)(4)N rings bridged through the N atom, and each pyrrolidinium ring involves various types of conformation. Theoretical DFT calculations for the [(CH2)(4)N(CH2)(4)](+) ion show that the distorted envelope-envelope conformers of the type E1-E1 and E1-E3 give relatively small energies. Observed Raman spectra of [(CH2)(4)N(CH2)(4)](+) BF4- crystals and the salt-rich DMC solution were satisfactorily explained in terms of the favorable presence of the sole envelope-envelope conformer of the type E1-E1.

    DOI: 10.5796/electrochemistry.75.628

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  • Ryo Kanzaki, Kumaki Uchida, Shota Hara, Yasuhiro Umebayashi, Shin-ichi Ishiguro, Satoshi Nomura .  Acid-base property of ethylammonium nitrate ionic liquid directly obtained using ion-selective field effect transistor electrode .  CHEMISTRY LETTERS36 ( 5 ) 684 - 685   2007.5Reviewed

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    Ethylammonium nitrate (EAN) is a protic room-temperature ionic liquid and classified into an amphoteric solvent. The equilibrium constant K-S = [EtNH2][HNO3] has directly been obtained for the first time by using an ion-selective field effect transistor (ISFET) electrode. The obtained K-S value is of 10(-10.0) mol(2) dm(-6), indicating that the neutral EAN involves HNO3 and EtNH2 molecules as much as 1.0 x 10(-5) mol dm(-3), or the pH (= - log[HNO3]) is 5 at 298 K.

    DOI: 10.1246/cl.2007.684

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  • Mitsunori Asada, Takao Fujimori, Kenta Fujii, Ryo Kanzaki, Yasuhiro Umebayashi, Shin-ichi Ishiguro .  Solvation structure of magnesium, zinc, and alkaline earth metal ions in N,N-dimethylformamide, N,N-dimethylacetamide, and their mixtures studied by means of Raman spectroscopy and DFT calculations - Ionic size and electronic effects on steric congestion .  JOURNAL OF RAMAN SPECTROSCOPY38 ( 4 ) 417 - 426   2007.4Reviewed

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    The solvation structure of magnesium, zinc(II), and alkaline earth metal ions in N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMA), and their mixtures has been studied by means of Raman spectroscopy and DFT calculations. The solvation number is revealed to be 6, 7, 8, and 8 for Mg2+, Ca2+, Sr2+, and Ba2+, respectively, in both DMF and DMA. The delta (O-C-N) vibration of DMF shifts to a higher wavenumber upon binding to the metal ions and the shift Delta nu (= nu(bound) - nu(free)) becomes larger, when the ionic radius of the metal ion becomes smaller. The nu (N-CH3) vibration of DMA also shifts to a higher wavenumber upon binding to the metal ions. However, the shift Delta nu saturates for small ions, as well as the transition-metal (II) ions, implying that steric congestion among solvent molecules takes place in the coordination sphere. It is also indicated that, despite the magnesium ion having practically the same ionic radius as the zinc(II) ion of six-coordination, their solvation numbers in DMA are significantly different. DFT calculations for these metalsolvate clusters of varying solvation numbers revealed that not only solvent-solvent interaction through space but also the bonding nature of the metal ion plays an essential role in the steric congestion. The individual solvation number and the Raman shift Delta nu in DMF-DMA mixtures indicate that steric congestion is significant for the magnesium ion, but not appreciable for calcium, strontium, and barium ions, despite the solvation number of these metal ions being large. Copyright (c) 2006 John Wiley & Sons, Ltd.

    DOI: 10.1002/jrs.1662

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  • 神崎 亮, 梅林泰宏, 竹内宗孝, 藤井健太 .  分子シミュレーションおよびX線回折法によるイオン液体の構造とダイナミクス .  アンサンブル9 ( 3 ) 18 - 21   2007.4分子シミュレーションおよびX線回折法によるイオン液体の構造とダイナミクス

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    DOI: 10.11436/mssj1998.9.39_18

  • 梅林泰宏, 福田周平, 竹内宗孝, 神崎 亮, 石黒慎一, 藤井健太, 高椋利幸 .  広角X線散乱実験および分子動力学計算によるイオン液体の液体構造 .  溶融塩および高温化学50 ( 3 ) 117 - 125   2007.4広角X線散乱実験および分子動力学計算によるイオン液体の液体構造Invited Reviewed

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  • Takao Fujimori, Kenta Fujii, Ryo Kanzaki, Kazumi Chiba, Hideo Yamamoto, Yasuhiro Umebayashi, Shin-ichi Ishiguro .  Conformational structure of room temperature ionic liquid N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl) imide - Raman spectroscopic study and DFT calculations .  JOURNAL OF MOLECULAR LIQUIDS131 ( SPEC. ISS. ) 216 - 224   2007.3Reviewed

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    Conformational structure of the N-butyl-N-methyl-pyrrolidinium (P-14(+)) ion within its bis(trifluoromethanesulfonyl) imide (TFSI-) and bromide salts has been studied by means of DFT calculations and Raman spectroscopy. The P-14(+) ion gives various types of conformations with respect to the pyrrolidinium ring and N-butyl group. DFT calculations indicate that, among others, the eq- and ax-envelope conformers with the N-butyl group at equatorial and axial positions, respectively, against planar C-4 atoms of the envelope pyrrolidinium ring (-NCH2CH2CH2CH2-) are relatively stable, and the former gives the global minimum. It revealed by comparing observed and calculated Raman spectra that the P-14(+) ion is present mainly as the ax-envelope conformer in the P14+Br- crystal, whilst the eq- and ax-envelope conformers are present in equilibrium in the P14+TFSI- ionic liquid. The presence of conformational equilibrium is further supported by Raman spectra measured by varying temperature. It is also established that conformation of the N-butyl group is restricted to the trans-TT, in which the butyl group locates trans against its nearest carbon atom in the pyrrolidinium ring, and all carbon atoms in the butyl chain are located trans each other. (C) 2006 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.molliq.2006.08.054

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  • Ryo Kanzaki, Yasuhiro Umebayashi, Mitsunori Asada, Shin-ichi Ishiguro, Taisuke Matsumoto, Akihiro Wakisaka .  Binuclear mu-perchlorato complexes of alkaline earth metal ions studied by electrospray ionization mass spectrometry and DFT calculations .  CHEMISTRY LETTERS35 ( 10 ) 1118 - 1119   2006.10Reviewed

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    Metal-ion clusters involving alkaline earth metal and perchlorate ions, and N,N-dimethylformamide (DMF) have been studied by electrospray ionization mass spectrometry (ESI-MS). Three types of metal-ion clusters, [M(DMF)(n)](2+), [M(ClO4)-(DMF)(n)](+), and [M-2(CIO4)(3)(DMF)(n)](+) (M = Mg, Ca, and Sr) are found. It is proposed on the basis of DFT calculations that the metal ion in the [M-2(CIO4)(3)(DMF)(6)](+) clusters is six-coordinated with three mu-CIO4- ions and three DMF molecules.

    DOI: 10.1246/cl.2006.1118

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  • Shin-ichi Ishiguro, Yasuhiro Umebayashi, Kenta Fujii, Ryo Kanzaki .  Solvent conformation and ion solvation: From molecular to ionic liquids .  PURE AND APPLIED CHEMISTRY78 ( 8 ) 1595 - 1609   2006.8Reviewed

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    Metal ions are solvated in solution, and, in a sterically congested organic solvent, those solvent molecules that are simultaneously bound to the metal ion will be subject to consequential steric interactions through space. The molecular structure of a solvent, particularly that of any functional groups in the vicinity of the coordinating atom to the metal ion, plays a key role in the solvation steric effect. Weak solvation steric effects lead to a distorted octahedral structure for six-coordinate transition-metal(II) ions, whereas strong steric effects lead to a decreased solvation number. In particular cases, the conformation of a solvent may undergo a change in response to coordination to the metal ion. Solvation steric effects play a decisive role in reaction thermodynamics and kinetics of the metal ion. Here, we show our recent results on solvation steric effects in terms of structure and thermodynamics, particularly, the conformational change of solvent and its effect on the metal-ion complexation.

    DOI: 10.1351/pac200678081595

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  • Kenta Fujii, Takao Fujimori, Toshiyuki Takamuku, Ryo Kanzaki, Yasuhiro Umebayashi, Shin-Ichi Ishiguro .  Conformational equilibrium of bis(trifluoromethanesulfonyl) imide anion of a room-temperature ionic liquid: Raman spectroscopic study and DFT calculations .  Journal of Physical Chemistry B110 ( 16 ) 8179 - 8183   2006.4Reviewed

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    The structure of bis(trifluoromethanesulfonyl) imide (TFSI) in the liquid state has been studied by means of Raman spectroscopy and DFT calculations. Raman spectra of 1-ethyl-3-methylimidazolium (EMI + ) TFSI - show relatively strong bands arising from TFSI - at about 398 and 407 cm - . Interestingly, the 407 cm -1 band, relative to the 398 cm -1 one, is appreciably intensified with raising temperature, suggesting that an equilibrium is established between TFSI - conformers in the liquid state. According to DFT calculations followed by normal frequency analyses, two conformers of C 2 and C 1 symmetry, respectively, constitute global and local minima, with an energy difference 2.2-3.3 kJ mol -1 . The wagging ω-SO 2 vibration appears at 396 and 430 cm -1 for the C 1 conformer and at 387 and 402 cm -1 for the C 2 one. Observed Raman spectra over the range 380-440 cm -1 were deconvoluted to extract intrinsic bands of TFSI - conformers, and the enthalpy of conformational change from C 2 to C 1 was evaluated. The enthalpy value is in good agreement with that obtained by theoretical calculations. We thus conclude that a conformational equilibrium is established between the C 1 and C 2 conformers of TFSI - in the liquid EMI + TFSI - , and the C 2 conformer is more favorable than the C 1 one. © 2006 American Chemical Society.

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  • 梅林 泰宏, 藤森 崇夫, 藤井健太, 神崎 亮, 石黒 慎一 .  DFT計算およびMDシミュレーションによるイオン液体中の金属イオン溶媒和 .  九州大学情報基盤センター広報   2006.4DFT計算およびMDシミュレーションによるイオン液体中の金属イオン溶媒和

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  • Yasuhiro Umebayashi, Takao Fujimori, Tetsuya Sukizaki, Mitsunori Asada, Kenta Fujii, Ryo Kanzaki, Shin-Ichi Ishiguro .  Evidence of conformational equilibrium of 1-ethyl-3-methylimidazolium in its ionic liquid salts: Raman spectroscopic study and quantum chemical calculations .  Journal of Physical Chemistry A109 ( 40 ) 8976 - 8982   2005.10Reviewed

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    Raman spectra of liquid 1-ethyl-3-methylimidazolium (EMI + ) salts, EMI + BF 4 - , EMI + PF 6 , EMI + CF 3 SO 3 - , and EMI + N(CF 3 SO 2 ) 2 - , were measured over the frequency range 200-1600 cm -1 . In the range 200-500 cm -1 , we found five bands originating from the EMI + ion at 241, 297, 387, 430, and 448 cm -1 . However, the 448 cm -1 band could hardly be reproduced by theoretical calculations in terms of a given EMI + conformer, implying that the band originates from another conformer. This is expected because the EMI + involves an ethyl group bound to the N atom of the imidazolium ring, and the ethyl group can rotate along the C-N bond to yield conformers. The torsion energy for the rotation was then theoretically calculated. Two local minima with an energy difference of ca. 2 kJ mol -1 were found, suggesting that two conformers are present in equilibrium. Full geometry optimizations followed by normal frequency analyses indicate that the two conformers are those with planar and nonplanar ethyl groups against the imidazolium ring plane, and the nonplanar conformer is favorable. It elucidates that bands at 241, 297, 387, and 430 cm-1 mainly originate from the nonplanar conformer, whereas the 448 cm-1 band does originate from the planar conformer. Indeed, the enthalpy for conformational change from nonplanar to planar EMI + experimentally obtained by analyzing band intensities of the conformers at varying temperatures is practically the same as that evaluated by theoretical calculations. We thus conclude that the EMI + ion exists as either a nonplanar or planar conformer in equilibrium in its liquid salts. © 2005 American Chemical Society.

    DOI: 10.1021/jp053476j

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  • Kenta Fujii, Yasuhiro Umebayashi, Ryo Kanzaki, Daisuke Kobayashi, Ryoko Matsuura, Shin-Ichi Ishiguro .  Thermodynamic aspects of metal-ion complexation in the structured solvent, N-methylformamide .  Journal of Solution Chemistry34 ( 7 ) 739 - 753   2005.7Reviewed

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    Chloride complexation of cobalt(II), nickel(II) and zinc(II) ions has been studied by calorimetry and spectrophotometry in N-methylformamide (NMF) containing 1.0 mol-dm -3 (n-C 4 H 9 ) 4 NClO 4 as an ionic medium at 298 K. A series of mononuclear complexes, MCl n (2 -n)+ (M=Co, Ni and Zn) with n = 1, 3 and 4 for cobalt(II), n = 1 for nickel(II), and n = 1-4 for zinc(II), are formed and their formation constants, enthalpies and entropies were obtained. It revealed that complexation is suppressed significantly in NMF relative to that in N,N-dimethylformamide (DMF) in all metal systems examined. The suppressed complexation in NMF is mainly ascribed to the smaller formation entropies in NMF reflecting that the solvent-solvent interaction or solvent structure in the bulk NMF is much stronger than that in the bulk DMF. Formation entropies, ΔS 1 o , of the monochloro complex in DMF, dimethyl sulfoxide and NMF are well correlated with the Marcus&#039; solvent parameter, ΔΔ v S o /R, according to ΔS 1 o /R = aΔΔ v S o /R+b. The a value is negative and similar in all metal systems examined, whereas the b value depends on the metal system. When a gaseous ion is introduced into a solvent, the ionic process of solvation is divided into two stages: the ion destroys the bulk solvent structure to isolate solvent molecules at the first stage and the ion then coordinates a part of isolated solvent molecules around it at the second stage. We propose that the a and b values may reflect the changes in the freedom of motion of solvent molecules at the first and second stages, respectively, of the ionic process of solvation. © 2005 Springer Science+Business Media, Inc.

    DOI: 10.1007/s10953-005-5114-9

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  • Kanzaki R., Umebayashi Y., Maki T., Ishiguro S.I. .  Thermodynamics and fluorescence spectra of 1,10-phenanthroline in micelles of poly (ethylene oxide)-type nonionic surfactant .  Journal of Solution Chemistry33 ( 6-7 ) 699 - 709   2004.6

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    The distribution of 1,10-phenanthroline (phen) in micellar solutions of the nonionic surfactants Triton X and C 12E n with varying poly (ethylene oxide) chain lengths has been studied by potentiometry, calorimetry, and fluorometry at 298 K. Micelles accommodate 1,10-phenanthroline according to the reaction, phen + Y m = Y m(phen), where Y m denotes a surfactant molecule aggregated in micelles. The constant K m for the reaction of Triton X increases as a linear function of n*, the number of ethylene oxide (EO) groups, as K m = K EOn* + K c. Nonzero K EO and K c values suggest a heterogeneous inner structure of the micelle, i.e., the hydrophobic core surrounded by a hydrophilic poly (ethylene oxide) (PEO) shell. On the basis of molar volumes, the intrinsic thermodynamic parameters of transfer of 1,10-phenantholine were extracted. The enthalpy and entropy of transfer of 1,10-phenanthroline from the PEO shell to the core are found to be small and negative. By using K EO and K c values for C 12E n obtained by fluorometry, individual fluorescence spectra of 1,10-phenanthroline in the PEO shell and core were extracted. The fluorescence intensity of 1,10-phenathroline accommodated in the core, like in organic solvents, is significantly reduced relative to that in water. These facts indicate that the aromatic rings of 1,10-phenanthroline penetrate into the hydrophobic core, while its hydrophilic N site is still hydrated in the PEO shell.

    DOI: 10.1023/B:JOSL.0000043634.09653.cb

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  • R Kanzaki, Y Umebayashi, T Maki, S Ishiguro .  Thermodynamics and fluorescence spectra of 1,10-phenanthroline in micelles of poly (ethylene oxide)-type nonionic surfactant .  JOURNAL OF SOLUTION CHEMISTRY33 ( 6-7 ) 699 - 709   2004.6Thermodynamics and fluorescence spectra of 1,10-phenanthroline in micelles of poly (ethylene oxide)-type nonionic surfactantReviewed

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:KLUWER ACADEMIC/PLENUM PUBL  

    The distribution of 1,10-phenanthroline (phen) in micellar solutions of the nonionic surfactants Triton X and C12En with varying poly (ethylene oxide) chain lengths has been studied by potentiometry, calorimetry, and fluorometry at 298 K. Micelles accommodate 1,10-phenanthroline according to the reaction, phen + Y-m = Y-m(phen), where Ym denotes a surfactant molecule aggregated in micelles. The constant Km for the reaction of Triton X increases as a linear function of n*, the number of ethylene oxide (EO) groups, as K-m = K(EO)n* + K-c. Nonzero K-EO and K-c values suggest a heterogeneous inner structure of the micelle, i.e., the hydrophobic core surrounded by a hydrophilic poly (ethylene oxide) (PEO) shell. On the basis of molar volumes, the intrinsic thermodynamic parameters of transfer of 1,10-phenantholine were extracted. The enthalpy and entropy of transfer of 1,10-phenanthroline from the PEO shell to the core are found to be small and negative. By using KEO and Kc values for C12En obtained by fluorometry, individual fluorescence spectra of 1,10-phenanthroline in the PEO shell and core were extracted. The fluorescence intensity of 1,10-phenathroline accommodated in the core, like in organic solvents, is significantly reduced relative to that in water. These facts indicate that the aromatic rings of 1,10-phenanthroline penetrate into the hydrophobic core, while its hydrophilic N site is still hydrated in the PEO shell.

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  • Ishiguro S.I., Umebayashi Y., Kanzaki R. .  Characterization of Metal Ions in Coordinating Solvent Mixtures by Means of Raman Spectroscopy .  Analytical Sciences20 ( 3 ) 415 - 421   2004.3

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    Titration Raman spectroscopy has been developed for studying the solvation structure of metal ions in solution. The method affords us the solvation number, and the value thus obtained in neat solvents is in good agreement with that determined by EXAFS. The method is then applied to solvent mixtures, and the individual solvation number for each solvent is extracted. In a solvent mixture of N,N-dimethylformamide (DMF) and N,N,N′,N′-tetramethylurea (TMU), the metal ion prefers DMF to TMU, which is ascribed to the solvation steric effect. The same applies also for the solvent mixture of N,N-dimethylpropionamide (DMPA) and DMF. However, unlike TMU, DMPA changes its conformation from the planar cis to non-planar staggered upon solvation to the metal ion. The enthalpy for the conformational change of DMPA is positive in the bulk, while it is significantly negative in the coordination sphere of the manganese(II) ion. Here, we briefly describe the procedure of measurements and analyses for the titration Raman spectroscopy, and review the solvation structure of the alkaline earth, first transition metal(II) and lanthanide(III) ions in some solvent mixtures in view of solvation steric effect.

    DOI: 10.2116/analsci.20.415

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  • Tei Maki, Ryo Kanzaki, Yasuhiro Umebayashi, Shin-Ichi Ishiguro .  Hysteretic behavior on the heat of protonation of diethylenetriamine in aqueous solution .  Chemistry Letters33 ( 2 ) 186 - 187   2004.2Reviewed

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    Hysteretic behavior was found on the heat of protonation of diethylenetriamine (dien) in aqueous solution at 298 K. We propose the presence of two conformers for Hdien+, which have significantly different proton affinities. Mutual transformation between the conformers may be practically forbidden, but is strongly accelerated upon their protonation to form H2dien2+.

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  • Yasuhiro Umebayashi, Mari Shin, Ryo Kanzaki, Shin-Ichi Ishiguro .  Thermodynamics of [Co(NCS)4]2- at poly(ethylene oxide) and octylphenyl moieties in micelles of nonionic surfactants .  Journal of Colloid and Interface Science237 ( 2 ) 167 - 173   2001.5Reviewed

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:Academic Press Inc.  

    Formation of cobalt(II)-thiocyanato complexes in nonionic surfactant solutions of poly(ethylene oxide) type with varying poly(ethylene oxide) chain lengths of 7.5 (Triton X-114), 30 (Triton X-305), and 40 (Triton X-405) has been studied by titration spectrophotometry and calorimetry at 298 K. Data were analyzed by assuming formation of a series of ternary complexes Co(NCS)nYm (2-n)+ (Y = surfactant) with an overall formation constant βnm. In all the surfactant systems examined, data obtained can be explained well in terms of formation of Co(NCS)+ and Co(NCS)2 in an aqueous phase (aq), and Co(NCS)4Y2- in micelles, and their formation constants, enthalpies, and entropies have been determined. The β41/β20 ratio increases and the corresponding enthalpy becomes significantly less negative with an increasing number of ethylene oxide groups. This suggests that micelles of these nonionic surfactants have a heterogeneous inner structure consisting of ethylene oxide and octylphenyl moieties. Indeed, on the basis of molar volumes of ethylene oxide and octylphenyl groups, intrinsic thermodynamic parameters have been extracted for the reaction Co(NCS)2(aq) + 2NCS-(aq) = Co(NCS)4Y2- (ΔrG°, ΔrH°, and ΔrS°) at each moiety. The ΔrG°, ΔrH°, and ΔrS° values are -16 kJ mol-1, -15 kJ mol-1, and 3 J K-1 mol-1, respectively, for the ethylene oxide moiety, and -15 kJ mol-1, -70 kJ mol-1, and -183 J K-1 mol-1 for octylphenyl. Significantly less negative ΔrH° and ΔrS° values for ethylene oxide imply that the hydrogen-bonded network structure of water is extensively formed at the ethylene oxide moiety, and the structure is thus broken around the Co(NCS)4 2- complex with weak hydrogen-bonding ability. © 2001 Academic Press.

    DOI: 10.1006/jcis.2001.7457

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  • Kanzaki R., Umebayashi Y., Uemura K., Ishiguro S.I. .  Distribution thermodynamics of 1,10-phenanthroline in non-ionic surfactant triton X-100 micelles .  Physical Chemistry Chemical Physics3 ( 5 ) 824 - 828   2001.3

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    The distribution thermodynamics of 1,10-phenanthroline (phen) and 2,9-dimethyl-1,10-phenanthroline (dmphen) in micelles of the non-ionic surfactant Triton X-100 were studied by potentiometry and titration calorimetry at 298 K. Both of these ligands form HL+ and HL2+ (L = phen and dmphen) in acidic solution. Their formation constants were determined in aqueous solutions containing various concentrations of Triton X-100, and were found to decrease with increasing concentration of the surfactant. The decrease is explained in terms of accommodation of neutral phenanthrolines in micelles by taking into account the surfactant solution as a heterogeneous solvent mixture. The case in which the surfactant is treated as the third reactant was also examined, and thermodynamic parameters for the interaction between the surfactant and phenanthrolines, i.e. the Gibb's energies, enthalpies and entropies of transfer of phenanthrolines from aqueous solution to a micellar pseudo-phase, were obtained. The Gibb's energies of transfer of the neutral ligand L are -8.2 and -11.7 kJ mol-1 for L = phen and dmphen, respectively. The corresponding enthalpies of transfer are both small and negative, implying that these neutral 1,10-phenanthrolines are still strongly hydrated in micelles, as well as in water, through the hydrophilic nitrogen sites.

    DOI: 10.1039/b009132o

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  • R Kanzaki, Y Umebayashi, K Uemura, S Ishiguro .  Distribution thermodynamics of 1,10-phenanthroline in non-ionic surfactant Triton X-100 micelles .  PHYSICAL CHEMISTRY CHEMICAL PHYSICS3 ( 5 ) 824 - 828   2001Distribution thermodynamics of 1,10-phenanthroline in non-ionic surfactant Triton X-100 micellesReviewed

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

    The distribution thermodynamics of 1,10-phenanthroline (phen) and 2,9-dimethyl-1,10-phenanthroline (dmphen) in micelles of the non-ionic surfactant Triton X-100 were studied by potentiometry and titration calorimetry at 298 K. Both of these ligands form HL+ and HL2+ (L = phen and dmphen) in acidic solution. Their formation constants were determined in aqueous solutions containing various concentrations of Triton X-100, and were found to decrease with increasing concentration of the surfactant. The decrease is explained in terms of accommodation of neutral phenanthrolines in micelles by taking into account the surfactant solution as a heterogeneous solvent mixture. The case in which the surfactant is treated as the third reactant was also examined, and thermodynamic parameters for the interaction between the surfactant and phenanthrolines, i.e. the Gibb's energies, enthalpies and entropies of transfer of phenanthrolines from aqueous solution to a micellar pseudo-phase, were obtained. The Gibb's energies of transfer of the neutral ligand L are -8.2 and -11.7 kJ mol(-1) for L = phen and dmphen, respectively. The corresponding enthalpies of transfer are both small and negative, implying that these neutral 1,10-phenanthrolines are still strongly hydrated in micelles, as well as in water, through the hydrophilic nitrogen sites.

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  • R Kanzaki, T Egashira, T Nakazato, Y Umebayashi, S Ishiguro .  Influence of charge on adduct formation of [M(phen)(3)](z+) (M = Ru2+, Co3+, Si4+) with 1,10-phenanthroline in aqueous solution .  PHYSICAL CHEMISTRY CHEMICAL PHYSICS2 ( 17 ) 3825 - 3830   2000.9Reviewed

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    Adduct formation of the inert complexes Ru(phen)(3)(2+), Co(phen)(3)(3+) and Si(phen)(3)(4+) with 1,10-phenanthroline (phen) has been studied by potentiometry and calorimetry in aqueous solution containing 0.1 mol dm(-3) NaCl as an ionic medium at 298 K. Formation of a 1:1 adduct, in which planar 1,10-phenanthroline molecules are stacked, has been found for all the inert complexes and their formation constants, enthalpies and entropies were obtained. Adduct formation constants are hardly influenced by the ionic charges of the metal center. The enthalpy values are all negative, indicating that a specific pi-pi interaction operates between stacked 1,10-phenanthroline molecules. The corresponding entropy values are positive for Ru(phen)(3)(2+) and Co(phen)(3)(3+), while it is negative for Si(phen)(3)(4+). The positive entropies indicate that reduction of hydrophobic hydration upon stacking also plays a key role in the adduct formation. Both enthalpy and entropy values significantly decrease with increasing charge, and they strongly compensate to give similar formation constants. This implies that hydrophobic hydration around aromatic rings within the inert complexes is reduced to a greater extent with increasing charge, Ru(phen)(3)(2+)&lt;Co(phen)(3)(3+)&lt;Si(phen)(3)(4+). 1,10-Phenanthroline forms protonated H(phen)(+) and H(phen)(2)(+) species in an acidic solution, and 1,10-phenanthroline molecules are stacked in the latter. The enthalpy and entropy of formation of H(phen)(2)(+) are significantly negative, also indicating that pi-pi interaction play an essential role in the formation of H(phen)(2)(+). On the other hand, both the enthalpy and entropy of solution of 1,10-phenanthroline remain unchanged in solution containing NaCl over the range 0.05-1 mol dm(-3), suggesting that hydrophobic hydration shells are restricted at the vicinity of 1,10-phenanthroline.

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  • Mari Shin, Yasuhiro Umebayashi, Ryo Kanzaki, Shin-Ichi Ishiguro .  Formation of copper(II) thiocyanato and cadmium(II) iodo complexes in micelles of nonionic surfactants with varying poly(ethylene oxide) chain lengths .  Journal of Colloid and Interface Science225 ( 1 ) 112 - 118   2000.5Reviewed

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:Academic Press Inc.  

    Formation of copper(II) thiocyanato and cadminum(II) iodo complexes in micelles of poly(ethylene oxide) (PEO)-type nonionic surfactants with varying PEO chain lengths of 9.5 (Triton X-100), 30 (Triton X-305), and 40 (Triton X- 405) has been studied by titration spectrophotometry and calorimetry at 298 K. In a given surfactant solution, all data obtained were analyzed by assuming formation of ternary complexes MX(n)Y(m)/(2-n)+ (M = Cu(II), Cd(II)
    X = SCN-, I-
    Y = surfactant), and the complexes thus form in aqueous phase (m = 0) or in micelles (m = 1). In the Cu(II)-SCN- system, spectrophotometric data obtained by varying concentrations of the surfactant can be explained well in terms of formation of Cu(NCS)2Y in micelles and Cu(NCS)+ and Cu(NCS)2 in an aqueous phase, and it turned out that formation constant of Cu(NCS)2Y increases with increasing PEO chain length. In the Cd(II)-I- system, the formation of CdI3Y- and CdI4Y2- is concluded in micelles, and that of CdI+, CdI- 3, and CdI2- 4 in an aqueous phase. Interestingly, formation enthalpies of CdI3Y- and CdI4Y2- become significantly less negative with increasing PEO chain length. This suggests that transfer of the complexes from aqueous solution to a hydrophobic octylphenyl (OP) moiety in micelles is significantly more exothermic than that to a hydrophilic PEO one. Thermodynamic parameters of transfer of CdI- 3 and CdI2- 4 from aqueous solution to the OP and PEO moieties of micelles have been evaluated. (C) 2000 Academic Press.

    DOI: 10.1006/jcis.2000.6722

    Scopus

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Books

  • Metal Ions and Complexes in Solution

    ed. Toshio Yamaguchi, Ingmar Persson( Role: Contributor ,  Chapter 1: Thermodynamic Measurements: Potentiometry, UV/Vis Spectrometry and Calorimetry)

    Royal Society of Chemistry  2023.12  ( ISBN:9781839168093

  • 化学便覧 基礎編 改訂6版

    日本化学会, 篠原, 久典( Role: Contributor ,  10.6.1 希釈エンタルピー(無機化合物水溶液)10.6.1 希釈エンタルピー(有機化合物水溶液)11.3 有機酸・塩基の酸解離定数)

    丸善出版  2021.1  ( ISBN:9784621305218

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    Total pages:xviii, 1509p   Language:Japanese

    CiNii Books

  • Geospatial science for smart land management : an Asian context

    Vries Walter Timo de, Rudiarto Iwan, Piyasena N. M. P. Milinda

    CRC Press  2024  ( ISBN:9781032393896

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    Language:English

    CiNii Books

  • Metal Ions and Complexes in Solution International journal

    ( Role: Joint author ,  Chapter 1: Thermodynamic Measurements: Potentiometry, UV/Vis Spectrometry and Calorimetry)

    Royal Society of Chemistry  2023.12 

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    Total pages:388   Responsible for pages:1-19   Language:English

    DOI: https://doi.org/10.1039/9781839169601

  • 化学便覧基礎編 改訂6版

    日本化学会(10.6.1, 10.6.2, 11.3)

    丸善出版  2021.1 

  • Handbook of Calorimetry and Thermal Analysis

    ( Role: Edit)

    2020.8 

  • コンパクト分析化学(978-4782705841)

    脇田久伸、横山拓史 編著、岡上吉広、神崎亮、栗崎敏、沼子千弥、白淑琴( Role: Joint author)

    三共出版  2013.3 

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    Language:Japanese Book type:Scholarly book

  • 金属錯体の機器分析(上)錯体化学会選書7(978-4782706398)

    大塩寛紀 編著、石黒慎一、尾関智二、海崎純男、神崎亮、齋藤一弥、坂本良太、寺岡淳二、西原寛 共著( Role: Joint author)

    三共出版  2010.10 

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    Language:Japanese Book type:Scholarly book

  • コンパクト分析化学

    神﨑 亮( Role: Joint author)

    三共出版 

  • 金属錯体の機器分析(上)錯体化学会選書7

    神﨑 亮

    三共出版 

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MISC

  • 特集「溶液の熱力学の新潮流」にあたって

    神﨑 亮

    熱測定   51 ( 1 )   2   2024.1

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  • Deep eutectic solvents for liquid–liquid extraction

    kanzaki R.

    Analytical Sciences   39 ( 7 )   1021 - 1022   2023.7

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    Language:Japanese   Publishing type:Article, review, commentary, editorial, etc. (scientific journal)   Publisher:Analytical Sciences  

    DOI: 10.1007/s44211-023-00362-0

    Scopus

    PubMed

  • プロトン性イオン液体のpHと酸塩基性 Reviewed

    神崎 亮

    分析化学   64 ( 3 )   189 - 196   2015.3

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    Language:Japanese   Publishing type:Article, review, commentary, editorial, etc. (scientific journal)  

  • インドネシア西ジャワ州チカニキ川周辺土壌中の水銀濃度分布に及ぼす金精錬活動の影響

    BARANSANO Christine, 河野百合子, 児玉谷仁, 神崎亮, RAHAJOE Joeni S., HIDAYATI Nuril, 冨安卓滋, 冨安卓滋

    分析化学討論会講演要旨集   75th   2015

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  • 鹿児島湾海水中水銀濃度変動に及ぼす海底噴気熱水活動の影響

    冨安卓滋, 冨安卓滋, 御手洗麻衣, 児玉谷仁, 河野百合子, GAMBOA RUIZ Wilder Leonardo, 神崎亮

    日本分析化学会年会講演要旨集   64th   2015

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  • Distribution of total and methyl-mercury concentrations in soils around a native mercury mine

    Kodamatani Hitoshi, Maeda Chihiro, Hokazono Toshimune, Kanzaki Ryo, Tomiyasu Takashi

    Abstracts of Annual Meeting of the Geochemical Society of Japan   61 ( 0 )   2014

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    Language:Japanese   Publisher:GEOCHEMICAL SOCIETY OF JAPAN  

    環境中に放出された水銀は、環境中で特に有毒なメチル水銀に変化し食物連鎖を通じ生体に蓄積することが知られている。しかしながら、環境中に放出された水銀がどこでどのようにメチル水銀化するのかは詳細には明らかになっていない。本研究では、自然水銀が産出することで知られた旧イトムカ水銀鉱山周辺で,水銀の環境挙動とメチル水銀の生成について調査した結果について報告する.

  • Distribution of total and organic mercury concentrations in sediments and living organisms around hydrothermal fumaroles

    Tomiyasu Takashi, Obata Katsuyoshi, Kodamatani Hitoshi, Kono Yuriko, Kanzaki Ryo, Yamamoto Masahiro, Takeuchi Akinori, Marumo Katsumi

    Abstracts of Annual Meeting of the Geochemical Society of Japan   61 ( 0 )   2014

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    Language:Japanese   Publisher:GEOCHEMICAL SOCIETY OF JAPAN  

    海底熱水噴出孔は海水中水銀の主要な起源の一つと考えられ、その周辺環境への影響に関心がもたれている。そこで、活発な熱水活動が行われている伊平屋北海丘と明神礁カルデラで採取された底質及び生体中の総水銀、有機水銀の濃度を測定し、熱水噴出孔から周辺への水銀の拡散や化学形の変化、また周辺に生息する生体への影響について考察した。

  • プロトン性イオン液体中における酸塩基反応熱力学 Reviewed

    神崎 亮

    熱測定   39 ( 1 )   2 - 8   2012

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    Language:Japanese   Publishing type:Article, review, commentary, editorial, etc. (scientific journal)  

  • イオンクロマトグラフィーを用いた鹿児島湾北部における熱水活動の影響評価

    御手洗麻衣, 梅田享, 児玉谷仁, 神崎亮, 河野百合子, 日高正康, 大木公彦, 冨安卓滋

    分析化学討論会講演要旨集   72nd   2012

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  • インドネシア共和国チカニキ川流域の金精錬活動による大気中水銀汚染の評価

    河野百合子, RAHAJOE Joeni S., HIDAYATI Nuril, 児玉谷仁, 神崎亮, 冨安卓滋

    分析化学討論会講演要旨集   72nd   2012

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  • インドネシア,ジャワ島西部小規模金採掘地域における土壌中総水銀濃度分布と土壌化学成分

    冨安卓滋, 河野百合子, 児玉谷仁, 神崎亮, NURIL Hidayati, JOENI Setijo Rahajoe

    日本分析化学会年会講演要旨集   60th   2011

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  • 鹿児島市における大気中水銀濃度変動

    河野百合子, 児玉谷仁, 神崎亮, 冨安卓滋

    日本分析化学会年会講演要旨集   60th   2011

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  • 非水溶液・イオン液体の酸塩基性とpH測定 Reviewed

    神崎 亮、宋 雪旦、石黒 慎一、梅林 泰宏

    Electrochemistry   78 ( 8 )   687 - 692   2010

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    Language:Japanese   Publishing type:Article, review, commentary, editorial, etc. (scientific journal)  

  • インドネシア,ジャワ島西部チカニキ川上流域における土壌及び河川底質中水銀濃度分布

    冨安卓滋, 河野百合子, 児玉谷仁, 神崎亮, NURIL Hidayati, JOENI Setijo Rahajoe

    分析化学討論会講演要旨集   71st   2010

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  • インドネシアジャワ島西部の小規模金採掘地域におけるシマオオタニワタリを用いた大気中水銀のバイオモニタリング

    河野百合子, JOENI Setijo Rahajoe, NURIL Hidayati, 児玉谷仁, 神崎亮, 冨安卓滋

    分析化学討論会講演要旨集   71st   2010

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  • インドネシアの小規模金採掘集落内および天然林内における大気中水銀濃度の経時変化

    河野百合子, RAHAJOE Joeni Setijo, 児玉谷仁, 神崎亮, 冨安卓滋

    日本分析化学会年会講演要旨集   59th   2010

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  • Raman分光法とDFT計算によるイオン液体N,N‐alkyl‐methylpyrrolidinium bis(trifluoromethanesulfonyl)imideの異性化に関する研究

    藤森崇夫, 藤井健太, 神崎亮, 梅林泰宏, 石黒慎一

    化学関連支部合同九州大会・外国人研究者交流国際シンポジウム講演予稿集   44th   64   2007.7

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    Language:Japanese  

    J-GLOBAL

  • Raman分光法によるイオン液体BMI<sup>+</sup>Tf<sub>2</sub>N<sup>-</sup>中のSr<sup>2+</sup>の溶媒和に関する研究

    山口大志, 藤森崇夫, 藤井健太, 神崎亮, 梅林泰宏, 石黒慎一

    電気化学会大会講演要旨集   74th   479   2007.3

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    Language:Japanese  

    J-GLOBAL

  • イオン液体1‐プロピル‐2,3,5‐トリメチルピラゾリウム‐ビストリフルオロメタンスルホニルイミドのコンフォメーションに関する研究

    光木卓志, 藤森崇夫, 藤井健太, 神崎亮, 千葉一美, 永松亮太, 梅林泰宏, 石黒慎一

    電気化学会大会講演要旨集   74th   480   2007.3

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    Language:Japanese  

    J-GLOBAL

  • 分子レベルでみるイミダゾリウム系イオン液体の構造

    高椋利幸, 副島靖史, 教正院康裕, 藤井健太, 藤森崇夫, 神崎亮, 梅林泰宏, 石黒慎一, 山口敏男

    溶液化学シンポジウム講演要旨集   29th   34   2006.11

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    Language:Japanese  

    J-GLOBAL

  • LAXS,NMRおよびMD法によるイオン液体の構造に関する研究

    教正院康裕, 副島靖史, 藤井健太, 藤森崇夫, 神崎亮, 梅林泰宏, 石黒慎一, 山口敏男, 高椋利幸

    化学関連支部合同九州大会・外国人研究者交流国際シンポジウム講演予稿集   43rd   34   2006.7

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    Language:Japanese  

    J-GLOBAL

  • Raman spectroscopic study on the Room Temperature Ionic Liquids and their metal ion solvation

    梅林泰宏, 藤森崇夫, 藤井健太, 神崎亮, 石黒慎一

    Jasco Rep   48 ( 1 )   1 - 10   2006.4

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    Language:Japanese  

    J-GLOBAL

  • MDシミュレーションと分光実験によるイオン液体1‐ethyl‐3‐methylimidazolium bis‐(trifluoromethanesulfonyl)imideの液体構造研究

    藤井健太, 梅林泰宏, 神崎亮, 藤森崇夫, 竹内宗孝, 高椋利幸, 石黒慎一

    分子シミュレーション討論会講演要旨集   20th   26 - 27   2006

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    Language:Japanese  

    J-GLOBAL

  • 分子動力学計算によるテトラフルオロほう酸1‐エチル‐3‐メチルイミダゾリウムイオン液体の研究

    藤森崇夫, 藤井健太, 神崎亮, 梅林泰宏, 石黒慎一

    電気化学秋季大会講演要旨集   2006   95   2006

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    J-GLOBAL

  • イオン液体1‐エチル‐3‐メチルイミダゾリウムテトラフルオロほう酸のMDシミュレーションおよび分光学的測定による研究

    神崎亮, 藤森崇夫, 梅林泰宏, 藤井健太, 竹内宗孝, 高椋利幸, 石黒慎一

    分子シミュレーション討論会講演要旨集   20th   28 - 29   2006

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    J-GLOBAL

  • イオン液体中の1‐ethyl‐3‐ethyl‐imidazoliumカチオンのコンフォメーション

    梅林泰宏, 藤森崇夫, 鋤崎哲也, 浅田光則, 藤井健太, 神崎亮, 石黒慎一

    溶液化学シンポジウム講演要旨集   28th   25   2005.11

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    J-GLOBAL

  • Characterization of metal ions in coordinating solvent mixtures by means of Raman spectroscopy

    S Ishiguro, Y Umebayashi, R Kanzaki

    ANALYTICAL SCIENCES   20 ( 3 )   415 - 421   2004.3

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    Language:English   Publishing type:Book review, literature introduction, etc.   Publisher:JAPAN SOC ANALYTICAL CHEMISTRY  

    Titration Raman spectroscopy has been developed for studying the solvation structure of metal ions in solution. The method affords us the solvation number, and the value thus obtained in neat solvents is in good agreement with that determined by EXAFS. The method is then applied to solvent mixtures, and the individual solvation number for each solvent is extracted. In a solvent mixture of N,N-dimethylformamide (DMF) and N,N,N',N'-tetramethylurea (TMU), the metal ion prefers DMF to TMU, which is ascribed to the solvation steric effect. The same applies also for the solvent mixture of N,N-dimethylpropionamide (DMPA) and DMF. However, unlike TMU, DMPA changes its conformation from the planar cis to non-planar staggered upon solvation to the metal ion. The enthalpy for the conformational change of DMPA is positive in the bulk, while it is significantly negative in the coordination sphere of the manganese(II) ion. Here, we briefly describe the procedure of measurements and analyses for the titration Raman spectroscopy, and review the solvation structure of the alkaline earth, first transition metal(H) and lanthanide(III) ions in some solvent mixtures in view of solvation steric effect.

    Web of Science

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Presentations

  • 神﨑 亮   電解質中における電解質の反応熱力学   Invited

    第13回イオン液体討論会サテライトミーティング  2023.11 

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    Event date: 2023.11

    Presentation type:Oral presentation (invited, special)  

  • Ryo KANZAKI, Mika SAKO, Hitoshi KODAMATANI, Takashi TOMIYASU, Clement GUIBERT, Jerome FRESNAIS, Veronique PEYRE   ENTHALPY PROFILE OF;PH-INDUCED FLOCCULATION AND REDISPERSION OF;POLYACRYLIC;ACID-COATED;NANOPARTICLES IN;PROTIC IONIC LIQUIDS  

    26th IUPAC International Conference on Chemical Thermodynamics (ICCT-2023)  2023.8 

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    Event date: 2023.7 - 2023.8

    Presentation type:Oral presentation (general)  

  • KANZAKI Ryo, SAKO Mika, KODAMATANI Hiroshi, TOMIYASU Takashi, PEYRE Veronique   Ionization thermodynamics of poly(acrylic acid) in ionic liquids  

    38th International Conference on Solution Chemistry  2023.7 

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    Event date: 2023.7

    Presentation type:Oral presentation (general)  

  • Kanzaki Ryo, Mika Sako, Hitoshi Kodamatani, Takashi Tomiyasu, Clement Guiber, Jerome Fresnais, Veronique Peyre   Dispersion mechanism of polyacrylic acid-coated maghemite nanoparticle in ionic liquids  

    11th International Conference on Fine Particle Magnetism (ICFPM 2022)  2022.10 

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    Event date: 2022.10

    Presentation type:Poster presentation  

  • KANZAKI Ryo, SAKO Mika, KODAMATANI Hitoshi, TOMIYASU Takashi   Calorimetric Detection of Aggregation;Redispersion of Polyacrylic acid-coated;Maghemite Nanoparticle in;Protic Ionic Liquids  

    37th International Conference on Solution Chemistry  2022.7 

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    Event date: 2022.7

    Presentation type:Oral presentation (general)  

  • 神﨑 亮   電解質中における電解質の反応熱力学   Invited

    イオン液体討論会サテライトミーティング  2023.11 

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    Event date: 2023.11

  • 日高朋也, 児玉谷仁, 冨安卓滋, 神﨑亮   リチウム(ビストリフルオロメタンスルホニル)イミドによる濃厚電解質水溶液中におけるイオンの反応性  

    日本分析化学会第72年会  2023.9 

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    Event date: 2023.9

    Presentation type:Oral presentation (general)  

  • 日高 朋也, 児玉谷 仁, 冨安 卓滋, 神﨑 亮   リチウム(ビストリフルオロメタンスルホニル)イミドによる濃厚電解質溶液を反応場とした酸塩基反応とそのメカニズム  

    日本分析化学会第71年会  2022.9 

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    Event date: 2022.9

    Presentation type:Poster presentation  

  • Ryo Kanzaki   Solvation and Reaction of Ions in Ionic Liquids   Invited International conference

    CATS 2017 (The 8th International and The 10th Japan-China Joint Symposium on. Calorimetry & Thermal Analysis) 

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    Event date: 2017.11

    Language:English   Presentation type:Oral presentation (keynote)  

    Venue:Fukuoka, Japan  

  • Ryo Kanzaki   Thermodynamic Approach on Chemical Reaction in Ionic Liquid   Invited International conference

    CALCON 2016 (Calorimetry conference 2016) 

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    Event date: 2016.7 - 2016.8

    Language:English   Presentation type:Oral presentation (invited, special)  

    Venue:Hawaii, USA  

  • Ryo Kanzaki, Hitoshi Kodamatani, Takashi Tomiyasu   Chloro Complex Formation of Cupper (II) in 1-Butyl-3-methylimidazolium Ionic Liquids   International conference

    34th International Conference on Solution Chemistry 

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    Event date: 2015.8 - 2015.9

    Language:English   Presentation type:Poster presentation  

    Venue:Prague, Czech Republic  

  • Ryo Kanzaki   Ionization Thermodynamics in Protic Ionic Liquids   Invited International conference

    The 5th International Symposium on the New Frontiers of Thermal Studies of Materials  The Fifth International Symposium on the New Frontiers of Thermal Studies of Materials

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    Event date: 2013.10

    Language:English   Presentation type:Oral presentation (invited, special)  

    Venue:Yokohama, Japan  

  • Ryo Kanzaki , Yuko Kusamura, Xuedan Song, Hiroyuki Doi, Yasuhiro Umebayashi   Ionization Reaction Thermodynamics in Protic Ionic Liquid, Ethylammonium Nitrate   International conference

    The 33rd International Conference on Solution Chemistry (33 ICSC)  The 33rd International Conference on Solution Chemistry (33 ICSC)

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    Event date: 2013.7

    Language:English   Presentation type:Oral presentation (general)  

    Venue:Kyoto, Japan  

  • 神崎 亮   イオン液体中におけるイオンの反応・平衡   Invited

    電気化学会創立第80周年記念大会  電気化学会創立第80周年記念大会

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    Event date: 2013.3

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Venue:仙台  

  • 神崎 亮   溶液内反応をプローブとした溶媒和の熱力学的研究   Invited

    第35回溶液化学シンポジウム  第35回溶液化学シンポジウム

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    Event date: 2012.11

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Venue:東京  

    国内学会

  • 神崎 亮   プロトン性イオン液体におけるpHと酸塩基反応   Invited

    日本化学会西日本大会  日本化学会西日本大会

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    Event date: 2012.11

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Venue:佐賀  

    国内学会

  • Ryo KANZAKI, Xuedan SONG, Yasuhiro UMEBAYASHI, Shin-ichi ISHIGURO   Ionization Thermodynamics of Acids and Bases in Protic Ionic Liquid, Ethylammonium Nitrate   International conference

    15th International Congress on Thermal Analysis and Calorimetry (15th ICTAC)  15th International Congress on Thermal Analysis and Calorimetry (15th ICTAC)

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    Event date: 2012.8

    Language:English   Presentation type:Oral presentation (general)  

    Venue:Osaka, Japan  

    国際学会

  • 神崎 亮   イオン液体中におけるpHと酸塩基反応   Invited

    第28回分析化学緑陰セミナー(日本分析化学会北海道支部)  第28回分析化学緑陰セミナー(日本分析化学会北海道支部)

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    Event date: 2012.6

    Language:Japanese   Presentation type:Symposium, workshop panel (nominated)  

    Venue:北海道(旭川)  

  • 神崎 亮   非水環境下における酸塩基反応熱力学   Invited

    第47回熱測定討論会  第47回熱測定討論会

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    Event date: 2011.10

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Venue:群馬  

  • Ryo KANZAKI, Xuedan SONG, Yasuhiro UMEBAYASHI,Shin-ichi ISHIGURO   Reaction Thermodynamics for Ionization of Acetic Acid in Protic Ionic Liquid, Ethylammonium Nitrate   International conference

    The 32nd International Conference on Solution Chemistry (32 ICSC)  The 32nd International Conference on Solution Chemistry (32 ICSC)

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    Event date: 2011.8

    Language:English  

    Venue:Montpelier, France  

    国際学会

  • Ryo Kanzaki, Xuedan Song, Yasuhiro Umebayashi, Shin-ichi Ishiguro   Study on the Acid-base Reaction and Solvation in Protic Ionic Liquids   International conference

    2010環太平洋国際化学会議/PACIFICHEM 2010  2010環太平洋国際化学会議/PACIFICHEM 2010

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    Event date: 2010.12

    Language:English  

    Venue:アメリカ合衆国(ハワイ)  

    国際学会

  • Ryo Kanzaki (invited)   Reaction Thermodynamics of Chemical Equilibria in Solution   International conference

    21st IUPAC International Conference on Chemical Thermodynamics-Young Scientists' Program  21st IUPAC International Conference on Chemical Thermodynamics-Young Scientists' Program

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    Event date: 2010.8

    Language:English  

    Venue:Tsukuba, Japan  

    国際学会

  • Ryo Kanzaki, Shinya Sato, Xuedan Song, Yasuhiro Umebayashi, Shin-ichi Ishiguro   Hydrophobic/Hydrophilic Hydration of Nucleobases Investigated in Micellar Solutions   International conference

    21st IUPAC International Conference on Chemical Thermodynamics  21st IUPAC International Conference on Chemical Thermodynamics

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    Event date: 2010.8

    Language:English  

    Venue:Tsukuba, Japan  

    国際学会

  • 神崎 亮(依頼)   酸・塩基の昔と今  

    第23回日本分析化学会九州支部春の講演会  第23回日本分析化学会九州支部春の講演会

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    Event date: 2010.5

    Language:Japanese  

    Venue:福岡  

    研究会

  • Ryo Kanzaki, Xuedan Song, Yasuhiro Umebayashi, Shin-ichi Ishiguro   Thermodynamic Study on the Acid-Base Reaction Mechanism in Protic Ionic Liquid, Ethylammonium Nitrate, and Its Aqueous Mixtures   International conference

    EUCHEM Conference on Molten Salts and Ionic Liquids 2010  EUCHEM Conference on Molten Salts and Ionic Liquids 2010

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    Event date: 2010.3

    Language:English  

    Venue:Bamberg, Germany  

    国際学会

  • Ryo Kanzaki, Xuedan Song, Yasuhiro Umebayashi, Shin-ichi Ishiguro   Thermodynamic Investigation of Acid-Base Property of N-Methylimidazolium-based Protic Ionic Liquids   International conference

    EUCHEM Conference on Molten Salts and Ionic Liquids 2010  EUCHEM Conference on Molten Salts and Ionic Liquids 2010

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    Event date: 2010.3

    Language:English  

    Venue:Bamberg, Germany  

    国際学会

  • Ryo Kanzaki, Xuedan Song, Yasuhiro Umebayashi, Shin-ichi Ishiguro   Thermodynamic Study on the Autoprotolysis in a Protic Ionic Liquid, Ethylammonium Nitrate, and Its Aqueous Mixtures   International conference

    The 31st International Conference on Solution Chemistry (31 ICSC)  The 31st International Conference on Solution Chemistry (31 ICSC)

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    Event date: 2009.8

    Language:English  

    Venue:Innsbruck, Austria  

    国際学会

  • Ryo Kanzaki, Xuedan Song, Shota Hara, Yasuhiro Umebayashi, Shin-ichi Ishiguro   Acid-base Properties and Liquid Structures of a Protic Ionic Liquid, Ethylammonium Nitrate, and Its Aqueous Mixtures   International conference

    The 3rd International Congress on Ionic Liquids (COIL-3)  The 3rd International Congress on Ionic Liquids (COIL-3)

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    Event date: 2009.6

    Language:English  

    Venue:Cairns, Australia  

    国際学会

  • Ryo Kanzaki, Xuedan Song, Shota Hara, Yasuhiro Umebayashi, Shin-ichi Ishiguro   Acidity and Basicity of Protic Ionic Liquids Depending on the Constituting Acid and Base   International conference

    The 3rd International Congress on Ionic Liquids (COIL-3)  The 3rd International Congress on Ionic Liquids (COIL-3)

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    Event date: 2009.6

    Language:English  

    Venue:Cairns, Australia  

    国際学会

  • Ryo Kanzaki (invited)   Thermodynamic Approach for Acid-Base Property of Protic Ionic Liquids   International conference

    九大-釜慶自然大学合同シンポジウム  九大-釜慶自然大学合同シンポジウム

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    Event date: 2009.3

    Language:English  

    Venue:Fukuoka, Japan  

    国際学会

  • KANZAKI Ryo   Acid-base equilibrium-based nanoparticle dispersion in ionic liquids   Invited

    55th JSCTA Workshop  2019.2 

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    Language:English   Presentation type:Oral presentation (invited, special)  

  • KANZAKI Ryo   Solvation and Reaction of Ions in Ionic Liquids   Invited International conference

    CATS 2017 (The 8th International and The 10th Japan-China Joint Symposium on. Calorimetry & Thermal Analysis)  2017.11 

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    Language:English   Presentation type:Oral presentation (keynote)  

  • 神﨑 亮   イオン液体 ~溶媒が電荷を持つということ~   Invited

    第79回分析化学討論会  2019.5 

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    Language:Japanese   Presentation type:Oral presentation (invited, special)  

  • 神﨑 亮   熱分析にかかる熱力学   Invited

    JAIMAセミナー  2019.9 

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    Language:Japanese   Presentation type:Public lecture, seminar, tutorial, course, or other speech  

  • KANZAKI Ryo   Ionization Thermodynamics in Protic Ionic Liquids   Invited International conference

    The 5th International Symposium on the New Frontiers of Thermal Studies of Materials  2013.10 

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    Language:English   Presentation type:Oral presentation (invited, special)  

  • KANZAKI Ryo   Hydrophobic/Hydrophilic Hydration of Nucleobases Investigated in Micellar Solutions   Invited International conference

    ICCT-2010 Young Scientists' Program  2010.8 

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    Language:English   Presentation type:Oral presentation (invited, special)  

  • KANZAKI Ryo   Heats of Mixing of Carboxylic Acids and N-Methylimidazole   Invited International conference

    14th ICTAC (International Confederation for Thermal Analysis and Calorimetry)  2008.9 

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    Language:English   Presentation type:Oral presentation (general)  

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Awards

  • 奨励賞

    2013.11   The Japan Association of Solution Chemistry  

    KANZAKI Ryo

  • JSCTA Research Encouragement Award

    2012.10   The Japan Society of Calorimetry and Thermal Analysis  

    KANZAKI Ryo

  • Kyushu Analytical Chemistry Award for Young Researchers

    2000.7   The Japan Society for Analytical Chemistry, Kyushu Branch  

    KANZAKI Ryo

  • 溶液化学研究会奨励賞

    2012.11   溶液化学研究会   溶液内反応をプローブとした溶媒和の熱力学的研究

    神﨑 亮

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    Country:Japan

  • 日本熱測定学会奨励賞

    2011.10   日本熱測定学会   非水環境下における酸塩基反応熱力学

    神﨑 亮

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    Country:Japan

  • The Grant Programme for Young Scientists

    2008.9   International Confederation for Thermal Analysis and CalorimetryInternational Confederation for Thermal Analysis and Calorimetry  

    KANZAKI Ryo

  • 九州分析化学奨励賞

    2000.7   分析化学会九州支部   非イオン性界面活性剤と疎水性化学種との相互作用

    神﨑 亮

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    Country:Japan

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Research Projects

  • Thermodynamic Approach on Chemical Reaction in Ionic Liquid

    Grant number:26410157  2014.4 - 2017.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (C)

    KANZAKI Ryo

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    Grant amount:\5070000 ( Direct Cost: \3900000 、 Indirect Cost:\1170000 )

    Chloro complex formation constants and the heats of complexation of copper (II) in ionic liquids lie within them in conventional molecular solvents such as DMF and acetonitrile. In addition, the entropy term was found to be the driving force of the complexation. They indicate that the complexation mechanism in ionic liquids is similar to that in the conventional liquids, despite their uniqueness as a solvent. On the contrary, minor solvent dependence of the complexation constants and athermal ligand exchange of the solvate are interestingly observed in ionic liquids. This will be attributed to the fact that the solvent species in ionic liquids have a negative charge that causes a significant inter-ligand interaction in the primary solvation shell.

  • 水-非水混合溶媒系におけるATPおよびその断片化学種の酸塩基反応

    Grant number:21118516  2009 - 2010

    日本学術振興会  科学研究費助成事業  新学術領域研究(研究領域提案型)

    神崎 亮

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    Grant amount:\4940000 ( Direct Cost: \3800000 、 Indirect Cost:\1140000 )

    22年度の研究計画としては、21年度の研究を継続し、プロトン性イオン液体(PIL)である硝酸エチルアンモニウム(EAN)中におけるATP断片化学種の特に小分子について、酸解離平衡の反応熱力学を明らかにすることにあった.特に、21年度の研究遂行において障害となっており、大きな課題と位置づけていた熱量滴定に要する試料量の低減に取り組んだ.熱量滴定装置のセル部分を改修した結果、初期体積を25mLから4mLに大幅に低減することに成功した.このことで、EAN中の酸塩基反応のみならず、一般的なイオン液体中における反応熱測定が可能となった.
    EANの酸塩基反応について、まず一般的な性質を知るため、簡単な酸および塩基として酢酸およびトリフルオロエチルアミンの酸解離反応熱力学量を決定した.その結果、反応エンタルピーは水溶液中と25~30kJ/mol、エントロピーも80J/mol・K程度の差があり、酸塩基反応メカニズムが大きく異なっていることが明らかとなった.PIL中におけるこれらの反応熱力学量の決定例は世界で初めてである.一方、自由エネルギー変化としては数kJ/mol程度の差しかなく、強いエンタルピー-エントロピー補償効果がはたらいていることが分かった.アデニンについても同様にエンタルピー・エントロピー補償効果が確認されたが、その程度は酢酸やトリフルオロエチルアミンより小さかった.このことは、アデニンが疎水的であるため、EAN中においても水溶液中と同様、疎水水和されていることを示唆する.しかしながら、PIL中における反応熱力学量の解釈や、EANの共役酸・共役塩基の溶存状態や一般的な性質についての情報は皆無で、比較対照も無いため、定量的な議論のためこれらを今後構築していくことになる.また、リン酸部位など他の断片化学種についても今後の検討課題となった.

  • Acid-base Equilibrium in Protic Ionic Liquids

    Grant number:19750062  2007 - 2008

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Young Scientists (B)

    KANZAKI Ryo

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    Grant amount:\2210000 ( Direct Cost: \2000000 、 Indirect Cost:\210000 )

  • コメのメチル水銀汚染リスク評価:土壌環境・化学組成・無機水銀形態が及ぼす影響

    Grant number:24H00782  2024.4 - 2028.3

    日本学術振興会  科学研究費助成事業  基盤研究(A)

    児玉谷 仁, 山本 正浩, 高木 善弘, 武内 章記, 一谷 勝之, 神崎 亮, 冨安 卓滋

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    Grant amount:\47970000 ( Direct Cost: \36900000 、 Indirect Cost:\11070000 )

  • コメのメチル水銀汚染リスク低減のための土壌環境評価法の検討

    Grant number:21H03621  2021.4 - 2024.3

    日本学術振興会  科学研究費助成事業  基盤研究(B)

    児玉谷 仁, 一谷 勝之, 山本 正浩, 武内 章記, 神崎 亮, 冨安 卓滋

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    Grant amount:\17550000 ( Direct Cost: \13500000 、 Indirect Cost:\4050000 )

    鹿児島大学農学部付属農場の1枚の水田(土壌総水銀濃度:0.2 mg/kg)を利用し、遺伝子的に大きく異なるコメの品種(WRC系統59品種)を育て、各品種の玄米に含まれる水銀濃度を測定した。この結果、最高 7.1 ng/g 最低1.7 ng/g (平均値 3.2 ng/g, 中央値 3.0 ng/g, n = 59)となり、同一土壌で育成した稲であっても品種によって含まれる水銀濃度が異なることを確認した。一方、水銀汚染土(水田土壌に2015年に10 mg/kgとなるように水銀イオンを添加し、毎年稲の栽培に利用している土壌、土壌総水銀濃度:8 mg/kg)を利用し、予備的に選ばれた5品種についてポット栽培を行った。2週間に一度、土壌を採取し、土壌のメチル水銀濃度の変化および稲に含まれる水銀量を測定した。玄米の水銀濃度は、日本晴(WRC1)で0.25 mg/kg となり、含まれる水銀のほとんどがメチル水銀であることを確認した。土壌のメチル水銀濃度が、湛水から1ヵ月程度で最大(約0.1 mg/kg)となり、徐々に低下していくこと、一方、稲は品種により出穂までの育成期間やバイオマスが大きく異なることから、土壌メチル水銀の影響を受けやすい、受けにくいの差が生じ、玄米の水銀濃度に品種差が生じている可能性も示唆された。
    土壌におけるメチル水銀生成と、存在する無機水銀形態の関係を明らかにするため、土壌に含まれる無機水銀形態を簡易に分析する手法について検討を進めた。様々な水銀汚染地域で得た土壌試料を利用し、加熱温度を段階的に変化させつつ、気化する水銀量を評価することで、存在する水銀形態の判別を試みた。試料によっては特徴的な結果が得られたが、気化温度と水銀形態の関係は明確には確認できなかった。今後、試料数を増やしつつ、存在形態別分析法として一般的に用いられている逐次抽出法と比較していく予定である。

  • Solution chemistry of extremely concentrated electrolyte solutions

    Grant number:21K05115  2021.4 - 2023.3

    Japan Society for the Promotion of Science  Grant-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research(C)

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    Authorship:Principal investigator 

    Grant amount:\4160000 ( Direct Cost: \3200000 、 Indirect Cost:\960000 )

  • 超濃厚リチウム水溶液中における反応熱力学

    2020.12 - 2022.3

    住友電工グループ学術・研究助成 

  • 超濃厚リチウム水溶液中における反応熱力学

    2020.12 - 2022.3

    住友電工グループ社会貢献基金  住友電工グループ学術・研究助成 

    神崎 亮

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    Authorship:Principal investigator 

  • 水系電池電解液の溶液化学

    Grant number:20-4720  2020.4 - 2021.3

    岩谷科学技術研究助成 

  • 水系電池電解液の溶液化学

    2020.4 - 2021.3

    公益財団法人 岩谷直治記念財団  岩谷科学技術研究助成 

    神﨑 亮

  • The Dynamics of Mercury and Selenium Released by Submarine Volcanic Activity in Kagoshima Bay

    Grant number:19H01168  2019.4 - 2023.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (A)

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    Grant amount:\45760000 ( Direct Cost: \35200000 、 Indirect Cost:\10560000 )

  • Behavior of MeHg production in a Hg(II) ion spiked paddy field soil during multi-year rice cultivation and the mechanism of MeHg accumulation in rice grain

    Grant number:18H03392  2018.4 - 2021.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (B)

    KODAMATANI Hitoshi

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    Grant amount:\17810000 ( Direct Cost: \13700000 、 Indirect Cost:\4110000 )

    To investigate the accumulation of methylmercury in rice grains, the uptake behavior of mercury by rice plant was examined through hydroponic experiments, which involved addition of mercury to the culture solution. In addition, the formation of methylmercury from mercury ion in waterlogged soil and the uptake of the formed methylmercury by rice plant were investigated. The results of hydroponic experiments showed that mercury ion and methylmercury, added to the culture solution, accumulated in the roots, and only methylmercury was transferred to the ears during ear growth. The concentration of methylmercury in the waterlogged soil fluctuated greatly during the rice cultivation period, with and without rice plants. Of note, methylmercury concentration increased with decreasing soil redox potential; however, with further decrease in soil redox potential, methylmercury concentration decreased.

  • Production of methylmercury in Hg contaminated paddy field and its effect to biological system

    Grant number:15H02832  2015.4 - 2018.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (B)

    KODAMATANI Hitoshi, YAMAMOTO Masahiro, MATSUYAMA Akito

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    Grant amount:\17160000 ( Direct Cost: \13200000 、 Indirect Cost:\3960000 )

    We prepared different samples of Hg(II) ion-contaminated soils and cultivated rice therein, to confirm the differences in MeHg production in soils and its effect on MeHg accumulation in rice grain. Pot experiments were performed in two different soil types, soil I and soil II, to each of which 10 mg/kg Hg(II) ion was added. Rice was planted on 2015, 2016, and 2017 at same soil.
    The maximum MeHg concentrations of soil I and II were obtained in 2015. However, MeHg concentrations of soils were decreased in 2016 and 2017 in comparison with 2015 . We believe that the reason is the change of added Hg(II) ion form to other inorganic Hg forms. MeHg concentrations in brown rice at each pots were decidedly affected by the MeHg concentration in soils. MeHg and T-Hg concentrations were measured in all three parts of the brown rice grain (embryo, bran, and endosperm) and found to be 3.18 and 3.86 mg/kg, 0.74 and 0.90 mg/kg, and 0.49 and 0.53 mg/kg, respectively.

  • イオン液体はどのような溶媒か?反応エネルギー論にもとづくアプローチ

    2014.4 - 2017.3

    科学研究費補助金  基盤研究(C)

  • The behavior of mercury in the contaminated site and its impact on ecosystems

    Grant number:25257302  2013.4 - 2016.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (A)

    Tomiyasu Takashi, MATSUYAMA Akito, IMURA Ryusuke, UCHIUMI Toshiki, KODAMATANI Hitoshi, KONO Yuriko, MIYAMOTO Junko, SATO Masanori, KANZAKI Ryo, Horvat Milena, Balogh Steven, Rahajoe Joeni S, Hidayati Nuril

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    Grant amount:\38610000 ( Direct Cost: \29700000 、 Indirect Cost:\8910000 )

    The distribution of total and methylmercury concentration was investigated with chemical composition of soil, TOC and TN around Idrija old mercury mine, Slovenia. Through the investigation, ethylmercury was found for the first time in soil of this area. The organic matter plays an important role for the formation of organic mercury compound. Significant relations were observed between mercury concentration in air, plant leaves and soil, which indicate a circulation of mercury through these media. In west Java, Indonesia, the dispersion and transport of mercury through river system was investigated and it was found that suspended particle is an important transporter of mercury. In muscle of fresh water snail living in paddy field, organic mercury concentration and the percentage of total mercury was considerably higher than the paddy field soil, which suggests that mercury discharged from small scale gold mining can give an impact on ecosystems.

  • Specific free energy picture and solvation structure formed in ionic liquids

    Grant number:23350033  2011.11 - 2014.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (B)

    UMEBAYASHI Yasuhiro, KAMEDA Yasuo, KANAKUBO Mitsuhiro, KANZAKI Ryo

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    Grant amount:\6630000 ( Direct Cost: \5100000 、 Indirect Cost:\1530000 )

    Ionic liqudis show specific liquid and/or solvation structure, which have never been found in ordinary solvents. In this subject, to elucidate specific solvation in ionic liquids at a molecular and/or atomistic level, we foucused on the CO2 solvation in ionic liquids and studied (1) CO2 solvation in ionic liquids in terms of solvation structure and energy by means of molecular simulation asisted liquid structure anakyses and free energy calculations, (2) structure and thermidynamics of CO2 protonatin in ionic liquids, and (3) CO2 electrochemical reduction in ionic liquids.

  • The environmental behavior of mercury in contaminatedsites

    Grant number:22404002  2010 - 2012

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (B)

    TOMIYASU Takashi, MATSUYAMA Akito, IMURA Ryusuke, MIYAMOTO Junko, KANZAKI Ryo, KODAMATANI Hitoshi, KONO Yuriko

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    Grant amount:\16250000 ( Direct Cost: \12500000 、 Indirect Cost:\3750000 )

    Distribution of mercury around small scale gold mining area had been investigated. The atmospheric concentration of mercury in the village was several μg m-3and that in the work place was 30 μg m-3. The highest concentration of mercury in river water was about 10 μg L-1.In soil samples, total mercury and methylmercury concentrations decreased with depth from the soil surface. The values showed significant positive relations with total organic carbon content. The fact suggests that the transported mercury through the air deposits on the ground surfaces and adsorb on the organic matter.

  • 水-非水混合溶媒系におけるATPおよびその断片化学種の酸塩基反応

    2009.4 - 2011.3

    科学研究費補助金  新学術領域研究

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    水-非水混合溶媒系におけるATPおよびその断片化学種の酸塩基反応

  • イオン液体に溶存する金属イオンの溶媒和錯体構造と錯形成

    2008.4 - 2011.3

    科学研究費補助金  基盤研究(B)

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    イオン液体に溶存する金属イオンの溶媒和錯体構造と錯形成

  • Metal ions solvation structure and complex formation in ionic liquids

    Grant number:20350037  2008 - 2010

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (B)

    ISHIGURO Shin-ichi, UMEBAYASHI Yasuhiro, KANZAKI Ryo

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    Grant amount:\19630000 ( Direct Cost: \15100000 、 Indirect Cost:\4530000 )

    Ionic liquids of novel solvent has been strongly expected to apply them as a separation/extraction media, materials for electric devices instead of ordinary aqueous/non-aqueous solvents in terms of low environmental load. Nevertheless, the knowledge on their properties as solvent(reaction fields) is not enough. In this study, to find unique chemical reactions in ionic liquids, we investigated proton and metal ion solvation structure and their reactivity to establish structure-reactivity relationship.

  • プロトン性イオン液体中の酸塩基反応と溶媒和

    Grant number:20031024  2008 - 2009

    日本学術振興会  科学研究費助成事業  特定領域研究

    石黒 慎一, 神崎 亮

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    Grant amount:\3600000 ( Direct Cost: \3600000 )

    プロトン性イオン液体(PIL)中には解離性のプロトンが過剰に含まれる.PILを電気化学デバイスへの組み込みや酸塩基反応媒体として応用する場合、溶存するプロトンの状態を知ることが不可欠である.本研究では、様々なPIL中における酸塩基性や酸塩基反応メカニズムについて、熱力学的手法をベースに明らかにすることを目標とした.
    【PIL中の酸塩基反応】EAN中におけるα-アラニンのカルボキシル基の酸解離定数を電位差滴定法によって調べると3.95であり、水溶液中(2.33)より大きかった.このことは、EAN中におけるH^+供与体がHNO_3であり、水溶液中(H_3O^+)より強酸であることを反映すると考えられる.すなわちEANは酸性溶媒に分類される.しかしながら、他にもいくつかの化合物の酸解離定数を決定したところ、そのシフト幅は一様ではなく、広い範囲の化合物の測定が必要である.
    【PIL中の溶媒和】PIL中では自己解離平衡が起こっており、自己解離定数pK_<IL>はPILの酸塩基性を示す指標となる.幅広い陽イオン・陰イオンの組み合わせからなるPILについてpK_<IL>を決定すると、水溶液中から見積もられた対応する物理量ΔpKaに対しpK_<IL>=ΔPKa-2に近い値であった.しかし、PIL中におけるこの反応のエンタルピー・エントロピー変化を調べると、水溶液中とは大きく異なっていた.酸塩基反応は化学種の電荷の増減をともなうため、PIL中と水溶液中では溶媒和状態が大きく異なるためだと考えられ、PILの酸塩基性を水溶液中の情報から予測することが困難であることが示された.

  • プロトン性イオン液体中における酸塩基平衡

    2007.4 - 2009.3

    科学研究費補助金  若手研究(B)

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    プロトン性イオン液体中における酸塩基平衡

  • Cluster Structure of Ionic Liquids and their Solvent Properties for Reactions in Solution

    Grant number:17350037  2005 - 2007

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (B)

    ISHIGURO Shin-ichi, UMEBAYASHI Yasuhiro, KANZAKI Ryo

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    Grant amount:\15540000 ( Direct Cost: \14700000 、 Indirect Cost:\840000 )

    Ionic Liquids have complicated molecular structures, and intramolecular and intermolecular interactions are overlapped over the range of 300-700 pm. In the present study, we aimed to isolate these interactions using X-ray scattering and theoretical DFT and MD simulation. Finally, we succeeded to extract not only short range cation-anion interactions, but also long range cation anion, cation-cation and anion-anion interactions in the range of < 2000 pm. Such a long-range interaction has been obtained for the first time over the world, and this method of approach can be applied for various types of ionic liquids. Indeed, this method of approach was applied for ionic liquids composed of imidazolium and pyrolidinium cations with varying length of alkyl chains, and the space distribution of anions around the cation, and detailed atom-atom interactions can be extracted.
    On the other hand, ionic liquids composed of alkylammonium ions anions are called as protic ionic liquids. Protic ionic liquids involve dissociable protons, and a part of protons within cations are transferred to anions to give acid and base molecules. The extent of proton transfer is expressed in terms of K_IL= [acid] [base], and the K_IL, is a measure of the acid-base property of protic ionic liquids. We determined the K_IL, value of ethylanmmonium nitrate ionic liquid directly by potentiometry using an IS FET (ion-selective field-effect transistor) electrode, for the first time over the world The K_IL, value strongly depends on the nature of anion, the hydrogen bonding ability of which usually leads to a Jorge K_IL, (or small pK_IL).

  • Solvation of proton in solution, acidity and basicity of the solution

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  • 溶液中のプロトン溶媒和状態・酸塩基性

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Academic Activities

  • Steering Committee, Session 1. Fluid & Phase Equilibria Chair

    Role(s): Panel moderator, session chair, etc.

    26th IUPAC International Conference on Chemical Thermodynamics (ICCT-2023)  2023.7 - 2023.8

  • 実行委員長

    Role(s): Planning, management, etc.

    第44回溶液化学シンポジウム  2022.10

  • National Committee

    Role(s): Planning, management, etc.

    11th International Conference on Fine Particle Magnetism (ICFPM 2022)  2022.10

  • 実行委員・シンポジウム「1.分析化学反応場における酸と塩基」オーガナイザー

    Role(s): Panel moderator, session chair, etc.

    日本分析化学会第72年会  2023.9