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Journal Articles

Extraction of Rh(III) from hydrochloric acid by protonated NTAamide(C6) and analogous compounds and understanding of extraction equilibria by using UV spectroscopy and DFT calculations

Sasaki, Yuji; Kaneko, Masashi; Ban, Yasutoshi; Kinoshita, Ryoma; Matsumiya, Masahiko*; Shinoku, Kota*; Shiroishi, Hidenobu*

Analytical Sciences, 39(9), p.1575 - 1583, 2023/09

 Times Cited Count:0 Percentile:0(Chemistry, Analytical)

Extraction of Rh from HCl can be performed by NTAamide(C6) (hexahexyl-nitrilotriacetamide) and other related compounds into n-dodecane. We use ion-pair extraction of anionic species of Rh-chloride and protonated extractant. Rh behave as anion in hydrochloric acid and the tertiary nitrogen atom in extractant may be protonated to produce the quaternary amine in acidic condition. From the present work, the maximum distribution ratio of Rh(III) is 16. The D(Rh) values are changeable during preparation of the aqueous solutions because different Rh-Cl-H$$_{2}$$O complexes are formed in HCl media and show the slow exchange rate between Cl and H$$_{2}$$O. Using the UV spectrum, Rh-chloride solution having the peak of spectrum at 504 nm can be extracted effectively, where RhCl$$_{4}$$(H$$_{2}$$O)$$^-$$ and RhCl$$_5$$(H$$_2$$O)$$^2$$$$^-$$ exist mainly from DFT calculation. Stoichiometry of one-one complex of Rh and NTAamide is obtained from slope analysis, and 85 mM of concentrated Rh ion can be extracted.

Journal Articles

Recent results on hydrogen and hydration in biology studied by neutron macromolecular crystallography

Niimura, Nobuo; Arai, Shigeki; Kurihara, Kazuo; Chatake, Toshiyuki*; Tanaka, Ichiro*; Bau, R.*

Cellular and Molecular Life Sciences, 63(3), p.285 - 300, 2006/02

 Times Cited Count:41 Percentile:37.86(Biochemistry & Molecular Biology)

Neutron diffraction provides an experimental method of directly locating hydrogen atoms in proteins and DNA oligomers. Three different types of high resolution neutron diffractometers for biological macromolecules have been constructed in Japan, France and the U.S.A., and they have all been actively used in recent years to determine the crystal structures of numerous proteins. Examples include the detailed geometries of hydrogen bonds, information on H/D exchange in proteins, the unambiguous location of protons, the role of key hydrogen atoms in enzymatic activity and thermostability, and the dynamical behavior of hydration structures, all of which have been extracted from these structural results and reviewed in this article. Other important techniques, such as the optimization of growth of large single crystals using phase diagrams, the preparation of fully deuterated proteins, the introduction of cryogenic techniques to neutron protein crystallography, and the establishment of a "hydrogen and hydration in proteins" database, will also be described in this paper.

Oral presentation

Characterization and thermodynamic study of the protonation of humic acid dissolved in deep groundwater at Horonobe, Hokkaido, Japan

Kimuro, Shingo*; Kirishima, Akira*; Akiyama, Daisuke*; Sato, Nobuaki*; Nagao, Seiya*; Saito, Takumi*; Amano, Yuki; Miyakawa, Kazuya

no journal, , 

In this study, size exclusion chromatography (SEC), flow-field flow fractionation (Fl-FFF) and calorimetry were applied to the humic acid isolated from the groundwater collected at 350m below the ground level at the Horonobe Underground Research Laboratory, JAEA. First, the characteristic molecular weight distribution of Horonobe humic acids were observed from the SEC analysis. Second, the small hydrodynamic diameter of Horonobe humic acids were observed by the Fl-FFF. Finally, the protonation enthalpies of Horonobe humic acids were determined by the combination of potentiometry and calorimetry. The values of protonation enthalpy of Horonobe humic acids were close to simple organic acids (i.e., benzoic acid and phenol). It was suggested that Horonobe humic acids have lower molecular weight than IHSS surface soil humic acids (Elliot Soil and Waskish Peat) and the simple protonation mechanism, which is not affected by the heterogeneity.

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