Local structure of rare earth elements (REE) in marine ferromanganese oxides by extended X-ray absorption fine structure and its comparison with REE in ion-adsorption type deposits

Nagasawa, Makoto*; Qin, H.-B.*; Yamaguchi, Akiko; Takahashi, Yoshio*

Chemistry Letters, 49(8), p.909 - 911, 2020/08

https://doi.org/10.1246/cl.200257

Bromine-isotope selective ionization using field-free alignment of IBr isotopologues with a switched nanosecond laser pulse

Akagi, Hiroshi*; Kumada, Takayuki; Otobe, Tomohito*; Itakura, Ryuji*; Hasegawa, Hirokazu*; Oshima, Yasuhiro*

Chemistry Letters, 49(4), p.416 - 418, 2020/04

https://doi.org/10.1246/cl.200024

Finding free-energy landmarks of chemical reactions

Shiga, Motoyuki; Tuckerman, M. E.*

Journal of Physical Chemistry Letters (Internet), 9(21), p.6207 - 6214, 2018/11

https://doi.org/10.1021/acs.jpclett.8b01958

Predicting reaction pathways is one of the most important goals in theoretical and computational chemistry. In this paper, we propose a novel approach to search for free-energy landmarks, i.e., minima and the saddle points, of chemical reactions in an automated manner using a combination of steepest descent and gentlest ascent methods. As demonstrations, we present applications to the ring-opening reaction of benzocyclobutene and an SN2 reaction in aqueous solution.

Sorption behavior of Np(V) on microbe pure culture and consortia

Onuki, Toshihiko; Kozai, Naofumi; Sakamoto, Fuminori; Utsunomiya, Satoshi*; Kato, Kenji*

Chemistry Letters, 46(5), p.771 - 774, 2017/05

https://doi.org/10.1246/cl.170068

The sorption behavior of Np(V) by the microbe consortia and by a single pure culture of Fe reducing bacterium was studied at pH between 3 and 7 in resting cell conditions. The sorption of Np(V) by the Fe reducing bacterium obtained in the inert condition and by the consortia in aerated condition were higher than by the Fe reducing bacterium in aerobic condition at pH below 5, strongly suggesting presence of other mechanism than the adsorption on microbial cell surface, i.e. reduction to Np(IV).

Complexing agents for oxonium anions of Mo and Re and their masking effects on extraction using N-donor extractants

Sasaki, Yuji; Suzuki, Tomoya; Morita, Keisuke; Tsubata, Yasuhiro

Chemistry Letters, 43(10), p.1538 - 1539, 2014/10

https://doi.org/10.1246/cl.140502

Several complexing agents including soft donor in their structures are examined for the masking effects of Mo and Re through solvent extraction. The available extractants are hexaoctyl-nitrilotriacetamide (NTAamide) and methyliminodioctylacetamide (MIDOA), whose extractants have high D(Mo, Re). It is clear that Mo and Re in HNO dissolving N-donor ligands, ethylenediamine, diethylenetriamine, and 1,3-diaminopropane, can be suppressed for extraction into organic phase. The ligands including sulfur donor, e.g., thiourea, are also tested, however, less masking effect can be seen.

Adsorption behavior of lanthanide ions on nonbiological phospholipid membranes; A Model study using liposome

Yamasaki, Shinya; Shirai, Osamu*; Kano, Kenji*; Kozai, Naofumi; Sakamoto, Fuminori; Onuki, Toshihiko

Chemistry Letters, 42(8), p.819 - 821, 2013/08

https://doi.org/10.1246/cl.130226

The adsorption behavior of lanthanide ions (except for Pm) on liposomes composed of phosphatidylcholine and cholesterol was examined to understand the interaction between lanthanide ions and the phosphoryl moiety of phospholipids. The adsorption of lanthanide ions increased with an increase in pH under the weakly acidic conditions. Selective adsorption with the local maximum at the Er ion and local minimum at the Er ion was observed, similar to the selective adsorption of the bacterial cell surface but different from that of orthophosphates. These results indicate that the adsorption of lanthanide on the phospholipid does not result from simple adsorption on orthophosphate functional groups but by the composition and molecular structure of the phospholipid. Our results strongly suggest that liposomes can be used as a simple biomembrane model without any biological activity for the study of adsorption of lanthanide ions.

Novel soft-hard donor ligand, NTAamide, for mutual separation of trivalent actinides and lanthanides

Sasaki, Yuji; Tsubata, Yasuhiro; Kitatsuji, Yoshihiro; Morita, Yasuji

Chemistry Letters, 42(1), p.91 - 92, 2013/01

https://doi.org/10.1246/cl.2013.91

The new N-donor extractant, NTAamide, is synthesized and tested for extraction and separation of Am-Cm-Ln. It was found that the high separation factors for An-Ln can be seen at 0.1-0.2M HNO, which suggest the de-protonation to N donor is important to show the high SF between An and Ln. From the present work, the stable N-donor extractant having high SF of An-Ln from nitric acid to n-dodecane can be obtained. The highest separation factor, 6.5, of Am-Cm for the condition of 0.5M NTAamide (C8) in n-dodecane and 10 mM TEDGA in 0.2M HNO as one of the highest SF values is found. NTAamide is the promising extractants for partitioning process of Am-Cm-Ln.

Isotope ratio analysis of individual plutonium and uranium-plutonium mixed oxide particles by thermal ionization mass spectrometry with a continuous heating method

Suzuki, Daisuke; Kokubu, Yoko; Lee, C. G.; Esaka, Fumitaka; Magara, Masaaki; Kimura, Takaumi

Chemistry Letters, 41(1), p.90 - 91, 2012/01

https://doi.org/10.1246/cl.2012.90

In conventional isotope ratio analysis of individual plutonium particles, the analytical procedure is complicated, because the particles have to be dissolved prior to the measurement. The chemical treatments may cause contamination of U existing in the environment. This makes it difficult to obtain accurate Pu/Pu isotope ratio. In the present work, an analytical method by a combination of single particle transfer and thermal ionization mass spectrometry with a continuous heating method is examined for individual plutonium particles, namely the particles are measured without any chemical treatments. In addition, the technique is applied to the analysis of individual uranium-plutonium mixed oxide (MOX) particles. The results of analysis of individual particles produced from standard solutions indicate that all isotope ratios are consistent with the certified values. There is no effect of isobaric interference on the results. In conclusion, the proposed analytical method is a useful tool for the isotope ratio analysis of plutonium and MOX particles without any chemical treatments.

Specific sorption behavior of actinoids on biogenic Mn oxide

Tanaka, Kazuya*; Tani, Yukinori*; Onuki, Toshihiko

Chemistry Letters, 40(8), p.806 - 807, 2011/08

https://doi.org/10.1246/cl.2011.806

We made sorption experiments of actinides on Mn oxide in dilute NaCl solution. Sorption affinity of actinides on synthetic Mn oxide was Th(IV) U(VI) Np(V). The specific sorption behavior of actinides on biogenic Mn oxide was observed. Thorium sorbed on biogenic Mn oxide was desorbed into solution with increasing time. Neptunium was not sorbed on biogenic Mn oxide. The specific sorption behavior is possibly due to organic ligands released from microorganisms and surface property of biogenic Mn oxide.

Fabrication of silica nanomaterials reflecting morphological transition of DNA mediated by a silane-appended ionic liquid

Shimojo, Kojiro; Mitamura, Hisayoshi; Mouri, Tsuyoshi; Naganawa, Hirochika

Chemistry Letters, 40(5), p.435 - 437, 2011/05

https://doi.org/10.1246/cl.2011.435

A simple fabrication strategy of DNA-transcribed silica materials has been developed. An ionic liquid incorporating an alkoxysilane group is capable of binding with DNA and acts as nuclei for subsequent sol-gel reaction with tetramethoxysilane. Unique silica materials with worm-like, rod-shaped, toroidal, or linearly fibrous structures are created from the same DNA template through the morphological transition of DNA induced by the ionic liquid.