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Pt-labeled platinum complex and evaluation of its biodistribution in healthy mice面川 真里奈*; 木村 寛之*; 初川 雄一*; 河嶋 秀和*; 塚田 和明; 屋木 祐介*; 内藤 行基*; 安井 裕之*
Bioorganic & Medicinal Chemistry, 97, p.117557_1 - 117557_6, 2024/01
被引用回数：0 パーセンタイル：0.01(Biochemistry & Molecular Biology)Pt was produced via the (n,2n) reaction induced by accelerator neutrons. [Pt]FGC-Pt was obtained through the accelerator neutron irradiation of FGC-Pt and K
PtCl
. Highly purified [Pt]FGC-Pt was obtained using the latter method, which suggests that the synthetic method using a Pt-labeled platinum reagent is suitable for the radioactivation of platinum complexes. We also investigated whether a significant correlation existed between the biodistribution of FGC-Pt and [Pt]FGC-Pt in healthy mice 24 h after tail vein administration. These results suggest that Pt-labeled compounds, synthesized using radioactive platinum reagents, can be used to confirm the biodistribution of platinum compounds. Our study on the biodistribution of [Pt]FGC-Pt is expected to contribute to the development of novel platinum-based drugs in the future.
Massey, D.*; Williams, C. D.*; Mu, J.*; Masters, A. J.*; 元川 竜平; 青柳 登; 上田 祐生; Antonio, M. R.*
Journal of Physical Chemistry B, 127(9), p.2052 - 2065, 2023/03
被引用回数：0 パーセンタイル：0(Chemistry, Physical)There is an ever-increasing body of evidence that metallic complexes, involving amphiphilic ligands, do not form normal solutions in organic solvents. Instead, they form complex fluids with intricate structures. For example, the metallic complexes may aggregate into clusters and these clusters themselves may aggregate into super-clusters. In order to gain a deeper insight into the mechanisms at play, we have used an improved force field to conduct extensive molecular dynamics simulations of a system composed of zirconium nitrate, water, nitric acid, tri-
-butyl phosphate and -octane. The important new finding is that a dynamic equilibrium between the cis and trans isomers of the metal complex is likely to play a key role in the aggregation behavior. The isolated cis and trans isomers have similar energies but simulation indicates that the clusters consist predominantly of cis isomers. With increasing metal concentration, we hypothesize that more clustering occurs and the chemical equilibrium shifts towards the cis isomer. It is possible that such isomeric effects play a role in the liquid-liquid extraction of other species and the inclusion of such effects in flowsheet modelling may lead to a better description of the process.
平田 早紀子*; 日下 良二; 明地 省吾*; 為国 誠太*; 奥寺 洸介*; 浜田 昇賢*; 坂本 知優*; 本田 匠*; 松下 高輔*; 村松 悟*; et al.
Inorganic Chemistry, 62(1), p.474 - 486, 2023/01
被引用回数：0 パーセンタイル：0.01(Chemistry, Inorganic & Nuclear)A new technique, surface-enhanced infrared absorption (SEIRA) spectroscopy, was used for the structural investigation of lanthanide (Ln) and actinide (An) complexes containing organic ligands. We synthesized thiol derivatives of organic ligands with coordination sites similar to those of diglycolamide (DGA), Cyanex-272, and 
-tetrakis(2-pyridinylmethyl)-1,2-ethanediamine (TPEN), which have been used for separating Ln and An through solvent extraction. These ligands were attached on a gold surface deposited on an Si prism through S-Au covalent bonds; the gold surface enhanced the IR absorption intensity of the ligands. Aqueous solutions of Ln (Eu
, Gd, Tb) and An (Am) ions were loaded onto the gold surface to form ion complexes. The IR spectra of the ion complexes were obtained using FT-IR spectroscopy in the attenuated total reflection mode. In this study, we developed a new sample preparation method for SEIRA spectroscopy that enabled us to obtain the IR spectra of the complexes with a small amount of ion solution (5 
L). This is a significant advantage for the IR measurement of radiotoxic Am complexes. In the IR spectra of DGA, the band attributed to C=O stretching vibrations at 
1630 cm
shifted to a lower wavenumber by 20 cm upon complexation with Ln and An ions. Moreover, the amount of the red-shift was inversely proportional to the extraction equilibrium constant reported in previous studies on solvent extraction. The coordination ability of DGA toward Ln and An ions could be assessed using the band position of the C=O band. The Cyanex-272- and TPEN-like ligands synthesized in this report also showed noticeable SEIRA signals for Ln and An complexes. This study indicates that SEIRA spectroscopy can be used for the structural investigation of ion complexes and provides a microscopic understanding of selective extraction of Ln and An.
日下 良二; 渡邉 雅之
Journal of Physical Chemistry Letters (Internet), 13(30), p.7065 - 7071, 2022/08
被引用回数：5 パーセンタイル：70.33(Chemistry, Physical)Understanding the chemistry of elements at the bottom of the periodic table is a challenging goal in chemistry. Observing actinide species at interfaces using interface-selective second-order nonlinear optical spectroscopy, such as vibrational sum frequency generation (VSFG) spectroscopy, is a promising route for developing heavy element chemistry; however, such attempts are scarce. Here, we investigated the phase transfer mechanism of uranyl ions (UO
) in solvent extraction using the di-(2-ethylhexyl)phosphoric acid (HDEHP) extractant dissolved in dodecane organic phase by probing the oil/water liquid-liquid interface using VSFG spectroscopy. The POO
symmetric stretch vibrational signals of the HDEHP ligands clearly demonstrated that uranyl ions form interfacial complexes with HDEHP at the oil/water interface. The interfacial uranyl-HDEHP complexes were formed with uranyl ions coming from both the aqueous and oil phases, strongly suggesting that the interfacial complex is an intermediate to cross the oil/water interface. Density functional theory (DFT) calculations proposed the molecular structure of the interfacial uranyl-HDEHP complex.
O-pentadentate planar ligands designed for the strongest and selective capture of uranium from seawater水町 匠*; 佐藤 みなみ*; 金子 政志; 竹山 知志*; 津島 悟*; 鷹尾 康一朗*
Inorganic Chemistry, 61(16), p.6175 - 6181, 2022/04
被引用回数：2 パーセンタイル：36.89(Chemistry, Inorganic & Nuclear)海水中のウランに対して強力かつ選択的に錯体を生成する平面五座配位子Hsaldian及びその誘導体を開発した。模擬海水条件において、saldian
はウランに対して非常に高い安定度定数を示し、従来開発されてきたアミドキシム型配位子よりも10桁以上の錯生成能を達成した。海水中に存在する他の夾雑イオンに対するウランの選択性についても、良好な結果が得られた。
G
tz, M.*; Yakushev, A.*; Gtz, S.*; Di Nitto, A.*; D
llmann, Ch. E.*; 浅井 雅人; Kindler, B.*; Krier, J.*; Lommel, B.*; 永目 諭一郎*; et al.
Radiochimica Acta, 110(2), p.75 - 86, 2022/02
被引用回数：2 パーセンタイル：31.78(Chemistry, Inorganic & Nuclear)揮発性超重元素カルボニル錯体の研究には、原子番号の増加とともに超アクチノイド元素の生成率が低下するためにより効率的な方法が必要となる。新規に開発したダブルチャンバーシステムを用いて、反跳槽と反応槽を分離することにより、カルボニル錯体合成の障害となる入射イオンビームによる反応分子の分解を回避することにより、これを実現する。軽い超アクチノイド元素Sg, Bh, Hs、およびMtの同族元素同位体として5d金属短寿命同位体を原子力機構タンデム加速器で合成し、モデル実験を行うことで、本手法の実現可能性を検証した。
日下 良二; 渡邉 雅之
Journal of Physical Chemistry B, 125(24), p.6727 - 6731, 2021/06
被引用回数：8 パーセンタイル：44.55(Chemistry, Physical)In the solvent extraction of metal ions, the transport mechanism of metal ions through the liquid-liquid organic/aqueous interface remains unclear. In this study, the adsorption process of trivalent lanthanide ions from the aqueous phase to the interface in the solvent extraction of lanthanides with di(2-ethylhexyl)phosphoric acid (HDEHP) extractant is investigated by using a model interface - water surface covered with HDEHP (air/HDEHP/aqueous interface). As a result, symmetric POO stretch signals of HDEHP observed by vibrational sum frequency generation spectroscopy and density functional theory calculations show that the stoichiometric ratio of lanthanide-HDEHP complexes formed at the air/HDEHP/aqueous interface is 1:1. The formation of the interfacial 1:1 lanthanide-HDEHP complex could be an elementary chemical process occurring just before the transfer of lanthanide ions to the side of the organic phase.
Kwon, H.*; Pietrasiak, E.*; 大原 高志; 中尾 朗子*; Chae, B.*; Hwang, C.-C.*; Jung, D.*; Hwang, I.-C.*; Ko, Y. H.*; Kim, K.*; et al.
Inorganic Chemistry, 60(9), p.6403 - 6409, 2021/05
被引用回数：0 パーセンタイル：0.01(Chemistry, Inorganic & Nuclear)The synthesis of sandwich-shaped multinuclear silver complexes with planar penta- and tetranuclear wheel-shaped silver units and a central anion is reported, along with complete spectroscopic and structural characterization. An NMR mechanistic study reveals that silver complexes were formed in the following order: 2Ag 
3Ag
5Ag
4Ag. The central hydroxides in 4Ag and 5Ag exhibit exotic physical properties due to the confined environment inside the complex. The size of these silver wheels can be tuned by changing the central anion or extracting/adding one silver atom. This study provides the facile way to synthesize discrete wheel-shaped multinuclear silver complexes and provides valuable insights into the dynamics of the self-assembly process.
Gtz, M.*; Gtz, S.*; Kratz, J.-V.*; Ballof, J.*; Dllmann, Ch. E.*; Eberhardt, K.*; Mokry, C.*; Renisch, D.*; Runke, J.*; 佐藤 哲也; et al.
Radiochimica Acta, 109(3), p.153 - 165, 2021/03
被引用回数：3 パーセンタイル：45.99(Chemistry, Inorganic & Nuclear)超重元素揮発性カルボニル錯体の化学研究のために、反跳によって標的もしくは線源から飛び出す核反応生成物または核分裂生成物を熱化し、さらに気相カルボニル錯体合成を行うための2槽型装置を開発した。この装置は、空間的にデカップルされ熱化チェンバーと気相化学反応チェンバーから成り立ち、核反応等で生成した短寿命核種が熱化チェンバーに満たされたガス中で熱化されたのち、気相化学反応チェンバーに送り込まれて、一酸化炭素と反応することでカルボニル錯体を形成する。
U中性子誘起核分裂および
Cm自発核分裂からの核分裂片を用いて検証したところ、全体効率として50%以上を達成した。また一連の結果により、熱化された核分裂生成物のカルボニル錯体形成が単一原子反応であり、熱原子反応ではないことを示した。
O-type Schiff base complexes of tetravalent f-elements (M(IV) = Ce, Th, U, Np, and Pu) in solid state and in solutionRadoske, T.*; Kloditz, R.*; Fichter, S.*; M
rz, J.*; Kaden, P.*; Patzschke, M.*; Schmidt, M.*; Stumpf, T.*; Walter, O.*; 池田 篤史
Dalton Transactions (Internet), 49(48), p.17559 - 17570, 2020/12
被引用回数：10 パーセンタイル：65.05(Chemistry, Inorganic & Nuclear)A series of tetradentate NO-type Schiff base complexes with tetravalent 4f- and 5f-block metals, [M(salpn)] (Hsalpn = 
-disalicylidene-1,3-diaminopropane; M = Ce, Th, U, Np, and Pu), were prepared to systematically investigate their solid state structure, and their complexation behaviour in solution with the goal to investigate the subtle differences between 4f- and 5f-elements. X-ray diffraction revealed that all investigated metal cations form [M(salpn)] complexes. All the complexes show the same ligand arrangement with meridional conformation, amongst which only Ce(IV) exhibits unique behaviour upon crystallisation. [Ce(salpn)] crystallises in two less symmetric systems (
or 2
/), whilst all the other [M(salpn)] crystallise in a more symmetric orthorhombic system (ban). Quantum chemical calculations suggest that the observed structural peculiarity of Ce(IV) stems from the geometrical flexibility due to the more "ionic" nature of bonds to the 4f element. 
H NMR measurements revealed that [M(salpn)] forms two different species in solution with and without an additional solvent molecule, where the relative distribution of the two species depends mainly on the ionic radius of the metal centre. Again, Ce(IV) behaves differently from the tetravalent actinides with a higher ratio of the solvent-molecule-coordinated species than the ratio expected from its ionic radius. Hence, this study is successful in observing subtle differences between 4f- (
Ce) and 5f-elements (actinides; Th, U, Np, and Pu) both in the solid state and in solution on an analytically distinguishable level, and in relating the observed subtle differences to their electronic structure.
数納 広哉; 町田 昌彦
RIST News, (66), p.3 - 16, 2020/10
原子力発電所事故により環境中に放出され陸域に降着した放射性セシウムは、森林内において、地衣類や菌類等に蓄積・保持されることが知られている。特にキノコにおいては、その傘部分に放射性セシウムの濃縮が観察され、セシウムイオンは傘の色素分子と錯体を形成すると考えられている。本研究では、キノコ色素分子の代表例としてノルバジオンA分子に着目し、最新の量子化学計算手法を用いて、水溶液中でのアルカリ金属イオン錯体の分子構造と錯体形成におけるセシウムイオンに対する選択性(他のアルカリイオンとの錯体形成自由エネルギーの差)を評価した。その結果、アルカリ性の水溶液中で、ノルバジオンAはセシウムイオンと選択的に錯体を形成することが分かった。この計算結果は、キノコにおける放射性セシウム濃縮の謎を解く鍵になると考えられる。
日下 良二
Journal of Nuclear and Radiochemical Sciences (Internet), 20, p.28 - 31, 2020/06
Vibrational sum frequency generation (VSFG) spectroscopy offers unique information about the molecular structure at liquid interfaces (gas/liquid, liquid/liquid, and solid/liquid) in the interfacial region, which is as thin as 1 nm. This paper presents some recent VSFG studies on liquid interfaces related to solvent extractions of lanthanide and actinide. In these studies, the organic phase of solvent extractions was excluded to prevent the transfer of lanthanide and actinide from the interface into the organic phase, and their complexes with extractants were attempted to observe at the air/aqueous solution interfaces using VSFG spectroscopy. For the Eu extraction system with the di-(2-ethylhexyl)phosphate (HDEHP) extractant, an interfacial Eu-HDEHP complex was observed, and Eu existed between HDEHP and water molecules, whereas for U extraction with the tributyl phosphate (TBP) extractant, no U-TBP interfacial complexes were observed. These results suggest that the two ions transfer into the organic phase from the aqueous phase via different phase transfer mechanisms. This paper demonstrates that VSFG spectroscopy is a powerful technique to obtain unique information about liquid interfaces pertaining to lanthanide and actinide chemistry.
元川 竜平; 小林 徹; 遠藤 仁; Mu, J.*; Williams, C. D.*; Masters, A. J.*; Antonio, M. R.*; Heller, W. T.*; 長尾 道弘*
ACS Central Science, 5(1), p.85 - 96, 2019/01
被引用回数：46 パーセンタイル：86.05(Chemistry, Multidisciplinary)We present a hierarchical aggregate model of an organic phase containing a coordination species that acts as a fundamental building unit of higher-order structures formed in the organic phase. We aimed to elucidate the fundamental aspects of the microscopic structure and phase separation occurring in ionic separation and recovery systems during solvent extraction. The coordination species aggregate through a hydrogen-bonding network formed by interaction between the hydrophilic part of the coordination species with extracted water and acid molecules. This reduces the hydrophilic surface area, resulting in subsequent formation of small primal clusters of 2 to 3 nm in diameter. The primal clusters further aggregate due to van der Waals interaction to form large aggregates of 
10 nm in diameter. The size of the primal cluster does not depend on the concentration of the coordination species, whereas the size of the large aggregate increases as the aggregation number of the primal clusters increases. We conclude that hybrid interaction is a key driving force in the formation and growth of the hierarchical aggregate and the induction of phase separation of the organic phase.
glycoprotein; Microbial transformation of heavy elements in the aquatic environment香西 直文; 坂本 文徳; 田中 万也; 大貫 敏彦; 佐藤 隆博*; 神谷 富裕*; Grambow, B.
Chemosphere, 196, p.135 - 144, 2018/04
被引用回数：5 パーセンタイル：17.65(Environmental Sciences)バクテリアや菌類等の微生物が環境中で重元素の化学状態を変化させることは知られているが、原生動物の作用についてはほとんど未解明である。本研究では、代表的な原生動物であるゾウリムシと水中のEu(III), Pb(II), U(VI)の反応を調べた。micro-PIXEを用いた非破壊分析では、ゾウリムシ生細胞に吸着した重元素はほとんど検出できなかったが、死滅細胞へは明らかな吸着が認められた。生細胞の細胞表面から自然に溶出する糖タンパク質と重元素が結合して擬似コロイドとなることを見いだした。本来は細胞に吸着するはずの元素が糖タンパク質と錯形成し水溶性の擬似コロイドとなることにより、生細胞への吸着が低下したことが示唆される。
本倉 健*; 福田 拓磨*; 上村 洋平*; 松村 大樹; 池田 まりか*; 南保 雅之*; Chun, W.-J.*
Catalysts, 8(3), p.106_1 - 106_8, 2018/03
被引用回数：4 パーセンタイル：10.01(Chemistry, Physical)In this study, mesoporous and nonporous silica-supported Pd complexes were synthesized and characterized. Variable-temperature XAFS measurements and a curve-fitting analysis showed a slightly larger contribution of 
when the Pd complexes were on a nonporous support in comparison to a mesoporous support. In contrast, the catalytic performance of the attached Pd complex in the Suzuki-Miyaura cross-coupling reaction was not affected by such small differences in the static disorder of the Pd complex.
ssbauer isomer shifts with density functional calculations金子 政志; 渡邉 雅之; 宮下 直*; 中島 覚*
Radioisotopes, 66(8), p.289 - 300, 2017/08
Eu錯体の配位結合におけるf電子の役割を理解することを目的として、相対論密度汎関数計算をEu(III)錯体に適用した。既報の
Euメスバウアー異性体シフト実験値とEu原子核位置での電子密度計算値の線形性を比較することによって、B2PLYP理論がメスバウアー異性体シフトを最もよく再現することが分かった。また、分子軌道に基づく電子密度の解析によって、d及びf電子が配位結合に大きく関与していることを明らかにした。
金子 政志
放射化学, (35), p.36 - 39, 2017/03
2016年日本放射化学会賞・奨励賞受賞者の受賞対象研究を紹介した解説記事である。メスバウアー分光パラメータと密度汎関数計算を用いて、鉄錯体のスピン相転移現象やランタノイド・アクチノイドの分離メカニズムを明らかにした研究成果について解説を行った。
中島 覚*; 金子 政志
Advances in Chemistry Research, Vol.36, p.171 - 195, 2017/01
集積型配位高分子のスピンクロスオーバー(SCO)現象について紹介する。1,2-ビス(4-ピリジル)エタンや1,3-ビス(4-ピリジル)プロパンのように構造異性体を有する架橋配位子を用いた場合、多様な集積構造が得られる。SCO現象は、集積型錯体のゲスト吸脱着に依存することを明らかにした。その原因を明らかにするため、密度汎関数法を適用し、SCOが起こるか否かが鉄イオン周りの局所構造に依存することを見出した。
元川 竜平; 小林 徹; 遠藤 仁*; 池田 隆司; 矢板 毅; 鈴木 伸一; 成田 弘一*; 阿久津 和宏*; Heller, W. T.*
Journal of Nuclear Science and Technology, 53(8), p.1205 - 1211, 2016/08
被引用回数：0 パーセンタイル：0.01(Nuclear Science & Technology)This study uses small-angle neutron scattering (SANS) to elucidate the coordination structure of the complex of mono-acetyl substituted dibenzo-20-crown-6-ether (ace-DB20C6) with Cs. SANS profiles obtained for the complex of ace-DB20C6 and Cs (ace-DB20C6/Cs) in deuterated dimethyl sulfoxide indicated that Cs coordination resulted in a more compact structure than the free ace-DB20C6. The data were fit well with SANS profiles calculated using Debye function for scattering on an absolute scattering intensity scale. For this theoretical calculation of the scattering profiles, the coordination structure proposed based on a density functional theory calculation. Consequently, we conclude that the SANS analysis experimentally supports the proposed coordination structure of ace-DB20C6/Cs and suggests the following: (1) the complex of ace-DB20C6 and Cs is formed with an ace-DB20C6/Cs molar ratio of 1/1; (2) the two benzene rings of ace-DB20C6 fold around Cs above the center of the crown ether ring of ace-DB20C6.
飯田 芳久; Barr, L.; 山口 徹治; 邉見 光
原子力バックエンド研究(CD-ROM), 23(1), p.3 - 8, 2016/06
高レベル放射性廃棄物処分の安全評価において、Th-229は重要核種の一つである。モンモリロナイトおよびイライトを対象としたThのバッチ収着試験を、pHおよび炭酸濃度をパラメータとして実施した。モンモリロナイトに対する分配係数はイライトに比べ高い値を示した。分配係数は炭酸濃度の上昇に伴い減少し、pH10付近で極小値を示した。Thの収着挙動を、静電項を考慮しない表面錯体モデル(NEM)により解析した。モデル計算は実験結果をよく説明し、分配係数の減少は、Thの水酸化炭酸錯体形成による溶存種の安定化によるものであることが示唆された。
