Understanding Am3+/Cm3+ separation with H4TPAEN and its hydrophilic derivatives: a quantum chemical study

被引:26
|
作者
Huang, Pin-Wen [1 ,2 ,3 ]
Wang, Cong-Zhi [1 ,2 ]
Wu, Qun-Yan [1 ,2 ]
Lan, Jian-Hui [1 ,2 ]
Song, Gang [4 ]
Chai, Zhi-Fang [1 ,2 ,5 ,6 ]
Shi, Wei-Qun [1 ,2 ]
机构
[1] Chinese Acad Sci, Lab Nucl Energy Chem, Inst High Energy Phys, Beijing 100049, Peoples R China
[2] Chinese Acad Sci, Key Lab Biomed Effects Nanomat & Nanosafety, Inst High Energy Phys, Beijing 100049, Peoples R China
[3] Zhejiang Univ Water Resources & Elect Power, Hangzhou 310018, Zhejiang, Peoples R China
[4] Guangdong Prov Key Lab Radionuclides Pollut Contr, Guangzhou 510006, Guangdong, Peoples R China
[5] Soochow Univ, Sch Radiol & Interdisciplinary Sci RAD X, Suzhou 215123, Peoples R China
[6] Soochow Univ, Collaborat Innovat Ctr Radiat Med, Jiangsu Higher Educ Inst, Suzhou 215123, Peoples R China
基金
国家自然科学基金重大项目; 中国博士后科学基金; 中国国家自然科学基金;
关键词
SELECTIVE AM(III) SEPARATION; SOLVENT-EXTRACTION; DIGLYCOLAMIDE TODGA; LANTHANIDE CATIONS; MINOR ACTINIDES; HARTREE-FOCK; DENSITY; COMPLEXATION; ENERGY; EU(III);
D O I
10.1039/c7cp08441b
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Am3+/Cm3+ separation is an extremely hard but important task in nuclear waste treatment. In this study, Am and Cm complexes formed with a back-extraction agent N,N,N,N-tetrakis[(6-carboxypyridin-2-yl)methyl]ethylene-diamine (H(4)TPAEN) and its two derivatives with hydrophilic substituents (methoxy and morpholine groups) were investigated using the density functional theory (DFT). The optimized geometrical structures indicated that the Am3+ cation matched better with the cavities of the three studied ligands than Cm3+, and the Am3+ cations were located deeper in the cavities of the ligands. The bond order and quantum theory of atoms in molecules (QTAIM) analyses suggested that ionic interactions dominated An-N and An-O (An = Cm and Am) bonds. However, weak and different extents of partial covalency could also be found in the Am-N and Cm-N bonds. The O donor atoms in the carboxylate groups preferably coordinated with Cm3+ rather than Am3+, whereas the N atoms preferred Am3+. Therefore, the Am3+/Cm3+ selectivity of H(4)TPAEN and its two hydrophilic derivatives may be ascribed to the competition between the An-N and An-O interactions and the few dissimilarities in their geometrical structures. Based on our calculations, the methoxy and morpholine groups in the two derivatives can serve as electron-donating groups and enhance the strength of the An-N-PY bonds (N-PY denotes the nitrogen atom of pyridine ring). When compared with the Am-complex, the Cm-complex exhibited significant strength effect, resulting in the relatively lower Am3+/Cm3+ separation ability of the H(4)TPAEN's hydrophilic derivatives.
引用
收藏
页码:14031 / 14039
页数:9
相关论文
共 50 条
  • [31] SPECTROSCOPIC STUDY OF FAST CONFORMATIONAL DYNAMICS IN PERDEUTERATED CYCLOPENTENE AND ITS MONOHYDROGENATED [3-H-1(1)] AND [4-H-1(1)] DERIVATIVES
    CAVAGNAT, D
    BANISAEIDVAHEDIE, S
    LESPADE, L
    RODIN, S
    JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1992, 88 (13): : 1845 - 1861
  • [32] SPECTROSCOPIC AND QUANTUM-CHEMICAL STUDY OF STRUCTURE OF 1,2-DIHYDRO-3-(2-HYDROXYPHENYL)-4-NITROPYRAZOLE-5(3H)-ONE
    DAVYDOV, VV
    ZAITSEV, BE
    SARABIA, MG
    ALIEV, AE
    SHEBAN, GV
    SAVELYEV, VL
    TROITSKAYA, VS
    KHIMIYA GETEROTSIKLICHESKIKH SOEDINENII, 1990, (11): : 1510 - 1516
  • [33] Synthesis and spectral analysis of 4-(4-chlorophenyl)-3,4,6,7,8,9-hexahydro-1H-cyclohepta-pyrimidin-2(5H)-one and study of its quantum chemical and thermodynamic properties
    Parveen, Huda
    Bishnoi, Abha
    Fatma, Shaheen
    Devi, Poornima
    Verma, Anil Kumar
    INDIAN JOURNAL OF PURE & APPLIED PHYSICS, 2019, 57 (04) : 250 - 260
  • [34] A quantum-chemical study of 1,2,3,4,5,6,7,8-octaazanaphthalene and its N-oxides
    Rezchikova, KI
    Churakov, AM
    Shlyapochnikov, VA
    Tartakovsky, VA
    RUSSIAN CHEMICAL BULLETIN, 1999, 48 (05) : 870 - 872
  • [35] First-principles study for electrochemical sensing of neurotoxin hydrazine derivatives via h-g-C3N4 quantum dot
    Qureshi, Sana
    Asif, Misbah
    Sajid, Hasnain
    Gilani, Mazhar Amjad
    Ayub, Khurshid
    Mahmood, Tariq
    SURFACES AND INTERFACES, 2022, 30
  • [36] Quantum-chemical study of the reaction of 2-methylbenzo[d][1,3,2]dioxaphosphinin-4(4H)-one with hexafluoroacetonimine
    Ya. A. Vereshchagina
    V. F. Mironov
    M. N. Dimukhametov
    P. P. Onys’ko
    Yu. V. Rassukanaya
    D. V. Chachkov
    Russian Journal of General Chemistry, 2014, 84 : 969 - 970
  • [37] Quantum-chemical study of the reaction of 2-methylbenzo[d][1,3,2]dioxaphosphinin-4(4H)-one with hexafluoroacetonimine
    Vereshchagina, Ya. A.
    Mironov, V. F.
    Dimukhametov, M. N.
    Onys'ko, P. P.
    Rassukanaya, Yu. V.
    Chachkov, D. V.
    RUSSIAN JOURNAL OF GENERAL CHEMISTRY, 2014, 84 (05) : 969 - 970
  • [38] Diethyl (2-Amino-3-Cyano-4H-Chromen-4-yl)Phosphonate and Its Halogenated Derivatives as Effective Drug: A Theoretical and an Experimental Spectroscopic Study
    Yadav, Krishna Kant
    Kumar, Abhishek
    Kumar, Amarendra
    Brahmachari, Goutam
    Misra, Neeraj
    POLYCYCLIC AROMATIC COMPOUNDS, 2022, 42 (05) : 2305 - 2322
  • [39] Vibrational spectra, X-ray and molecular structure of 1H- and 3H-imidazo[4,5-b]pyridine and their methyl derivatives:: DFT quantum chemical calculations
    Lorenc, J.
    Dyminska, L.
    Talik, Z.
    Hanuza, J.
    Maczka, M.
    Waskowska, A.
    Macalik, L.
    JOURNAL OF RAMAN SPECTROSCOPY, 2008, 39 (01) : 1 - 15
  • [40] 1H, 13C, 17O NMR and quantum-chemical study of the stereochemistry of the sulfoxide and sulfone derivatives of 3-arylidene-1-thioflavan-4-one epoxides
    Kovács, J
    Tóth, G
    Simon, A
    Lévai, A
    Koch, A
    Kleinpeter, E
    MAGNETIC RESONANCE IN CHEMISTRY, 2003, 41 (03) : 193 - 201