Complexation of trivalent lanthanides and actinides with diethylenetriaminepentaacetic acid: Theoretical unraveling of bond covalency
作者：
Chen, Yan-Mei;Wang, Cong-Zhi;Wu, Qun-Yan;Lan, Jian-Hui;Chai, Zhi-Fang;...
期刊：
Journal of Molecular Liquids ,2020年299:112174 ISSN：0167-7322
通讯作者：
Shi, Wei-Qun
作者机构：
[Nie, Chang-Ming; Chen, Yan-Mei] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;[Chen, Yan-Mei; Wu, Qun-Yan; Chai, Zhi-Fang; Wang, Cong-Zhi; Lan, Jian-Hui; Shi, Wei-Qun] Chinese Acad Sci, Inst High Energy Phys, Lab Nucl Energy Chem, Beijing 100049, Peoples R China.;[Chai, Zhi-Fang] Chinese Acad Sci, Ningbo Inst Ind Technol, Engn Lab Adv Energy Mat, Ningbo 315201, Zhejiang, Peoples R China.
通讯机构：
[Shi, Wei-Qun] C;Chinese Acad Sci, Inst High Energy Phys, Lab Nucl Energy Chem, Beijing 100049, Peoples R China.
关键词：
Solvent extraction;Actinides;Lanthanides;Californium;Density functional theory
摘要：
Separation of trivalent actinides (An(III)) and lanthanides (Ln(III)) is a pivotal step with respect to the treatment of nuclear waste based on the partitioning and transmutation (P&T) strategy, which is also extraordinarily challenging due to their similar coordination chemistry. The diethylenetriaminepentaacetate (DTPA) ligand has been demonstrated to possess selective separation ability toward An(III) over Ln(III) in aqueous media. Nevertheless, the extracted complexes of An(III)/Ln(III) with DTPA, and the origin of selectivity for An(III) are still not well deciphered. In this work, from theoretical perspective and at the molecular level, the geometrical structures, bonding nature as well as thermodynamic behaviors of possible complexes of An(III) (An = Am, Cm, Cf) and Ln(III) (Ln = Nd, Eu) with DTPA in the aqueous phase have been systematically studied using scalar relativistic density functional theory (DFT). All bonding analyses indicate that the metal-ligand bonds possess weak but non-negligible covalent interactions, and An(III)-DTPA species demonstrate more covalency compared to Ln(III) analogues. In addition, the covalency of the metal-ligand bonding of An(III)-DTPA increases across the actinide series from Am to Cf, which stems from the increased orbital degeneracy of the 5f orbitals of actinides and the 2p orbitals of the ligands. According to thermodynamic analysis, the anhydrous species [Cf(HDTPA)](-) is the most likely species for Cf(III) in acidic solution, whereas [M(HDTPA)(H2O)](-) are more favorable for Am(III) and Cm (III), probably due to the different bonding nature of the transplutonium series. This work affords new theoretical insights into the coordination chemistry of An(III)/Ln(III)-DTPA complexes, and paves the way to further design efficient DTPA-based ligands for An(III)/Ln(III) separation. Moreover, the DTPA ligand may also be applied for in-group separation of trivalent actinides, which is quite meaningful for the extraction of Cf(III). (C) 2019 Elsevier B.V. All rights reserved.
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Theoretical insights into selective separation of trivalent actinide and lanthanide by ester and amide ligands based on phenanthroline skeleton
作者：
Wang, Cui;Wu, Qun-Yan* ;Wang, Cong-Zhi;Lan, Jian-Hui;Nie, Chang-Ming* ;...
期刊：
DALTON TRANSACTIONS ,2020年49(13):4093-4099 ISSN：1477-9226
通讯作者：
Nie, Chang-Ming;Wu, Qun-Yan;Shi, Wei-Qun
作者机构：
[Nie, Chang-Ming; Wang, Cui] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;[Wu, Qun-Yan; Shi, Wei-Qun; Chai, Zhi-Fang; Wang, Cong-Zhi; Lan, Jian-Hui; Wang, Cui] Chinese Acad Sci, Inst High Energy Phys, Lab Nucl Energy Chem, Beijing 100049, Peoples R China.;[Chai, Zhi-Fang] Chinese Acad Sci, Ningbo Inst Ind Technol, Engn Lab Adv Energy Mat, Ningbo 315201, Zhejiang, Peoples R China.
通讯机构：
[Nie, Chang-Ming] U;[Wu, QY; Shi, WQ] C;Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;Chinese Acad Sci, Inst High Energy Phys, Lab Nucl Energy Chem, Beijing 100049, Peoples R China.
摘要：
Phenanthroline based ligands have shown potential performance for partitioning trivalent actinides from lanthanides. In this work, we have explored four ester and amide ligands based on the phenanthroline skeleton and elucidated the separation mechanism between Am(iii) and Eu(iii) ions. The molecular geometries and extraction reactions of the metal-ligand complexes were modeled by using scalar-relativistic density functional theory. The results show that the amide based ligands have stronger coordination ability with the metal ions than the corresponding ester based ligands. According to the thermodynamic results, ligands N,N′-diethyl-N,N′-ditolyl-2,9-diamide-1,10-phenanthroline (L2) and N,N′-(1,10-phenanthroline-2,9-diyl)bis(N-ethyl-P-methyl-N-(p-tolyl)phosphinic amide) (L4) appear to have the strongest complexing ability, which is supported by the result of electrostatic potential (ESP) and the M-OL bond orders. Moreover, ligand L2 has excellent selectivity for Am(iii)/Eu(iii) among the four ligands. Additionally, the bonding properties between the metal ions and the ligands reveal that the Am(iii)/Eu(iii) selectivity stems from the Am-N bonds with more covalent character, which is supported by the analysis of the hardness of the ligands and the bond orders. This work provides useful information for understanding the Am(iii)/Eu(iii) selectivity of phenanthroline derived ligands bearing ester and amide groups. This journal is © The Royal Society of Chemistry.
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英文
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Theoretical Insights into Modification of Nitrogen-Donor Ligands to Improve Performance on Am(III)/Eu(III) Separation
作者：
Chen, Yan-Mei;Wang, Cong-Zhi;Wu, Qun-Yan;Lan, Jian-Hui;Chai, Zhi-Fang;...
期刊：
INORGANIC CHEMISTRY ,2020年59(5):3221-3231 ISSN：0020-1669
通讯作者：
Nie, Chang-Ming;Shi, Wei-Qun
作者机构：
[Nie, Chang-Ming; Chen, Yan-Mei] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;[Chen, Yan-Mei; Wu, Qun-Yan; Chai, Zhi-Fang; Wang, Cong-Zhi; Lan, Jian-Hui; Shi, Wei-Qun] Chinese Acad Sci, Inst High Energy Phys, Lab Nucl Energy Chem, Beijing 100049, Peoples R China.;[Chai, Zhi-Fang] Chinese Acad Sci, Ningbo Inst Ind Technol, Engn Lab Adv Energy Mat, Ningbo 315201, Zhejiang, Peoples R China.
通讯机构：
[Nie, Chang-Ming] U;[Shi, Wei-Qun] C;Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;Chinese Acad Sci, Inst High Energy Phys, Lab Nucl Energy Chem, Beijing 100049, Peoples R China.
摘要：
Nitrogen-donor ligands have been considered to be promising agents for separating trivalent actinides (An(III)) from lanthanides (Ln(III)). Thereinto, how to decorate these ligands for better extraction performance is urgent to design "perfect" separating extractants. In this work, we systematically explored a series of heterocyclic N-donor ligands (L1 = dipyridazino[4,3-c:3′,4′-h]acridine, L2 = dipyridazino[3,4-a:4′,3′-j]phenazine, L3 = 2,6-di(cinnolin-3-yl)pyridine)), as well as their substituted derivatives, and compared their extraction and complexation ability toward An(III) and Ln(III) ions by using quasi-relativistic density functional theory (DFT). We found that the pyridazine N atoms probably play a notable role in electron donation to metal cations by molecular orbital (MO) and bond order analyses. Besides, the calculated results clearly verified that these N-donor ligands possess higher coordination affinity toward Am(III) over Eu(III). The rigid ligands (L1 and L2) exhibit higher selective abilities for the Am(III)/Eu(III) separation compared with that of the flexible ligand (L3). For each ligand, the 1:2 (metal/ligand) extraction reaction is predicted to be most probable in the separation process. The introduction of an alkyl group on the lateral chain or an electron-donating group on the main chain gives rise to a better extraction performance of the ligands, and the CyMe4 or MeO substituted ligands show higher extraction and separation ability. Simultaneous introduction of CyMe4 and MeO groups can enhance the extraction ability of the ligand to metal ions, but the separating ability depends on the differences of the extraction capacity of An(III) and Ln(III). This work can help to gain a more in-depth understanding the selectivity differences of similar N-donor ligands and provide more theoretical insights into the design of novel extractants for An(III)/Ln(III) separation. Copyright © 2020 American Chemical Society.
语种：
英文
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pH调控合成U型配体介导的八核铀酰草酸网络
作者：
Wu Si* ;Mei Lei;Hu Kong-Qiu;Chai Zhi-Fang;Nie Chang-Ming;...
期刊：
无机材料学报 ,2020年35(2):243-249 ISSN：1000-324X
通讯作者：
Wu Si
作者机构：
[Wu Si; Nie Chang-Ming] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;[Mei Lei; Hu Kong-Qiu; Wu Si; Shi Wei-Qun; Chai Zhi-Fang] Chinese Acad Sci, Inst High Energy Phys, Lab Nucl Energy Chem, Beijing 100049, Peoples R China.;[Chai Zhi-Fang] Chinese Acad Sci, Ningbo Inst Ind Technol, Engn Lab Adv Energy Mat, Ningbo 315201, Peoples R China.
通讯机构：
[Wu Si] U;[Wu Si] C;Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;Chinese Acad Sci, Inst High Energy Phys, Lab Nucl Energy Chem, Beijing 100049, Peoples R China.
关键词：
actinide coordination polymers;octa-nuclear uranyl;U-shaped Linker;pH effect
摘要：
In this work, we report a novel octa-nuclear uranyl (U8) motif [(UO2)(8)O-4(mu(3)-OH)(2)(mu(2)-OH)(2)](4+) embedded in a uranyl-oxalate coordination polymer (compound 1) based on a U-shaped linker with extra-long xylylene chains for stabilizing the resulting high-nuclear motif through additional cross-linking connectivity. A comparison with dimeric and monomeric uranyl compounds obtained at different pH value from the same hydrothermal system reveals that, solution pH plays a vital role in formation of this octa-nuclear uranyl motif by promoting hydrolysis of uranyl source. Since high similarity of eight uranium centers in this nearly planar U8 motif here, overlapping and broadening of signals in fluorescence, infra-red (IR) and Raman spectra can be found.
语种：
英文
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R/S-不对称硫取代铀酰-Salophen与手性吗啉醇的配位及对映选择性研究
作者：
代林林;聂长明
期刊：
南华大学学报(自然科学版) ,2020年34(04):72-79 ISSN：1673-0062
作者机构：
南华大学 化学化工学院,湖南 衡阳421001;[聂长明; 代林林] 南华大学
关键词：
R/S-不对称硫取代铀酰-salophen;RRS/SSR-3,5-二甲基-2-（3-氟苯基）-2-吗啉醇;对映选择性识别;密度泛函理论
摘要：
采用密度泛函理论对R/S-不对称硫取代铀酰-salophen进行研究,发现其存在Λ/V-型两种非对映异构体.以Λ/V-型两种非对映异构体为受体探讨了它们与客体分子RRS/SSR-3,5-二甲基-2-(3-氟苯基)-2-吗啉醇的配位作用以及对映选择性识别性能.结果表明:由R/S-不对称硫取代铀酰-salophen的非对映异构体与客体分子所形成的配合物间的几何构型、Wiberg键序、红外光谱等参数差别不大,但在真空和水、丙酮、甲苯溶剂环境条件下,Λ/V-R型受体比Λ/V-S型受体对客体分子具有更好的对映选择性,且Λ-R型受体在真空和水、甲苯溶剂环境条件下,对客体分子具有良好的对映选择性识别性能.
语种：
中文
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Synthesis of bipolar tetradentate ligand and determination of fructose 1,6-diphosphate by resonance light scattering of its supramolecular polymer
作者：
Li, Zhiyang;Xiao, Xilin* ;Su, Changlin;Hu, Nan;Nie, Changming;...
期刊：
Journal of Radioanalytical and Nuclear Chemistry ,2020年323(1):431-438 ISSN：0236-5731
通讯作者：
Liao, Lifu;Xiao, Xilin;Liu, Yong
作者机构：
[Su, Changlin; Liao, Lifu; Nie, Changming; Li, Zhiyang; Zhang, Di] Univ South China, Sch Chem & Chem Engn, Hunan Prov Key Lab Design & Applicat Actinide Com, Hengyang City 421001, Hunan, Peoples R China.;[Wang, Zhimei; Xiao, Xilin; Hu, Nan; Xiao, XL; Liu, Yong] Univ South China, Hunan Prov Engn Res Ctr Radioact Control Technol, Sch Resource & Environm & Safety Engn, Hengyang City 421001, Hunan, Peoples R China.;[Wang, Zhimei; Xiao, Xilin; Hu, Nan; Xiao, XL; Liu, Yong] Univ South China, Hunan Prov Engn Technol Res Ctr Uranium Tailings, Hengyang City 421001, Hunan, Peoples R China.;[Xiao, Xilin] Hunan Univ, State Key Lab Chemo & Biosensing & Chemometr, Changsha 410082, Hunan, Peoples R China.
通讯机构：
[Liao, Lifu; Xiao, XL; Liu, Y] U;[Xiao, Xilin] H;Univ South China, Sch Chem & Chem Engn, Hunan Prov Key Lab Design & Applicat Actinide Com, Hengyang City 421001, Hunan, Peoples R China.;Univ South China, Hunan Prov Engn Res Ctr Radioact Control Technol, Sch Resource & Environm & Safety Engn, Hengyang City 421001, Hunan, Peoples R China.;Univ South China, Hunan Prov Engn Technol Res Ctr Uranium Tailings, Hengyang City 421001, Hunan, Peoples R China.
关键词：
Fructose 1,6-diphosphate;Bipolar tetradentate schiff base;Supramolecular polymer;Uranyl;Resonance light scattering
摘要：
In this paper, a novel method was established for determination of fructose 1,6-diphosphate (F-1,6-BP) based on resonance light scattering (RLS), and a type of bipolar tetradentate schiff base H4L was synthesized. The study showed that under the optimization condition with the ligand concentration of 5 nmol mL(-1), pH 6.5, the reaction temperature of 25 degrees C, the reaction time of 30 min, RLS intensity had good linearity with the concentration of F-1,6-BP within the range of 0.4-5.0 nmol mL(-1), the limit of detection was 0.16 nmol mL(-1) and the relative standard deviation (RSD) was 1.83%. In vitro feasibility study, four groups of medical injections and two groups of human urine were analyzed, the RSD of six parallel experiments was approximately 2%, and the recovery value changed from 98.0 to 102.5%. As shown herein, this method has high sensitivity, good precision and recovery.
语种：
英文
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Metal-Carboxyl Helical Chain Secondary Units Supported Ion-Exchangeable Anionic Uranyl–Organic Framework
作者：
Mei, Lei;Liu, Kang;Wu, Si;Kong, Xiang-He;Hu, Kong-Qiu;...
期刊：
CHEMISTRY-A EUROPEAN JOURNAL ,2019年25(44):10309-10313 ISSN：0947-6539
通讯作者：
Shi, Wei-Qun
作者机构：
[Mei, Lei; Liu, Kang; Wu, Si; Kong, Xiang-He; Hu, Kong-Qiu; Yu, Ji-Pan; Chai, Zhi-Fang; Shi, Wei-Qun] Chinese Acad Sci, Inst High Energy Phys, Beijing 100049, Peoples R China;[Wu, Si; Nie, Chang-Ming] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Hunan, Peoples R China;[Chai, Zhi-Fang] Chinese Acad Sci, Engn Lab Adv Energy Mat, Ningbo Inst Ind Technol, Ningbo 315201, Zhejiang, Peoples R China;[Liu, Kang] Univ Chinese Acad Sci, Beijing 100039, Peoples R China
通讯机构：
[Shi, Wei-Qun] C;Chinese Acad Sci, Inst High Energy Phys, Beijing 100049, Peoples R China.
关键词：
actinides;anionic framework;helical chain;ion exchange;uranyl–organic compounds
摘要：
As a less explored avenue, actinide-based metal-organic frameworks (MOFs) are worth studying for the particularity of actinide nodes in coordination behaviour and assembly modes. In this work, an azobenzenetetracarboxylate-based anionic MOF supported by uranyl–carboxyl helical chain units was synthesized, incorporating linear uranyl as the metal centre. This kind of helical chain-type building unit is reported for the first time in uranyl-based MOFs. Structural analysis reveals that the formation of helical chain secondary units can be attributed to restricted equatorial coordination of rigid flat azobenzene ligand to uranyl centres. Meanwhile, this newly-synthesized anionic material has been used to remove Eu3+ ions, as a non-radioactive surrogate of Am3+ ion, through an ion-exchange process with [(CH3)2NH2]+ ions in its open channels, as evidenced by a combination of 1H NMR spectroscopy, EDS and PXRD. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
语种：
英文
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锕系元素的三硫化物■的几何结构和键合作用的理论研究
作者：
聂长明;陶鹏
期刊：
南华大学学报(自然科学版) ,2019年33(3):87-93 ISSN：1673-0062
作者机构：
南华大学 化学化工学院,湖南 衡阳,421001;[聂长明; 陶鹏] 南华大学
关键词：
密度泛函;三硫化物;几何结构;键合作用
摘要：
采用密度泛函理论的B3LYP/cc-pVTZ水平对锕系元素的三硫化物AnS3（An=Pa,U,Np,Pu）进行理论模拟和计算。结果表明基态的PaS3和US3都具有一个对称面Cs点群的近平面结构,而基态的NpS3和PuS3则是具有两个对称面C2v点群的平面型分子,且PuS3几乎成T型结构。根据分子轨道分析,在这四个分子中的NpS3最易被激发,US3最难被激发。并且在这些分子中存在着共轭结构,根据π轨道的电子定域化分析（ELF-π）表明在AnS3分子中的共轭程度大小趋势:US3> PaS3> NpS3>PuS3。
语种：
中文
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Insight into Coordination of Uranyl Ions with N,N′-bis(2-five-membered heterocyclidene)-1,8-anthradiamines
作者：
Long, Li-yu;Tao, Peng;Li, Tian-liang;Wu, Si;Kong, Xiang-he;...
期刊：
Applied Organometallic Chemistry ,2019年33(6):e4931- ISSN：0268-2605
通讯作者：
Nie, Chang-ming
作者机构：
[Liao, Li-fu; Wu, Si; Long, Li-yu; Li, Tian-liang; Xiao, Xi-lin; Kong, Xiang-he; Tao, Peng; Nie, Chang-ming] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;[Liao, Li-fu; Long, Li-yu; Xiao, Xi-lin; Tao, Peng; Nie, Chang-ming] Key Lab Hunan Prov Design & Applicat Nat Actinide, Hengyang 421001, Peoples R China.
通讯机构：
[Nie, Chang-ming] U;Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.
关键词：
coordination;nitrogen family nonmetal elements;oxygen family nonmetal elements;uranyl;uranyl-BFHADAs
摘要：
To find new adsorbents for uranyl ions, the density functional theory (DFT) was adopted to design a series of new ligands containing an anthracene and two five-membered heterocycles with nitrogen family nonmetal elements (N, P, As) or oxygen family nonmetal elements (O, S, Se, Te), for example, ligands N,N′-bis(2-five-membered heterocyclidene)-1,8-anthradiamines (BFHADAs). Then the uranyl ions were coordinated with BFHADAs to generate five new coordination complexes (Uranyl-BFHADAs) with heteroatoms N, S, As, Se and Te, respectively. The five-membered heterocyclic rings of Uranyl-BFHADA with oxygen atoms were broken under the structural optimization and Uranyl-BFHADA with heterocyclic atoms P was not obtained. Several structures and property parameters of the ligands BFHADAs (containing heteroatoms N, S, As, Se and Te) and their uranyl complexes Uranyl-BFHADAs were theoretically investigated and analyzed. The results showed that uranyl ions could form stable coordination complexes with these five BFHADAs. The formed bonds between uranyl ions and the heteroatoms in BFHADAs were coordination bonds rather than other types of bonds. These results could provide insightful information and theoretical guidance for the coordination of uranyl with the atoms N, S, Se, As and Te in other ligands. © 2019 John Wiley & Sons, Ltd.
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英文
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Theoretical Insights into the Selective Extraction of Americium(III) over Europium(III) with Dithioamide-Based Ligands.
作者：
Wang, Cui;Wu, Qun-Yan;Kong, Xiang-He;Wang, Cong-Zhi;Lan, Jian-Hui;...
期刊：
INORGANIC CHEMISTRY ,2019年58(15):10047-10056 ISSN：0020-1669
通讯作者：
Shi, Wei-Qun
作者机构：
[Wu, Qun-Yan; Kong, Xiang-He; Chai, Zhi-Fang; Wang, Cong-Zhi; Lan, Jian-Hui; Shi, Wei-Qun; Wang, Cui] Chinese Acad Sci, Inst High Energy Phys, Lab Nucl Energy Chem, Beijing 100049, Peoples R China.;[Nie, Chang-Ming; Kong, Xiang-He; Wang, Cui] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;[Chai, Zhi-Fang] Chinese Acad Sci, Ningbo Inst Ind Technol, Engn Lab Adv Energy Mat, Ningbo 315201, Zhejiang, Peoples R China.
通讯机构：
[Shi, Wei-Qun] C;Chinese Acad Sci, Inst High Energy Phys, Lab Nucl Energy Chem, Beijing 100049, Peoples R China.
摘要：
Separation of trivalent actinides An(III) from lanthanides Ln(III) is a worldwide challenge owing to their very similar chemical behaviors. It is highly desirable to understand the nature of selectivity for the An(III)/Ln(III) separation with various ligands through theoretical calculations because of their radiotoxicity and experimental difficulties. In this work, we have investigated three dithioamide-based ligands and their extraction behaviors with Am(III) and Eu(III) ions using the scalar-relativistic density functional theory. The results show that the dithioamide-based ligands have stronger electron donating ability than do the corresponding diamide-based ones. All analyses including geometry, Mulliken population, QTAIM (quantum theory of atoms in molecules), and NBO (natural bond orbital) suggest that the Am-S/N bonds possess more covalency compared to the Eu-S/N bonds, and the M-S bonds have more covalent character than the M-N bonds. Thermodynamic results reveal that N2,N9-diethyl-N2,N9-di-p-tolyl-1,10-phenanthroline-2,9-bis(carbothioamide) (L1) has a stronger complexing ability with metal ions owing to its rigid structure and that N6,N6′-diethyl-N6,N6′-di-p-tolyl-[2,2′-bipyridine]-6,6′-bis(carbothioamide) (L2) shows a higher selectivity for the Am(III)/Eu(III) separation. In addition, these dithioamide-based ligands possess Am(III)/Eu(III) selectivity higher than those of the corresponding diamide-based ones, although the former have weaker complexing ability with metal ions, probably due to the greater covalency of the M-S bonds. This theoretical evaluation provides valuable insights into the nature of the selectivity for the Am(III)/Eu(III) separation and information on designing of efficient An(III)/Ln(III) separation with dithioamide-based ligands. © 2019 American Chemical Society.
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英文
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Preparation of core-shell structure Fe3O4@C@MnO2 nanoparticles for efficient elimination of U(VI) and Eu(III) ions.
作者：
Dai, Shuhui;Wang, Ning;Qi, Chenjia;Wang, Xiangxue;Ma, Yan;...
期刊：
Science of The Total Environment ,2019年685:986-996 ISSN：0048-9697
通讯作者：
Nie, Changming;Hu, Baowei;Wang, Xiangke
作者机构：
[Wang, Ning; Nie, Changming; Dai, Shuhui] Univ South China, Sch Chem & Chem Engn, 28 Chang Sheng West Rd, Hengyang 421001, Henan, Peoples R China.;[Hu, Baowei; Dai, Shuhui] Shaoxing Univ, Sch Life Sci, Huancheng West Rd 508, Shaoxing 312000, Peoples R China.;[Wang, Xiangke; Wang, Xiangxue; Yang, Lu; Huang, Qiang; Wang, Ning; Qi, Chenjia; Liu, Xiaoyan; Dai, Shuhui; Ma, Yan] North China Elect Power Univ, Coll Environm Sci & Engn, Beijing 102206, Peoples R China.
通讯机构：
[Nie, Changming] U;[Hu, Baowei] S;[Wang, Xiangke] N;Univ South China, Sch Chem & Chem Engn, 28 Chang Sheng West Rd, Hengyang 421001, Henan, Peoples R China.;Shaoxing Univ, Sch Life Sci, Huancheng West Rd 508, Shaoxing 312000, Peoples R China.
关键词：
Elimination;Eu(III);Fe(3)O(4)@C@MnO(2);Pollution treatment;U(VI)
摘要：
Radionuclide contamination has become an urgent problem with the development of nuclear power plants. Herein, chemical-decorated core-shell magnetic manganese dioxide (denoted as Fe3O4@[email protected]2) composites were synthesized via transforming KMnO4 to MnO2 on the carbon-covered magnetite (Fe3O4@C) microsphere surface. It was employed to remove U(VI) and Eu(III) ions from aqueous solution under various conditions. The kinetic adsorption data were well simulated by the pseudo-second-order model and adsorption isotherms were fitted well by Langmuir model. Moreover, the maximum uptake capacities were up to 77.71 mg/g for U(VI) and 51.01 mg/g for Eu(III) at pH = 5.0 and T = 298 K. Adsorption behavior was strongly related to pH values but weakly affected by ionic strength, implying that the interaction of U(VI)/Eu(III) with Fe3O4@[email protected]2 was mainly dominated by inner-sphere surface complexation. XPS analysis illustrated that the interaction of Eu(III)/U(VI) with Fe3O4@[email protected]2 was associated with the strong metal bonds (Mn–O), hydroxyl bonded on metal (Mn-OH) and carboxyl groups (-COOH) by surface complexation and zeta potential results implied that the adsorption process was governed by electrostatic attraction. This research highlighted the outstanding performance of Fe3O4@[email protected]2 in eliminating Eu(III)/U(VI) ions from aqueous solutions, which was of great significance in the future application in radionuclides' pollution treatment. © 2019
语种：
英文
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Theoretical investigation into the coordination of R-/S-asymmetric uranyl–salophens containing six-membered ring lactam with cis−/trans-cyclohexylamines
作者：
Yang, Liang-Liang;Kong, Xiang-He;Wu, Zhi-Lin;Lin, Ying-Wu;Liao, Li-Fu;...
期刊：
Applied Organometallic Chemistry ,2018年32(7):e4387- ISSN：0268-2605
通讯作者：
Nie, Chang-Ming
作者机构：
[Liao, Li-Fu; Nie, Chang-Ming; Wu, Zhi-Lin; Yang, Liang-Liang; Kong, Xiang-He; Lin, Ying-Wu] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.
通讯机构：
[Nie, Chang-Ming] U;Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.
关键词：
coordination selectivity;density functional theory;molecular recognition;R-/S-asymmetric uranyl–salophens
摘要：
A six-membered ring lactam derivative was introduced in a parallel manner into uranyl–salophens with R/S configuration (R-/S-AUSRLs), which were used as receptors to coordinate with guests of cis−/trans-methylcyclohexylamines (cis−/trans-MCHAs). Using density functional theory calculations at the B3LYP/6-311G** level and RECP, an insight into the coordination complexes of the R-/S-AUSRLs with cis−/trans-MCHAs was obtained. The results showed that the U atoms of receptors could coordinate with the N atoms of four kinds of cis−/trans-1,2 or − 1,4 guests, but the two kinds of cis−/trans-1,3 guests could not be converged by the same method in the process of structural optimization due to steric hindrance, and thus the cis−/trans-1,3 guests could not be coordinated with the R-/S-AUSRLs. The mode of coordination of the R-/S-AUSRLs with the guests displayed a significant difference. And the change of R-AUSRL coordination ability to the cis−/trans-MCHAs was very large, but that of S-AUSRL was small. Overall, the stability of the R-series coordination complexes was higher than that of the corresponding S-series coordination complexes, and the R-AUSRL receptor had better coordination selectivity and higher molecular recognition to the cis−/trans-MCHA guests than the S-AUSRL receptor. However, the coordination ability of S-AUSRL with the cis−/trans-MCHAs was stronger than that of R-AUSRL. It was expected that these results could provide insightful information and theoretical guidance for understanding the molecular recognition of R-/S-AUSRLs for cis−/trans-type cyclohexylamine derivatives.<br/> Copyright ©2018 John Wiley & Sons, Ltd.
语种：
英文
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Uranyl-Organic Coordination Compounds Incorporating Photoactive Vinylpyridine Moieties: Synthesis, Structural Characterization, and Light-Induced Fluorescence Attenuation
作者：
Wu, Si;Mei, Lei;Li, Fei-ze;An, Shu-wen;Hu, Kong-qiu;...
期刊：
INORGANIC CHEMISTRY ,2018年57(23):14772-14785 ISSN：0020-1669
通讯作者：
Shi, Wei-qun
作者机构：
[Wu, Si; Li, Fei-ze; Hu, Kong-qiu; Mei, Lei; An, Shu-wen; Chai, Zhi-fang; Shi, Wei-qun] Chinese Acad Sci, Inst High Energy Phys, Lab Nucl Energy Chem, Beijing 100049, Peoples R China.;[Wu, Si; Nie, Chang-ming] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;[Chai, Zhi-fang] Chinese Acad Sci, Ningbo Inst Ind Technol, Engn Lab Nucl Energy Mat, Ningbo 315201, Zhejiang, Peoples R China.
通讯机构：
[Shi, Wei-qun] C;Chinese Acad Sci, Inst High Energy Phys, Lab Nucl Energy Chem, Beijing 100049, Peoples R China.
摘要：
The fluorescence of uranyl originated from electronic transitions (S 11 -S 00 and S 10 -S 0v , v = 0-4) of the ligand-to-metal charge transfer (LMCT) process is an intrinsic property of many uranyl coordination compounds. However, light-induced regulation on fluorescence features of uranyl hybrid materials through photoactive functional groups is less investigated. In this work, the photoactive vinyl group-containing ligands, (E)-methyl 3-(pyridin-4-yl)acrylate and (E)-methyl 3-(pyridin-3-yl)acrylate, have been used in the construction of uranyl coordination polymers in the presence of 1,10-phenanthroline (phen). Five compounds (UO 2 ) 3 (μ 3 -O)(μ 2 -OH) 2 (L 1 ) 2 (phen) 2 (1), (UO 2 ) 3 (μ 3 -O)(μ 2 -OH) 3 (L 1 )(phen) 2 (2), (UO 2 ) 3 (μ 3 -O)(μ 2 -OH) 3 (L 2 )(phen) 2 (3), [(UO 2 ) 2 (μ 2 -OH) 2 (L 2 ) 2 (phen) 2 ]·2H 2 O (4), and (UO 2 )Zn(SO 4 )(phen)(H 2 O)(OH) 2 (5) were obtained under hydrothermal conditions. Compounds 1-4 are polynuclear uranyl structures with abundant π-π interactions and hydrogen bonds contributed to the 3D crystal packing of them. As model compounds, 1 and 3 are selected for exploring photoresponsive behaviors. The emission intensities of these two compounds are found to decrease gradually over the exposure time of UV irradiation. X-ray single crystal structural analysis suggests that the fluorescence attenuation can be explained by the slight rotation of pyridinyl groups around the carbon-carbon double bond during UV irradiation, which is accompanied by the change of weak interactions, i.e., π-π interactions and hydrogen bonds in strength and density. This feature of light-induced fluorescence attenuation may enable these two compounds to act as potential photoresponsive sensor materials. © Copyright 2018 American Chemical Society.
语种：
英文
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Study on Antitumor Activity of Isoflavene-Thiosemicarbazone Hybrids and Their Molecular Structure Characterizations
作者：
Qi-qi CHEN;Chang-ming NIE;Ying-wu LIN;Zhi-lin WU;Li-fu LIAO
期刊：
,2018年:540-547 ISSN：2475-8841
作者机构：
[Qi-qi CHEN; Chang-ming NIE; Ying-wu LIN; Zhi-lin WU; Li-fu LIAO] School of Chemistry and Chemical Engineering,University of South China
会议名称：
2018 International Conference on Modeling, Simulation and Optimization(MSO 2018)
会议时间：
2018-01-21
会议地点：
中国广东深圳
摘要：
The insight into antitumor activity of isoflavene-thiosemicarbazone hybrids and their molecular structure characterizations were studied by using density functional theory(DFT) method at the level of
语种：
英文
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Computational insight into asymmetric uranyl-salophen coordinated with α, β-unsaturated aldehydes and ketones
作者：
Lan, Wen-Bo;Wang, Xiao-Feng* ;He, Li-Ping;Meng, Yan-Bin;Li, Jun;...
期刊：
Applied Organometallic Chemistry ,2018年32(3):e4137- ISSN：0268-2605
通讯作者：
Wang, Xiao-Feng;Nie, Chang-Ming
作者机构：
[Li, Jun; Lan, Wen-Bo; Meng, Yan-Bin; He, Li-Ping; Wang, Xiao-Feng] Xiangnan Univ, Sch Publ Hlth, Chenzhou 423000, Hunan, Peoples R China.;[Nie, Chang-Ming; Lan, Wen-Bo] Univ South China, Sch Chem & Chem Engn, Hengyang, Peoples R China.;[Qiu, Bin] Chenzhou City Ctr Dis Control & Prevent, Chenzhou 423000, Hunan, Peoples R China.
通讯机构：
[Wang, Xiao-Feng] X;[Nie, Chang-Ming] U;Xiangnan Univ, Sch Publ Hlth, Chenzhou 423000, Hunan, Peoples R China.;Univ South China, Sch Chem & Chem Engn, Hengyang, Peoples R China.
关键词：
alpha,beta-unsaturated aldehydes and ketones;asymmetric uranyl-salophen;coordination
摘要：
The study of the catalytic activity and activation mechanism of asymmetric uranyl-salophens with α, β-unsaturated aldehydes or α, β-unsaturated ketones, is a research hotspot. In this paper, the complexes of the uranyl–salophen(U-S) modified by unilateral benzene, coordinated with cyclohexenone, cyclopentenone and acrolein, were investigated using density functional theory calculations at the level of B3LYP/6-311G(d, p) basis set. The results showed that the uranyl-salophen(U-S) weakened the large π bond between C=C and C=O of the α, β-unsaturated aldehydes and ketones, making the unsaturated aldehydes and ketones activated. In addition, the molecular-recognition selectivity of the asymmetrical uranyl-salophen for cyclohexenone and cyclopentenone were much higher than for acrolein. Copyright © 2017 John Wiley & Sons, Ltd.
语种：
英文
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A novel resonance fluorescence chemosensor based on the formation of heterobinuclear complex with a di-tetradentate macrocyclic ligand and europium (III) for the determination of uranium (VI)
作者：
Wang, Jiao;Xiao, Xilin* ;He, Bo;Jiang, Min;Nie, Changming;...
期刊：
Sensors and Actuators B-Chemical ,2018年262:359-364 ISSN：0925-4005
通讯作者：
Xiao, Xilin;Liao, Lifu
作者机构：
[Xiao, XL; Liao, Lifu; Wang, Jiao; Xiao, Xilin; Jiang, Min; Nie, Changming; Lin, Ying-Wu; He, Bo] Univ South China, Sch Chem & Chem Engn, Key Discipline Lab Natl Def Biotechnol Uranium Mi, Hengyang City 421001, Hunan, Peoples R China.
通讯机构：
[Xiao, XL; Liao, LF] U;Univ South China, Sch Chem & Chem Engn, Key Discipline Lab Natl Def Biotechnol Uranium Mi, Hengyang City 421001, Hunan, Peoples R China.
关键词：
Uranium;Resonance fluorescence chemosensor;Heterobinuclear complex;Di-tetradentate macrocyclic ligand;Europium
摘要：
In this paper, we synthesized and characterized a di-tetradentate macrocyclic ligand as a novel resonance fluorescence probe for the determination of uranium. The ligand contains two tetradentate ligand moieties and can chelate two cations to form binuclear complex. We found that when the ligand only chelates a uranyl ion or europium (III) ion, the formed complex can only produce weak resonance fluorescence. When the ligand chelates simultaneously uranyl and europium (III) to form heterobinuclear complex, the formed complex can produce strong resonance fluorescence due to the cation-cation interaction between uranyl and europium (III). Based on this finding, we established a resonance fluorescence chemosensor for the determination of uranium (VI) by utilizing the formation of the heterobinuclear complex. Under optimal conditions, the linear range for the determination of uranium (VI) is 0.008-1.2 nmol mL(-1) with a detection limit of 0.002 nmol mL(-1). The method has been applied to determine uranium (VI) in environmental water samples with the recoveries between 95.7% and 103.6%. (C) 2018 Elsevier B.V. All rights reserved.
语种：
英文
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逆向案例教学法在普通化学教学中的应用及体会
作者：
肖锡林;廖力夫;林英武;王宏青;聂长明;...
期刊：
大学化学 ,2017年32(1):31-35 ISSN：1000-8438
作者机构：
南华大学化学化工学院,湖南 衡阳,421001;[谭春红; 聂长明; 王宏青; 赵玉宝; 樊华; 林英武; 肖锡林; 廖力夫; 周昕] 南华大学
关键词：
逆向案例教学;普通化学;教学方法
摘要：
分析了普通化学课程目前在教学环节所存在的问题，并针对这些问题提出了逆向案例教学法的改革举措。
语种：
中文
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气相色谱测定江永香姜中有机磷农药残留
作者：
罗晶晶;聂长明;刘小文;任红英;袁志辉;...
期刊：
南华大学学报(自然科学版) ,2017年31(1):91-95 ISSN：1673-0062
作者机构：
南华大学 化学化工学院,湖南 衡阳 421001;湖南科技学院 化学与生物工程学院,湖南 永州 425000;南华大学 化学化工学院,湖南 衡阳,421001;湖南科技学院 化学与生物工程学院,湖南 永州,425000;永州市食品质量安全监督检验中心,湖南 永州,425000
关键词：
气相色谱法;有机磷农药;江永香姜;残留检测
摘要：
为建立气相色谱法(GC)测定江永香姜中有机磷农药残留量的分析方法,从永州市江永县采集香姜试样,将试样用含体积比为1%乙酸的乙腈溶液提取,再经无水硫酸镁和醋酸钠净化,以C18色谱柱分离待测物,基质匹配标准溶液外标法定量,最后用气相色谱法(GC)法检测香姜中有机氯农药残留,从而达到定性的效果.试验表明,6种有机磷农药在0~1 mg/L的范围内线性关系良好,相关系数均大于0.990,检出限为0.012~ 0.071mg/kg,相对标准偏差2.22%~9.30%,试样添加回收试验的平均回收率为68.0%~111.0%.以上结果表明,气相色谱法具有测定有机磷农药种类多、净化效果好、准确度和精密度高等优点,能够满足香姜农药残留检测要求.
语种：
中文
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讲台与实验台互跨式研究生双语教学模式探索与实践
作者：
林英武;高淑琴;何博;杜可杰;聂长明;...
期刊：
大学化学 ,2017年32(2):42-46 ISSN：1000-8438
作者机构：
南华大学化学化工学院,湖南 衡阳 421001;南华大学蛋白质结构与功能实验室,湖南 衡阳 421001;南华大学蛋白质结构与功能实验室,湖南 衡阳,421001;南华大学化学化工学院,湖南 衡阳,421001;[聂长明; 文格波; 杜可杰; 何博; 高淑琴; 林英武] 南华大学
关键词：
研究生;双语教学;讲台;实验台;生物无机化学
摘要：
研究生双语教学是研究生教育国际化进程的必然要求。针对目前研究生双语教学中存在的问题,本文提出了一种新的研究生双语教学模式,即讲台与实验台互跨式研究生双语教学。以生物无机化学研究生双语课程为例,我们探索了讲台与实验台互跨式双语教学的实施方法。实践表明,讲台与实验台互跨式研究生双语教学模式解决了研究生培养中理论与实践相脱节的问题,不但可以全面提高研究生科研素质,而且可以提升教师科研水平。
语种：
中文
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氯化铋在LiCl-KCl熔盐中的电化学行为
作者：
庞敬雯;刘奎;石伟群;聂长明
期刊：
山东化工 ,2017年46(6):40-42 ISSN：1008-021X
作者机构：
南华大学化学化工学院;[刘奎; 石伟群] 中国科学院高能物理研究所;[聂长明; 庞敬雯] 南华大学
关键词：
氯化铋;LiCl-KCl熔盐;电化学
摘要：
研究了BiCl_3-Li-KCl熔盐中BiCl_3在钨电极上的电化学行为,采用循环伏安法研究了Bi~（3＋）在熔盐中的还原过程,并计算了转移电子数,采用恒电位沉积法研究了铋在钨电极上的沉积行为,并用XRD对沉积产物进行了表征。
语种：
中文
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