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Dilanthanide complexes with one-electron delocalization are important targets for understanding the specific 4f/5d-bonding feature in lanthanide chemistry. Here, we report an isolable azide-bridged dicerium complex 3 [{(TrapenTMS)Ce}2(µ-N3)]⢠[Trapen = tris (2-aminobenzyl)amine; TMS = SiMe3], which is synthesized by the reaction of tripodal ligand-supported (TrapenTMS)CeIVCl complex 2 with NaN3. The structure and bonding nature of 3 are fully characterized by X-ray crystal diffraction analysis, electron paramagnetic resonance (EPR), magnetic measurement, cyclic voltammetry, X-ray absorption spectroscopy, and quantum-theoretical studies. Complex 3 presents a trans-bent central Ce-N3-Ce unit with a single electron of two mixed-valent Ce atoms. The unique low-temperature (2 K) anisotropic EPR signals [g = 1.135, 2.003, and 3.034] of 3 indicate that its spin density is distributed on the central Ce-N3-Ce unit with marked electron delocalization. Quantum chemical analyses show strong 4f/5d orbital mixing in the singly occupied molecular orbital of 3, which allows for the unpaired electron to extend throughout the cerium-azide-cerium unit via a multicentered one-electron (Ce-N3-Ce) interaction. This work extends the family of mixed-valent dilanthanide complexes and provides a paradigm for understanding the bonding motif of ligand-bridged dilanthanide complexes.
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BACKGROUND: Shenzhen is one of the most populated metropolises in southern China where thalassemia is highly prevalent. The prevention of thalassemia inheritance is an ambition of child-bearing couples. METHODS AND RESULTS: A total of 22,098 peripheral blood samples were collected from 11,049 potentially at-risk couples of childbearing age from Shenzhen. Thalassemia mutations were determined by PCR-based flow-through hybridization. The results identified 45.02% of the participants (9948 out of 22,098) as harboring globin gene mutations, distributed into 18 α-thalassemia alleles detected in 71.48% (7111 out of 9948) and 15 ß-thalassemia alleles detected in 32.68% (3252 out of 9948) of all mutant individuals, among which 415 individuals carried both α- and ß-thalassemia alleles. The most frequent phenotypes for α-globin variations were --SEA/αα (63.37%), -α3.7/αα (18.66%), and -α4.2/αα (7.31%), and those for ß-globin variations were ß41-42/ßN (34.96%), ß654/ßN (28.11%), and ß17/ßN (13.84%). A total of 970 high-risk couples who could possibly give birth to offspring with thalassemia intermedia or major were identified. In addition, the hematological indices were compared among thalassemia genotypes. Significant differences in MCH, MCV, Hb A, and Hb A2 levels among α-thalassemia minor (α+), trait (α0), and intermediate phenotypes (P < 0.05) and between ßE/ßN and the other ß-thalassemia phenotypes (P < 0.05) were found. Moreover, GAP-PCR and next-generation sequencing further identified 42 rare mutations, 13 of which were first reported in the Chinese population. A novel mutation in the ß-globin gene (HBB: c.246 C > A (rs145669504)) was also discovered. CONCLUSIONS: This study presented a comprehensive analysis of thalassemia variations in a population from Shenzhen and may offer valuable insights for thalassemia control and intervention strategies in this area.
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Talassemia alfa , Talassemia beta , Humanos , Criança , Talassemia alfa/epidemiologia , Talassemia alfa/genética , Epidemiologia Molecular , Alelos , Globinas beta/genéticaRESUMO
BACKGROUND: Gastric cancer (GC) is a common malignancy with high incidence and mortality, and its pathogenesis involves the regulation of circular RNAs (circRNAs). However, the molecular mechanism of circTMEM87A in GC malignant progression is uncertain. METHODS: Quantitative real-time polymerase chain reaction (qRT-PCR) was performed to detect the expressions of circTMEM87A, miR-1276, and solute carrier family 7 membrane 11 (SLC7A11). Western blot was applied to detect protein expression levels of EMT-related proteins (vimentin and E-cadherin) and SLC7A11. Cell counting kit-8 assay (CCK8) and thymidine analog 5-ethynyl-2'-deoxyuridine (EdU) were performed to assess cell proliferation. Apoptosis was investigated using flow cytometry. Transwell assay and wound healing assay were carried out to examine the migration of MKN-7 and AGS cells. The Cellular ROS Assay Kit, Iron Assay Kit, and GSH/GSSG Ratio Detection Assay Kit were utilized to monitor lipid ROS level, iron level, and GSH/GSSG ratio, respectively. The interaction between miR-1276 and circTMEM87A or SLC7A11 was investigated using dual-luciferase reporter assay and RNA immunoprecipitation (RIP) assay. A xenograft mouse model was constructed to explore the function of circTMEM87A in tumor formation in vivo. RESULTS: CircTMEM87A and SLC7A11 were upregulated, while miR-1276 was downregulated in GC tissues and cells. Knockdown of circTMEM87A suppressed the proliferation and migration and promoted apoptosis and ferroptosis of GC cells. CircTMEM87A served as a sponge for miR-1276, and miR-1276 inhibitor relieved the circTMEM87A knockdown-induced effects on GC cell phenotypes. Similarly, SLC7A11, a downstream gene of miR-1276, rescued miR-1276 overexpression-induced effects on GC cell function. Furthermore, circTMEM87A knockdown inhibited GC cell tumor phenotypes in vivo. CONCLUSION: CircTMEM87A promoted the proliferation and migration and inhibited apoptosis and ferroptosis of GC cells by increasing SLC7A11 expression through binding to miR-1276.
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MicroRNAs , Neoplasias Gástricas , Humanos , Animais , Camundongos , Neoplasias Gástricas/genética , Dissulfeto de Glutationa , Espécies Reativas de Oxigênio , Carcinogênese/genética , Transformação Celular Neoplásica , Proliferação de Células/genética , Modelos Animais de Doenças , Ferro , MicroRNAs/genética , Linhagem Celular Tumoral , Sistema y+ de Transporte de Aminoácidos/genéticaRESUMO
Efficient transfer of charge carriers through a fast transport pathway is crucial to excellent photocatalytic reduction performance in solar-driven CO2 reduction, but it is still challenging to effectively modulate the electronic transport pathway between photoactive motifs by feasible chemical means. In this work, we propose a thermally induced strategy to precisely modulate the fast electron transport pathway formed between the photoactive motifs of a porphyrin metal-organic framework using thorium ion with large ionic radius and high coordination number as the coordination-labile metal node. As a result, the stacking pattern of porphyrin molecules in the framework before and after the crystal transformations has changed dramatically, which leads to significant differences in the separation efficiency of photogenerated carriers in MOFs. The rate of photocatalytic reduction of CO2 to CO by IHEP-22(Co) reaches 350.9 µmol·h-1·g-1, which is 3.60 times that of IHEP-21(Co) and 1.46 times that of IHEP-23(Co). Photoelectrochemical characterizations and theoretical calculations suggest that the electron transport channels formed between porphyrin molecules inhibit the recombination of photogenerated carriers, resulting in high performance for photocatalytic CO2 reduction. The interaction mechanism of CO2 with IHEP-22(Co) was clarified by using in-situ electron paramagnetic resonance, in-situ diffuse reflectance infrared Fourier transform spectroscopy, in-situ extended X-ray absorption fine structure spectroscopy, and theoretical calculations. These results provide a new method to regulate the efficient separation and migration of charge carriers in CO2 reduction photocatalysts and will be helpful to guide the design and synthesis of photocatalysts with superior performance for the production of solar fuels.
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Excellent "CHON" compatible ligands based on a heterocyclic skeleton for the separation of trivalent actinides [An(III)] from lanthanides [Ln(III)] have been widely explored, the aim being spent nuclear fuel reprocessing. The combination mode of a soft/hard (N/O) donor upon the coordination chemistry of An(III) and Ln(III) should play a vital role with respect to the performance of ligands. As such, in this work, two typical experimentally available phenanthroline-derived tetradentate ligands, CyMe4-BTPhen (L1) and Et-Tol-DAPhen (L4), and two theoretically designed asymmetric tetradentate heterocyclic ligands, L2 and L3, with various N/O donors were investigated using scalar relativistic density functional theory. We have evaluated the electronic structures of L1-L4 and their coordination modes, bonding properties, and extraction reactions with Am(III) and Eu(III). We found that the Am/Eu-N interactions play a more important role in the orbital interactions between the ligand and Am(III)/Eu(III) ions. Compared with those of L1, the coordinated O atoms of L2 and L4 weaken the metal-N bonds. The Am(III)/Eu(III) selectivity follows the order L1 > L2 > L4 based on the change in Gibbs free energy, reflecting the fact that the Am(III)/Eu(III) selectivity of the ligand is affected by the number of coordinated N atoms. In addition, L3 displays the strongest binding ability for Am(III)/Eu(III) ions and the smallest Am(III)/Eu(III) selectivity among the four ligands, due to its structural preorganization. This work clarifies the influence of the number of coordinated N and O atoms of ligands on Am(III)/Eu(III) selectivity, which provides valuable fundamental information for the design of efficient ligands with N and O donors for An(III)/Ln(III) separation.
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Separation of trivalent actinides (An(III)) and lanthanides (Ln(III)) poses a huge challenge in the reprocessing of spent nuclear fuel due to their similar chemical properties. N,N'-Diethyl-N,N'-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen) is a potential ligand for the extraction of An(III) from Ln(III), while there are still few reports on the effect of its substituent including electron-withdrawing and electron-donating groups on An(III)/Ln(III) separation. Herein, the interaction of Et-Tol-DAPhen ligands modified by the electron-withdrawing groups (CF3, Br) and electron-donating groups (OH) with Am(III)/Eu(III) ions was investigated using scalar relativistic density functional theory (DFT). The analyses of bond order, quantum theory of atoms in molecules (QTAIM), and molecular orbital (MO) indicate that the substitution groups have a slight effect on the electronic structures of the [M(L-X)(NO3)3] (X = CF3, Br, OH) complexes. However, the thermodynamic results suggest that a ligand with the electron-donating group (L-OH) improves the extraction ability of metal ions, and the ligand modified by the electron-withdrawing group (L-Br) has the best Am(III)/Eu(III) selectivity. This work could render new insights into understanding the effect of electron-withdrawing and electron-donating groups in tuning the selectivity of Et-Tol-DAPhen derivatives and pave the way for designing new ligands modified by substituted groups with better extraction ability and An(III)/Ln(III) selectivity.
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The separation of lanthanides and actinides has attracted great attention in spent nuclear fuel reprocessing up to date. In addition, liquid-liquid extraction is a feasible and useful way to separate An(III) from Ln(III) based on their relative solubilities in two different immiscible liquids. The hydrophilic bipyridine- and phenanthroline-based nitrogen-chelating ligands show excellent performance in separation of Am(III) and Eu(III) as reported previously. To profoundly explore the separation mechanism, herein, we first of all designed four hydrophilic sulfonated and phosphorylated ligands L1, L2, L3, and L4 based on the bipyridine and phenanthroline backbones. In addition, we studied the structures of these ligands and their neutral complexes [ML(NO3)3] (M = Am, Eu) as well as the thermodynamic properties of complexing reactions through the scalar relativistic density functional theory. According to the changes of the Gibbs free energy for the back-extraction reactions, the phenanthroline-based ligands L2 and L4 have stronger complexing capacity for both Am(III) and Eu(III) ions while the phosphorylated ligand L3 with the bipyridine framework has the highest Am(III)/Eu(III) selectivity. In addition, the charge decomposition analysis revealed a higher degree of charge transfer from the ligand to Am(III), suggesting stronger donor-acceptor interactions in the Am(III) complexes. This study can provide theoretical insights into the separation of actinide(III)/lanthanide(III) using hydrophilic sulfonated and phosphorylated N-donor ligands.
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Separation of minor actinides from lanthanides is one of the biggest challenges in spent fuel reprocessing due to the similar physicochemical properties of trivalent lanthanides (Ln(III)) and actinides (An(III)). Therefore, developing ligands with excellent extraction and separation performance is essential at present. As an excellent pre-organization platform, calixarene has received more attention on Ln(III)/An(III) separation. In this work, we systematically explored the complexation behaviors of the diglycolamide (DGA)/dimethylacetamide (DMA)-functionalized calix[4]arene extractants for Eu(III) and Am(III) using relativistic density functional theory (DFT). These calix[4]arene-derived ligands were obtained by functionalization with two or four binding units at the narrow edge of the calix[4]arene platform. All bonding nature analyses suggested that the Eu-L complexes possess stronger interaction compared to Am-L analogues, resulting in the higher extraction capacity of the these calix[4]arene ligands toward Eu(III). Thermodynamic analysis demonstrates that these pre-organized ligands on the calix[4]arene platform with four binding units yield better extraction abilities than the single ligands. Although DMA-functionalized ligands show stronger complexation stability for metal ions, in acidic solutions, the calix[4]arene ligands with DGA binding units have better extraction performance for Eu(III) and Am(III) due to the basicity of the DMA ligand. This work enabled us to gain a deeper understanding of the bonding properties between supramolecular ligands and lanthanides/actinides and afford useful insights into designing efficient supramolecular ligands for separating Ln(III)/An(III).
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The separation of plutonium (Pu) from spent nuclear fuel was achieved by effectively adjusting the oxidation state of Pu from +IV to +III in the plutonium uranium reduction extraction (PUREX) process. Acetaldoxime (CH3CHNOH) as a free salt reductant can rapidly reduce Pu(IV), but the reduction mechanism remains indistinct. Herein, we explore the reduction mechanism of two Pu(IV) ions by one CH3CHNOH molecule, where the second Pu(IV) reduction is the rate-determining step with the energy barrier of 19.24 kcal mol-1, which is in line with the experimental activation energy (20.95 ± 2.34 kcal mol-1). Additionally, the results of structure and spin density analyses demonstrate that the first and second Pu(IV) reduction is attributed to hydrogen atom transfer and hydroxyl ligand transfer, respectively. Analysis of localized molecular orbitals unveils that the reduction process is accompanied by the breaking of the Pu-OOH bond and the formation of the OOH-H and C-OOH bonds. The reaction energies confirm that the reduction of Pu(IV) by acetaldoxime is both thermodynamically and kinetically accessible. In this work, we elucidate the reduction mechanism of Pu(IV) with CH3CHNOH, which provides a theoretical understanding of the rapid reduction of Pu(IV).
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An efficient approach to Np separation in the Plutonium Uranium Reduction EXtraction (PUREX) process is to adjust Np(VI) to Np(V) by free-salt reductants, such as hydrazine and its derivatives. Recently, carbohydrazide (CO(N2H3)2), a derivative of hydrazine and urea, has received much attention, which can reduce Np(VI) to Np(V) in the extraction reprocessing of spent nuclear fuel. Herein, according to the experimental observations, we examine the reduction mechanism of four Np(VI) by one carbohydrazide molecule using multiple theoretical calculations. The fourth Np(VI) reduction with a 22.26 kcal mol-1 energy barrier is the rate-determining step, which is in accordance with the experimental observations (20.54 ± 1.20 kcal mol-1). The results of spin density reflect that the reduction of the first and third Np(VI) ion is an outer-sphere electron transfer, while that of the second and fourth Np(VI) ion is the hydrogen transfer. Localized molecular orbitals (LMOs) uncover that the breaking of the N-H bond and formation of the Oyl-H bond are accompanied by the reaction from initial complexes (ICs) to intermediates (INTs). This work offers basic perspectives for the reduction mechanism of Np(VI) to Np(V) by CO(N2H3)2, which is also expected to design excellent free-salt Np(VI) reductants for the separation of Np in the advanced PUREX process.
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OBJECTIVE: Glucose-6-phosphate dehydrogenase (G6PD) deficiency is an X-linked genetic disorder that results in impaired enzyme activity. The G6PD/6PGD ratio assay was routinely used for G6PD deficiency screening in China, but there is an apparent defect of missed diagnosis in heterozygous females. The study aims to explore the means to improve its accuracy. METHODS: A total of 4161 Chinese females of childbearing age were collected in this retrospective study. All samples were first subjected to G6PD/6PGD ratio assay and then screened by amplification refractory mutation system PCR (ARMS-PCR) for six hotspot mutants in Chinese population (c.1376G>T, c.1388G>A, c.95A>G, c.1024C>T, c.392G>T, and c.871G>A). For the samples with G6PD/6PGD ratio <1.0 and no mutations were found by ARMS-PCR, next-generation sequencing (NGS) was performed. Sanger sequencing was finally used to verify all the variants. RESULTS: The prevalence of G6PD deficiency in Shenzhen females of childbearing age was 7.31%. The proportion of the six hotspot mutations accounted for 98.03% of all 304 G6PD variants carriers. Taking the ARMS-PCR/NGS results as a reference, the missed diagnosis rate of the G6PD/6PGD ratio assay was 33.88%. Using ARMS-PCR to retest the samples with a G6PD/6PGD ratio between 1.00~1.10 or 1.00~1.15 could reduce the missed diagnosis rate from the original 33.88% to 18.09% or 12.05% separately. CONCLUSION: ARMS-PCR is an appropriate supplementary method for discovering most carriers missed by the G6PD/6PGD ratio assay.
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The bistriazinyl-phenanthroline representative ligand, BTPhen, shows excellent extraction and separation ability for trivalent actinides and lanthanides. Herein, we first designed three phenanthroline-based nitrogen-donor ligands (L1, L2, and L3), and then studied the structural and bonding properties as well as thermodynamic properties of the probable complexes, ML(NO3)3 (M = Am or Eu and L = L1, L2, or L3), using scalar relativistic density functional theory. Our charge decomposition analysis revealed an obviously higher charge transfer from the ligand to Am(III) compared with the Eu(III) case for the studied complexes. Spin density analysis further showed a more significant degree of Am-to-ligand spin delocalization and the corresponding spin polarization on the ligands. According to the thermodynamic analysis, ligand L3 has the strongest complexation capacity for both Am(III) and Eu(III) ions, while ligand L1 has the highest Am(III)/Eu(III) selectivity in binary octanol/water solutions. We expected that this work can provide valuable theoretical support for the design of effective ligands for actinide(III)/lanthanide(III) separation in high level liquid waste.
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Designing ligands with efficient actinide (An(III))/lanthanide (Ln(III)) separation performance is still one of the key issues for the disposal of accumulated radioactive waste and the recovery of minor actinides. Recently, the hydrophilic ligands as promising extractants in the innovative Selective ActiNide Extraction (i-SANEX) process show excellent selectivity for Am(III) over Eu(III), such as hydroxylated-based ligands. In this work, we investigated the selective back-extraction toward Am(III) over Eu(III) with three hydrophilic hydroxylated triazolyl-based ligands (the skeleton of pyridine La, bipyridine Lb, and phenanthroline Lc) using scalar-relativistic density functional theory. The properties of three hydrophilic hydroxylated ligands and the coordination structures, bonding nature, and thermodynamic properties of the Am(III) and Eu(III) complexes with three ligands have been evaluated using multiple theoretical methods. The results of molecular orbitals (MOs), quantum theory of atoms in molecules (QTAIMs), and natural bond orbital (NBO) reveal that Am-N bonds possess more covalent character compared to Eu-N bonds. The thermodynamic results indicate that the complexing ability of Lb and Lc with metal ions is almost the same, which is stronger than that of La. However, La has the best Am(III)/Eu(III) selectivity among three ligands, which is attributed to the largest difference in covalency between Am-Ntrzl and Eu-Ntrzl bonds in MLa(NO3)3. This work provides an in-depth understanding of the preferential selectivity of the hydrophilic hydroxylated ligands with An(III) over Ln(III) and also provides theoretical support for designing potential hydrophilic ligands with excellent separation performance of Am(III)/Eu(III).
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Effective separation and recovery of chemically similar transplutonium elements from adjacent actinides is extremely challenging in spent fuel reprocessing. Deep comprehension of the complexation of transplutonium elements and ligands is significant for the design and development of ligands for the in-group separation of transplutonium elements. Because of experimental difficulties of transplutonium elements, theoretical calculation has become an effective means of exploring transplutonium complexes. In this work, we systematically investigated the coordination mechanism between transplutonium elements (An = Am, Cm, Bk, Cf) and two crown ether macrocyclic ligands [N,N'- bis[(6-carboxy-2-pyridyl)methyl]-1,10-diaza-18-crown-6 (H2bp18c6) and N,N'-bis[(6-methylphosphinic-2-pyridyl)methyl]-1,10-diaza-18-crown-6 (H2bpp18c6)] through quasi-relativistic density functional theory. The extraction complexes of [Anbp18c6]+ and [Anbpp18c6]+ possess similar geometrical structures with actinide atoms located in the cavity of the ligands. Bonding nature analysis indicates that the coordination ability of the coordinating atoms in pendent arms is stronger than that in the crown ether macrocycle because of the limitation of the macrocycle. Most of the coordination atoms of the H2bp18c6 ligand have a stronger ability to coordinate with metal ions than those of the H2bpp18c6 ligand. In addition, the bonding strength between the metal ions and ligands gradually weakens from Am to Cf, which is mainly attributed to the size selectivity of the ligands. Thermodynamic analysis shows that the H2bp18c6 ligand has a stronger extraction capacity than the H2bpp18c6 ligand, while the H2bpp18c6 ligand is superior in terms of the in-group separation ability. The extraction capacity of the two ligands for metal ions gradually decreases across the actinide series, indicating that these crown ether macrocycle ligands have size selectivity for these actinide cations as a result of steric constraint of the crown ether ring. We hope that these results offer theoretical clues for the development of macrocycle ligands for in-group transplutonium separation.
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The involvement of the 2-phosphaethynolate anion species with ambident nucleophilic properties serves as an essential protocol for synthesizing oxygen-bound or phosphorus-bound complexes. This work mainly describes the synthesis and characterization of U, Th, and Ti phosphaethynolate complexes featuring a preferential O-coordination fashion. Among these complexes, the first examples of a Ti(IV)-OCP complex 3A, Th(IV)-OCP complex 3B, and U(IV)-OCP complex 3C were assembled by a salt metathesis reaction between M(TrapenTMS)(Cl) (M = Ti, Th, U) and NaOCP(dioxane)2.5 and were all crystallographically characterized. The structural similarity of this series of phosphaethynolate complexes allows us to compare the bonding properties of d- and f-block elements in the corresponding compounds. The well-established density functional theory (DFT) computational method was employed to explore the electronic structures and covalency in M-O bonding, and the results showed a consistent pattern. The calculation result showed that 2-phosphaethynolate complexes exhibited the covalency trend of U-O > Th-O > Ti-O due to the involvement of 5f orbitals.
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Owing to the electron-deficient nature of boron atoms, the structures and properties of boron clusters can be enriched by doping various metal atoms, including lanthanide metal atoms. Nevertheless, the viability of actinide analogues has not been fully elucidated up to now. Here we demonstrate a series of highly stable low-valent actinide(III) boron clusters AnB7 (An = Pa, U, Np, and Pu) using first-principles calculations. The predicted global minimum structures of all the AnB7 complexes possess half-sandwich geometries with C6v symmetry and belong to MIII[B7]3--type species. In each AnB7 species, the B73- ligand possesses double aromaticity features with six delocalized π electrons and six delocalized σ electrons. Bonding analysis shows that although there is a substantial contribution of electrostatic interaction in each cluster, covalent interaction is responsible for the stability of AnB7. All the AnB7 species show significantly high formation energies, especially for NpB7, which is in line with the stronger Np-B covalent bonds. In addition, the simulated photoelectron spectroscopy analysis confirms the high electronic stability of neutral AnB7. These results imply that these ultrastable actinide(III) complexes are accessible in the gas phase at room temperature. This work may provide a theoretical basis for the design of highly stable boron-based nanomaterials as well as preparation of low-valent actinide complexes.
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Similar to graphene and fullerene, metal-doping has been considered to be an effective approach to the construction of highly stable boron clusters. In this work, a series of actinide metal-doped boron clusters AnB36 (An = Pa, Np, Pu, Am, Cm, Bk, and Cf) have been explored using extensive first-principles calculations. We found that the quasi-planar structure of B36 transforms to an endohedral borospherene An@B36 after actinide metal doping. Actinoborospherenes exhibit C2h symmetry with Pa, Np, and Pu dopants and for Am, Cm, Bk and Cf dopants with larger atomic radii, the symmetry of An@B36 is reduced to Ci. Bonding property analyses such as bond order, molecular orbital (MO) and quantum theory of atoms in molecules (QTAIM) analysis show that the covalency of the An-B bonds in C2h An@B36 (An = Pa, Np, and Pu) is higher than that in Ci An@B36 (An = Am, Cm, Bk, and Cf). These endohedral borospherenes are robust according to thermodynamic and dynamic analyses. As expected, the Ci An@B36 clusters are less stable compared to C2h An@B36, which is consistent with the stronger covalent bonds of the latter. These results indicate that the existence of the actinide-boron bonding is essential for the high stability of the An@B36 clusters, confirming that the fullerene-like boron cages can be stabilized by actinide encapsulation. This work is expected to provide potential routes for the construction of robust borospherenes.
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Effectively adjusting and controlling the valence state of neptunium (Np) is essential in its separation during spent fuel reprocessing. Hydrazine and its derivatives as free-salts can selectively reduce Np(VI) to Np(V). Reduction mechanisms of Np(VI) with hydrazine and four derivatives have been explored using multiple theoretical methods in our previous works. Herein, we examine the reduction mechanism of Np(VI) with hydrazinopropionitrile (NCCH2N2H3) which exhibits faster kinetics than most other hydrazine derivatives probably due to its σ-π hyperconjugation effect. Free radical ion pathways I, II and III involving the three types of hydrazine H atoms were found that correspond to the experimentally established mechanism of reduction of two Np(VI) via initial oxidation to [NCCH2N2H3]+Ë, followed by conversion to NCCH2N2H (+2H3O+) and ultimately to CH3CN + N2. Potential energy profiles suggest that the second redox stage is rate-determining for all three pathways. Pathway I with water-mediated proton transfer is energetically preferred for hydrazinopropionitrile. Analyses using the approaches of localized molecular orbitals (LMOs), quantum theory of atoms in molecules (QTAIM), and intrinsic reaction coordinate (IRC) elucidate the bonding evolution for the structures on the reaction pathways. The results of the spin density reveal that the reduction of the first Np(VI) ion is the outer-sphere electron transfer, while that of the second Np(VI) ion is the hydrogen transfer. This work offers new insights into the nature of reduction of Np(VI) by hydrazinopropionitrile via water-mediated proton transfer, and provides a basis for designing free-salt reductants for Np separations.
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Extraction of uranium from seawater is one of the important ways to solve the shortage of terrestrial uranium resources. Thereinto, the competition between uranyl and vanadium cations is a significant challenge in the commonly used amidoxime-based adsorbents for extracting uranium from seawater. An in-depth understanding of the extraction behaviors of modified amidoxime groups with uranyl and vanadium ions is one of the effective means to design and develop efficient adsorbents for selective uranium sequestration. In this work, we have designed and systematically investigated the alkyl and amino functionalized amidoxime, (Z)-2-amino-N'-hydroxy-N,N-dimethylbenzimidamide (L1), and its phenyl and methoxy derivatives ((Z)-3-amino-N'-hydroxy-N,N-dimethyl-2-naphthimidamide (L2) and (Z)-2-amino-N'-hydroxy-4-methoxy-N,N-dimethylbenzimidamide (L3)) by quantum chemistry calculations. In the uranyl complexes, the amidoxime groups prefer to act as η2-coordinated ligands as the amidoximes increase, and there exist substantial hydrogen bond interactions, which are different from the vanadium complexes. Various bonding analyses show that the L1 ligand possesses a stronger binding affinity to UO22+, and the -C6H5 and -CH3O substituent groups seem to have no effect on the improvement of extraction ability. Thermodynamic analysis confirms that the L1 ligand has a stronger extraction capability to uranyl ion compared to L2 and L3. According to the calculations of the vanadium (V) (VO2+ and VO3+) complexes with the L1 ligand, L1 is more likely to react with [H2VO4]- and [HVO4]2- to form VO2+ complexes. Expectantly, thermodynamic analysis displays a higher extraction capacity for uranyl ions than vanadium ions. Therefore, these alkyl and amino functionalized amidoxime ligands demonstrate high selectivity for uranyl over vanadium ions, which is mainly due to the coordination mode changes of these ligands toward vanadium in conjunction with the considerable hydrogen bonds in the uranyl complexes. These results are expected to afford useful clues for the design of efficient adsorbents for uranium extraction from seawater.
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Metal doping has been considered to be an effective approach to stabilize various boron clusters. In this work, we constructed a series of largest metal-centered double-ring tubular boron clusters An@B24 (An = Th, Pa, Pu, and Am). Extensive global minimum structural searches combined with density functional theory predicted that the global minima of An@B24 (An = Th, Pu, and Am) are double-ring tubular structures. Formation energy analysis indicates that these boron clusters are highly stable, especially for Th@B24 and Pa@B24. Detailed bonding analysis shows that the significant stability of An@B24 is determined by the covalent character of the An-B bonding, which stems from the interactions of An 5f and 6d orbitals and B 2p orbitals. These results show that actinide metal doping is a feasible route to construct stable large metal-centered double-ring tubular boron clusters, offering the possibility to design boron nanomaterials with special physiochemical properties.