Intelligent Devices Harnessing Underwater Superoleophobic and Underoil Superhydrophobic Quartz Sands for the Separation of Diverse Stratified and Emulsified Water-Oil Mixtures.

To achieve the green, sustainable, and controllable recovery of oil-water resources and to address the limited functionality of single superwet materials in oil-water separation, this study reports a multifunctional oil-water separation strategy by compositing the underwater superoleophobic and underoil superhydrophobic materials (HS). The underwater superoleophobic quartz sands with an oil contact angle of 152.68° were prepared by adjusting the particle size. This material demonstrated a water flux of 4688 L m-2 h-1 and a low-density oil and water mixture separation efficiency of 98.6%, which remained above 97.9% over 50 cycles. It was effective in separating oil-in-water emulsions with a separation efficiency of >99%. For HS, quartz sands were modified with dodecyltrimethoxysilane. The optimized HS-4 exhibited superhydrophobic properties with a water contact angle of 157.06°. It achieved an oil flux of 5775 L m-2 h-1 and a water and dichloromethane mixture separation efficiency of 98.4%. Additionally, they exhibited significant potential in the separation of water-in-oil emulsions. Furthermore, by placing the underwater superoleophobic and underoil superhydrophobic units at the bottom of the filter, we achieved cyclic separation of high-density oil and water mixtures, low-density oil and water mixtures, water-in-oil emulsions, and oil-in-water emulsions. The separation efficiency consistently exceeded 96.5% over 10 cycles. In addition, the oil-water separation mechanism of underwater oleophobic and underoil hydrophobic materials was demonstrated by the relative concentration distribution of water and oil with molecular dynamics simulations. This intelligent oil-water separation method marks a significant advancement in the sustainable separation of diverse oil-water mixtures.

Spicy food consumption reduces the risk of ischaemic stroke: a prospective study.

Previous studies revealed that consuming spicy food reduced mortality from CVD and lowered stroke risk. However, no studies reported the relationship between spicy food consumption, stroke types and dose­response. This study aimed to further explore the association between the frequency of spicy food intake and the risk of stroke in a large prospective cohort study. In this study, 50 174 participants aged 30­79 years were recruited. Spicy food consumption data were collected via a baseline survey questionnaire. Outcomes were incidence of any stroke, ischaemic stroke (IS) and haemorrhagic stroke (HS). Multivariable-adjusted Cox proportional hazard models estimated the association between the consumption of spicy food and incident stroke. Restricted cubic spline analysis was used to examine the dose­response relationship. During the median 10·7-year follow-up, 3967 strokes were recorded, including 3494 IS and 516 HS. Compared with those who never/rarely consumed spicy food, those who consumed spicy food monthly, 1­2 d/week and 3­5 d/week had hazard ratio (HR) of 0·914 (95 % CI 0·841, 0·995), 0·869 (95 % CI 0·758, 0·995) and 0·826 (95 % CI 0·714, 0·956) for overall stroke, respectively. For IS, the corresponding HR) were 0·909 (95 % CI 0·832, 0·994), 0·831 (95 % CI 0·718, 0·962) and 0·813 (95 % CI 0·696, 0·951), respectively. This protective effect showed a U-shaped dose­response relationship. For obese participants, consuming spicy food ≥ 3 d/week was negatively associated with the risk of IS. We found the consumption of spicy food was negatively associated with the risk of IS and had a U-shaped dose­response relationship with risk of IS. Individuals who consumed spicy food 3­5 d/week had a significantly lowest risk of IS.

Sequential Water Sorption/Desorption of a Nonporous Adaptive Organic Ligand Bridged Coordination Polymer for Atmospheric Moisture Harvesting.

Moisture harvesters with favourable attributes such as easy synthetic availability and good processability as alternatives for atmospheric moisture harvesting (AWH) are desirable. This study reports a novel nonporous anionic coordination polymer (CP) of uranyl squarate with methyl viologen (MV2+ ) as charge balancing ions (named U-Squ-CP) which displays intriguing sequential water sorption/desorption behavior as the relative humidity (RH) changes gradually. The evaluation of AWH performance of U-Squ-CP shows that it can absorb water vapor under air atmosphere at a low RH of 20 % typical of the levels found in most dry regions of the world, and have good cycling durability, thus demonstrating the capability as a potential moisture harvester for AWH. To the authors' knowledge, this is the first report on non-porous organic ligand bridged CP materials for AWH. Moreover, a stepwise water-filling mechanism for the water sorption/desorption process is deciphered by comprehensive characterizations combining single-crystal diffraction, which provides a reasonable explanation for the special moisture harvesting behaviour of this non-porous crystalline material.

Heterocyclic Ligands with Different N/O Donor Modes for Am(III)/Eu(III) Separation: A Theoretical Perspective.

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.

Theoretical Insights into the Substitution Effect of Phenanthroline Derivatives on Am(III)/Eu(III) Separation.

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.

Theoretical Insights on the Complexation of Americium(III) and Europium(III) with Diglycolamide- and Dimethylacetamide-Functionalized Calix[4]arenes.

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).

Theoretical Insights into the Selectivity of Hydrophilic Sulfonated and Phosphorylated Ligands to Am(III) and Eu(III) Ions.

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.

Insights into the Reduction Mechanisms of Np(VI) to Np(V) by Carbohydrazide.

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.

Unveiling the Reduction Mechanism of Pu(IV) by Acetaldoxime.

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).

Age at smoking initiation and smoking cessation influence the incidence of stroke in China: a 10-year follow-up study.

Our study aimed to explore the correlation between age at smoking initiation and smoking cessation for the risk for stroke in China. We investigated 50,174 participants from one of the urban areas of China Kadoorie Biobank (CKB) Study. Hazard ratios (HRs) and 95% confidence intervals (95% CIs) for association between smoking and incidence of stroke were estimated using Cox regression model. During a median of 10.7 years of follow-up, 4370 total stroke cases were documented. Among men, comparing current smokers to never smokers, the HR of total stroke for current smokers was 1.279 (95% CI, 1.134-1.443) for total stroke. The HRs of total stroke were 1.344 (1.151-1.570) for those started smoking at age less than 20 years, 1.254 (1.090-1.443) for those started smoking at age 20-30 years, and 1.205 (1.012-1.435) for those started smoking at age 30 year and above, with a dose-response relation (P for trend, 0.004). Comparing former smokers to current smokers, in the low pack-year group, those stopped smoking at age less than 65 years had a 18.2% decreased risk for total stroke (0.818; 0.673-0.994). The decreased risk was not found in those stopped smoking at age 65 years and above. Similar results were observed in the high pack-year group. In conclusion, we found that current smokers had a higher stroke risk than never smokers, and the risk increased with a younger age at smoking initiation. Smoking cessation can reduce the risk for stroke, especially could benefit from cessation at a younger age.

[Quality evaluation of Huocao based on UPLC fingerprint and multi-component content determination].

Huocao(a traditional Chinese herbal medicine) moxibustion is a characteristic technology in Yi medicine suitable for cold-dampness diseases. Huocao, as the moxibustion material, is confusedly used in clinical practice and little is known about its quality control. In this study, UPLC method was used to establish the chemical fingerprint of non-volatile components in Huocao, and the contents of eight phenolic acids such as chlorogenic acid were determined. Multivariate statistical analysis was performed to obtain the indicator components of Huocao for quality evaluation, and thus a comprehensive evaluation system for the quality of Huocao was built. The UPLC fingerprints of 49 batches of Huocao were established, and there were 20 common peaks, of which eight phenolic acids including neochlorogenic acid and chlorogenic acid were identified. Except for three batches of Huocao, the similarity of the other 46 batches was higher than 0.89, suggesting that the established fingerprint method could be used for quality control of the medicinal herb. The correlation coefficient between entropy weight score of the eight phenolic acids and comprehensive fingerprint score in Huocao was 0.875(P<0.01), which indicated that the eight phenolic acids could be used as indicator components for the quality evaluation of Huocao. Furthermore, in multivariate statistical analysis on the common peaks of fingerprint and the contents of the eight phenolic acids, chlorogenic acid, isochlorogenic acid A and isochlorogenic acid C were screened to be the indicator components. The results revealed that the proposed method achieved a simple and accurate quality control of Huocao based on UPLC fingerprint and multi-component content determination, which provided useful data for establishing the quality standard of Huocao.

Outcome after allogeneic hematopoietic stem cell transplantation following Venetoclax-based therapy among AML and MDS patients.

The use of Bcl-2 inhibitor Venetoclax (VEN) combined with hypomethylating agents or chemotherapy has shown efficacy in treating acute myeloid leukemia (AML) as frontline treatment and for relapse, allowing more patients to bridge to allogeneic hematopoietic stem cell transplantation (allo-HSCT). However, the influence of VEN-based therapy on the prognosis of subsequent allogeneic HSCT remains unknown. We retrospectively collected data from patients who proceeded to allo-HSCT between November 2018 and November 2020 after VEN-based therapy at five transplant centers in Zhejiang Province, China. A total of 39 patients were analyzed. Thirty-one patients were diagnosed with AML (28 de novo, 3 secondary to MDS), 6 with MDS, and 2 with CMML. The majority (74.4%) of patients received VEN-based therapy for the treatment of relapse (38.5%) or refractory disease (35.9%); 5 (12.8%) received it as an initial treatment, and 5 (12.8%) patients who were already in complete remission (CR) received VEN for further consolidation or deep remission before HSCT. Twenty-seven (69.2%) patients were in CR at the time of HSCT. Day + 100 cumulative incidences of grade I-IV acute graft-versus-host disease (aGVHD) and grade II-IV aGVHD were 43.6% and 15.4%, respectively. Of 34 evaluable patients, 6.4% and 25.6% developed chronic GVHD at 1 year and 2 years. The 100-day cytomegalovirus (CMV) reactivation occurred in 76.3% of patients and Epstein-Barr virus (EBV) reactivation occurred in 29.7% of patients. With a median follow-up of 14.7 months, overall survival, progression-free survival, relapse, and non-relapse mortality incidence at 1 year were 75.5%, 61.6%, 16.7%, and 21.7%, respectively. Both univariate and multivariate analysis revealed that relapsed/refractory (R/R) disease was associated with inferior PFS (HR 4.849, 95% CI 1.009-23.30; p = 0.049). Prior poor response to VEN was found to be a significant factor predicting higher risk of relapse (HR 4.37, 95% CI 1.130-16.9; p = 0.033). Our results showed that VEN-based regimen therapy followed by allo-HSCT in AML patients is feasible and does not increase the risk of transplant-related mortality and toxicity.

Theoretical Probing of Size-Selective Crown Ether Macrocycle Ligands for Transplutonium Element Separation.

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.

Theoretical Insights into the Selective Separation of Am(III)/Eu(III) Using Hydrophilic Triazolyl-Based Ligands.

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).

Theoretical Insights into Phenanthroline-Based Ligands toward the Separation of Am(III)/Eu(III).

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.

Reduction of Np(VI) with hydrazinopropionitrile via water-mediated proton transfer.

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]+˙, 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.

Actinide-doped boron clusters: from borophenes to borospherenes.

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.

Construction of the Largest Metal-Centered Double-Ring Tubular Boron Clusters Based on Actinide Metal Doping.

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.

Theoretical Insights on Improving Amidoxime Selectivity for Potential Uranium Extraction from Seawater.

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.

[Chemical constituents and anti-liver fibrosis mechanism of Meconopsis quintuplinervia based on UPLC-Q-Exactive-MS/MS and network pharmacology].

In this study, UPLC-Q-Exactive-MS/MS was used to rapidly analyze the chemical constituents of Meconopsis quintupli-nervia, and the anti-liver fibrosis mechanism of M. quintuplinervia was preliminarily analyzed by network pharmacology, molecular docking, and cell experiments. The chemical constituents of M. quintuplinervia were identified according to the information of MS~1 and MS~2, as well as the data in the literature and databases. SwissTargetPrediction and TargetNet were used to predict the potential targets. The targets related to liver fibrosis were collected from GeneCards and OMIM. The protein-protein interaction(PPI) network was constructed by STRING. Cytoscape 3.6.1 was used to construct and analyze the "constituent-target-disease" network to obtain key targets and their corresponding constituents in the network. DAVID 6.8 was used for GO analysis and KEGG signaling pathway enrichment analysis. Finally, the preliminary verification was carried out by molecular docking and cell experiments. As a result, 106 chemical constituents were identified from M. quintuplinervia, including 66 flavonoids, 16 alkaloids, 18 phenolic acids, 1 anthocyanin, and 5 other constituents. Among them, 3 constituents were identified as potential new compounds, and 59 constituents were reported in M. quintuplinervia for the first time. Network pharmacology analysis showed that M. quintuplinervia presumably acted on AKT1, SRC, JUN, EGFR, STAT3, HSP90 AA1, MAPK3, and other core targets through luteolin, isorhamnetin, quercetin, apigenin, kaempferide, amurine, 2-methylflavinantine, allocryptopine, the multi and other active compounds, thereby regulating the PI3 K/AKT signaling pathway, pathways in cancer, proteoglycans in cancer, FoxO signaling pathway, and other pathways to exert anti-liver fibrosis effects. M. quintuplinervia extract(MQE) could significantly down-regulate PI3 K and AKT protein levels in the HSC-T6 cell model induced by TGF-ß1, suggesting that MQE may have the ability to regulate the PI3 K/AKT signaling pathway. The findings of this study indicated that the anti-liver fibrosis effect of M. quintuplinervia had multi-constituent, multi-target, and multi-pathway characteristics, which may provide a scientific basis for the research on the pharmacodynamic materials, action mechanism, and quality markers of M. quintupli-nervia.