Determination of tolfenpyrad residues in green tea by GC-MS/MS based on acetonitrile extractant, dispersion solid phase extraction purification.

Green tea is one of people's favorite drinks. However, pesticide residues in green tea can cause harm to the human body, and therefore, detection of pesticide residues in green tea is very important. In recent years, the detection of pesticide residues in tea has become a research hotspot. In this paper, a gas chromatography-mass spectrometry/mass spectrometry (GC-MS/MS) detection method of tolfenpyrad pesticide residues in green tea was established by using acetonitrile extractant, dispersive solid-phase extraction purification, temperature programming and application retention time lock with the database. After the sample was extracted with acetonitrile, then the sample was purified by QuEChERS extraction purification tube, afterward isomer B was used as the internal standard for the determination by multiple reaction monitoring mode (MRM) of GC-MS/MS. The results indicated that the experimental data accorded with the criterion on quality control of laboratoris(chemical testing of food), and the requirements of recovery, calibration curve, precision.This method was used to detect tolfenpyrad residues in actual green tea samples in multiple batches, and the satisfactory results were obtained.

Two Fe(III)/Eu(III) Salophen complex-based optical sensors for determination of organophosphorus pesticide monocrotophos.

Monocrotophos (MP), an organophosphorus pesticide, poses a serious threat to human health, so a rapid and simple technique is needed to detect it. In this study, two novel optical sensors for MP detection were created using the Fe(III) Salophen complex and Eu(III) Salophen complex, respectively. One sensor is an Fe(III) Salophen complex (I-N-Sal), which can bind MP selectively and form a supramolecule, resulting in a strong resonance light scattering (RLS) signal at 300 nm. Under the optimum conditions, the detection limit was 30 nM, the linear range was 0.1-1.1 µM, the correlation coefficient R2 = 0.9919, and the recovery rate range was 97.0-103.1%. Interaction properties between the sensor I-N-Sal and MP and the RLS mechanism were investigated using density functional theory (DFT). And another sensor is based on the Eu(III) Salophen complex and 5-aminofluorescein derivatives. The Eu(III) Salophen complex was immobilized on the surface of amino-silica gel (Sigel-NH2) particles as the solid phase receptor (ESS) of MP and 5-aminofluorescein derivatives as the fluorescent (FL)-labeled receptor (N-5-AF) of MP, which can selectively bind the MP and form a sandwich-type supramolecule. Under the optimum conditions, the detection limit was 0.4 µM, the linear range was 1.3-7.0 µM, the correlation coefficient R2 = 0.9983, and the recovery rate range was 96.6-101.1%. Interaction properties between the sensor and MP were investigated by UV-vis, FT-IR, and XRD. Both sensors were successfully applied to the determination of MP content in tap water and camellia.

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 into the separation of Am(III)/Eu(III): designing ligands based on a preorganization strategy.

Separation of trivalent actinide (An(III)) and lanthanide (Ln(III)) is a worldwide challenge of nuclear waste treatment. Designing ligands with efficient An(III)/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, N-heterocyclic ligands modified with amide groups have shown excellent An(III)/Ln(III) separation performance. The preorganized structure of the ligands has a great impact on the An(III)/Ln(III) separation performance. We theoretically investigated the extraction behaviors of Am(III) and Eu(III) using phenanthroline (L1 and L2) and bipyridine (L3 and L4) based ligands with a completely or partially preorganized structure. The properties of these ligands and their coordination structures, bonding nature and thermodynamic behaviors with the Am(III) and Eu(III) complexes have been systematically studied in a theoretical fashion. The analyses of the bonding nature suggest that the Am-N bonds possess more covalence than the Eu-N bonds. The thermodynamic results indicate that L2 with a completely preorganized structure has the strongest extraction ability and the best Am(III)/Eu(III) selectivity, while L3 with the most flexible skeleton appears to have the weakest extraction ability and the lowest Am(III)/Eu(III) selectivity. And L1 and L4 have similar performances with regard to Am(III)/Eu(III) selectivity. The results suggest that a certain degree of preorganization of the ligand structure can enhance the extraction ability and Am(III)/Eu(III) selectivity. This work provides valuable information for designing efficient ligands for An(III)/Ln(III) separation by the preorganization strategy.

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.

Complexation and enantioselectivity of novel bridge-like uranyl- 2-((1Z,9Z)-9-(2-Hydroxyphenyl)-3,5,6,8-tetrahydrobenzo[h][1,4,7,10] dioxadiazacyclododecin-2-yl)-5-methoxyphenol with chiral organophosphorus pesticide enantiomers of R/S-malathions.

Designing new uranyl complexes with enantioselectivity is of great significance for the identification and separation of enantiomers of chiral pesticides. In this paper, a new asymmetric rigid uranyl-2-((1Z,9Z)-9-(2-Hydroxyphenyl)-3,5,6,8-tetrahydrobenzo[h][1,4,7,10] dioxadiaza-cyclododecin-2-yl)-5-methoxyphenol(Uranyl-HTDM) was designed, we used Uranyl-HTDM as a receptor to selectively coordinate with the guests of the chiral organophosphorus pesticide R/S-malathions(R/S-MLTs) to explore the receptor's enatioselectivity recognition of the chiral guests of R/S-MLTs. Density functional theory (DFT) method was used to comprehensively study the complexation mode of the receptor with enantiomers. The results showed that the U of Uranyl-HTDM could coordinate with both the thiophosphoryl sulfur and carbonyl oxygens of R/S-MLTs in different environments, respectively. The thermodynamics calculations further indicated that the receptor could selectively recognize the thiophosphoryl sulfur and carbonyl oxygen atoms of R/S-malathions, and the complexation abilities of Uranyl-HTDM to the R/S-malathions under different solvents were not the same. The smaller the polarity of solvents, the stronger the complexation ability of Uranyl-HTDM with R-malathion, toluene was an ideal solvent with large △G change and enatioselectivity coefficient of 99.55%. The study provides useful references for the design of new uranyl-salophens and for the experimental study on the molecular recognition of chiral organophosphorus pesticides.

Theoretical probing of twenty-coordinate actinide-centered boron molecular drums.

The exploration of metal-doped boron clusters has a great significance in the design of high coordination number (CN) compounds. Actinide-doped boron clusters are probable candidates for achieving high CNs. In this work, we systematically explored a series of actinide metal atom (U, Np, and Pu) doped B20 boron clusters An@B20 (An = U, Np, and Pu) by global minimum structural searches and density functional theory (DFT). Each An@B20 cluster is confirmed to be a twenty-coordinate complex, which is the highest CN obtained in the chemistry of actinide-doped boron clusters so far. The predicted global minima of An@B20 are tubular structures with actinide atoms as centers, which can be considered as boron molecular drums. In An@B20, U@B20 has a relatively high symmetry of C2, while both Np@B20 and Pu@B20 exhibit C1 symmetry. Extensive bonding analysis demonstrates that An@B20 has σ and π delocalized bonding, and the U-B bonds possess a relatively higher covalency than the Np-B and Pu-B bonds, resulting in the higher formation energy of U@B20. Therefore, the covalent character of An-B bonding may be crucial for the formation of these high CN actinide-centered boron clusters. These results deepen our understanding of actinide metal doped boron clusters and provide new clues for developing stable high CN boron-based nanomaterials.

Stepwise Assembly of a Multicomponent Heterometallic Metal-Organic Framework via Th6-Based Metalloligands.

Herein we present a new metalloligand, Th6L12 [IHEP-10; L = 4-pyrazolecarboxylic acid (H2PyC)], which can be used to generate a novel multicomponent heterometallic metal-organic framework (MOF), [[Cu3(µ3-OH)(NO3)(H2O)2]2Th6(µ3-O)4(µ3-OH)4(PyC)6(HPyC)6(H2O)6](NO3)2 (IHEP-11), through further assembly with second [Cu3(µ3-OH)(PyC)3] clusters. In IHEP-11, six Cu3 clusters are connected by six NO3- anions to form an unprecedented annular Cu18 cluster, which can be viewed as a 12-connected node to link with 12 Th6 clusters, resulting a 4,12-connected shp net. Benefiting from the cationic framework and 3D porous structure, IHEP-11 can efficiently remove ReO4- (an analogue of radioactive 99TcO4-) from aqueous solution in a wide pH range. This work highlights the feasibility of constructing multicomponent MOFs through a step-by-step synthesis strategy based on metalloligands.

Double-Layer Nitrogen-Rich Two-Dimensional Anionic Uranyl-Organic Framework for Cation Dye Capture and Catalytic Fixation of Carbon Dioxide.

A novel two-dimensional double-layer anionic uranyl-organic framework, U-TBPCA {[NH2(CH3)2][(UO2)(TBPCA)], where H3TBPCA = 4,4',4″-s-triazine-1,3,5-triyltripamino-methylene-cyclohexane-carboxylate}, with abundant active sites and stability was obtained by assembling UO2(NO3)2·6H2O and a triazine tricarboxylate linker, TBPCA3-. Due to the flexibility of the ligand and diverse coordination modes between carboxyl groups and uranyl ions, U-TBPCA exhibits an intriguing topological structure and steric configuration. This double-layer anionic uranyl-organic framework is highly porous and can be used for selective adsorption of cationic dyes. Due to the presence of high-density metal ions and basic -NH- groups, U-TBPCA acts as an effective heterogeneous catalyst for the cycloaddition reaction of carbon dioxide with epoxy compounds. Moreover, the various modes of coordination between the tricarboxylic ligand and uranyl ion were studied by density functional theory calculations, and several simplified models were established to probe the influence of hydrogen bonding between carbon dioxide and U-TBPCA on the ability of U-TBPCA to bind carbon dioxide. This work should aid in improving our understanding of the coordination behavior of uranyl ion as well as the development and utilization of new actinide materials.

Construction of Hybrid Bimetallic Uranyl Compounds Based on a Preassembled Terpyridine Metalloligand.

Six hybrid uranyl-transition metal compounds [UO2 Ni(cptpy)2 (HCOO)2 (DMF)(H2 O)] (1), [UO2 Ni(cptpy)2 (BTPA)2 ] (2), [UO2 Fe(cptpy)2 (HCOO)2 (DMF)(H2 O)] (3), [UO2 Fe(cptpy)2 (BTPA)2 ] (4), [UO2 Co(cptpy)2 (HCOO)2 (DMF)(H2 O)] (5), and [UO2 Co(cptpy)2 (BTPA)2 ] (6), based on bifunctional ligand 4'-(4-carboxyphenyl)-2,2':6',2''-terpyridine (Hcptpy) are reported (H2 BTPA = 4,4'-biphenyldicarboxylic acid). Single-crystal XRD revealed that all six compounds feature similar metalloligands, which consist of two cptpy- anions and one transition metal cation. The metalloligand M(cptpy)2 can be considered to be an extended linear dicarboxylic ligand with length of 22.12 Å. Compounds 1, 3, and 5 are isomers, and all of them feature 1D chain structures. The adjacent 1D chains are connected together by hydrogen bonds and π-π interactions to form a 3D porous structure, which is filled with solvent molecules and can be exchanged with I2 . Compounds 2, 4, and 6 are also isomers, and all of them feature 2D honeycomb (6,3) networks with hexagonal units of dimensions 41.91×26.89 Å, which are the largest among uranyl compounds with honeycomb networks. The large aperture allows two sets of equivalent networks to be entangled together to result in a 2D+2D→3D polycatenated framework. Remarkably, these uranyl compounds exhibit high catalytic activity for cycloaddition of carbon dioxide. Moreover, the geometric and electronic structures of compounds 1 and 2 are systematically discussed on the basis of DFT calculations.

Theoretical insights into selective separation of trivalent actinide and lanthanide by ester and amide ligands based on phenanthroline skeleton.

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.

Theoretical Insights into Modification of Nitrogen-Donor Ligands to Improve Performance on Am(III)/Eu(III) Separation.

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.

Preparation of core-shell structure Fe3O4@C@MnO2 nanoparticles for efficient elimination of U(VI) and Eu(III) ions.

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@C@MnO2) 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@C@MnO2 was mainly dominated by inner-sphere surface complexation. XPS analysis illustrated that the interaction of Eu(III)/U(VI) with Fe3O4@C@MnO2 was associated with the strong metal bonds (MnO), 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@C@MnO2 in eliminating Eu(III)/U(VI) ions from aqueous solutions, which was of great significance in the future application in radionuclides' pollution treatment.

Theoretical Insights into the Selective Extraction of Americium(III) over Europium(III) with Dithioamide-Based Ligands.

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.

Metal-Carboxyl Helical Chain Secondary Units Supported Ion-Exchangeable Anionic Uranyl-Organic Framework.

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 )2 NH2 ]+ ions in its open channels, as evidenced by a combination of 1 H NMR spectroscopy, EDS and PXRD.

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

Pyridylpyrazole ligands have shown excellent competence for partitioning actinides from lanthanides. As far as we know, the preorganization structure of the ligand has a great impact on the extraction separation ability. However, the mechanism that works well for some ligands but fails for others needs to be clearly elucidated. In this work, we designed three various pyridylpyrazole ligands, BPP, BPBP, and BPPhen, and further preorganized one or both side pyrazole rings of these ligands. The properties of these ligands and the coordination structures, bonding nature and thermodynamic behaviors of the related Am(III) and Eu(III) complexes have been systematically studied in a theoretical fashion. All analyses of geometries, charge transfer, QTAIM (quantum theory of atoms in molecules) and NBO (natural bond orbital) suggest that the Am-N bonds possess more covalence compared to that of Eu-N bonds. According to the thermodynamic results, increasing the rigidity of the bridging skeleton rather than the side chain can enhance the extraction ability and Am(III)/Eu(III) selectivity of the ligand. This work may identify the reasonability of a useful approach on achieving highly efficient Am(III)/Eu(III) separation through tuning the preorganization level of the ligand and further provide meaningful theoretical basis on the input of preorganization toward ligand design and screening.

Uranyl-Organic Coordination Compounds Incorporating Photoactive Vinylpyridine Moieties: Synthesis, Structural Characterization, and Light-Induced Fluorescence Attenuation.

The fluorescence of uranyl originated from electronic transitions (S11-S00 and S10-S0v, 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 (UO2)3(µ3-O)(µ2-OH)2(L1)2( phen)2(1), (UO2)3(µ3-O)(µ2-OH)3(L1)( phen)2 (2), (UO2)3(µ3-O)(µ2-OH)3(L2)( phen)2 (3), [(UO2)2(µ2-OH)2(L2)2( phen)2]·2H2O (4), and (UO2)Zn(SO4)(phen)(H2O)(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.

Insight into the Extraction Mechanism of Americium(III) over Europium(III) with Pyridylpyrazole: A Relativistic Quantum Chemistry Study.

Separation of trivalent actinides (An(III)) and lanthanides (Ln(III)) is one of the most important steps in spent nuclear fuel reprocessing. However, it is very difficult and challenging to separate them due to their similar chemical properties. Recently the pyridylpyrazole ligand (PypzH) has been identified to show good separation ability toward Am(III) over Eu(III). In this work, to explore the Am(III)/Eu(III) separation mechanism of PypzH at the molecular level, the geometrical structures, bonding nature, and thermodynamic behaviors of the Am(III) and Eu(III) complexes with PypzH ligands modified by alkyl chains (Cn-PypzH, n = 2, 4, 8) have been systematically investigated using scalar relativistic density functional theory (DFT). According to the NBO (natural bonding orbital) and QTAIM (quantum theory of atoms in molecules) analyses, the M-N bonds exhibit a certain degree of covalent character, and more covalency appears in Am-N bonds compared to Eu-N bonds. Thermodynamic analyses suggest that the 1:1 extraction reaction, [M(NO3)(H2O)6]2+ + PypzH + 2NO3- → M(PypzH)(NO3)3(H2O) + 5H2O, is the most suitable for Am(III)/Eu(III) separation. Furthermore, the extraction ability and the Am(III)/Eu(III) selectivity of the ligand PypzH is indeed enhanced by adding alkyl-substituted chains in agreement with experimental observations. Besides this, the nitrogen atom of pyrazole ring plays a more significant role in the extraction reactions related to Am(III)/Eu(III) separation compared to that of pyridine ring. This work could identify the mechanism of the Am(III)/Eu(III) selectivity of the ligand PypzH and provide valuable theoretical information for achieving an efficient Am(III)/Eu(III) separation process for spent nuclear fuel reprocessing.

Computational insight into complex structures of thorium coordination with N, N'- bis(3-allyl salicylidene)-o-phenylenediamine.

Theoretical calculations on the structure of Th(IV) complex containing N, N'- bis(3-allyl salicylidene)-o-phenylenediamine (BASPDA) were performed using density functional theory (DFT) at the B3LYP/6-311G** level. The geometrical structural parameters and infrared spectra results of the Th(BASPDA)2 from the calculation were compared with the parallel dislocated structure (PDS) obtained in laboratory. The calculated structural parameters were in good agreement with the experimental results. In addition, based on the calculations, a stereoisomer SFS (staggered finger " + " structure) of the Th(BASPDA)2 complex was forecasted by the analysis of a comprehensive method. The charge distribution, structural parameters, bond order indices, spectral properties and thermodynamic properties as well as the molecular orbitals of the two possible crystal structures of Th(BASPDA)2 were also systematically studied. It was expected that this work could provide insightful information for understanding the properties of Th (BASPDA)2 complex at the molecular level.

Regulating the nitrite reductase activity of myoglobin by redesigning the heme active center.

Heme proteins perform diverse functions in living systems, of which nitrite reductase (NIR) activity receives much attention recently. In this study, to better understand the structural elements responsible for the NIR activity, we used myoglobin (Mb) as a model heme protein and redesigned the heme active center, by introducing one or two distal histidines, and by creating a channel to the heme center with removal of the native distal His64 gate (His to Ala mutation). UV-Vis kinetic studies, combined with EPR studies, showed that a single distal histidine with a suitable position to the heme iron, i.e., His43, is crucial for nitrite (NO2(-)) to nitric oxide (NO) reduction. Moreover, creation of a water channel to the heme center significantly enhanced the NIR activity compared to the corresponding mutant without the channel. In addition, X-ray crystallographic studies of F43H/H64A Mb and its complexes with NO2(-) or NO revealed a unique hydrogen-bonding network in the heme active center, as well as unique substrate and product binding models, providing valuable structural information for the enhanced NIR activity. These findings enriched our understanding of the structure and NIR activity relationship of heme proteins. The approach of creating a channel in this study is also useful for rational design of other functional heme proteins.