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A simple aqueous complexing system of UO22+ with F- is selected to systematically illustrate the application of Raman spectroscopy in exploring uranyl(VI) chemistry. Five successive complexes, UO2F+, UO2F2(aq), UO2F3-, UO2F42-, and UO2F53-, are identified, as well as the formation constants except for the 1 : 5 species UO2F53-, which was experimentally observed here for the first time. The standard relative molar Raman scattering intensity for each species is obtained by deconvolution of the spectra collected during titrations. The results of relativistic quantum chemical first-principles and ab initio calculations are presented for the complete set of [UO2(H2O)mFn]2-n complexes (n = 0-5), both for the gas phase as well as for aqueous solution modelling bulk water using the conductor-like screening model. Electronic structure calculations at the Møller-Plesset second-order perturbation theory level provide accurate geometrical parameters and in particular reveal that k water molecules in the second coordination sphere coordinating to the F- ligands in the resulting [UO2(H2O)mFn]2-n(H2O)k complexes need to be treated explicitly in order to obtain vibrational frequencies in very good agreement with experimental data. The thermodynamics and structural information obtained in this work and the developed methodology could be instructive for the future experimental and computational research on the complexation of the uranyl ion.
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BACKGROUND: Pneumocystis jirovecii pneumonia (PJP) is a life-threatening and severe disease in immunocompromised hosts. A synergistic regimen based on the combination of sulfamethoxazole-trimethoprim (SMX-TMP) with caspofungin and glucocorticosteroids (GCSs) may be a potential first-line therapy for PJP. Therefore, it is important to explore the efficacy and safety of this synergistic therapy for treating non-HIV-related PJP patients. METHODS: We retrospectively analysed the data of 38 patients with non-HIV-related PJP at the First Affiliated Hospital of Xi'an Jiaotong University. Patients were divided into two groups: the synergistic therapy group (ST group, n = 20) and the monotherapy group (MT group, n = 18). All patients were from the ICU and were diagnosed with severe PJP. In the ST group, all patients were treated with SMX-TMP (TMP 15-20 mg/kg per day) combined with caspofungin (70 mg as the loading dose and 50 mg/day as the maintenance dose) and a GCS (methylprednisolone 40-80 mg/day). Patients in the MT group were treated only with SMX-TMP (TMP 15-20 mg/kg per day). The clinical response, adverse events and mortality were compared between the two groups. RESULTS: The percentage of patients with a positive clinical response in the ST group was significantly greater than that in the MT group (100.00% vs. 66.70%, P = 0.005). The incidence of adverse events in the MT group was greater than that in the ST group (50.00% vs. 15.00%, P = 0.022). Furthermore, the dose of TMP and duration of fever in the ST group were markedly lower than those in the MT group (15.71 mg/kg/day vs. 18.35 mg/kg/day (P = 0.001) and 7.00 days vs. 11.50 days (P = 0.029), respectively). However, there were no significant differences in all-cause mortality or duration of hospital stay between the MT group and the ST group. CONCLUSIONS: Compared with SMZ/TMP monotherapy, synergistic therapy (SMZ-TMP combined with caspofungin and a GCS) for the treatment of non-HIV-related PJP can increase the clinical response rate, decrease the incidence of adverse events and shorten the duration of fever. These results indicate that synergistic therapy is effective and safe for treating severe non-HIV-related PJP.
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Pneumocystis carinii , Neumonía por Pneumocystis , Humanos , Neumonía por Pneumocystis/tratamiento farmacológico , Combinación Trimetoprim y Sulfametoxazol/efectos adversos , Caspofungina/uso terapéutico , Estudios Retrospectivos , Centros de Atención Terciaria , Corticoesteroides/uso terapéuticoRESUMEN
The similarity of the coordination chemistry of Am(III) and Eu(III) and two homologous tridentate ligands, N,N-di-2-ethylhexyl-6-amide-pyridine-2-carboxylic acid (DEHAPA, HL') in solvent extraction and N,N-dimethyl-6-amide-pyridine-2-carboxylic acid (DMAPA, HL) in aqueous solution and in the solid state, is revealed structurally and spectroscopically with complexes ML'3 (org), ML3 (aq) and ML3 (s), respectively.
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Lipophilic N,N,N',N'-tetraalkyl-diglycolamides (TRDGAs) are promising extractants for actinides separation in spent nuclear fuel reprocessing. Usually, in the extracted complexes of actinide and lanthanide ions of various oxidation states, the metal ions are completely surrounded by 2 or 3 TRDGA molecules, and the counter anions do not directly coordinate with them. In contrast, the extracted complexes of U(iv) from different media presenting different absorption spectra indicate that the anions (Cl- and NO3-) are directly involved in the coordination with U(iv) in the first inner sphere. Based on this exceptional observation in solvent extraction, taking the coordination of U(iv) with N,N,N',N'-tetramethyl-diglycolamide (TMDGA, the smallest analogue of TRDGA) as the research object, we mimic the behaviours of counterions (Cl- and NO3-) and the water molecule during coordination of TMDGA with U(iv), especially combining with the simulation of the absorption spectra. We demonstrate that during the complexing of TMDGA to U(iv), the counterion Cl- will occupy one coordination number in the inner coordination sphere, and NO3- will occupy two by bidentate type; however, the ubiquitous water cannot squeeze in the inner coordination sphere. In addition, the coordination of Cl- and NO3- is proved to favour the extraction with the lower binding energy. Moreover, the simulation of absorption spectra is in good agreement with the observation from experiments, further verifying the aforementioned conclusion. This work in some way will provide guidance to improve the computation methods in research of actinides by mimicking the absorption spectra of actinide ions in different complexes.
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A new graphene oxide (GO) model with reasonable functional group types and distribution modes was proposed by integrating potentiometric titrations and ab initio calculations. Due to the complex synthesis mechanism, the atomic structure of GO has been controversial for a long time. Here, we use density functional theory calculations to mimic the oxidation process, and a series of GO fragments (GOFs) were deduced. A new pKa calculation method (RCDPKA) developed specifically in this work was further used to predict pKa values of the fragments. Then, we performed potentiometric titrations on four different GO samples to confirm the existence of these GOFs and determine the content of functional groups. Interestingly, different GO samples present the same pKa values in titration, and the results are consistent with the predicted ones. Based on the evidence from titration and calculation, prominent correlations between functional groups could be found. Groups at the edges are mainly double-interactive carboxyls (pKa1 ≈ 3.4, pKa2 ≈ 5.7) and double-adjacent phenolic hydroxyls (pKa1 ≈ 8.8, pKa2 ≈ 12.1), while groups on the plane are mainly collocated epoxies and hydroxyls (pKa1 ≈ 11.1, pKa2 ≈ 13.8) on both sides of the plane with a meta-positional hydrogen bond interaction. These findings were further validated by multiple characterizations and GO modifications. These results not only stimulate a fundamental understanding of the GO structure but also provide a quantitative analysis method for functional groups on GO.
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The recycling of uranium in wastewater is not only beneficial to the protection of ecological safety but also has great significance for the sustainable development of nuclear energy. However, there is no satisfactory method to recover and reuse uranium efficiently up to now. Here, we have developed an efficient and economical strategy that can achieve uranium recovery and direct reuse in wastewater. The feasibility analysis verified that the strategy still had good separation and recovery ability in acidic, alkaline, and high-salinity environments. The purity of uranium recovered from the separated liquid phase after electrochemical purification was up to about 99.95%. Ultrasonication could greatly increase the efficiency of this strategy, and 99.00% of high-purity uranium could be recovered within 2 h. We further improved the overall recovery rate by recovering the residual solid-phase uranium, and the overall recovery of uranium was increased to 99.40%. Moreover, the concentration of impurity ions in the recovered solution met the World Health Organization guidelines. In summary, the development of this strategy is of great importance for the sustainable use of uranium resources and environmental protection.
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Energía Nuclear , Uranio , Purificación del Agua , Aguas Residuales , Purificación del Agua/métodosRESUMEN
As the primary functional groups of amidoxime sorbents for uranium recovery from seawater, di(amidoxime) ligands can be cyclized in situ into different ligands in the presence of Cu(II)/Ni(II) at different pH values. Here we first found that a linear ligand glutardiamidoxime can be catalyzed into a cyclic ligand glutarimidedioxime by Ni(II) in acidic solution.
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Due to the highly acidic and high-salinity nature of the high-level radioactive waste liquid (HLLW), selective extraction of TcO4- from HLLW remains to be a challenging task. Traditional anion exchangers show low selectivity and unsatisfactory extraction performance due to the lack of functional groups that can interact strongly with TcO4-. In this work, a tailor-made binding site was constructed by decorating two acetamide functional groups on imidazolium cation to fabricate a new Tc separation material, which exhibits high selectivity. Unlike most reported Tc separation materials, which can only perform well under low acidic, neutral, or alkaline conditions, this material still has good extraction performance in highly acidic solutions. In the simulated high-level waste liquid of 3 M nitric acid, the extraction efficiency of 0.5 mol/L organic phase for Tc can reach 96.5% through the first-stage extraction. Our theoretical simulations suggest that ReO4-/TcO4- anions were adsorbed on the top of the imidazolium ring during the extraction process, with p-π and p-p interactions acting as the driving forces.
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The complexation of uranium(VI) [U(VI)] with dipicolinic acid was revisited with respect to the missing protonated complex species existing in acidic solutions. For the first time, the presence of the protonated complex, UO2HL+, in aqueous solutions was confirmed and the stability constant was determined by fluorescence spectroscopy. Considering the protonated species, which was missing in previous investigations, the overestimated stability constants of the two known complexes, UO2L and UO2L22-, were carefully reevaluated with potentiometry using N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid as a competing ligand. While a single crystal of the solid compound UO2(HL)2(H2O)4 with two monoprotonated HL- bonding UO22+ in a tridentate mode was successfully grown from aqueous solutions, the corresponding complex species UO2(HL)2(aq) could not yet be clearly identified and characterized.
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Five complex species of Nd(III) with HA have been spectroscopically and compositionally identified as NdA3, NdA3(HA), NdA3(HA)H2O, NdA3(H2O)3, and Nd(H2O)23·3A (HA, bis(2,4,4-trimethylpentyl)dithiophosphinic acid) with the help of X-ray diffraction analysis on single crystals of Nd(H2O)9·H2O·3B (HB = bis(iso-butyl)dithiophosphinic acid.
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To improve the weak mechanical properties of the foamed concrete that resulted from a large number of pores, a plant fiber is used as fill with the matrix. In this study, five contents of sisal fiber are added into the foamed concrete to investigate the static and fatigue performance of composites. The static and fatigue experimental results show that the sisal fiber can improve the mechanical properties of the foamed concrete. When the content of sisal fiber is less than 0.15%, the higher the content of sisal fiber, the greater the bending strength and fatigue life of the foamed concrete. In contrast, if the sisal fiber content is larger than 0.15%, the bending strength and fatigue life decrease with the increasing fiber content. From the regression analyses, the results show that the double linear relationships exist not only between the sisal fiber content and the flexural strength, but also between the sisal fiber content and the fatigue life of the foamed concrete. In this study, the optimal content of sisal fiber mixed in the foamed concrete can be inferred to be 0.133%.
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The complexation and selectivity of N,N-di(2-ethylhexyl)-diglycolamic acid (HDEHDGA/kerosene, HA) toward the light lanthanides, La(III), Ce(III), Pr(III), and Nd(III), are presented for the extraction from chloride media. In the low pH region (pH 1.8-2.8), the obtained data reveal that the extraction of Ln(III) is governed by cation-exchange mechanism and is driven by the negative change in enthalpy. The results from the slope analysis method suggest the formation of LnA3·(HA)1or2 in the extraction process. As major extracted species with a core of LnA3 in the first coordination sphere, LnA3 might connect with one or two additional HA molecules in the second coordination sphere by hydrogen bonding. The LnA3 core might share similar coordination geometry to those of 1:3 Ln(III) complexes (LnA'3) with water-soluble N,N-dimethyl-diglycolamic acid (HDMDGA, HA') formed in aqueous solutions or in solid-state compounds. The correlation between the extraction with HDEHDGA (HA) as an extractant and the complexation with HDMDGA (HA') as a chelator has been explored by interpreting the separation factors for HA with the difference in the stability constants for HA'. Consequently, the ratios of the stability constants of the corresponding 1:3 complexes (LnA'3) with HDMDGA could be reasonably translated to the separation factors (SFs) with HDEHDGA, providing a valuable approach for understanding the origin of the extraction/separation mechanism. By comparing the extraction selectivity of HDEHDGA with that of the currently deployed extractants in the industry such as P204, P507, and Cyanex 272, HDEHDGA offers outstanding selectivity with considerable SFs (SFCe/La = 6.68, SFPr/Ce = 2.79, and SFNd/Pr = 2.65) for light Ln(III) pairs under conditions of low acid concentrations.
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The Raman band at about 870 cm-1 originating from the symmetric stretch vibration (ν1) of uranyl, UO22+, has proven to be very informative for investigating the complexation of uranyl using perchlorate or nitrate of known concentration as internal standards. The concentration of uranyl can be conveniently calculated by using the ratio of the directly read band intensities of uranyl and the added reference, ClO4-, with a factor of 1.72. While with NO3- of concentration lower than 1.8 M as the reference, a factor of 0.85 should be used. Furthermore, with added internal standards, the linear relationship between the Raman intensity and the concentration of the corresponding species is illustrated by the spectral titration of U(vi) with a very strong ligand, dipicolinic acid (DPA); and the application of a spectral titration method with Raman spectroscopy in studying the complexation of uranyl is demonstrated by the titration of U(vi) with oxalate. The stepwise changes in the Raman shift of 18, 17, and 6 cm-1, corresponding to the three oxalate anions successively bonding to UO22+, imply that the coordination modes are different. In the 1 : 1 and 1 : 2 ratios of metal to ligand complexes, the oxalate anions bond to the uranyl ion in side-on bidentate mode, but in the 1 : 3 complex the third oxalate bonds in head-on mode, which is much weaker than the first two.
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Tetraalkyldiglycolamide (TRDGA) ligands have potential utilization for the separation of actinide and lanthanide ions in the nuclear industry as chelates in aqueous solution if water-soluble or as extractants in organic solvents if water-insoluble. Here, a spectral titration method is extensively applied to investigating the complexation of fluorescent Sm(iii), Eu(iii), and Tb(iii) with TRDGA ligands in aqueous solutions and a solvent extraction system. In aqueous solutions using N,N,N',N'-tetramethyldiglycolamide (TMDGA, LI) as chelate, three successive complex species of Ln(iii), including [LnLI]3+, [LnL]3+, and [LnL]3+, are identified for each Ln(iii) (Ln = Sm, Eu, and Tb), and their stability constants are determined with fluorescence spectral titration method at 25 °C in 1 M NaNO3. The coordination mode in [LnL]3+ is illustrated by single-crystal structures of the solid compounds LnL(ClO4)3 (Ln = Sm, Eu, Tb, and LI = TMDGA) grown from aqueous solutions by slow evaporation. The crystal structures show that in the complexes Ln(iii) ions are coordinated by nine oxygen atoms from three tridentate LI ligands in a distorted tricapped trigonal prism geometry. To provide parallels to solvent extraction chemistry, the extracted Ln(iii) complexes with N,N'-dimethyl-N,N'-dioctyldiglycolamide (DMDODGA, LII, a lipophilic analogue of TMDGA) are prepared, and the fluorescence spectra are collected as well for comparison. The fluorescence spectra of the extracted Ln(iii) complexes with LII in an organic phase of 40-60% (v/v) n-octanol-kerosene are nearly identical to the corresponding deconvoluted spectra of [LnL]3+ in aqueous solution. The similarity in fluorescence spectra suggests that Ln(iii) ion in the extracted complexes is also coordinated by three tridentate LII ligands and that the nitrate anions acting just as counterions do not directly bond to Ln(iii) in the organic phase of solvent extraction.
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Porous aromatic frameworks (PAFs) incorporating a high concentration of acid functional groups possess characteristics that are promising for use in separating lanthanide and actinide metal ions, as required in the treatment of radioactive waste. These materials have been shown to be indefinitely stable to concentrated acids and bases, potentially allowing for multiple adsorption/stripping cycles. Additionally, the PAFs combine exceptional features from MOFs and inorganic/activated carbons giving rise to tunable pore surfaces and maximum chemical stability. Herein, we present a study of the adsorption of selected metal ions, Sr(2+), Fe(3+), Nd(3+), and Am(3+), from aqueous solutions employing a carbon-based porous aromatic framework, BPP-7 (Berkeley Porous Polymer-7). This material displays high metal loading capacities together with excellent adsorption selectivity for neodymium over strontium based on Langmuir adsorption isotherms and ideal adsorbed solution theory (IAST) calculations. Based in part upon X-ray absorption spectroscopy studies, the stronger adsorption of neodymium is attributed to multiple metal ion and binding site interactions resulting from the densely functionalized and highly interpenetrated structure of BPP-7. Recyclability and combustibility experiments demonstrate that multiple adsorption/stripping cycles can be completed with minimal degradation of the polymer adsorption capacity.
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Efficient separation processes for recovering uranium and plutonium from spent nuclear fuel are essential to the development of advanced nuclear fuel cycles. The performance characteristics of a new salt-free complexing and reducing reagent, glutarimidedioxime (H2A), are reported for recovering plutonium in a PUREX process. With a phase ratio of organic to aqueous of up to 10:1, plutonium can be effectively stripped from 30% tributyl phosphate (TBP) in kerosene into 1 M HNO3 with H2A. The complexation-reduction mechanism is illustrated with the combination of UV/Vis absorption spectra and the crystal structure of a Pu(IV) complex with the reagent. The fast stripping rate and the high efficiency for stripping Pu(IV), through the complexation-reduction mechanism, is suitable for use in centrifugal contactors with very short contact/resident times, thereby offering significant advantages over conventional processes.
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The complexation of neptunium(v) with carbonate has been studied at temperatures from 10 to 70 °C in 0.1 M LiClO4 by spectrophotometry. Three NpO2(+)-CO3(2-) complex species, NpO2(CO3)n((2n-1)-) (n = 1, 2, 3), are identified and the stability constants are calculated by using the absorption spectra in the near-IR region collected from titrations at varying temperatures. The enthalpies and entropies are calculated with van't Hoff equations in the temperature range of 10 to 70 °C, indicating that the formation of all NpO2(+)-CO3(2-) complexes is mainly entropy driven. The structures of the NpO2(+)-CO3(2-) complex species in aqueous solutions are also reviewed. Based on the molar absorptivity of Np(v) in the near-IR region the structure of NpO2(CO3)2(3-) is re-constructed as NpO2(CO3)2(H2O)(3-)of low symmetry but not as NpO2(CO3)2(H2O)2(3-)of high symmetry as suggested in a previous study.
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Complexation of Am(iii) with tetramethyl-3-oxa-glutaramide (TMOGA, L(I)) is studied by spectrophotometric titrations and single crystal X-ray diffraction. Three successive complex species, [AmL(I)](3+), [AmL](3+), and [AmL](3+), have been identified and their stability constants are calculated to be 3.71 ± 0.012, 5.95 ± 0.021, and 6.93 ± 0.034 respectively, from the absorption spectra collected from the titrations of Am(iii) with L(I) at 25 °C in 1 M NaNO3. Single crystals of AmL(ClO4)3 have been grown from a HClO4 solution containing Am(3+) and L(I). The crystal structure of AmL(ClO4)3 shows that Am(iii) is coordinated by nine oxygen atoms from three L(I) ligands. The deconvoluted UV-Vis absorption spectrum of [AmL](3+) in aqueous solution is nearly identical to the diffusion reflectance spectrum of AmL(ClO4)3 in the solid state, indicating that the coordination geometry of the complexes is nearly the same. In addition, to provide parallels to solvent exaction, the extracted Am(iii) complex with N,N'-dimethyl-N,N'-dioctyl-3-oxa-glutaramide (DMDOOGA, L(II)) is also prepared and studied using spectrophotometry. The similarity in UV-Vis absorption of the extracted complex of Am(iii) with L(II) and [AmL](3+) suggests that the Am(iii) ion is also coordinated by three tridentate L(II) ligands existing as [AmL](3+) in the organic phase of solvent extraction.
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Separation of trivalent actinides (An(III)) from trivalent lanthanides (Ln(III)) is a challenging task because of the nearly identical chemical properties of these groups. Diethylenetriaminepentaacetate (DTPA), a key reagent used in the TALSPEAK process that effectively separates An(III) from Ln(III), is believed to play a critical role in the An(III)/Ln(III) separation. However, the underlying principles for the separation based on the difference in the complexation of DTPA with An(III) and Ln(III) remain unclear. In this work, the complexation of DTPA with Cm(III) at 10-70 °C was investigated by spectrophotometry, luminescence spectroscopy, and microcalorimetry, in conjunction with computational methods. The binding strength, the enthalpy of complexation, the coordination modes, and the luminescence properties are compared between the Cm(III)-DTPA and Eu(III)-DTPA systems. The experimental and computational data demonstrated that the difference between Cm(III) and Eu(III) in the binding strength with DTPA can be attributed to the stronger covalence bonding between Cm(III) and the nitrogen donors of DTPA.