RESUMO
The thermodynamics of Th(iv) complexes with N,N,N',N'-tetramethyl-2,2'-bipyridine-6,6'-dicarboxamide (TMBiPDA) and N,N,N',N'-tetramethyl-1,10-phenanthroline-2,9-dicarboxamide (TMPhenDA) in CH3OH/10%(v)H2O (CH3OH : H2O = 9 : 1 by volume) were determined by spectrophotometry and calorimetry. The ligand TMBiPDA/TMPhenDA coordinates with the central Th atom by the tetradentate (O-N-N-O) mode, which is validated by 1H NMR in solution and crystallography in the solid. The single crystal X-ray diffraction data show that ten-coordinated thorium coordinates with two ligand molecules and two solvent molecules (water or methanol). Both ThL and ThL2 complexes (L = TMPhenDA or TMBiPDA) were detected in solution. In thermodynamics, the formation of all complexes is driven by both enthalpy and entropy. In a comparison, enthalpy is more favorable to the formation of TMBiPDA complexes, while entropy is more favorable to the formation of TMPhenDA complexes; the entropy advantages of the TMPhenDA complexes override the enthalpy advantages of the corresponding TMBiPDA complexes, giving the TMPhenDA complexes higher stability constants than the TMBiPDA complexes. In crystallography, ligand distortions occur in ThL2 complexes, and TMBiDA distorts more than TMPhenDA does; the Th-O and Th-N bonds involving TMBiPDA are slightly shorter than those involving TMPhenDA.
RESUMO
N-(2-Hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid (HEDTA, denoted as H3L) is a strong chelating ligand that is widely used in the separation of f elements as relevant to the nuclear fuel cycle. There is much to be known about the structure and composition of the coordination sphere of the complexes of HEDTA with lanthanides. The complexation of HEDTA with light lanthanides (La3+, Nd3+, and Eu3+) was investigated thermodynamically and structurally in aqueous solutions. Potentiometry and microcalorimetry were performed to acquire the complexation constants (25-70 °C) and enthalpies (25 °C), respectively, at I = 1.0 mol·L-1 NaClO4. Coordination modes of the complexes were analyzed by luminescence spectroscopy and NMR spectroscopy. The results indicate that there are two successive Ln3+/HEDTA complexes, LnLaq and Ln2(H-1L)22- (Ln3+ refers to La3+, Nd3+, and Eu3+; H-1L4- refers to deprotonation of the hydroxyl group) during titration. The hydroxyl group of HEDTA is coordinated in the Ln3+/HEDTA complex. The dinuclear Ln2(H-1L)22- complex is present as a carboxyl-bridged centrosymmetric dimer, and two carboxyl groups in bridging positions are coordinated to two adjacent Ln3+ cations. Complexation of NdLaq is exothermic, while formation of the hydrolytic complex Nd2(H-1L)22- is endothermic. Both NdLaq and Nd2(H-1L)22- complexes are driven by entropic force. These data will help to predict the behavior of lanthanides in the separation process, where HEDTA is used as the aqueous complexant.
RESUMO
The thermodynamics of Nd(III) and Eu(III) complexes with N, N, N', N'-tetramethyl-2,2'-bipyridine-6,6'-dicarboxamide (TMBiPDA) and N, N, N', N'-tetramethyl-1,10-phenanthroline-2,9-dicarboxamide (TMPhenDA) in CH3OH/10%(v)H2O solutions were studied. Stability constants and enthalpies of complexation were determined by absorption spectrophotometry, luminescence, and calorimetry. The stability constants of corresponding lanthanide complexes decrease in the order of TMPhenDA > TMBiPDA, while those of the corresponding ligand complexes with lanthanides decrease in the order of Nd(III) > Eu(III). The stepwise reactions for all 1:1 complexes as well as for the 1:2 Nd(III) complexes are driven by both enthalpy and entropy, while those for the 1:2 Eu(III) complexes are driven by entropy. The stronger affinity of TMPhenDA to Nd(III) and Eu(III) than that of TMBiPDA is predominantly arisen from its high preorganization. The spectra of the complexes in solutions are similar, implying that Nd(III) and Eu(III) coordinate with the two ligands in the same mode, which have been validated by 1H and 13C NMR titrations using La(III) as lanthanide tracer. The luminescence lifetimes of the Eu(III) complexes with TMBiPDA and TMPhenDA were evaluated by TRLFS. Structures of Nd(III)/TMPhenDA and Eu(III)/TMPhenDA complexes, identified by single-crystal X-ray diffractometry, show that ligand coordinates to metal in a tetradentate mode via two aromatic N-donors and two amide O-donors, and the central cation (Nd(III) or Eu(III)) is 10-coordinated by two whole TMPhenDA and two solvent (water or methanol) molecules. The M-O bond distances are almost identical, while the Nd-N bond distance is shorter than the Eu-O bond.
RESUMO
The stability constants (log ß) of 1:1 uranyl complexes with three N,O-mixed donor ligands (L = 2,2'-dipyridyl-6,6'-dicarboxylate, 3,3'-dimethyl-2,2'-bipyridine-6,6'-dicarboxylate, and 1,10-phenanthroline-2,9-dicarboxylate, denoted as BiPDA, DmBiPDA, and PhenDA, respectively) in aqueous and DMSO/20%(v)H2O solutions were determined by spectrophotometry in 0.1 M tetraethylammonium perchlorate. The effects of ligand preorganization, steric hindrance, and solvation on the binding strength of U(VI) with the three ligands were discussed. In aqueous solution, PhenDA forms stronger complexes with U(VI) than BiPDA due to its well-preorganized structure. In DMSO/20%(v)H2O solution, in contrast, the strong solvation effect of DMSO on the ligands reduces the energy gap between the trans- and cis-conformations of BiPDA, resulting in log ß(UO2(BiPDA)) > log ß(UO2(PhenDA)). The steric hindrance of methyl groups on DmBiPDA makes the complex UO2(DmBiPDA) of the lowest stability in both aqueous and DMSO/20%(v)H2O solutions. Single-crystal structural data of U(VI) complexes with the three ligands indicate that the ligand coordinates with UO22+ via aromatic nitrogen atoms and carboxylate oxygen atoms. There is no clear correlation between the trend of the stability constants in solutions and the U-N/O bond lengths of the three crystal complexes. Nevertheless, DmBiPDA coordinates to UO22+ in a high-strain fashion as a result of the steric hindrance of methyl groups while BiPDA in a low-strain fashion, which is in accordance with the relative complexation strength of the two respective complexes. The results from this work help us understand the effect of ligand preorganization and solvation on the binding strength of actinides with multidentate N,O-mixed ligands in solid and solutions, which is of importance in designing ligands for the partitioning of actinides from nuclear wastes.
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Positive charged porphyrins have long been regarded as effective biocidal agents, however neutral porphyrins have rarely been studied in their ability photoinactivating microbials, and the structure-activity relationship such as correlation of electronic effect and biocidal activity of porphyrins still remains unclear. Herein, four neutral porphyrins with various electronic effects were selected to undergo light-induced biocidal processes. It turned out that the TPPOH and TPPNH2 with electron-donating groups NH2 and OH, respectively, exhibited much more powerful light-induced biocidal activities against E. coli and S. aureus than TPP and TPPNO2 with electron-withdrawing group NO2. This phenomenon suggested that neutral porphyrins may be treated as a new class of biocidal agents and functional groups with various electronic effects on porphyrins can dramatically affect porphyrins' light-induced biocidal activities. Mechanistic studies demonstrate that despite a better light-induced antibacterial ability of TPPOH, its singlet oxygen generation efficacy is a little lower than that of TPPNH2, together with charge characteristics and lipophilicity, it is clear that (1) the oxidative species singlet oxygen and ROS played the key role in the photo-activated antimicrobial processes of porphyrins, and (2) higher singlet oxygen or ROS yields of TPPOH and TPPNH2 may originate from their structural characteristics, namely electron-donating groups OH or NH2, and (3) a synergistic effect of all other factors including the electrostatic and hydrophobic effects must involve in the process and cooperatively determine their biocidal activities.
Assuntos
Antibacterianos/farmacologia , Escherichia coli/efeitos dos fármacos , Luz , Fármacos Fotossensibilizantes/farmacologia , Porfirinas/química , Staphylococcus aureus/efeitos dos fármacos , Antibacterianos/química , Escherichia coli/efeitos da radiação , Lipossomos/química , Lipossomos/metabolismo , Fármacos Fotossensibilizantes/química , Porfirinas/farmacologia , Oxigênio Singlete/química , Oxigênio Singlete/metabolismo , Staphylococcus aureus/efeitos da radiaçãoRESUMO
N-(2-Hydroxyethyl)ethylenediamine- N, N', N'-triacetic acid (HEDTA, denoted as H3L in this work, and the three dissociable protons represent those of the three carboxylic groups) is a strong chelating ligand and plays an important role in the treatment and disposal of nuclear wastes as well as separation sciences of f-elements. In this work, the complexation of HEDTA with U(VI) was studied thermodynamically and structurally in aqueous solutions. Potentiometry and microcalorimetry were used to measure the complexation constants (298-343 K) and enthalpies (298 K), respectively, at I = 1.0 mol·L-1 NaClO4. Thermodynamic studies identified three 1:1 U(VI)/HEDTA complexes with different degrees of deprotonation, namely, UO2(HL)(aq), UO2L-, and UO2(H-1L)2-, where H-1 represents the deprotonation of the hydroxyl group. The results indicated that all three complexation reactions are endothermic and driven by entropy only. Coordination modes of the three complexes were investigated by NMR and extended X-ray absorption fine structure spectroscopies. In the UO2(HL)(aq) complex, HEDTA holds a tridentate mode, and the coordination occurs to the end of the ethylenediamine backbone. Two oxygens of the two carboxylic groups and one nitrogen of the amine group participate in the coordination. In both UO2L- and UO2(H-1L)2-, HEDTA holds a tetradentate mode and coordinates to U(VI) along the side of the ethylenediamine backbone. The difference is that in the UO2(H-1L)2- complex, the alkoxide form of the HEDTA hydroxyl group directly binds to the U(VI) atom, forming a highly strong chelation.
RESUMO
A number of oligo-p-phenylene-ethynylenes (OPEs) have exhibited excellent biocidal activity against both Gram-negative and Gram-positive bacteria. Although cell death may occur in the dark, these biocidal compounds are far more effective in the light as a result of their abilities to generate cell-damaging reactive oxygen species. In this study, the interactions of four OPEs with Escherichia coli and Staphylococcus aureus have been investigated. Compared to the OPEs with quaternary ammonium salts (Q-OPE), the OPEs with tertiary ammonium (T-OPE) effectively kill many more bacterial cells under light irradiation, presumably by severe perturbations of the bacterial cell wall and cytoplasmic membrane. According to the findings from this study, such intriguing light-induced antibacterial behavior is probably attributed to the combination of bacterial membrane disruption and the interfacial or intracellular generation of singlet oxygen or other ROS. Singlet oxygen was proved to be formed from irradiation of the OPEs, whereas the varying cell membrane perturbation abilities of OPEs enhance antibacterial activity.
Assuntos
Antibacterianos/farmacologia , Alcinos , Escherichia coli , Éteres , Viabilidade Microbiana , Oxigênio Singlete , Staphylococcus aureusRESUMO
A simple and convenient method for radiochemical separation 89Zr with no harmful substance was explored. The separated 89Zr was found to be [89Zr]Zr-chloride, and the recovery of the radioactivity was 85%±3% with high radionuclidic purity (99.99%). The yields of 89Zr via the reaction of (p, n) or (d, 2n) on Y target were also evaluated on CS-30 cyclotron, indicating the latter was more favorable for the production of 89Zr with a yield of 58±4 MBq/µA·h.
RESUMO
Glyphosate [N-(phosphonomethyl)glycine] has been described as the ideal herbicide because of its unique properties. There is some conflicting information concerning the structures and conformations involved in the protonation process of glyphosate. Protonation may influence the chemical and physical properties of glyphosate, modifying its structure and the chemical processes in which it is involved. To better understand the species in solution associated with changes in pH, thermodynamic study (potentiometry, calorimetry and NMR spectroscopy) about the protonation pathway of glyphosate is performed. Experimental results confirmed that the order of successive protonation sites of totally deprotonated glyphosate is phosphonate oxygen, amino nitrogen, and finally carboxylate oxygen. This trend is in agreement with the most recent theoretical work in the literature on the subject (J. Phys. Chem. A 2015, 119, 5241-5249). The result is important because it confirms that the protonated site of glyphosate in pH range 7-8, is not on the amino but on the phosphonate group instead. This corrected information can improve the understanding of the glyphosate chemical and biochemical action.
Assuntos
Calorimetria/métodos , Glicina/análogos & derivados , Herbicidas/química , Espectroscopia de Ressonância Magnética/métodos , Potenciometria/métodos , Termodinâmica , Glicina/química , Prótons , Soluções/química , Água/química , GlifosatoRESUMO
The complexation of lanthanides (Nd(3+) and Eu(3+)) with glutaroimide-dioxime (H2L), a cyclic imide dioxime ligand that has been found to form stable complexes with actinides (UO2(2+) and NpO2(+)) and transition metal ions (Fe(3+), Cu(2+), etc.), was studied by potentiometry, absorption spectrophotometry, luminescence spectroscopy, and microcalorimetry. Lanthanides form three successive complexes, M(HL)(2+), M(HL)L, and M(HL)2(+) (where M stands for Nd(3+)/Eu(3+) and HL(-) stands for the singly deprotonated ligand). The enthalpies of complexation, determined by microcalorimetry, show that the formation of these complexes is exothermic. The stability constants of Ln(3+)/H2L complexes are several orders of magnitude lower than that of the corresponding Fe(3+)/H2L complexes but are comparable with that of UO2(2+)/H2L complexes. A structure of Eu(3+)/H2L complex, identified by single-crystal X-ray diffractometry, shows that the ligand coordinates to Eu(3+) in a tridentate mode, via the two oxygen atoms of the oxime group and the nitrogen atom of the imide group. The relocation of protons of the oxime groups (-CHâN-OH) from the oxygen to the nitrogen atom, and the deprotonation of the imide group (-CH-NH-CH-) result in a conjugated system with delocalized electron density on the ligand (-O-N-C-N-C-N-O-) that forms strong complexes with the lanthanide ions.
RESUMO
Thermodynamics of the U(VI) complexation with benzoic acid (HL) was studied by spectrophotometry at varied temperatures (298-353 K) with constant ionic strength (1.05 mol kg(-1) NaClO4). Two U(VI) benzoate complexes, UO2L(+) and UO2(OH)L(aq), were identified and their formation constants determined. The formation of both complexes is endothermic and driven exclusively by entropy. Two types of U(VI)/benzoate complex crystals were synthesized from aqueous solutions at different pH and ligand/metal ratios. Their structures were determined by single-crystal X-ray diffractometry. One structure is a 1 : 3 U(VI) benzoate complex (Na[UO2(C7H5O2)3]·2H2O), each benzoate holding a bidentate coordination mode to U(VI) in the equatorial plane of UO2(2+). The other is a U(VI) hydroxobenzoate complex with unique µ3-OH bridging ([(UO2)2(C7H5O2)2(µ3-OH)2]·4H2O). In the structure, each UO2(2+) ion holds five coordination oxygens in its equatorial plane, two carboxylate oxygens from two benzoate ligands and three oxygens from three µ3-OH groups.
RESUMO
Extraction complexes of Eu(III), Tb(III), Tm(III), and Am(III) with three 1,10-phenanthroline-type ligands have been studied, primarily using density functional theory (DFT). The same accuracies and optimized structural geometries were obtained whether optimization of the [ML2(NO3)](2+) complexes was performed at the B3LYP/6-31G(d)/RECP or the MP2/6-31G(d)/RECP level of theory. Calculations carried out at the B3LYP/6-311G(d, p)/RECP level of theory indicated that solvation does not favor the formation of these complexes. Moreover, the ΔGg and ΔGsolv values for the reactions leading to the formation of [LnL2(NO3)](2+) complexes were seen to decrease with increasing atomic number of the lanthanide (from Eu to Tb to Tm). In addition, when a strongly hydrophobic benzo[e][1,2,4]triazine group was created in each ligand, ligand selectivity for actinides/lanthanides in acidic media improved. Even greater ligand selectivity for actinides/lanthanides in acidic media was obtained when a 5,6-diphenyl-1,2,4-triazine group was created in each ligand instead of a benzo[e][1,2,4]triazine group. Vibrational analysis and NMR spectroscopic analysis were also performed on all of the studied ligands and the metal complexes that included them. Further in-depth investigations should be undertaken in this field.
Assuntos
Amerício/química , Complexos de Coordenação/química , Európio/química , Fenantrolinas/química , Térbio/química , Túlio/química , Interações Hidrofóbicas e Hidrofílicas , Cinética , Ligantes , Modelos Moleculares , Teoria Quântica , Termodinâmica , Triazinas/químicaRESUMO
Complexation of Am(III), Nd(III), and Eu(III) with a new heterocyclic nitrogen-donor ligand, 2,9-di(quinazolin-2-yl)-1,10-phenanthroline (denoted as BQPhen in this paper), was studied by thermodynamic measurements and theoretical computations. The stability constants of two successive complexes in dimethylformamide, ML(3+) and ML2(3+) where M stands for Nd, Eu, or Am while L stands for the BQPhen ligand, were determined by absorption spectrophotometry. The enthalpy of complexation was determined by microcalorimetry. Results show that BQPhen forms ten times stronger complexes with Am(III) than Eu(III) or Nd(III) under identical conditions, suggesting that BQPhen could be used as an efficient extractant for the separations of trivalent actinides from lanthanides. The higher binding strength of BQPhen towards Am(III) than Nd(III) or Eu(III) is mainly due to the more favourable enthalpy of complexation for Am(III)/BQPhen complexes, implying a higher degree of covalence in the Am(III)/BQPhen complexes than the lanthanide(III)/BQPhen complexes. The thermodynamic trend was corroborated with computational results and validated by solvent extraction experiments that demonstrated BQPhen preferably extracted Am(III) more than Eu(III), with a separation factor of about 10. Discussions have been made to compare BQPhen with other phenanthroline derivatives such as CyMe4-BTPhen, a bis-triazine-phenanthroline derivative that was reported in the literature. Data suggest that, under identical conditions, BQPhen would form stronger complexes with Am(III), Eu(III), and Nd(III) than CyMe4-BTPhen.
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A radioactive metallofullerene 177LuxLu(3-x)N@C80 was firstly synthesized by means of neutron irradiation on Lu3N@C80. After modification by methoxypolyethylene glycol amine, in vivo investigation on tumor-bearing mice was performed. The results reveal favorable affinity toward tumors, suggesting that the obtained 177LuxLu(3-x)N@C80-PCBPEG could be promising for tumor diagnosis and therapy.
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The reagent Rh-C, incorporating a rhodamine moiety and a coumarin backbone and prepared via click chemistry, was developed as the first single molecule for detecting Cu2+, Fe3+ and Cr3+. Its response to Cu2+ in different solutions is visible to the naked eye and it exhibits a ratiometric fluorescence response to Fe3+ in methanol and Cr3+ in acetonitrile.
Assuntos
Cromo/análise , Colorimetria/métodos , Cobre/análise , Corantes Fluorescentes/química , Ferro/análise , Rodaminas/síntese química , Rodaminas/química , Espectrometria de Fluorescência , Espectrofotometria UltravioletaRESUMO
A tritium beta-voltaic battery using a crystalline silicon convertor composed of (100)Si/SiO2/Si3N4 film degrades remarkably with radiation from a high intensity titanium tritide film. Simulation and experiments were carried out to investigate the main factor causing the degradation. The radiation damages mainly comes from the x-ray emitted from the titanium tritide film and beta particle can relieve the damages. The x-ray radiation induced positive charges in the SiO2 film destroying the output property of the PN diode with the induction of an electric field.
RESUMO
In this paper, the biosorption mechanisms of uranium on an aerobic Bacillus sp. dwc-2, isolated from a potential disposal site for (ultra-) low uraniferous radioactive waste in Southwest China, was explored by transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis, FT-IR spectroscopy, proton induced X-ray emission (PIXE) and enhanced proton backscattering spectrometry (EPBS). The biosorption experiments for uranium were carried out at a low pH (pH 3.0), where the uranium solution speciation is dominated by highly mobile uranyl ions. The bioaccumulation was found to be the potential mechanism involved in uranium biosorption by Bacillus sp. dwc-2, and the bioaccumulated uranium was deposited in the cell interior as needle shaped particles at pH 3.0, as revealed by TEM analysis as well as EDX spectra. FTIR analysis further suggested that the absorbed uranium was bound to amino, phosphate and carboxyl groups of bacterial cells. Additionally, PIXE and EPBS results confirmed that ion-exchange also contributed to the adsorption process of uranium. All the results implied that the biosorption mechanism of uranium on Bacillus sp. is complicated and at least involves bioaccumulation, ion exchange and complexation process.
Assuntos
Bacillus/metabolismo , Urânio/metabolismo , Biodegradação AmbientalRESUMO
Hexagonal tungsten oxide (hex-WO3) has the potential to separate (137)Cs and (90)Sr from nuclear power plant or fission (99)Mo production waste. This study aims to increase the capacity of hex-WO3 to adsorb Sr(2+). Ta-doped hex-WO3 was synthesized by the hydrothermal treatment of sodium tungstate dihydrate and tantalum chloride in concentrated HCl, in the presence of ammonium sulfate. Incorporating Ta into the WO3 framework caused the interlayer spacing to expand, and the band gap to shift to higher energy. The Sr(2+) adsorption capacity of Ta-doped hex-WO3 was significantly higher than that of hex-WO3. Sr(2+) adsorption reached equilibrium within 2h in acidic solution. Maximum Sr(2+) removal occurred at pH 4. Sr(2+) uptake by hex-WO3 was described better by the Freundlich model than by the Langmuir model. Sr(2+) adsorption on hex-WO3 was spontaneous under the studied conditions.
Assuntos
Óxidos/química , Estrôncio/isolamento & purificação , Tantálio/química , Tungstênio/química , Adsorção , Modelos QuímicosRESUMO
To understand intramolecular hydrogen bonding in effecting liquid-liquid extraction behavior of CMPO-calixarenes, three CMPO-modified calix[4]arenes (CMPO-CA) 5a-5c with hydrogen-bonded spacer were designed and synthesized. The impact of spacer rotation that is hindered by introduction of intramolecular hydrogen bonding upon extraction of La(3+), Eu(3+), Yb(3+), Th(4+), and UO2(2+) has been examined. The results show that 5b and 5c containing only one hydrogen bond with a less hindered rotation spacer extract La(3+) more efficiently than 5a containing two hydrogen bonds with a more hindered rotation spacer, demonstrating the importance of local rigidification of spacer in the design of extractants in influencing the coordination environment. The large difference in extractability between La(3+) and Yb(3+) (or Eu(3+)) by 5b (or 5c), and the small difference by 5a, suggests intramolecular hydrogen bonding do exert pronounced influence upon selective extraction of light and heavy lanthanides. Log-log plot analysis indicates a 1:1, 2:1 and 1:1 stoichiometry (ligand/metal) for the extracted complex formed between 5b and La(3+), Th(4+), UO2(2+), respectively. Additionally, their corresponding acyclic analogs 7a-7c exhibit negligible extraction toward these metal ions. These results reveal the possibility of selective extraction via tuning local chelating surroundings of CMPO-CA by aid of intramolecular hydrogen bonding.
Assuntos
Elementos da Série Actinoide/isolamento & purificação , Calixarenos/química , Carbamoil-Fosfato/química , Elementos da Série dos Lantanídeos/isolamento & purificação , Ligação de Hidrogênio , Extração Líquido-LíquidoRESUMO
Simulations on the self-absorption of tritium electrons in titanium tritide films and the energy deposition in a silicon Schottky barrier diode are carried out using the Geant4 radiation transport toolkit. Energy consumed in each part of the Schottky radiovoltaic battery is simulated to give a clue about how to make the battery work better. The power and energy-conversion efficiency of the tritium silicon Schottky radiovoltaic battery in an optimized design are simulated. Good consistency with experiments is obtained.