Kinetic features of solvent extraction by N,O-donor ligands of f-elements: a comparative study of diamides based on 1,10-phenanthroline and 2,2'-bipyridine.

A variant of microfluidic setup design for the study of extraction kinetics has been proposed. Mass transfer constants for Am(III) and Eu(III) and observed rate constants were obtained for N-,O-donor ligands featuring phenanthroline and bipyridyl cores. The possibility of determining rate constants for cations independently of each other makes it possible to observe the kinetic effect of separation. The extraction rate was found to be lower for the bipyridyl ligand, compared to phenanthroline. The values of the rotation barriers for the ligands were calculated using the DFT method. The values correlate with the obtained low extraction rate for the bipyridyl ligand. Also, crystallographic data showing anti-conformation for the bipyridyl ligand align with the kinetic data. Surface tension was also determined for the systems with the studied ligands. It is shown that at equal ligand concentrations, the value of surface tension agrees with the extraction rate. Furthermore, it is shown that for the bipyridyl ligand, prior contact of the organic phase with nitric acid significantly affects the surface tension.

Influence of Diluent on Extraction Parameters of Systems for Separation Am(III) and Ln(III) Based on 1,10-Phenanthroline-2,9-Diamide.

A systematic study of extraction systems for the separation of f-elements using the tetradentate N,O-donor diamide of 1,10-phenanthroline-2,9-dicarboxylic acid (L) in various molecular and ionic solvents was performed. It was demonstrated that the nature of a diluent has a significant impact on solvent extraction of Am(III) and Ln(III) and the stoichiometry of formed complexes with f-elements. The mechanism of complexation and forms of complexes in different diluents were investigated by radiometric methods, UV-vis titration, and XRD.

4-Oxo-7-fluoro-1,10-phenanthroline-2,9-diamides: Synthesis, Structural Features, Lanthanide Complexes, and Am(III)/Ln(III) Solvent Extraction.

A highly efficient synthetic approach was developed for the synthesis of unsymmetrical 1,10-phenanthroline-2,9-diamides with two different substituents in the fourth and seventh positions of the phenanthroline core. The structures of these ligands were confirmed using various spectral methods including 2D-NMR and X-ray analysis. Quantum chemical calculations supported the presence of tautomeric forms of these ligands. Furthermore, it was discovered that these compounds exhibit polydentate ligand behavior toward lanthanide nitrates. The structural characteristics of the complexes formed between these ligands and lanthanide nitrates were investigated both in the solid state and in solution. To further understand the binding properties of these novel unsymmetrical ligands, the binding constants for potential complexes were quantitatively measured by using UV-vis spectrophotometric titration. This allowed for a comprehensive analysis of the binding affinity and stability of these complexes. Extraction experiments of f-elements were performed for symmetrical and unsymmetrical diamides. Overall, this study presents significant advancement in the synthesis and characterization of unsymmetrical 1,10-phenanthroline-2,9-diamides and provides valuable insights into their potential applications as polydentate ligands for lanthanide nitrates.

Solvation-Anionic Exchange Mechanism of Solvent Extraction: Enhanced U(VI) Uptake by Tetradentate Phenanthroline Ligands.

Phenanthroline diamides (L) demonstrated a unique ability to extract uranium from nitric acid solutions into a polar organic solvent forming complexes of 1:2 stoichiometry as tight ion pairs {[UO2LNO3]+[UO2(NO3)3]-} by a novel extraction mechanism, which is a combination of two already well-known mechanisms: solvation and ion-pair anion exchange. A UV-vis study was used to confirm the formation of such complexes directly in the organic phase. Moreover, chemical synthesis and single crystal growth were performed to confirm unambiguously the structure of the complexes in the solid state.

Pyrrolidine-Derived Phenanthroline Diamides: An Influence of Fluorine Atoms on the Coordination of Lu(III) and Some Other f-Elements and Their Solvent Extraction.

Three pyrrolidine-derived phenanthroline diamides were studied as ligands for lutetium trinitrate. The structural features of the complexes have been studied using various spectral methods and X-ray. The presence of halogen atoms in the structure of phenanthroline ligands has a significant impact on both the coordination number of lutetium and the number of solvate water molecules in the internal coordination sphere. The stability constants of complexes with La(NO3)3, Nd(NO3)3, Eu(NO3)3, and Lu(NO3)3 were measured to demonstrate higher efficiency of fluorinated ligands. NMR titration was performed for this ligand, and it was found that complexation with lutetium leads to an approximately 13 ppm shift of the corresponding signal in the 19F NMR spectrum. The possibility of formation of a polymeric oxo-complex of this ligand with lutetium nitrate was demonstrated. Experiments on the liquid-liquid extraction of Am(III) and Ln(III) nitrates were carried out to demonstrate advantageous features of chlorinated and fluorinated pyrrolidine diamides.

First 24-Membered Macrocyclic 1,10-Phenanthroline-2,9-Diamides-An Efficient Switch from Acidic to Alkaline Extraction of f-Elements.

A reaction of acyl chlorides derived from 1,10-phenanthroline-2,9-dicarboxylic acids with piperazine allows the preparation of the corresponding 24-membered macrocycles in good yield. The structural and spectral properties of these new macrocyclic ligands were thoroughly investigated, revealing promising coordination properties towards f-elements (Am, Eu). It was shown that the prepared ligands can be used for selective extraction of Am(III) from alkaline-carbonate media in presence of Eu(III) with an SFAm/Eu up to 40. Their extraction efficiency is higher than calixarene-type extraction of the Am(III) and Eu(III) pair. Composition of macrocycle-metal complex with Eu(III) was investigated by luminescence and UV-vis spectroscopy. The possibility of such ligands to form complexes of L:Eu = 1:2 stoichiometry is revealed.

Competing Routes in the Extraction of Lanthanide Nitrates by 1,10-Phenanthroline-2,9-diamides: An Impact of Structure of Complexes on the Extraction.

The fact of the fracture of the extraction curve of lanthanides by 1,10-phenanthroline-2,9-diamides is explained in terms of the structure of complexes, solvent extraction data and quantum chemical calculations. The solvent extraction proceeds in two competing directions: in the form of neutral complexes LLn(NO3)3 and in the form of tight ion pairs {[LLn(NO3)2 H2O]+ (NO3-).

First Trifluoromethylated Phenanthrolinediamides: Synthesis, Structure, Stereodynamics and Complexation with Ln(III).

The first examples of 1,10-phenanthroline-2,9-diamides bearing CF3-groups on the side amide substituents were synthesized. Due to stereoisomerism and amide rotation, such complexes have complicated behavior in solutions. Using advanced NMR techniques and X-ray analysis, their structures were completely elucidated. The possibility of the formation of complex compounds with lanthanoids nitrates was shown, and the constants of their stability are quantified. The results obtained are explained in terms of quantum-chemical calculations.

PyRad: A software shell for simulating radiolysis with Qball package.

The assessment of the radiolytic stability of media is an important task in the fields of nuclear power engineering and radiochemistry. Such studies must be carried out in special laboratory conditions with the use of sources of ionizing radiation, which may increase personal doses of the staff. In addition, difficulties arise in studying the products of irradiated media. While it is impossible to abandon experiments to obtain reliable results in this area, computational methods of quantum chemistry can reduce the number of experiments and help understand the mechanisms of the reactions that occur during radiolysis. Here we would like to present a software shell of the Qb@ll program performing time-dependent density functional theory simulations of the radiolysis process.

Way to Enforce Selectivity via Steric Hindrance: Improvement of Am(III)/Eu(III) Solvent Extraction by Loaded Diphosphonic Acid Esters.

Hybrid donor extractants are a promising class of compounds for the separation of trivalent actinides and lanthanides. Here, we investigated a series of sterically loaded diphosphonate ligands based on bipyridine (BiPy-PO-iPr and BiPy-PO-cHex) and phenanthroline (Phen-PO-iPr and Phen-PO-cHex). We studied their complex formation with nitrates of trivalent f-elements in solvent extraction systems (Am and Eu) and homogeneous acetonitrile solutions (Nd, Eu, and Lu). Phenanthroline extractants demonstrated the highest efficiency and selectivity [SF(Am/Eu) up to 14] toward Am(III) extraction from nitric acid solutions among all of the studied diphosphonates of N-heterocycles. The binding constants established by UV-vis titration also indicated stronger binding of sterically impaired diphosphonates compared to the primary substituted diphosphonates. NMR titration and slope analysis during solvent extraction showed the formation of 2:1 complexes at high concentrations (>10-3 mol/L) for phenanthroline-based ligands. According to UV-vis titrations at low concentrations (10-5-10-6 mol/L), the phenanthroline-based ligands formed 1:1 complexes. Bipyridine-based ligands formed 1:1 complexes regardless of the ligand concentration. Luminescence titrations revealed that the quantum yields of the complexes with Eu(III) were 81 ± 8% (BiPy-PO-iPr) and 93 ± 9% (Phen-PO-iPr). Single crystals of the structures [Lu(µ2,κ4-(iPrO)2P(O)Phen(O)2(OiPr))(NO3)2]2 and Eu(Phen-PO-iPr)(NO3)3 were obtained by chemical synthesis with the Phen-PO-iPr ligand. X-ray diffraction studies revealed a closer contact of the f-element with the aromatic N atoms in the case of sterically loaded P═O ligands compared with sterically deficient ligands. Density functional theory calculations allowed us to rationalize the observed selectivity trends in terms of the bond length, Mayer bond order, and preorganization energy.

A search of a quantitative quantum-chemical approach for radiolytic stability prediction.

Radiolytic stability is one of the main requirements of the substances that are used in the chemistry of nuclear cycle or in the radiopharmaceutical chemistry. Herein, we proposed an approach for the prediction of radiolytic stability by the estimation of the molecular reactivity. The DFT calculations of the atom-wise reactivity descriptor were made for a number of organic molecules. The theoretical simulations were validated by the experimental data. We irradiated the molecules by gamma-radiation and studied the products of radiolysis and changes in the molecular concentration by HPLC-MS analysis. The importance of the inclusion of the conformational influence and the steric accessibility in the calculation is shown in this study. We presente a new chemical reactivity descriptor (CRD) and recommend using CRD as the new quantitative estimation of the reactivity. A good correlation between the CRD and the constants of the radiolysis was obtained.

Simple Automatized Tool for Exchange-Correlation Functional Fitting.

Density functional theory is, perhaps, the most popular and convenient tool in computational chemistry. DFT methods allow solving different chemical tasks with a good balance of accuracy and computational time. Dozens of existing functionals cover a majority of possible systems, and the development of new ones is still ongoing. However, despite the existence of different databases with accurate quantum-chemical data, the functional design remains a complicated and time-demanding task. Here, we propose a novel approach for simplifying and accelerating this process. The approach is based on a Bayesian search with stochastic sub-sampling that allows considering the 'history' of fitting steps, reduces the computational time for each step, and avoids overfitting to training data. Besides the general testing of the approach efficiency, we also showed an example of training specialized DFT functionals, outperforming the popular ones. The approach is presented as a free code with built-in analysis tools. Using the code with an appropriate reference database can help in constructing a DFT approximation for a highly specialized task.

The electronic structure and the nature of the chemical bond in CeO2.

The X-ray photoelectron spectral structure of CeO2 valence electrons in the binding energy range of 0 to ∼50 eV was analyzed. The core-electron spectral structure parameters and the results of relativistic discrete-variational calculations of CeO8 and Ce63O216 clusters were taken into account. Comparison of the valence and the core-electron spectral structures showed that the formation of the inner (IVMO) and the outer (OVMO) valence molecular orbitals contributes to the spectral structure more than the many-body processes. The Ce 4f electrons were established to participate directly in chemical bond formation in CeO2 losing partially their f character. They were found to be localized mostly within the outer valence band. The Ce 5p atomic orbitals were shown to participate in the formation of both the inner and the outer valence molecular orbitals (MOs). A large part in the IVMO formation is taken by the filled Ce 5p1/2, 5p3/2 and O 2s atomic shells, while the Ce 5s electrons participate weakly in the chemical bond formation. The composition and the sequent order of the molecular orbitals in the binding energy range of 0 to ∼50 eV were established. A quantitative scheme for the molecular orbitals of CeO2 was built. This scheme is fundamental for understanding the nature of chemical bonding and also for the interpretation of other X-ray spectra of CeO2. Evaluations revealed that the IVMO electrons weaken the chemical bond formed by the OVMO electrons by 37%.

Predicting Magnetoelectric Coupling in Layered and Graded Composites.

Magnetoelectric (ME) interaction in magnetostrictive-piezoelectric multiferroic structures consists in inducing the electric field across the structure in an applied magnetic field and is a product property of magnetostriction and piezoelectricity in components. ME voltage coefficient that is the ratio of induced electric field to applied magnetic field is the key parameter of ME coupling strength. It has been known that the ME coupling strength is dictated by the product of the piezoelectric and piezomagnetic coefficients of initial phases. As a result, using the laminates with graded piezoelectric and piezomagnetic parameters are a new pathway to the increase in the ME coupling strength. Recently developed models predict stronger ME interactions in composites based on graded components compared to homogeneous ones. We discuss predicting the ME coupling strength for layered structures of homogeneous and compositionally graded magnetostrictive and piezoelectric components based on the graphs of ME voltage coefficients against composite parameters. For obtaining the graphs, we developed equations for ME output in applied magnetic field for possible modes of operation and layered structure configurations. In particular, our studies have been performed on low-frequency ME coupling, enhanced ME effect in electromechanical resonance (EMR) region for longitudinal and bending modes. Additionally, ME coupling at magnetic resonance in magnetostrictive component and at overlapping the EMR and magnetic resonance is investigated. We considered symmetric trilayers and asymmetric bilayers of magnetostrictive and piezoelectric components and multilayered structures based on compositionally stepped initial components.

Sensitivity Enhancement in Magnetic Sensors Based on Ferroelectric-Bimorphs and Multiferroic Composites.

Multiferroic composites with ferromagnetic and ferroelectric phases have been studied in recent years for use as sensors of AC and DC magnetic fields. Their operation is based on magneto-electric (ME) coupling between the electric and magnetic subsystems and is mediated by mechanical strain. Such sensors for AC magnetic fields require a bias magnetic field to achieve pT-sensitivity. Novel magnetic sensors with a permanent magnet proof mass, either on a ferroelectric bimorph or a ferromagnetic-ferroelectric composite, are discussed. In both types, the interaction between the applied AC magnetic field and remnant magnetization of the magnet results in a mechanical strain and a voltage response in the ferroelectric. Our studies have been performed on sensors with a Nd-Fe-B permanent magnet proof mass on (i) a bimorph of oppositely-poled lead zirconate titanate (PZT) platelets and (ii) a layered multiferroic composite of PZT-Metglas-Ni. The sensors have been characterized in terms of sensitivity and equivalent magnetic noise N. Noise N in both type of sensors is on the order of 200 pT/√Hz at 1 Hz, a factor of 10 improvement compared to multiferroic sensors without a proof mass. When the AC magnetic field is applied at the bending resonance for the bimorph, the measured N ≈ 700 pT/√Hz. We discuss models based on magneto-electro-mechanical coupling at low frequency and bending resonance in the sensors and theoretical estimates of ME voltage coefficients are in very good agreement with the data.

Concept of a multichannel spin-resolving electron analyzer based on Mott scattering.

The concept of a multichannel electron spin detector based on optical imaging principles and Mott scattering (iMott) is presented. A multichannel electron image produced by a standard angle-resolving (photo) electron analyzer or microscope is re-imaged by an electrostatic lens at an accelerating voltage of 40 kV onto the Au target. Quasi-elastic electrons bearing spin asymmetry of the Mott scattering are imaged by magnetic lenses onto position-sensitive electron CCDs whose differential signals yield the multichannel spin asymmetry image. Fundamental advantages of this concept include acceptance of inherently divergent electron sources from the electron analyzer or microscope focal plane as well as small aberrations achieved by virtue of high accelerating voltages, as demonstrated by extensive ray-tracing analysis. The efficiency gain compared with the single-channel Mott detector can be a factor of more than 10(4) which opens new prospects of spin-resolved spectroscopies in application not only to standard bulk and surface systems (Rashba effect, topological insulators, etc.) but also to buried heterostructures. The simultaneous spin detection combined with fast CCD readout enables efficient use of the iMott detectors at X-ray free-electron laser facilities.

Effect of fish and krill oil supplementation on glucose tolerance in rabbits with experimentally induced obesity.

PURPOSE: This study was conducted to investigate the effect of fish oil (FO) and krill oil (KO) supplementation on glucose tolerance in obese New Zealand white rabbits. METHODS: The experiments were carried out with 24 male rabbits randomly divided into four groups: KO-castrated, treated with KO; FO-castrated, treated with FO; C-castrated, non-treated; NC-non-castrated, non-treated. At the end of treatment period (2 months), an intravenous glucose tolerance test (IVGTT) was performed in all rabbits. RESULTS: Fasting blood glucose concentrations in FO and KO animals were significantly lower than in group C. The blood glucose concentrations in FO- and KO-treated animals returned to initial values after 30 and 60 min of IVGTT, respectively. In liver, carnitine palmitoyltransferase 2 (Cpt2) and 3-hydroxy-3-methyl-glutaryl-CoA synthase 2 (Hmgcs2) genes were significantly increased in FO-fed rabbits compared with the C group. Acetyl-CoA carboxylase alpha (Acaca) expression was significantly reduced in both KO- and FO-fed rabbits. In skeletal muscle, Hmgcs2 and Cd36 were significantly higher in KO-fed rabbits compared with the C group. Acaca expression was significantly lower in KO- and FO-fed rabbits compared with the C group. CONCLUSION: The present results indicate that FO and KO supplementation decreases fasting blood glucose and improves glucose tolerance in obese New Zealand white rabbits. This could be ascribed to the ameliorated insulin sensitivity and insulin secretion and modified gene expressions of some key enzymes involved in ß-oxidation and lipogenesis in liver and skeletal muscle.

Clinical pharmacology in Russia-historical development and current state.

Clinical pharmacology in Russia has long history and is currently active, but rather unrecognized internationally. It is governmentally approved as a teaching/scientific specialty since 1983 and as a medical specialty since 1997. Courses of clinical pharmacology are included in the undergraduate curricula in the 5th and/or 6th year of education at all medical schools in the Russian Federation. Postgraduate education includes initial specialization in internal medicine with further residency in clinical pharmacology. Governmental legislation recommends that every healthcare institution has either a department or a single position of clinical pharmacologist. Major routine duties include information about and monitoring of medication use, consultations in difficult clinical situations, pharmacogenetic counseling, therapeutic drug monitoring, pharmacovigilance, and participation in drug and therapeutics (formulary) committees. There are official experts in clinical pharmacology in Russia responsible for coordinating relevant legislative issues. The chief expert clinical pharmacologist represents the discipline directly at the Ministry of Health. Research in clinical pharmacology in Russia is extensive and variable, but only some of it is published internationally. Russia is a participant of international societies of clinical pharmacology and therapeutics and collaboration is actively ongoing. There are still certain problems related to the development of the discipline in Russia-some healthcare institutions do not see the need for clinical pharmacology. However, the number of clinical pharmacologists in Russia is increasing as well as their role in physicians' education, national healthcare, and research.

Level, distribution and sources of Np, Pu and Am isotopes in Peter the Great Bay of Japan sea.

Transuranium elements such as Np, Pu and Am, are considered to be the most important radioactive elements in view of their biological toxicity and environmental impact. Concentrations of 237Np, Pu isotopes and 241Am in two sediment cores collected from Peter the Great Bay of Japan Sea were determined using radiochemical separation combined with inductively coupled plasma mass spectrometry (ICP-MS) measurement. The 239,240Pu and 241Am concentrations in all sediment samples range from 0.01 Bq/kg to 2.02 Bq/kg and from 0.01 Bq/kg to 1.11 Bq/kg, respectively, which are comparable to reported values in the investigated area. The average atomic ratios of 240Pu/239Pu (0.20 ± 0.02 and 0.21 ± 0.01) and 241Am/239+240Pu activity ratios (3.32 ± 2.76 and 0.45 ± 0.17) in the two sediment cores indicated that the sources of Pu and Am in this area are global fallout and the Pacific Proving Grounds through the movement of prevailing ocean currents, and no measurable release of Np, Pu and Am from the local K-431 nuclear submarine incident was observed. The extremely low 237Np/239Pu atomic ratios ((2.0-2.5) × 10-4) in this area are mainly attributed to the discrepancy of their different chemical behaviors in the ocean due to the relatively higher solubility of 237Np compared to particle active plutonium isotopes. It was estimated using two end members model that 23% ± 6% of transuranium radionuclides originated from the Pacific Proving Grounds tests, and the rest (ca. 77%) from global fallout.

Laser-induced fluorescence of uranyl complexes in aqueous solutions: the role of diffusion-controlled excited states annihilation.

We present the analysis of diffusion-controlled annihilation of excited U(VI) complexes in aqueous media that leads to appearance of rapid non-exponential fluorescence decay. We show that under typical experimental conditions the impact of annihilation processes can't be neglected when determining U(VI) complexes fluorescence lifetimes: at excitation intensities between 10(6) W/cm(2) and 10(8) W/cm(2), the rate of excited states deactivation increases, and then an opposite trend is observed. The latter can be interpreted as the consequence of optical breakdown in water.