Прием разнолигандного комплексообразования с хелатирующим тридентатным лигандом диэтилентриамином (DETA) использован для модифицирования строения слоистого координационного полимера на основе пропионата (Prop) лантана. Синтезирован моногидрат пропионата лантана, для которого совокупностью методов анализа установлены состав и кристаллическая структура, также определено строение комплексов пропионатов лантана и никеля с диэтилентриамином. Показано, что исходный [La 2 (H 2 O) 2 Prop 6 ] обладает слоистым строением, в то время как разнолигандный комплекс [La 2 (DETA)Prop 6 ] ⋅ MeCN (MeCN – ацетонитрил) представлен цепочечной структурой. Разработана методика химического осаждения из раствора, позволяющая получать фазово-чистые ориентированные пленки LaNiO 3 , демонстрирующие металлическую проводимость и допускающие применение в качестве проводящих подслоев.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
A mixed-ligand complexation approach implying the reaction of metal carboxylates with the chelating tridendate diethylenetriamine (DETA) ligand has been applied to modify the structure of the layered coordination polymer based on lanthanum propionate (Prop). Lanthanum propionate monohydrate has been synthesized and characterized by a set of analytical methods to determine its crystal structure and chemical composition. The crystal structures of lanthanum propionate and nickel propionate complexes with DETA have additionally been determined. The native lanthanum propionate monohydrate [La 2 (H 2 O) 2 Prop 6 ] has been proven to have a 2D-layered topology, whereas the mixed-ligand complex [La 2 (DETA)Prop 6 ] ⋅ MeCN (where MeCN stands for acetonitrile) has a chain structure. A chemical solution deposition procedure has been developed to produce phase-pure oriented LaNiO 3 thin films. These films exhibit metallic conductivity and can be used as conductive sublayers.
Rare-earth (RE, Ln) carboxylates are widely studied as precursors of RE oxide-based nanomaterials; however, no systematic studies of RE L-lactates (HLact = 2-hydroxypropanoic acid) have been reported to date. In the present work, a profound structural investigation of RE L-lactates is carried out. A family of RE lactate complexes of the general formula LnLact3∙nH2O (Ln = La, Ce–Nd, Sm–Lu, Y; n = 2–3) are synthesized and characterized by CHN, TGA, and FTIR as well as by powder and single-crystal XRD methods.The existence of four novel structural types (1-Ln–4-Ln) is revealed. Compounds of the 1-Ln type (Ln = La, Ce, Pr) exhibit a chain polymeric structure, whereas 2-Ln–4-Ln compounds are molecular crystals consisting of dimeric (2-Ln; Ln = La, Ce–Nd) or monomeric (3-Ln–Ln = Sm–Lu, Y; 4-Ln–Ln = Sm–Gd, Y) species. The crystal structures of 1-Ln–4-Ln compounds are discussed in terms of their coordination geometry and supramolecular arrangement. Solutions of yttrium and lanthanum lactates with diethylenetriamine are applied for the chemical deposition of Y2O3 and La2O3 thin films.
Highly volatile and stable complexes of rare-earth elements with mononuclear structure are of great importance for gas phase deposition of functional thin film materials. Mixed ligand complexes with beta-diketonate anions (e.g. thd = 2,2,6,6-tetrametylheptane-3,5-dionate) and ancillary neutral donor ligands demonstrate mononuclear structure and sufficient volatility, however, they are unstable to neutral ligand elimination especially in case of light rare earth elements. Here diethylenetriamine (deta) has been applied as tridentate neutral ligand to improve the stability of mixed ligand complexes due to macrochelate effect and additional weak intramolecular interactions, e.g. hydrogen bonds. Synthesis of a series of mixed-ligand [Ln(thd)(3)(deta)], Ln = La (1L), Pr (2L), Nd (3L), Sm (4L) and Gd (5L) complexes, their X-ray single crystal structure characterization, DFT calculations, and thermal behavior study have been performed. Compounds 1L-5L demonstrate similar mononuclear molecular structure, but different molecular packing of three types, which may undergo mutual transformation. Compounds 1L-4L sublime intact in temperature range of 140-160 degrees C in vacuum without decomposition. 1L was successfully applied as volatile precursors for MOCVD preparation of epitaxial complex oxide thin films, (0 0 l) LaMnO3 and (0 0 l) LaAlO3, on (0 0 l) MgO and (0 0 l) SrTiO3 substrates. (C) 2020 Elsevier Ltd. All rights reserved.
Synthesis of new lanthanide‐based poly‐hydroxo clusters is a key challenge in the deliberate design of novel metal‐organic frameworks with functional properties. Most of the current approaches fail to isolate stable hexanuclear entities to be used as pre‐existing building blocks for such frameworks. Herein we highlight the new two‐step synthetic route for the new family of hexanuclear lanthanide hydroxo pivalate compounds: self‐controlled hydrolysis and subsequent introduction of amine ligand. Three different octahedral architectures stabilized by intermolecular hydrophobic interactions and intramolecular H‐bonds have been found within the system of lanthanide pivalate and diethylenetriamine, and supramolecular organization of the compounds was examined. This is the first demonstration of isolation of hollow and O‐centered LnIII6(OH)8 cluster from the same system.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
Superconducting wires are not perfectly homogeneous in term of critical current as well as stabilization. In resistive fault current limiter applications this could lead to hot spots if the fault current is only slightly above the nominal current of the device. Increasing stabilization by using thicker silver coating for example may prevent this problem but this method implies longer wire length to maintain the same impedance during a fault. Very efficient cooling in another way to prevent hot spots, this can be achieved in nucleate boiling regime. Optimal insulation can be used to prevent film boiling regime, staying in nucleate boiling regime in a much broader temperature range. In this work a novel technique is used to monitor in real time the temperature of the wire during the quench. Using this method several increasing insulation thicknesses are tested, measuring for each the heat exchange rate to the nitrogen bath. Exchange rate measurements are made in quasistatic regime and during the re-cooling of the wire. SuperOx wires provided with different insulation thicknesses exhibit an excellent stability, far above a bare wire. On the other side, for very thick insulations the stability gain is lost. Re-cooling speeds dependency on insulation thicknesses is measured too.
Fourteen 1D coordination polymers of rare earth pivalates [Ln(Piv)3]∞ (Ln = Y, La, Pr, Nd, Sm−Lu) were synthesized and characterized by powder X-ray diffraction, IR spectroscopy, TGA, and conventional elemental analysis. Crystal structures of [La(Piv)3]∞, [Yb(Piv)3]∞, [Lu(Piv)3]∞ were determined by means of single crystal X-ray analysis at 120K, those of [Y(Piv)3]∞ and [Ho(Piv)3]∞ — from powder XRD data at 293K. Transformation of [Ln(Piv)3]∞ structure and Piv– anions coordination mode along the whole row has been derived from powder XRD and IR spectroscopy results, and shown to crucially affect the relative location of 1D chains in the crystal structure, as well as the Ln···Ln distance within the single chain. Negative thermal expansion along 1D [Ln(Piv)3]∞ chain was revealed for Ln = Tm, Yb, Lu. Enforcement of 1D polymeric structure with the decrease of Ln ionic radius has been established from solid-state DFT calculations.
Aluminum hydroxocarboxylates derived from butyric, pivalic, valeric, and isovaleric acids were synthesized and characterized. The synthesized hydroxocarboxylates were suspended in isopropanol and reacted with diethylenetriamine and monoethanolamine, which acted as hydrolyzing and complex-forming agents, to obtain precursor solutions for chemical deposition of smooth amorphous alumina films on metal substrates.
Primary immunodeficiencies (PIDs) are a group of congenital diseases of the immune system, which numbers more than 230 nosological entities associated with lost, decreased, or wrong function of its one or several components. Due to the common misconception that these are extremely rare diseases that occur only in children and lead to their death at an early age, PIDs are frequently ruled out by physicians of related specialties from the range of differential diagnosis. The most common forms of PIDs, such as humoral immunity defects, common variable immune deficiency, X-linked agammaglobulinemia, selective IgA deficiency, etc., are milder than other forms of PID, enabling patients to attain their adult age, and may even manifest in adulthood. Bronchopulmonary involvements are the most common manifestations of the disease in patients with a defect in humoral immunity. Thus, a therapist and a pulmonologist are mostly the first doctors who begin to treat these patients and play a key role in their fate, since only timely diagnosis and initiation of adequate therapy can preserve not only the patient’s life, but also its quality, avoiding irreversible complications. Chest computed tomography changes play a large role in diagnosis. These are not specific for PID; however, there are a number of characteristic signs that permit this diagnosis to be presumed.
Reproducibility of superconducting properties and suitability for specific applications by means of customised finish are two important attributes required from commercial 2G HTS wire. This paper reviews the consistent performance of SuperOx production 2G HTS wire and describes two novel customisation options: surround polyimide varnish insulation and composite bulk materials assembled with 2G HTS wires soldered together.
Replacement immunotherapy with intravenous immunoglobulin (IVIG) has been used successfully for the treatment of primary immunodeficiency (PID) for over 60 years. During this time, a huge step forward in purification and manufacturing methods has been made. In addition IVIG therapy has been approved for other diseases and this number is steadily expanding causing an appearance of new IVIG on the pharmaceutical market. These drugs vary in composition, manufacturing technology and, as a consequence, in safety, administration rate, and efficacy. The new IVIG on the Russian market IG Vena was recently introduced. It has already proved its safety and efficacy abroad. This article presents the experience of using the drug IG Vena in adults with PID in immunopathology department of the Institute of Immunology FMBA Russia.
Compositions of mixed ligand acetate, propionate, and pivalate complexes of rare earth metals of the cerium and yttrium groups with monoethanolamine are predetermined by the synthesis conditions and the nature of the carboxylate ligand and rare earth metal ion. Solid mixed ligand complexes [Ln(Piv)5(MEAH)][MEAH] and [Ln(Piv)3(MEA)], homoligand complexes [Ln(Piv)3] (HPiv is 2,2-dimethylpropionic (pivalic) acid), and gel-like hydroxo complexes [Ln(Carb)3–x–y (NO3) x -(OH) y (MEA) w (H2O) z ] (HCarb is acetic (HAc) or propionic (HProp) acid) are isolated using original synthesis procedures involving ion pairs [MEAH]+[Carb]– (MEA is monoethanolamine). The compounds are studied by IR spectroscopy, 1H NMR spectroscopy, elemental and thermal analyses, and mass spectrometry. Specific features for the complex formation of rare earth metal pivalates with MEA are additionally studied using quantum-chemical simulation.
Chemical solution deposition of smooth amorphous Al2O3 thin films has been successfully used for planarization of long-length metallic substrates for 2G HTS superconducting wires production. A series of metal-organic precursors based on Al((PrO)-Pr-i)(3), Al(acac)(3), acetic acid, monoethanolamine (MEA) and diethylenetriamine (DETA) was developed. Correlations between the precursor composition and the features of its two-step thermal-induced transformation to amorphous Al2O3 were studied by H-1 NMR, IR spectroscopy and thermal analysis. Utilizing the solutions of {Al((PrO)-Pr-i)(3) + 2.5MEA + 6HAcet} in (PrOH)-Pr-i and {Al(acac)(3) + nDETA} in HAcet (n = 1-3) as precursors for dip-coating, we obtained the long-length Hastelloy C276 substrate covered by uniform amorphous 50-550 nm thick alumina films with surface roughness of about 0.5-1.5 nm. A 20 m long sample of 2G HTS wire with a commercial level of superconducting critical current of up to 300A was prepared based on Hastelloy substrate tape planarized with Al2O3. (C) 2016 Elsevier Ltd. All rights reserved.
Intravenous immunoglobulins (IVIGs) were initially designed to treat patients with primary immunodeficiencies (PID). Due to the multidirectional effect of IVIGs on the immune system, a range of nosological entities, in which these agents are successfully administered, is steadily expanding. As of now, IVIGs are successfully used in neurology, rheumatology, hematology, and oncology and they are essential drugs for many patients. In spite of the long experience with IVIGs, their mechanism of action remains unclear, numerous investigations for their clinical introduction are being continued. Therefore, there is a growing need to increase the production of the drugs, which gives rise to the emergence of novel medications, which differ in their composition and manufacture technologies, on the pharmacological market. The 10% intravenous immunoglobulin privigen, the safety and efficacy of which has been proven in foreign practice, is a novel drug on the Russian market.
Common variable immunodeficiency (CVID) is the most prevalent clinically important form of primary immunodeficiencies (PID). CVID is characterized by a wide variability of complications which can affect almost all organs and systems. Infectious complications are more typical, but non-infectious complications, in particular granulomatous lymphocytic interstitial lung disease (GLILD), have more strong influence on the course, prognosis and severity of the disease and the patient’s quality of life. GLILD is a challenge not only from a diagnostic point of view (manifestations are often misdiagnosed and treated as sarcoidosis, tuberculosis, lymphoproliferative disease), but also in terms of treatment strategy selection. Rituximab - is one of the most promising methods of GLILD therapy, which showed its efficiency in limited clinical observations. A clinical case of successful treatment of GLILD associated with CVID, using rituximab on the background of a regular replacement immunotherapy with immunoglobulin for intravenous administration (IVIG) is described in this article.