Structural and Spectroscopic Investigation of Novel 2D and 3D Uranium Oxo-Silicates/Germanates and Some Statistical Aspects of Uranyl Coordination in Oxo-Salts

Synthesis, structural and spectroscopic characterization, and topological analysis of five novel uranyl-based silicates and germanates have been performed. The open-framework K4(UO2)2Si8O20·4H2O has been synthesized under hydrothermal conditions and is based upon [USi6] heptamers interconnected via edge-sharing. Its structure is composed of sechser silicate layers with 4-, 8-, and 16-membered rings. The largest 16-membered rings have an average dimension of ∼8.93 × 9.42 Å2. β-K2(UO2)Si4O10 has been obtained by the high-temperature flux growth method. Its 3D framework contains a loop-branched sechser single layer with 4- and 8-membered rings and consists of the same [USi6] heptamers as observed in K4(UO2)2Si8O20·4H2O. Na6(UO2)3(Si2O7)2 has also been synthesized from melted fluxes and represents a 2D layer structure composed by [USi4] pentamers. Two iso-structural compounds A+(UO2)(HGeO4)·H2O (A+ = Rb+, Cs+) were synthesized via the hydrothermal method, and their structures are of the α-uranophane type. The 2D layers consist of [U2Ge2] tetramer secondary building units (SBUs). The Raman spectra of all novel phases were collected, and bands were assigned according to the existing oxo-silicate rings and oxo-germanium units. Additionally, we performed a statistical investigation of the local coordination of uranyl ions in all known inorganic structures with different oxo-anions (TOx, T = B3+, Si/Ge4+, P/As5+, S/Se/Te6+, Cr/Mo/W6+, P/As3+, and Se/Te4+). We found a direct correlation between the ionic potential of the central cations T in oxo-anions in their higher oxidation states and the coordination number of uranyl groups

The Role of Acidity in the Synthesis of Novel Uranyl Selenate and Selenite Compounds and Their Structures

Herein, the novel uranyl selenate and selenite compounds Rb2[(UO2)2(SeO4)3], Rb2[(UO2)3(SeO3)2O2], Rb2[UO2(SeO4)2(H2O)]·2H2O, and (UO2)2(HSeO3)2(H2SeO3)2Se2O5 have been synthesized using either slow evaporation or hydrothermal methods under acidic conditions and their structures were refined using single crystal X-ray diffraction. Rb2[(UO2)2(SeO4)3] synthesized hydrothermally adopts a layered 2D tetragonal structure in space group P42/ncm with a = 9.8312(4) Å, c = 15.4924(9) Å, and V = 1497.38(15) Å, where it consists of UO7 polyhedra coordinated via SeO4 units to create units UO2(SeO4)58− moieties which interlink to create layers in which Rb+ cations reside in the interspace. Rb2[(UO2)3(SeO3)2O2] synthesized hydrothermally adopts a layered 2D triclinic structure in space group P1¯ with a = 7.0116(6) Å, b = 7.0646(6) Å, c = 8.1793(7) Å, α = 103.318(7)°, β = 105.968(7)°, γ = 100.642(7)° and V = 365.48(6) Å3, where it consists of edge sharing UO7, UO8 and SeO3 polyhedra that form [(UO2)3(SeO3)2O2] layers in which Rb+ cations are found in the interlayer space. Rb2[UO2(SeO4)2(H2O)]·2H2O synthesized hydrothermally adopts a chain 1D orthorhombic structure in space group Pmn21 with a = 13.041(3) Å, b = 8.579(2) Å, c = 11.583(2) Å, and V = 1295.9(5) Å3, consisting of UO7 polyhedra that corner share with one H2O and four SeO42− ligands, creating infinite chains. (UO2)2(HSeO3)2(H2SeO3)2Se2O5 synthesized under slow evaporation conditions adopts a 0D orthorhombic structure in space group Cmc21 with a = 28.4752(12) Å, b = 6.3410(3) Å, c = 10.8575(6) Å, and V = 1960.45(16) Å3, consisting of discrete rings of [(UO2)2(HSeO3)2(H2SeO3)2Se2O5]2. (UO2)2(HSeO3)2(H2SeO3)2Se2O5 is apparently only the second example of a uranyl diselenite compound to be reported. A combination of single crystal X-ray diffraction and bond valance sums calculations are used to characterise all samples obtained in this investigation. The structures uncovered in this investigation are discussed together with the broader family of uranyl selenates and selenites, particularly in the context of the role acidity plays during synthesis in coercing specific structure, functional group, and topology formation

Achieving and Stabilizing Uranyl Bending via Physical Pressure

Applying physical pressure in the uranyl–sulfate system has resulted in the formation of the first purely inorganic uranyl oxo-salt phase with a considerable uranyl bend: Na4[(UO2)(SO4)3]. In addition to a strong bend of the typically almost linear O═U═O, the typically equatorial plane is broken up by two out-of-plane oxygen positions. Computational investigations show the origin of the bending to lie in the applied physical pressure and not in the electronic influence or steric hindrance. The increase in pressure onto the system has been shown to increase uranyl bending. Furthermore, the phase formation is compared with a reference phase of a similar structure without uranyl bending, and a transition pressure of 2.5 GPa is predicted, which is well in agreement with the experimental results

Achieving and Stabilizing Uranyl Bending via Physical Pressure

Applying physical pressure in the uranyl–sulfate system has resulted in the formation of the first purely inorganic uranyl oxo-salt phase with a considerable uranyl bend: Na4[(UO2)(SO4)3]. In addition to a strong bend of the typically almost linear O═U═O, the typically equatorial plane is broken up by two out-of-plane oxygen positions. Computational investigations show the origin of the bending to lie in the applied physical pressure and not in the electronic influence or steric hindrance. The increase in pressure onto the system has been shown to increase uranyl bending. Furthermore, the phase formation is compared with a reference phase of a similar structure without uranyl bending, and a transition pressure of 2.5 GPa is predicted, which is well in agreement with the experimental results

Unexpected Behavior of Np in Oxo-selenate/Oxo-selenite Systems

A study of neptunium (Np) chemistry in the complex oxo-selenium system has been performed. Hereby, two sets of precipitation experiments were conducted, investigating the influence of the initial oxidation state of selenium using Se^IVO₂ and H₂Se^VIO₄ with Np^V in alkali nitrate solution, keeping the ratio of Np/Se constant. Surprising results were observed. Five novel neptunium and selenium bearing compounds have been obtained by slow evaporation from aqueous solution. The novel Np^IV phase K_4‑<i>x</i>[Np­(SeO₃)_4‑<i>x</i>­(HSeO₃)_<i>x</i>]­·(H₂O)_1.5 (<b>1</b>) crystallizes in green-colored, plate-shaped crystals and was obtained by adding SeO₂ and ANO₃ to a Np^V stock solution. Single-crystal X-ray diffraction reveals one-dimensional chain structures composed of square antiprismatic NpO₈ polyhedra linked via four trigonal pyramidal SeO₃ and HSeO₃ units. Raman spectral analysis supports the presence of both selenite and hydroselenite due to the presence of corresponding modes within the spectra. The addition of selenic acid to a Np^V stock solution resulted in the precipitation of elongated rose prisms of K₂[(NpO₂)₂­(SeO₄)₃­(H₂O)₂]­·(H₂O)_1.5 (<b>2</b>), Rb₂[(NpO₂)₂­(SeO₄)₃­(H₂O)₂]­·(H₂O)₂ (<b>3</b>) and K₉[(NpO₂)₉­(SeO₄)_13.5­(H₂O)₆]­·(H₂O)₁₂ (<b>4</b>) as well as light red plates of Cs₂[(NpO₂)₂­(SeO₄)₃] (<b>5</b>). To our knowledge, this is the first report of Np^VI selenates. All four structures show two-dimensional layered structures with alkali cations acting as charge balancing counter cations. Hereby the layers of compounds <b>2</b> and <b>3</b> are found to be orientational geometric isomers. Distinctly different phenomena are made responsible for the phase formation within these systems. The kinetically driven process of Np^V disproportionation led to the formation of the Np^IV selenites in the Se^IV-based system, whereas the oxidation of Np^V by reduction of nitrate in acidic conditions is responsible for the formation of the Np^VI selenates in the Se^VI system. The influence of air oxygen is also discussed for the latter reaction

Reduced microglia activity in patients with long-term immunosuppressive therapy after liver transplantation

Purpose!#!Calcineurin inhibitors (CNI) can cause long-term impairment of brain function. Possible pathomechanisms include alterations of the cerebral immune system. This study used positron emission tomography (PET) imaging with the translocator protein (TSPO) ligand !##!Methods!#!PET was performed in 22 liver-transplanted patients (3 CNI free, 9 with low-dose CNI, 10 with standard-dose CNI immunosuppression) and 9 healthy controls. The total distribution volume (V!##!Results!#!In controls, V!##!Conclusion!#!Our results provide evidence of chronic suppression of microglial activity in liver-transplanted patients under CNI therapy especially in patients with high sensitivity to CNI toxicity

Reduced microglia activity in patients with long-term immunosuppressive therapy after liver transplantation

Purpose Calcineurin inhibitors (CNI) can cause long-term impairment of brain function. Possible pathomechanisms include alterations of the cerebral immune system. This study used positron emission tomography (PET) imaging with the translocator protein (TSPO) ligand F-18-GE-180 to evaluate microglial activation in liver-transplanted patients under different regimens of immunosuppression. Methods PET was performed in 22 liver-transplanted patients (3 CNI free, 9 with low-dose CNI, 10 with standard-dose CNI immunosuppression) and 9 healthy controls. The total distribution volume (V-T) estimated in 12 volumes-of-interest was analyzed regarding TSPO genotype, CNI therapy, and cognitive performance. Results In controls, V-T was about 80% higher in high affinity binders (n = 5) compared to mixed affinity binders (n = 3). Mean V-T corrected for TSPO genotype was significantly lower in patients compared to controls, especially in patients in whom CNI dose had been reduced because of nephrotoxic side effect. Conclusion Our results provide evidence of chronic suppression of microglial activity in liver-transplanted patients under CNI therapy especially in patients with high sensitivity to CNI toxicity