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The crystal structure of NH4VO3was refined by the geometry optimization done by total energy minimization in solid state using DFTplane waves approach. The lattice parameters were derived by the Le Bail technique from the low temperature Xray 40293 K and synchrotron 100293 K powder diffraction data. The structure is formed by the infinite chains of irregular VO4tetrahedra running approximately parallel to the caxis, which are interlinked by the ammonium ions placed between them. The ammonium ions link to the [VO4]∞chains through one linear, one bifurcated and two trifurcated NH…O hydrogen bonds. Considering their stability there are six distinct NH…O hydrogen bonds: two strong with the NH…O bond angles close to the straight, two medium with the bond angles of 123° and 148° and two very bent 105° and 107° and hence weak hydrogen bonds. There is a reasonable agreement between the energies of the stretching νNH modes estimated using the optimised N…O contact distances and those obtained experimentally. © 2009 WILEYVCH Verlag GmbH & Co. KGaA, Weinheim [ABSTRACT FROM AUTHOR]

Germanium is a promising basis for nanomaterials due to its low toxicity and valuable optical and electronic properties. However, germanium nanomaterials have seen little research compared to other group 14 elements due to unpredictable chemical behavior and high costs. Here, we report the dehydrocoupling of o-tolylgermanium trihydride to amorphous nanoparticles. The reaction is facilitated through reflux at 162 °C and can be accelerated with an amine base catalyst. Through cleavage of both H 2 and toluene, new Ge-Ge bonds form. This results in nanoparticles consisting of crosslinked germanium with o-tolyl termination. The particles are 2-6 nm in size and have masses above approximately 3500 Da. The organic substituents are promising for further functionalization. Combined with strong absorption up to 600 nm and moderate solubility and air stability, there are numerous possibilities for future applications., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Drinking water plumbing systems appear to be a unique environment for microorganisms as they contain few nutrients but a high mineral concentration. Interactions between mineral content and bacteria, such as microbial calcium carbonate precipitation (MCP) however, has not yet attracted too much attention in drinking water sector. This study aims to carefully examine MCP behavior of two drinking water bacteria species, which may potentially link scaling and biofouling processes in drinking water distribution systems. Evidence from cell density evolution, chemical parameters, and microscopy suggest that drinking water isolates can mediate CaCO 3 precipitation through previously overlooked MCP mechanisms like ammonification or biosorption. The results also illustrate the active control of bacteria on the MCP process, as the calcium starts to concentrate onto cell surfaces only after reaching a certain cell density, even though the cell surfaces are shown to be the ideal location for the CaCO 3 nucleation., (Copyright © 2021. Published by Elsevier Ltd.)

Direct ethanol fuel cells (DEFC) still lack active and efficient electrocatalysts for the alkaline ethanol oxidation reaction (EOR). In this work, a new instant reduction synthesis method was developed to prepare carbon supported ternary PdNiBi nanocatalysts with improved EOR activity. Synthesized catalysts were characterized with a variety of structural and compositional analysis techniques in order to correlate their morphology and surface chemistry with electrochemical performance. The modified instant reduction synthesis results in well-dispersed, spherical Pd 85 Ni 10 Bi 5 nanoparticles on Vulcan XC72R support (Pd 85 Ni 10 Bi 5 /C (II-III) ), with sizes ranging from 3.7 ± 0.8 to 4.7 ± 0.7 nm. On the other hand, the common instant reduction synthesis method leads to significantly agglomerated nanoparticles (Pd 85 Ni 10 Bi 5 /C (I) ). EOR activity and stability of these three different carbon supported PdNiBi anode catalysts with a nominal atomic ratio of 85:10:5 were probed via cyclic voltammetry and chronoamperometry using the rotating disk electrode method. Pd 85 Ni 10 Bi 5 /C (II) showed the highest electrocatalytic activity (150 mA⋅cm -2 ; 2678 mA⋅mg -1 ) with low onset potential (0.207 V) for EOR in alkaline medium, as compared to a commercial Pd/C and to the other synthesized ternary nanocatalysts Pd 85 Ni 10 Bi 5 /C (I) and Pd 85 Ni 10 Bi 5 /C (III) . This new synthesis approach provides a new avenue to developing efficient, carbon supported ternary nanocatalysts for future energy conversion devices. Graphical AbstractThe modified instant reduction method for synthesis of ternary Pd 85 Ni 10 Bi 5 /C (II) nanocatalyst using Vulcan XC72R as carbon support initiates an agglomeration reduction, provides low average particle size, and enables enhanced activity for the alkaline ethanol oxidation reaction (EOR) compared to the common instant reduction method and to a commercial Pd/C catalyst., Competing Interests: Conflict of InterestThe authors declare that they have no conflict of interest., (© The Author(s) 2019.)

For the development of safe and long-lasting lithium-ion batteries we need electrolytes with excellent ionic transport properties. Argyrodite-type Li6PS5X (X: Cl, Br, I) belongs to a family of such a class of materials offering ionic conductivities, at least if Li6PS5Br and Li6PS5Cl are considered, in the mS cm-1 range at room temperature. Although already tested as ceramic electrolytes in battery cells, a comprehensive picture about the ion dynamics is still missing. While Li6PS5Br and Li6PS5Cl show an exceptionally high Li ion conductivity, that of Li6PS5I with its polarizable I anions is by some orders of magnitude lower. This astonishing effect has not been satisfactorily understood so far. Studying the ion dynamics over a broad time and length scale is expected to help shed light on this aspect. Here, we used broadband impedance spectroscopy and 7Li NMR relaxation measurements and show that very fast local Li ion exchange processes are taking place in all three compounds. Most importantly, the diffusion-induced NMR spin-lattice relaxation in Li6PS5I is almost identical to that of its relatives. Considering the substitutional disorder effects in Li6PS5X (X = Br, Cl), we conclude that in structurally ordered Li6PS5I the important inter-cage jump processes are switched off, hindering the ions from taking part in long-range ion transport.

We have measured the quasi-elastic neutron scattering (QENS) of an electrohydrodynamic liquid bridge formed between two beakers of pure water when a high voltage is applied, a setup allowing to investigate water under high-voltage without high currents. From this experiment two proton populations were distinguished: one consisting of protons strongly bound to oxygen atoms (immobile population, elastic component) and a second one of quasi-free protons (mobile population, inelastic component) both detected by QENS. The diffusion coefficient of the quasi-free protons was found to be D = (26 ± 10) × 10(-5) cm(2) s(-1) with a jump length lav ∼ 3 Å and an average residence time of τ0 = 0.55 ± 0.08 ps. The associated proton mobility in the proton channel of the bridge is ∼9.34 × 10(-7) m(2) V(-1) s(-1), twice as fast as diffusion-based proton mobility in bulk water. It also matches the so-called electrohydrodynamic or "apparent" charge mobility, an experimental quantity which so far has lacked molecular interpretation. These results further corroborate the proton channel model for liquid water under high voltage and give new insights into the molecular mechanisms behind electrohydrodynamic charge transport phenomena and delocalization of protons in liquid water.

Chemical reactions induced by mechanical treatment may give access to new compounds whose properties are governed by chemical metastability, defects introduced and the size effects present. Their interplay may lead to nanocrystalline ceramics with enhanced transport properties being useful to act as solid electrolytes. Here, the introduction of large amounts of La into the cubic structure of BaF2 served as such an example. The ion transport properties in terms of dc-conductivity values of the F(-) anion conductor Ba1-xLaxF2+x (here with x = 0.4) considerably exceed those of pure, nanocrystalline BaF2. So far, there is only little knowledge about activation energies and jump rates of the elementary hopping processes. Here, we took advantage of both impedance spectroscopy and (19)F NMR relaxometry to get to the bottom of ion jump diffusion proceeding on short-range and long-range length scales in Ba0.6La0.4F2.4. While macroscopic transport is governed by an activation energy of 0.55 to 0.59 eV, the elementary steps of hopping seen by NMR are characterised by much smaller activation energies. Fortunately, we were able to deduce an F(-) self-diffusion coefficient by the application of spin-locking NMR relaxometry.

A new thermographic phosphor based on chromium(III)-doped yttrium aluminum borate (YAB) is obtained as single crystals by high temperature flux growth and as a microcrystalline powder via solution combustion synthesis. The phosphor is excitable both in the blue (lambda(max) 422 nm) and in the red part of the spectrum (lambda(max) 600 nm) and shows bright NIR emission. The brightness of the phosphor is comparable to that of a well-known lamp phosphor Mn(IV)-doped magnesium fluorogermanate. At ambient temperatures, the Cr(III)-doped YAB shows high temperature dependence of the luminescence decay time, which approaches 1% per deg. The material shows no decrease in luminescence intensity at higher temperatures. The new phosphor is particularly promising for applications in temperature-compensated optical chemosensors (including those based on NIR-emitting indicators) and in pressure-sensitive paints.

The syntheses, structural characterization, and magnetic behaviour of three new 3D manganese(II) complexes with the empirical formulae [Mn(N3)2(5-Brpym)]n (1), [Mn(N3)2(Mepyz)]n (2) and [Mn(N3)2(2-acpy)]n (3), (5-Brpym=5-bromopyrimidine, Mepyz=methylpyrazine, 2-acpy=2-acetylpyridine), are reported. In 1, each manganese atom is linked to the four nearest neighbours by only end-to-end azido bridges, forming square layers. These layers are further connected to 3D networks by the N,N'-bridging ligand. In 2, Mn2(micro(1,1)-N3)2 subunits are connected to the four nearest neighbours by end-to-end azido bridges to form a 3D Mn-azido-sublattice. The Mn2(micro(1,1)-N3)2 subunits are further linked by pairs of N,N'-bridging Mepyz ligands to form 1D ribbons extended along the c-axis of the unit cell. The Mepyz pairs show pi-pi-interactions. In 3, the only end-to-end azido bridges form a diamondoid-like 3D Mn-azido-sublattice. The magnetic properties of 1-3 are reported. At high temperatures, the plots of chiM or chiMTvs.T for can be fitted as a homogeneous 2D system with J=-5.4 cm(-1), g=2.05. Also, at high temperatures the plots of chiM or chiMTvs.T for compound can be fitted with the simple cubic expansion series with J=-1.6 cm(-1), g=2.04. Compound 1 shows spontaneous magnetization below Tc=45 K, which corresponds to the presence of spin-canted antiferromagnetism, whereas 2 and 3 do not show spontaneous magnetization up to 2 K.

The syntheses, structural characterization, and magnetic behavior of five new 2D manganese(II) complexes with empirical formulas [Mn(N(3))(2)(2,6-DiMepyz)(H(2)O)](n)() (1), [Mn(N(3))(2)(Etpyz)(H(2)O)](n)() (2), [Mn(N(3))(2)(H(2)O)(2)](n)()(2,3-DiMepyz)(n)() (3), [Mn(N(3))(2)(Clpyz)(2)](n)() (4), and [Mn(N(3))(2)(Ipyz)(2)](n)() (5) (pyz = pyrazine (1,4-diazine)) are reported. 1 crystallizes in the monoclinic system, space group P2(1)/c, with unit cell parameters a = 7.513(4) A, b = 17.438(7) A, c = 8.404(4) A, beta = 94.53(4) degrees , and Z = 4. 2 crystallizes in the triclinic system, space group P, with unit cell parameters a = 7.386(2) A, b = 8.434(2) A, c = 9.442(3) A, alpha = 71.82(2) degrees , beta = 72.08(2) degrees , gamma = 88.54(2) degrees , and Z = 2. 3 crystallizes in the monoclinic system, space group C2/c, with unit cell parameters a = 20.438(7) A, b = 7.711(2) A, c = 7.457(2) A, beta = 93.76(3) degrees , and Z = 4. 4 crystallizes in the orthorhombic system, space group Pbca, with unit cell parameters a = 8.600(2) A, b = 13.440(4) A, c = 24.083(7) A, and Z = 8. 5 crystallizes in the orthorhombic system, space group Pbca, with unit cell parameters a = 8.521(2) A, b = 13.787(3) A, c = 26.237(5) A, and Z = 8. The compounds 1-5 have only azido bridging ligands. In 1-3 each manganese atom is linked to the four nearest neighbors by only end-to-end azido bridges, forming square layers. 4 and 5 show alternating end-to-end and end-on azido bridges between manganese atoms. The magnetic properties of 1-5 are reported. At high temperatures the plots of chi(M) or chi(M)T vs T for the 1-3 compounds can be fitted as homogeneous 2D systems with J = -4.9, -4.4, and -3.9 cm(-)(1) for 1-3, respectively. For 1, 3, and 5 magnetic ordering and spontaneous magnetizations is achieved below T(c) = 35, 29, and 22 K, respectively, whereas 2 and 4 do not show spontaneous magnetization up to 2 K.

Introduction: Correct ligamentous balancing is an important determinant of the clinical outcome in total knee arthroplasty (TKA). Many surgeons prefer a tight rather than a lax knee during implantation of a TKA. The hypothesis in this study was that patients with a slightly laxer knee joint might perform better than patients with a tight knee joint after implantation of a TKA., Patients and Methods: Twenty-two patients with bilateral knee arthroplasties were clinically and radiologically evaluated at a mean follow-up of 4.5 years, ranging from 2 to 7 years. There were 12 women and 10 men with an average age of 68.9 years (range 32-82 years) at the time of surgery. A modified HSS score (excluding laxity), varus and valgus stress X-rays in 30 degrees of knee flexion, and the subjective outcome of both knees were compared. A knee was considered tight when it opened less than 4 degrees and lax if it opened 4 degrees or more on stress X-ray., Results: There was a trend towards improved range of motion and HSS score for the laxer knee joints. However, the difference did not achieve statistical significance. Eleven of the 22 patients considered one side subjectively better than the other side. In 10 out of these 11 TKA, the slacker knee joint was the preferred side ( p<0.05)., Conclusions: As the present study compared bilateral knee joints after TKA, the same patient could act as a control group, and subtle subjective differences were revealed which are not quantifiable. The results showed that patients with a preferred side felt significantly more comfortable on the laxer side, indicating that during intraoperative ligamentous tensioning, some varus and valgus laxity at 20-30 degrees of flexion might be preferable to an over-tight knee joint. Further biomechanical and prospective investigations will be necessary to establish the correct soft-tissue tensioning.