Revisiting Mg solubility in CuO nanorods: limit probed by neutron diffraction and effect on the particle toxicity towards bacteria in water.

Both nanometer-sized CuO and MgO particles exhibit bactericidal activities against Staphylococcus aureus and Escherichia coli, two bacteria causing healthcare-associated infections. The solid solution Cu1-xMgxO is potentially interesting for biomedical applications as one of the compositions could have a much higher bactericidal activity than the parent CuO and MgO oxides considered separately. But, to date, no Vegard's law proves the real existence of such a solid solution. This study was aimed at shedding light on the solubility of Mg2+ ions in CuO nanoparticles and its impact on the free oxygen radicals they produce, the quantity of which determines their bactericidal performance. The solid solution Cu1-xMgxO does exist and particles were synthesized as nanorods of 50-60 nm length by thermally decomposing at 400 °C the single source precursors Cu1-xMgx(OH)2. Vegard's laws exist only in the compositional range 0 ≤ x ≤ 0.1, due to the low capacity of the distorted NaCl-type structure to accommodate regular coordination [MgO6] octahedra. Only neutron diffraction allowed the detection of the small amount of MgO nanoparticles present as impurity in a 10 g sample beyond the solubility limit of x = 0.1. In this series, CuO nanorods remain the most active against E. coli and S. aureus with reduction in viability of 99.998% and 98.7% after 180 min in water, respectively. Our synthesis route has significantly increased the activity of pure CuO nanoparticles beyond the values reported so far, especially against E. coli. The bactericidal performances of CuO and the magnesium-substituted counterparts (i.e. Cu1-xMgxO) are not linked to cupric ions they release in water since their mass concentrations after 180 min are much lower than minimal concentrations inhibiting the growth of E. coli and S. aureus. These CuO nanorods kill bacteria in water because they produce a large quantity of free oxygen radicals in the presence of H2O2 only, the majority of which are highly toxic HO˙ radicals. Mg2+ ions have a detrimental effect on this production, thus explaining the lowest bactericidal performance of Cu1-xMgxO nanorods. Definitive knowledge of the toxicity of Cu1-xMgxO nanoparticles towards bacteria in water is now available.

Understanding the bactericidal mechanism of Cu(OH)2 nanorods in water through Mg-substitution: high production of toxic hydroxyl radicals by non-soluble particles.

To date, there is still a lack of definite knowledge regarding the toxicity of Cu(OH)2 nanoparticles towards bacteria. This study was aimed at shedding light on the role played by released cupric ions in the toxicity of nanoparticles. To address this issue, the bactericidal activity of Cu(OH)2 was at first evaluated in sterile water, a medium in which particles are not soluble. In parallel, an isovalent substitution of cupric ions by Mg2+ was attempted in the crystal structure of Cu(OH)2 nanoparticles to increase their solubility and determine the impact on the bactericidal activity. For the first time, mixed Cu1-xMgx(OH)2 nanorods (x ≤ 0.1) of about 15 nm in diameter and a few hundred nanometers in length were successfully prepared by a simple co-precipitation at room temperature in mixed alkaline (NaOH/Na2CO3) medium. For E. coli, 100% reduction of one million CFU per mL (6 log10) occurs after only 180 min on contact with both Cu(OH)2 and Cu0.9Mg0.1(OH)2 nanorods. The entire initial inoculum of S. aureus is also killed by Cu(OH)2 after 180 min (100% or 6 log10 reduction), while 0.01% of these bacteria stay alive on contact with Cu0.9Mg0.1(OH)2 (99.99% or 4 log10 reduction). The bactericidal performances of Cu(OH)2 and the magnesium-substituted counterparts (i.e. Cu1-xMgx(OH)2) are not linked to cupric ions they release in water since their mass concentrations after 180 min are much lower than minimal concentrations inhibiting the growth of E. coli and S. aureus. Finally, an EPR spin trapping study reveals how these nanorods kill bacteria in water: only the presence of hydrogen peroxide, a by-product of the normal metabolism of oxygen in aerobic bacteria, allows the Cu(OH)2 and its magnesium-substituted counterparts to produce a lethal amount of free radicals, the majority of which are the highly toxic HO˙.

Hydration and bactericidal activity of nanometer- and micrometer-sized particles of rock salt-type Mg1-xCuxO oxides.

Copper substitution together with nano-structuring are applied with the aim to increase the bactericidal performances of the rocksalt-type MgO oxide. The partial substitution of magnesium ions with Cu2+ has been successfully achieved in both micrometer- and nanometer-sized particles of MgO up to 20 mol% in increments of 5 mol%. Microstructural analyses using the Integral Breadth method revealed that the thermal decomposition of the single source precursor Mg1-xCux(OH)2-2y(CO3)y.zH2O at 400 °C creates numerous defects in 10-20 nm-sized particles of Mg1-xCuxO thus obtained. These defects make the surface of nanoparticles highly reactive towards the sorption of water molecules, to the extent that the cubic cell a parameter in as-prepared Mg1-xCuxO expands by +0.24% as soon as the nanoparticles are exposed to ambient air (60% RH). The hydration of Mg1-xCuxO particles in liquid water is based on a conventional dissolution-precipitation mechanism. Particles of a few microns in size dissolve all the more slowly the higher the copper content and only Mg(OH)2 starts precipitating after 3 h. In contrast, the dissolution of all 10-20 nm-sized Mg1-xCuxO particles is complete over a 3 h period and water suspension only contains 4-12 nm-sized Mg1-xCux(OH)2 particles after 3 h. Thereby, the bactericidal activity reported for water suspension of Mg1-xCuxO nanoparticles depends on the speed at which these nanoparticles dissolve and Mg1-xCux(OH)2 nanoparticles precipitate in the first 3 h. Only 10 mol% of cupric ions in MgO nanoparticles are sufficient to kill both E. coli and S. aureus with a bactericidal kinetics faster and reductions in viability at 3 h (6.5 Log10 and 2.7 Log10, respectively) higher than the conventional antibacterial agent CuO (4.7 Log10 and 2 Log10 under the same conditions). EPR spin trapping study reveals that "hydroxylated" Mg0.9Cu0.1O as well as Mg0.9Cu0.1(OH)2 nanoparticles produce more spin-adducts with highly toxic hydroxyl radicals than their copper-free counterparts. The rapid mass adsorption of Mg0.9Cu0.1(OH)2 nanoparticles onto the cell envelopes following their precipitation together with their ability to produce Reactive Oxygen Species are responsible for the exceptionally high bactericidal activity measured in the course of the hydroxylation of Mg0.9Cu0.1O nanoparticles.

Organic-inorganic interactions revealed by Raman spectroscopy during reversible phase transitions in semiconducting [(C2H5)4N]FeCl4.

The alkylammonium halogenoferrate families are subjected to diverse studies according to their wide field application. However, these compounds show various transitions depending on the preparation process. In this paper, the [(C2H5)4N]FeCl4 compound was successfully synthesized using a slow evaporation solution growth method at room temperature. An optical absorption measurement confirms the semiconductor nature with a band gap around 2.95 eV. The X-ray powder diffraction (XRPD) data confirmed the formation of a single-phase with hexagonal-type structure. The differential scanning calorimetry (DSC) indicated that the [(C2H5)4N]FeCl4 compound undergoes eight reversible phase transitions between 193 and 443 K. At high temperature (T > 423 K) the plastic nature of the crystals was confirmed. Temperature-controlled X-ray diffraction reveals that the thermal expansion of the crystal structure is non homothetic in the (a,b) plane and along the c axis. The temperature dependence of the Raman spectra up to 443 K revealed specific reorientations and molecular displacements of the organic and inorganic components associated with the phase transitions. We aim to thermally stabilize the [(C2H5)4N]FeCl4 compound which has a band gap suitable for photocatalytic processes.

Enhanced bactericidal activity of brucite through partial copper substitution.

Brucite Mg(OH)2 belongs to a family of two-dimensional compounds with a CdI2-type structure built up from layers of edge-sharing octahedra delineating 2D galleries. In the current study, nanometer-sized platelets of copper substituted Mg(OH)2 were prepared by co-precipitation at room temperature in mixed alkaline (NaOH/Na2CO3) medium. Very weak substitution of a few hydroxyl ions by carbonate groups was highlighted at first by infrared spectroscopy and then quantified by thermogravimetric (TG) and mass spectrometric (MS) evolved gas analyses. The presence in a very low amount of water molecules in the galleries induces disorder in the stacking of layers of edge-sharing octahedra along the c-axis. The dehydration of the hydroxides taking place below 225 °C preserves the brucite-type structure of the samples while suppressing the stacking disorder. Copper substitution greatly enhances the bactericidal activity of nanometer-sized platelets of brucite against two bacteria frequently involved in healthcare-associated-infections. 10 mol% of cupric ions in Mg(OH)2 (a copper loading of 0.102 mg mL-1 in the suspension) were sufficient to induce, after 3 h in contact, 100% and 99.3% reductions in viability of Gram-negative E. coli and Gram-positive S. aureus, respectively (reductions as low as 23% and 48% are reported for the parent compound Mg(OH)2 in the same conditions). A good compromise between fast bactericidal kinetics and a high reduction in viability is reached by the 15 mol% copper-substituted Mg(OH)2 hydroxide. Its use gives the opportunity to five-fold reduce the copper loading of the bactericidal agent while being at least equally or even more efficient compared to the conventional CuO (a Cu loading of 0.799 mg mL-1 and 0.154 mg mL-1 in the suspension of CuO and 15 mol% copper substituted Mg(OH)2 particles, respectively).

Copper-Substituted NiTiO3 Ilmenite-Type Materials for Oxygen Evolution Reaction.

Single Ni1-xCuxTiO3 (0.05 ≤ x ≤ 0.2) Ilmenite-type phases were successfully prepared through a solid-state reaction route using divalent metal nitrates as precursors and characterized. Their electrocatalytic performance for oxygen evolution reaction (OER) in alkaline media is presented. The Cu content was determined (0.05 ≤ x ≤ 0.2) by X-ray diffraction. A thorough powder neutron diffraction study was carried out to identify the subtle changes caused by copper substitution in the structure of NiTiO3. The evolution of the optical and magnetic properties with the Cu content was also investigated on the raw micrometer-sized particles. A reduction in particle size down to ≈15 nm was achieved by ball-milling the raw powder prepared by the solid-state reaction. The best catalytic activity for OER was obtained for nanometer-sized particles of Ni0.8Cu0.2TiO3 drop-casted on the Cu plate. For this electrode, a current density of 10 mA cm-2 for oxygen production was generated at 345 and 470 mV applied overpotentials with 1 and 0.1 M NaOH solutions as electrolytes, respectively. The catalyst retained this OER activity at 10 mA cm-2 for long-term electrolysis with a faradic efficiency of 90% for O2 production in a 0.1 M NaOH electrolyte.

Reducing the thermal conductivity of La2Mo2O9 with a trivalent praseodymium substitution for its potential use as a thermal barrier coating.

(La1-xPrx)2Mo2O9 powders were synthesized by solid state reaction for x = 0.00, 0.10, 0.25, 0.50, 0.75 and 1.00. Dense pellets were obtained by conventional sintering in air. Their thermal stability and thermal conductivity were measured from 100 to 700 °C and their cell parameters refined from X-ray powder diffraction pattern by the Rietveld method. A 50 mol% isovalent substitution of lanthanum in La2Mo2O9 by praseodymium stabilizes the high temperature ß phase while reducing the thermal conductivity of the parent compound by 11-18%. For a praseodymium content x higher than 0.75, the thermal conductivity increases and a phase transition similar to that of La2Mo2O9 is observed except that the room temperature phase appears to be this time triclinic in symmetry.

Extension of the A nB nO3 n+2 Slicing/Oxidizing Process from 2D Layered to 1D Columnar Perovskites: The La7W7-xM xO30 Structural Family with Di-, Tri-, and Tetravalent Transition Metal M Substitutes to Tungsten.

The A7B7O30 structural type is a columnar-perovskite-type arrangement originally evidenced in La7Mo7O30 [Goutenoire et al. J. Solid State Chem. 1999, 142, 228], an intermediate reduction product of fast oxide-ion conductor La2Mo2O9. Subsequently, this new structural family has been extended to La7W6+4M5+3O30 (M = Nb, Ta) [Goutenoire et al. J. Solid State Chem. 2005, 178, 2811]. Here we show that it is possible to further extend the solid solution through partial substitution of hexavalent tungsten by di-, tri-, or tetravalent transition metals. The general formula is La3+7W6+7- xM m+ xO30 with x = 3/(6 - m), or m = 6 - 3/ x. Single phase samples with M m+ = Zn2+, Fe3+, and Ti4+ have been prepared, and their crystal structure refined using X-ray powder diffraction. In the structure, the transition metal with lower valence is preferentially located in the octahedral site shared by consecutive trans-connected perovskite cages, whose diagonal runs along the threefold axis of the structure. Close similarities are noticed with the cationic repartition and distortion of coordination polyhedra in compounds belonging to the A nB nO3 n+2 series of layered perovskites. A rationale is proposed, which includes the A7B7O30 structural type as a subsequent 1D step to the 3D → 2D A nB nO3 n+2 scheme of perovskite framework slicing by progressive oxygen insertion through decreasing n.

Synthesis and characterization of nickel-doped ceria nanoparticles with improved surface reducibility.

Nickel-doped ceria nanoparticles (Ni0.1Ce0.9O2-x NPs) were fabricated from Schiff-base complexes and characterized by various microscopic and spectroscopic methods. Clear evidence is provided for incorporation of nickel ions in the ceria lattice in the form of Ni3+ species which is considered as the hole trapped state of Ni2+. The Ni0.1Ce0.9O2-x NPs exhibit enhanced reducibility in H2 as compared to conventional ceria-supported Ni particles, while in O2 the dopant nickel cations are oxidized at higher valence than the supported ones.

On the local order of amorphous La2Mo2O6.7.

The amorphous reduction product of the oxide ion conductor La2Mo2O9 was previously shown to be a good, sulphur-tolerant, anode material for solid oxide fuel cell devices (X. C. Lu, J. H. Zhu, J. Electrochem. Soc., 2008, 155(10), B1053). In this paper, we study the local order of amorphous La2Mo2O6.7 using X-ray absorption spectroscopy analyses and electronic paramagnetic resonance. The extended X-ray absorption fine structure analysis of local arrangements around Mo in La2Mo2O6.7 is first carried out on the basis of strong distortions from three crystalline models of La2Mo2O9, La7Mo7O30 and La2Mo2O7. The extended X-ray absorption fits obtained from both La2Mo2O9 and La7Mo7O30 yield similar atomic arrangements in the amorphous phase, upon large atomic displacements. However it is also possible to fit the spectrum using the paths of La2Mo2O7, in better agreement with EPR results suggesting the presence of Mo-Mo pairs. Simpler arrangements, built from theoretical single scattering paths, are considered. All models are discussed and compared. A most probable short range structure around Mo in this amorphous phase is proposed. It both fulfills EPR results and appears coherent with the presence of ionic conductivity.

Instability of the Ionic Conductor Li6BaLa2B2O12 (B = Nb, Ta): Barium Exsolution from the Garnet Network Leading to CO2 Capture.

The instability of the two garnets Li6BaLa2B2O12 (B = Nb, Ta) has been studied on samples prepared in powder form by solid-state reaction. For this study, we coupled different techniques: powder X-ray diffraction, IR spectrometry, thermal analysis, transmission electron microscopy, and complex impedance spectroscopy. We showed that in ambient air and at low temperature (<150 °C), a spontaneous Li+/H+ exchange occurs. At higher temperature (500-700 °C), a progressive exsolution of the barium from the garnet framework is observed, leading to the formation of a second garnet, BaCO3, and a 3D cubic perovskite. To conclude this work, we studied the impact of barium exsolution on the ionic conductivity measured by complex impedance spectroscopy. We observed a significant decrease in the starting bulk conductivity (60%) when the pellet is heated at 500 °C for 5 h.

Cationic Intermixing and Reactivity at the La2 Mo2 O9 /La0.8 Sr0.2 MnO3-δ Solid Oxide Fuel Cell Electrolyte-Cathode Interface.

Among standard high-temperature cathode materials for solid oxide fuel cells, La0.8 Sr0.2 MnO3-δ (LSM) displays the least reactivity with the oxide-ion conductor La2 Mo2 O9 (LMO), yet a reaction is observed at high processing temperatures, identified by using XRD and focused ion beam secondary-ion mass spectrometry (FIB-SIMS) after annealing at 1050 and 1150 °C. Additionally, Sr and Mn solutions were deposited and annealed on LMO pellets, as well as a Mo solution on a LSM pellet. From these studies several reaction products were identified by using XRD and located by using FIB-SIMS on the surface of pelletised samples. We used depth profiling to show that the reactivity extended up to ∼10 µm from the surface region. If Sr was present, a SrMoO4 -type scheelite phase was always observed as a reaction product, and if Mn was present, LaMnO3+δ single crystals were observed on the surface of the LMO pellets. Additional phases such as La2 MoO6 and La6 MoO12 were also detected depending on the configuration and annealing temperature. Reaction mechanisms and detailed reaction formulae are proposed to explain these observations. The strongest driving force for cationic diffusion appears to originate from Mo(6+) and Mn(3+) cations, rather than from Sr(2+) .

Reduction Kinetics of La2Mo2O9 and Phase Evolution during Reduction and Reoxidation.

An amorphous reduced form of oxide ion conductor La2Mo2O9 had been proposed as sulfur-tolerant anode material for solid oxide fuel cell, but its oxygen content was not known. In this paper, we investigate the reduction kinetics by diluted hydrogen of La2Mo2O9 to amorphous, and the oxygen range of the amorphous form. The reduction kinetics is studied as a function of the powder specific surface area and of the temperature, on powders synthesized by solid state reaction and by polyol process using two different solvents. The reduction process was carried out by TGA under 10% H2 diluted in argon, and its kinetics is analyzed and modeled. As expected, small particles and high temperature lead to higher reduction rates. Several reduction steps were identified by XRD during the process. At 700 °C La2Mo2O9 is directly reduced into the amorphous phase La2Mo2O7-y, whereas at 760 °C reduction occurs through an intermediate crystallized La7Mo7O30 (≅ La2Mo2O8.57) phase before amorphization. In both cases, further reduction of La2Mo2O6.2 amorphous phase leads to an exsolution of metallic molybdenum and a molybdenum deficiency in the amorphous phase. Reoxidation of amorphous La2Mo2O7-y was studied by TGA, DTA and XRD. At low temperature in air, the reduced compounds are reoxidized while remaining amorphous. The annealing for 60 h at 350 °C in air of reduced La2Mo2O6.66, obtained beforehand by solid state reaction, gives an amorphous phase with composition La2Mo2O8.85. The existence domain of the reduced amorphous phase in terms of oxygen content therefore ranges at least from O6.2 to O8.85, thus including the composition La2Mo2O8.50 of the amorphous surface layer at the origin of a huge increase of ionic conductivity recently reported in nanowires of La2Mo2O9.

Thermodynamic stability of La2Mo2-yWyO9, La2Mo2-yWyO8.96+0.02y and La7Mo7(2-y)/2W7y/2O30 (y = 0, 0.5 and 1.0).

The role of W content on the limit oxygen partial pressure (pO2) for stability of fast oxygen-ion conductors La2Mo2-yWyO9 with y = 0, 0.5 and 1.0 has been studied by means of thermogravimetric analysis (TGA) under controlled atmospheres. At 718 °C, below the pO2 stability limit of La2Mo2-yWyO9, the perovskite related compounds La7Mo7(2-y)/2W7y/2O30 were stabilized even for y = 1.0. At 608 °C, the first stage of reduction of ß-La2Mo2-yWyO9 leads to the formation of the crystallized oxygen deficient La2Mo2-yWyO8.6+0.02y phase. X-ray powder diffraction shows that the stabilization of the high temperature ß-form through tungsten substitution observed in fully oxidized La2Mo2-yWyO9 samples is preserved upon slight reduction. The n-type conductivity arising from the mixed valence state of molybdenum becomes less and less predominant as the W content increases. Further reduction causes amorphization. At both temperatures, W substitution does not enhance the thermodynamic stability of the La2Mo2-yWyO9 ion conductor under a reducing atmosphere but only slows down the kinetics of reduction.

Thermodynamic stability, structural and electrical characterization of mixed ionic and electronic conductor La2Mo2O(8.96).

Thermogravimetric analysis (TGA) technique in controlled oxygen partial pressure (pO(2)) atmospheres has been used to obtain equilibrium oxygen content data as a function of pO(2) on the La(2)Mo(2)O(9-δ) system resulting from the partial reduction of fast oxide-ion conductor La(2)Mo(2)O(9) (LM). Thermodynamic conditions for stabilization of crystalline La(7)Mo(7)O(30) and amorphous La(2)Mo(2)O(7-y) at 718 °C have been determined and discussed. At 608 °C, the compound reported for the first time La(2)Mo(2)O(8.96) (LM896) has been found. The crystalline form and transition temperature in LM896 have been identified by X-ray diffraction at room temperature (XRD) and at controlled temperature. Conductivity curves obtained by electrochemical impedance spectroscopy (EIS) as a function of temperature for both LM and LM896 have been compared. The results indicate that LM896 is a mixed ionic and electronic conductor (MIEC).

Analysis of the local structure of phosphorus-substituted LAMOX oxide ion conductors.

The effect of partial substitution of molybdenum by phosphorus on the global and local structural arrangement of the fast oxide-ion conductor La(2)Mo(2)O(9) (LAMOX) has been studied by X-ray powder diffraction as well as (139)La and (31)P solid state NMR. The diffraction patterns show that La(2)Mo(2-y)P(y)O(9-y/2) forms a solid solution at low phosphorus concentrations, and that there is a structural phase transition upon increasing phosphorus concentration. This phase transition is also reflected in (139)La and (31)P NMR spectra. The possibility to excite (31)P multiple-quantum coherences of one of the (31)P NMR signals gives evidence of an accumulation of phosphorus atoms on neighbouring Mo-type sites already before formation of three-dimensional precipitates. On the basis of our X-ray and NMR results we propose a possible structural arrangement of the compound La(2)Mo(2-y)P(y)O(9-y/2) that explains the experimental observations by crystal twinning.

Topological metastability and oxide ionic conduction in La(2)-(x)Eu(x)Mo(2)O(9).

The effect of partial substitution, up to x = 0.4, of La by trivalent Eu on the phase stability, thermal expansion, and transport properties of La2Mo2O9 are investigated using temperature-controlled X-ray powder diffraction, differential thermal analysis, and complex impedance spectroscopy. At low europium content (x < or = 0.1), the alpha-beta phase transition is observed at a temperature dependent on the sample shaping (powder, pellet, etc.). At high europium content (x > or = 0.25), the samples remain cubic (beta phase), regardless of the shaping. In the intermediate range of europium content (x = 0.15, 0.2), the phase stability is highly sensitive to the thermal history and the sample shaping, with a double-reversed beta-alpha-beta transition suppressed by the shaping/sintering process. The influence of the amount of europium on the transport mechanisms and parameters is studied in both low- (Arrhenius) and high-temperature (Vogel-Tammann-Fulcher = VTF) regimes. If the effect of substitution is rather mild and monotonous within each transport regime and crystallographic phase, an abrupt change in the Arrhenius parameters between the alpha- and beta-type phases is observed.

PbnI4n+2(2n+2)- ribbons (n = 3, 5) as dimensional reductions of 2D perovskite layers in cystamine cation based hybrids, also incorporating iodine molecules or reversible guest water molecules.

Pb(n)I(4n+2)((2n+2)-) (n = 3, 5) ribbons, which can be regarded as dimensional reductions of 2D perovskite layers, are stabilized by diprotonated cystamine cations in (NH(3)(CH(2))(2)SS(CH(2))(2)NH(3))(4)Pb(3)I(14),I(2) (1) and (NH(3)(CH(2))(2)SS(CH(2))(2)NH(3))(6)Pb(5)I(22).4H(2)O (2). Both 1 and 2 have interesting structural characteristics; it is unprecedented that the ribbons are linked via I(2) molecules incorporated in the lattice of 1, while tetrameric water clusters are trapped in the structure of 2. 2 undergoes a (reversible) water desorption process at 310 K leading to (NH(3)(CH(2))(2)SS(CH(2))(2)NH(3))(6)Pb(5)I(22).2H(2)O (3). The electrical behavior of 2 and 3 has been investigated in the ranges 293-310 K and 310-358 K respectively. Above 310 K, the electronic contribution remains constant while the ionic transference number tends towards unity showing almost pure ionic transport at 360 K (6 x 10(-7) S cm(-1) at 330 K) originating probably from the migration of protons through the hydrogen bonds connecting the water molecules to the cystamine counter cations.

On the flexibility of the structural framework of cubic LAMOX compounds, in relationship with their anionic conduction properties.

A mathematical analysis of the cubic crystal structure of fast oxide-ion conductor beta-La(2)Mo(2)O(9) (and derived members of the LAMOX family) shows that its cationic sublattice can behave as a semirigid framework. Tilt/rotation of rigid [O1La(3)Mo] anti-tetrahedral units about their 3-fold axis can open up tunnels in the cationic framework, therefore favoring the mobility of O2 and O3 oxide ions located in these tunnels, as confirmed by molecular dynamics simulations. Such a process is likely to assist the anionic transport and explain the postulated transition from Arrhenius-type to VTF (Vogel-Tamman-Fulcher)-type behavior propounded to account for the peculiar conductivity curvature observed at high temperature in all the cubic LAMOX compounds. It also clarifies the correlated extra cell volume expansion observed at the same temperature in all these materials.