Sequestration of some biogenic amines and poly(allyl)amine by high molecular weight polycarboxylic ligands in aqueous solution

The interactions of two high molecular weight polycarboxylic ligands [polyacrylic-co-maleic, MW = 70 kDa, and poly(methyl vinyl ether-co-maleic acid), MW = 15 kDa] with some polyamines [1,4-diaminobutane (or putrescine), histamine and poly(allyl)amine, MW = 15 kDa] were studied, at t = 25 °C and at low ionic strength (I = 0.015 mol L^? 1) by potentiometric measurements. For all investigated systems, the formation of (am)(L)H_i species was found (am = amine, L = polycarboxylic ligand, i = 1…4); the stability of polyammonium–polycarboxylate complexes is fairly high and the formation percentage of most species reaches ～ 90% in the experimental conditions (mmolar concentration of reactants). The dependence on temperature and ionic strength of the stability of polyamine–polycarboxylate species was studied using some semiempirical equations and enthalpy data for the protonation of both components. The sequestering ability of polyelectrolytes towards amines was modeled by a sigmoid Boltzman type equation and was defined by calculating the parameter pL₅₀ (the total ligand concentration, as ? log C_L, able to bind 50% of cation); this parameter gives an objective representation of this ability. The dependence of pL₅₀ on pH, ionic strength and temperature was studied too.     

Synthesis and electrical properties of nanocrystalline Ca1 − xEuxMnO3 ± δ (0.1 ≤ x ≤ 0.4) powders prepared at low temperature using citrate gel method

Nanopowders of Ca_1 − xEu_xMnO₃ (0.1 ≤ x ≤ 0.4) manganites were synthesized as a single phase using the auto gel-combustion method. The citrate method shows to be simple and appropriate to obtain single phases avoiding segregation or contamination. The Ca_1 − xEu_xMnO₃ system has been synthesized at 800 °C during 18 h, against the conventional method of mixing oxides used to obtain these materials at higher temperatures of synthesis. The formation reaction was monitored by X-ray diffraction (XRD) analysis and an infrared absorption technique (FTIR). The polycrystalline powders are characterised by nanometric particle size, ∼ 48 nm as determined from X-ray line broadening analysis using the Scherrer equation. Morphological analysis of the powders, using the scanning electron microscope (SEM), revealed that all phases are homogeneous and the europium-substituted samples exhibit a significant decrease in the grain size when compared with the undoped samples. The structure refinement by using the Rietveld method indicates that the partial calcium substitution by europium (for x ≥ 0.3) modifies the orthorhombic structure of the CaMnO₃ perovskite towards a monoclinic phase. All manganites show two active IR vibrational modes around 400 and 600 cm^− 1. The high temperature dependence of electrical resistivity (between 25 and 600 °C) allows us to conclude that all the samples exhibit a semiconductor behaviour and the europium causes a decrease in the electrical resistivity by more than one order of magnitude. The results can be well attributed to the Mn⁴⁺/Mn³⁺ ratio.     

The interaction of O2 with the surface of polycrystalline gadolinium at the temperature range 300–670 K

Auger-Electron-Spectroscopy (AES) and Direct-Recoils-Spectrometry (DRS) were applied to study the interaction of O₂ with a polycrystalline gadolinium surface, in the temperature range 300–670 K and oxygen pressure up to 2 × 10^? 6 Torr. It has been found that initial uptake of oxygen, at coverage measurable by the techniques used here, results in rapid oxide island formation. The subsurface is believed to be a mixture of oxide particles and oxygen dissolved in the Gd metal, the latter being the mobile species, even at relatively low temperatures.Enhanced inward diffusion of oxygen starts as early as 420 K and dictates the surface oxygen concentration and effective thickness of the forming oxide. The oxygen accumulation rate at the near-surface region, as measured by the O(KLL) AES signal intensity, goes through a maximum as a function of temperature at 420 K. This is a result of the combination of still efficient oxygen chemisorption that increases surface occupation and slow inward diffusion. The thickest oxide, ~ 1.7 nm, is formed at 300 K and its effective thickness was found to decrease with increasing temperature (due to oxygen dissolution into the metal bulk).Diffusion coefficients of the oxygen dissolution into the bulk were evaluated for various temperatures utilizing models for infinitely thin oxide layer and thick oxide layer, respectively. The best fit under our experimental procedure was obtained by the thick layer model, and the coefficients that were calculated are D₀ = 2.2 × 10^? 16m²s^? 1 and E_a = 46kJ/mol.     

Structural,XPS and impedance analysis of LixCoVO4 (x = 0.8, 1.0, 1.2)

Lithium cobalt vanadate Li_xCoVO₄ (x = 0.8; 1.0; 1.2) has been prepared by a solid state reaction method. The XRD analysis confirms the formation of the sample. A new peak has been observed for Li_1.0CoVO₄ and for Li_1.2CoVO₄ indicating the formation of a new phase. The XPS analysis indicates the reduction in the oxidation of vanadium and oxygen with the addition of Li in Li_xCoVO₄ (x = 0.8, 1.0, 1.2). The impedance analysis gives the conductivity value as 2.46 × 10^− 5, 6.16 × 10^− 5, 9 × 10^− 5 Ω^− 1 cm^− 1 for Li_xCoVO₄ (x = 0.8; 1.0; 1.2), all at 623 K. The similarity in the bulk activation energy (E_a) and the activation enthalpy for migration of ions (E_ω) indicate that the conduction in Li_1.2CoVO₄ has been due to hopping mechanism.     

Self-induced polarization rotation of laser beam in fullerene (C70) solutions

Nonlinear self-rotation of elliptically polarized laser pulses (λ = 532 nm, τ_FWHM ~ 12 ns) in toluene, benzene and binary mixture (toluene + ethanol) solutions of fullerene C₇₀ has been investigated experimentally. Absolute values and signs of the nonlinear refractive indices (n₂) and nonlinear optical susceptibilities χ⁽³⁾(ω, ? ω, ω) of C₇₀ solutions in toluene and benzene at different values of polarization ellipse (θ = 0.2 ÷ 0.8) have been determined. High-resolution transmission electron microscope studies of C₇₀ solutions showed that in toluene + ethanol mixtures ball-shaped C₇₀ clusters are formed with particle sizes in the range ~ 100 ÷ 500 nm. It has been demonstrated, that the clusters sizes depend on the C₇₀ concentration and volume fraction of ethanol in toluene. Correlation between the processes of C₇₀ clusters formation in solutions and the values of polarization self-rotation angle of transmitted laser beam has been demonstrated. Physical mechanisms of laser induced optical activity in fullerene solutions have been discussed.     

Interaction of dioxouranium(VI) ion with EDTA at different ionic strengths

The formation of complex species of dioxouranium(VI) ion with EDTA was studied in the pH range of 1–3.5 and at 25 °C using a combination of potentiometric and spectrophotometric techniques. Results showed evidence for formation of the following species: [UO₂H₄EDTA]²⁺, [UO₂H₃EDTA]⁺, and [UO₂H₂EDTA]. Investigations were performed in sodium perchlorate as background electrolyte at 0.1, 0.3, 0.5, 0.7, and 1.0 mol dm^? 3. The parameters based on the formation constants were calculated, and the dependences of protonation and the stability constants on ionic strength are described. The dependence on ionic strength of the formation constants was analyzed using the specific ion interaction theory (SIT) model. The stability constant values at infinite dilution, obtained using SIT model, are log β°₁₄₁ = 6.77, log β°₁₃₁ = 5.99 and log β°₁₂₁ = 9.29, where indexes for the overall stability constant, β_pqr, refer to the equilibrium pUO₂²⁺ + qH⁺ + rL^4? ? M_pH_qL_r^{(2p + q ? 4r)}. The specific interaction coefficients are also reported.     

Microfluidic acoustic trapping force and stiffness measurement using viscous drag effect

It has recently been demonstrated that it was possible to individually trap 70 μm droplets flowing within a 500 μm wide microfluidic channel by a 24 MHz single element piezo-composite focused transducer. In order to further develop this non-invasive approach as a microfluidic particle manipulation tool of high precision, the trapping force needs to be calibrated to a known force, i.e., viscous drag force arising from the fluid flow in the channel. However, few calibration studies based on fluid viscosity have been carried out with focused acoustic beams for moving objects in microfluidic environments.In this paper, the acoustic trapping force (F_trapping) and the trap stiffness (or compliance k) are experimentally determined for a streaming droplet in a microfluidic channel. F_trapping is calibrated to viscous drag force produced from syringe pumps. Chebyshev-windowed chirp coded excitation sequences sweeping the frequency range from 18 MHz to 30 MHz is utilized to drive the transducer, enabling the beam transmission through the channel/fluid interface for interrogating the droplets inside the channel. The minimum force (F_min,trapping) required for initially immobilizing drifting droplets is determined as a function of pulse repetition frequency (PRF), duty factor (DTF), and input voltage amplitude (V_in) to the transducer. At PRF = 0.1 kHz and DTF = 30%, F_min,trapping is increased from 2.2 nN for V_in = 22 V_pp to 3.8 nN for V_in = 54 V_pp. With a fixed V_in = 54 V_pp and DTF = 30%, F_min,trapping can be varied from 3.8 nN at PRF = 0.1 kHz to 6.7 nN at PRF = 0.5 kHz. These findings indicate that both higher driving voltage and more frequent beam transmission yield stronger traps for holding droplets in motion.The stiffness k can be estimated through linear regression by measuring the trapping force (F_trapping) corresponding to the displacement (x) of a droplet from the trap center. By plotting F_trapping – x curves for certain values of V_in (22/38/54 V_pp) at DTF = 10% and PRF = 0.1 kHz, k is measured to be 0.09, 0.14, and 0.20 nN/μm, respectively. With variable PRF from 0.1 to 0.5 kHz at V_in = 54 V_pp, k is increased from 0.20 to 0.42 nN/μm. It is shown that a higher PRF leads to a more compliant trap formation (or a stronger F_trapping) for a given displacement x. Hence the results suggest that this acoustic trapping method has the potential as a noninvasive manipulation tool for individual moving targets in microfluidics by adjusting the transducer’s excitation parameters.     

Ultrasound assisted synthesis of TiO2–WO3 heterostructures for the catalytic degradation of Tergitol (NP-9) in water

TiO₂–WO₃ heterostructures were synthesized at room temperature, ambient pressure, and short reaction time via a sonochemical approach. TEM and EDX images show that the prepared TiO₂–WO₃ heterostructures consist of globular agglomerates (∼250 nm in diameter) composed of very small (<5 nm) dense particles (WO₃) dispersed inside the globules. The observed less intense monoclinic WO₃ diffraction peak (around 2θ = 22° belonging to (0 0 1) plane) and the high intense hexagonal WO₃ diffraction peak (around 2θ = 28° belonging to (2 0 0) plane) in XRD indicate that there may be phase transition occurring due to the formation of intimate bond between TiO₂ and WO₃. In addition, the formation of such new phase was also observed from Raman spectra with a new peak at 955 cm⁻¹, which is due to the symmetric stretching of W = O terminal. The catalytic activity of TiO₂–WO₃ heterostructures was tested for the degradation of wastewater pollutant containing Tergitol (NP-9) by a process combined with ozonation and it showed two-fold degradation rate compared with ozone process alone.     

Magnetic fluid thermochemotherapy of murine tumors

Four series of water-based dextran-ferrite (DF) magnetic fluids (MFs) containing Melphalan (MP) were prepared. Their saturation magnetization (M_s) was from 0.8 to 7.8 kA/m; specific power absorption rates were 240 W/g Fe. After nine courses of magnetic fluid thermochemotherapy with MP containing DF MF (M_s 7.5 kA/m, pH 6.6, ζ+15 mV) at 44–46 °C for 30 min in an AC magnetic field (0.88 MHz, 9.3 kA/m, 0.3 kW), complete P388 tumor regression was seen in 30% of BDF₁ mice. Furthermore, a life span increase of 180% was achieved.     

Thermal and sonochemical synthesis of porous (Ce,Zr)O2 mixed oxides from metal β-diketonate precursors and their catalytic activity in wet air oxidation process of formic acid

Porous (Ce_0.5Zr_0.5)O₂ solid solutions were prepared by thermolysis (T = 285 °C) or sonolysis (20 kHz, I = 32 W cm⁻², P_ac = 0.46 W mL⁻¹, T = 200 °C) of Ce(III) and Zr(IV) acetylacetonates in oleylamine or hexadecylamine under argon followed by heat treatment of the precipitates obtained in air at 450 °C. Transmission Electron Microscopy images of the samples show nanoparticles of ca. 4–6 nm for the two synthetic approaches. The powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray and μ-Raman spectroscopy of solids obtained after heat treatment indicate the formation of (Ce_0.5Zr_0.5)O₂ solid solutions with a metastable tetragonal crystal structure for the two synthetic routes. The specific surface area of the samples varies between 78 and 149 m² g⁻¹ depending on synthesis conditions. The use of Barrett–Joyner–Halenda and t-plot methods reveal the formation of mixed oxides with a hybrid morphology that combines mesoporosity and microporosity regardless of the method of preparation. Platinum nanoparticles were deposited on the surface of the mixed oxides by sonochemical reduction of Pt(IV). It was found that the materials prepared by sonochemistry exhibit better resistance to dissolution during the deposition process of platinum. X-ray photoelectron spectroscopy analysis shows the presence of Pt(0) and Pt(II) on the surface of mixed oxides. Porous (Ce_0.5Zr_0.5)O₂ mixed oxides loaded with 1.5 %wt. platinum exhibit high activity in catalytic wet air oxidation of formic acid at 40 °C.     

Bulk and surface properties of ionic salt CsH5(PO4)2

We report a comparative study of transport and thermodynamic properties of single-crystal and polycrystalline samples of the ionic salt CsH₅(PO₄)₂ possessing a peculiar three-dimensional hydrogen-bond network. The observed potential of electrolyte decomposition ≈ 1.3 V indicates that the main charge carriers in this salt are protons. However, in spite of the high proton concentration, the conductivity appears to be rather low with a high apparent activation energy E_a ≈ 2 eV, implying that protons are strongly bound. The transport anisotropy though is not large, correlates with the crystal structure: the highest conductivity is found in the [001] direction (σ_130 °C ∼ 5.6 × 10^− 6 S cm^− 1) while the minimal conductivity is in the [100] direction (σ_130 °C ∼ 10 ⁻⁶ S cm^− 1). The conductivity of polycrystalline samples appears to exceed the bulk one by 1–3 orders of magnitude with a concomitant decrease of the activation energy (E_a ≈ 1.05 eV), which indicates that a pseudo-liquid layer with a high proton mobility is formed at the surface of grains. Infrared and Raman spectroscopy used to study the dynamics of the hydrogen-bond system in single-crystal and polycrystalline samples have confirmed the formation of such a modified surface layer in the latter. However, no bulk phase transition into the superionic disordered phase is observed in CsH₅(PO₄)₂ up to the melting point T_melt ∼ 151.6 °C, in contrast to its closest relative compound CsH₂PO₄.     

Oxygen-rich Ti1−xO2 pillar growth at a gold nanoparticle–TiO2 contact by O2 exposure

In-situ gas-injection transmission electron microscopy revealed that a pillar grew at the edge of the interface of a gold nanoparticle and a TiO₂ substrate during exposure to O₂ gas at 100 Pa. The pillar was found to have a titanium-deficient chemical composition of Ti_1 ? xO₂ (x > 0) by electron energy loss spectroscopy (EELS). The spectra showed a chemical shift of oxygen and titanium ions to have ionic states of Ti³⁺ and O^y? (y < 3/2). The formation of the Ti_1 ? xO₂ at the contact edge of gold–Ti_1 ? xO₂ interface is discussed from the perspective of an O₂ affinity, which plays an important role in CO oxidation process of supported gold particle.     

Inelastic neutron scattering on iron-based superconductor BaFe2(As,P)2

Inelastic neutron scattering has been performed on powder sample of an iron-based superconductor BaFe₂(As_0.65P_0.35)₂ with superconducting transition temperature (T_c) = 30 K, whose superconducting (SC) order parameter is expected to have line node. In the normal state, constant-E scan of dynamical structure factor, S(Q, E), exhibits a peak structure centered at momentum transfer Q ～ 1.20 Å^?1, corresponding to antiferromagnetic wave vector. Below T_c, the redistribution of the magnetic spectral weight takes place, resulting in the formation of a peak at E ～ 12 meV and a gap below 6 meV. The enhanced magnetic peak structure is ascribed to the spin resonance mode, evidencing sign change in the SC order parameter similar to other iron-based high-T_c superconductors. It suggests that fully-gapped s_± symmetry dominates in this superconductor, which gives rise to high-T_c (=30 K) despite the nodal symmetry.     

Scanning electron microscopy of Ancylostoma spp. dog infective larvae captured and destroyed by the nematophagous fungus Duddingtonia flagrans

The interaction between the nematode-trapping fungus Duddingtonia flagrans (isolate CG768) against Ancylostoma spp. dog infective larvae (L₃) was evaluated by means of scanning electron microscopy. Adhesive network trap formation was observed 6 h after the beginning of the interaction, and the capture of Ancylostoma spp. L₃ was observed 8 h after the inoculation these larvae on the cellulose membranes colonized by the fungus. Scanning electron micrographs were taken at 0, 12, 24, 36 and 48 h, where 0 is the time when Ancylostoma spp. L₃ was first captured by the fungus. Details of the capture structure formed by the fungus were described. Nematophagous Fungus Helper Bacteria (NHB) were found at interactions points between the D. flagrans and Ancylostoma spp. L₃. The cuticle penetration by the differentiated fungal hyphae with the exit of nematode internal contents was observed 36 h after the capture. Ancylostoma spp. L₃ were completely destroyed after 48 h of interaction with the fungus. The scanning electron microscopy technique was efficient on the study of this interaction, showing that the nematode-trapping fungus D. flagrans (isolate CG768) is a potential exterminator of Ancylostoma spp. L₃.     

Ab-initio study of Sr-doping effects on nitric oxide adsorption on the LaO (001) surface of LaFeO3

Density-functional calculations of molecular nitric oxide (NO) on defective (La,Sr)O (001) surfaces of (La,Sr)FeO_3 ? δ using slab models are performed to elucidate the oxygen vacancy formation problem on the LaO (001) surface of LaFeO_3 ? δ.From the estimation of the NO adsorption energy, NO adsorption is found on (La,Sr)O surfaces of (La_0.83,Sr_0.17)FeO_3 ? δ with δ = 0 or 0.25.The absolute value of the NO adsorption energy shows a remarkable increase at oxygen vacancies in the top surface layer, where the nitrogen atoms of the adsorbed molecules are embedded in the first (La,Sr)O layer, because a bond with Fe in the second FeO₂ layer is formed.Our data shows that Sr doping promotes formation of oxygen vacancies, which keep the NO adsorption ability high.Thus, we conclude that if Sr doping increases the number of oxygen vacancy sites by a charge compensation effect, NO adsorption on LaFeO₃ is enhanced, which provides an explanation for several experimental observations.     

Exploring the role of samarium in the modification of rhodium catalysts through surface science approach

In this paper we review the preparation and reaction properties of ordered SmRh surface alloys and SmO_x/Rh(1 0 0) model catalyst which have been systematically investigated by low energy electron diffraction (LEED), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), high-resolution electron energy loss spectroscopy (HREELS) and temperature desorption spectroscopy (TDS). The growth of Sm on Rh(1 0 0) at room temperature follows the Stranski-Krastanov mode. Thermal treatment of the Sm films on Rh(1 0 0) leads to the formation of ordered SmRh surface alloys. An “inverse” SmO_x/Rh(1 0 0) model catalyst is produced under controlled oxidation of the SmRh surface alloy. CO adsorption on the SmRh alloy and SmO_x/Rh(1 0 0) surfaces gives rise to five TDS characteristic features originating from different adsorption sites. Both the site blocking of SmO_x and the electron transfer between SmO_x and Rh substrate significantly affect the CO adsorption. Acetate decomposition on both Rh(1 0 0) and the SmO_x/Rh(1 0 0) surfaces are found to undergo two competitive pathways that yields either (i) CO(a) and O(a) or (ii) CO₂(g) and H₂(g) at high temperature. The reactive desorption of acetic acid on SmO_x/Rh(1 0 0) is dramatically different from that on Rh(1 0 0). A rapid decomposition of acetic acid to produce CO(g) and CO₂(g) can be observed only on SmO_x/Rh(1 0 0), where CO(g) becomes the predominant product at 225 K, indicating a strong promotional effect of SmO_x in the selective decomposition of acetate. Finally, we briefly describe the future outlook of research on rare earth oxide/metal model catalysts.     

Synthesis and characterization of layered Li1−x(Ni0.5Co0.5)1−yFeyO2(0 ≤ (1 − x) ≤ 1 and 0 ≤ y ≤ 0.2) cathodes

Layered Li(Ni_0.5Co_0.5)_1−yFe_yO₂ cathodes with 0 ≤ y ≤ 0.2 have been synthesized by firing the coprecipitated hydroxides of the transition metals and lithium hydroxide at 700 °C and characterized as cathode materials for lithium ion batteries to various cutoff charge voltages (up to 4.5 V). While the y = 0.05 sample shows an improvement in capacity, cyclability, and rate capability, those with y = 0.1 and 0.2 exhibit a decline in electrochemical performance compared to the y = 0 sample. Structural characterization of the chemically delithiated Li_1−x(Ni_0.5Co_0.5)_1−yFe_yO₂ samples indicates that the initial O3 structure is maintained down to a lithium content (1 − x) ≈ 0.3. For (1 − x) < 0.3, while a P3 type phase is formed for the y = 0 sample, an O1 type phase is formed for the y = 0.05, 0.1 and 0.2 samples. Monitoring the average oxidation state of the transition metal ions with lithium contents (1 − x) reveals that the system is chemically more stable down to a lower lithium content (1 − x) ≈ 0.3 compared to the Li_1−xCoO₂ system. The improved structural and chemical stabilities appear to lead to better cyclability to higher cutoff charge voltages compared to that found before with the LiCoO₂ system.     

Formation of nickel and nickel,zinc-bearing ferrite in aqueous suspension by air oxidation

Stoichiometric Ni-bearing ferrite was formed by air oxidation of an iron(II) hydroxide suspension at an initial Ni : Fe_tot mol ratio (r_Ni) of 0.20 : 2.80 at pH 10.0 and 65°C. Most of products formed at r_Ni=0.40 : 2.60 and 0.60 : 2.40 were Ni-bearing ferrites, of which vacancies of Fe³⁺ ion on the lattice points may be considered. Only Ni, Zn-bearing ferrites were formed in the suspensions at initial (Ni + Zn)  : Fe_tot mol ratios (r_{Ni + Zn}) of 0.20 : 2.80–0.60 : 2.40 at pH 10.0 and 65°C. At higher r_Ni or r_{Ni + Zn} by-products containing Ni, Fe and O₄²⁻ were formed. The formation of the by-products was depressed in the suspensions containing chloride ions in the place of sulfate ions.     

Hole superconductivity in Nd2 − zCezCuO4

The reclassification of Nd_2 − zCe_zCuO₄from an electron superconductor to a hole superconductor is suggested by simple valence and electrostatics arguments: In Nd_2 − zCe_zCuO₄, isolated Ce substituting for Nd is not an electron donor; the proposed actual dopant is a defect-complex of Ce and interstitial oxygen which provides holes, making Nd_2 − zCe_zCuO₄a hole superconductor.     

Lithium-ionic diffusion and electrical conduction in the Li7La3Ta2O13 compounds

The electrical properties and the mechanism of lithium ionic diffusion in the Li₇La₃Ta₂O₁₃ compounds were investigated. The bulk and total conductivity at 300 K of the Li₇La₃Ta₂O₁₃ compound are about 3.3 × 10^? 6 S/cm and 2.6 × 10^? 6 S/cm, respectively. The activation energy of bulk and total conductivity is in the range of 0.38–0.4 eV. A prominent internal friction peak in Li₇La₃Ta₂O₁₃ compounds was observed around 280 K at 0.5 Hz, which is actually composed of two subpeaks (P₁ peak at lower temperature and P₂ peak at higher temperature). From the shift of peak position with frequency, the activation energy of 1.0 eV and the pre-exponential factor of relaxation time in the order of 10^? 18–10^? 21 s were obtained if one assumes Debye relaxation processes. These values of relaxation parameters strongly suggest the existence of interaction between the relaxation species (here lithium ions or vacancies). Based on the coupling model, the relaxation activation energies are deduced as 0.45 eV and the pre-exponential factor of relaxation time as 10^? 15 s. Judging from these relaxation parameters and the similarity of structure between Li₇La₃Ta₂O₁₃ and Li₅La₃Ta₂O₁₂ compounds, the P₁ and P₂ peaks are suggested to be related with the lithium ionic diffusion between 48g?48g and 24d?48g.