Dynamic contrast-enhanced MRI of gastric cancer: Correlations of the pharmacokinetic parameters with histological type,Lauren classification,and angiogenesis

PurposeTo compare the pharmacokinetic parameters derived from dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI) in gastric cancers of different histological type and Lauren classification, and to investigate whether DCE-MRI parameters correlate with vascular endothelial growth factor (VEGF) expression levels in gastric cancer.MethodsIncluded were 32 patients with gastric cancer who underwent DCE-MRI of the upper abdomen before tumor resection. DCE-MRI parameters including the volume transfer coefficient (K^trans), reverse reflux rate constant (K_ep), and extracellular extravascular volume fraction (V_e) were calculated from the tumor region. Post-operative specimens were used for determination of histological differentiation (i.e., non-mucinous, mucinous, or signet-ring-cell adenocarcinoma) as well as Lauren classification (intestinal type or diffuse type). VEGF expression was examined for assessing angiogenesis. DCE-MRI parameters with different histological type and Lauren classification were compared using independent samples t-test and analysis of variance, respectively. Correlations between DCE-MRI parameters and VEGF expression grades were tested using Spearman correlation analysis.ResultsAmong gastric adenocarcinomas of three different histological types, mucinous adenocarcinomas showed a higher V_e and lower K^trans than the others (P < 0.01). Between the two Lauren classifications, the diffuse type showed a higher V_e than the intestinal type (P < 0.001). The mean K^trans showed a significantly positive correlation with VEGF (r = 0.762, P < 0.001).ConclusionDCE-MRI permits noninvasive prediction of tumor histological type and Lauren classification and estimation of tumor angiogenesis in gastric cancer. DCE-MRI parameters can be used as imaging biomarkers to predict the biologic aggressiveness of a tumor as well as patient prognosis.     

Flow versus permeability weighting in estimating the forward volumetric transfer constant (Ktrans) obtained by DCE-MRI with contrast agents of differing molecular sizes

PurposeTo quantify the differential plasma flow- (F_p-) and permeability surface area product per unit mass of tissue- (PS-) weighting in forward volumetric transfer constant (K^trans) estimates by using a low molecular (Gd-DTPA) versus high molecular (Gadomer) weight contrast agent in dynamic contrast enhanced (DCE) MRI.Materials and methodsDCE MRI was performed using a 7T animal scanner in 14 C57BL/6J mice syngeneic for TRAMP tumors, by administering Gd-DTPA (0.9 kD) in eight mice and Gadomer (35 kD) in the remainder. The acquisition time was 10 min with a sampling rate of one image every 2 s. Pharmacokinetic modeling was performed to obtain K^trans by using Extended Tofts model (ETM). In addition, the adiabatic approximation to the tissue homogeneity (AATH) model was employed to obtain the relative contributions of F_p and PS.ResultsThe K^trans values derived from DCE-MRI with Gd-DTPA showed significant correlations with both PS (r² = 0.64, p = 0.009) and F_p (r² = 0.57, p = 0.016), whereas those with Gadomer were found only significantly correlated with PS (r² = 0.96, p = 0.0003) but not with F_p (r² = 0.34, p = 0.111). A voxel-based analysis showed that K^trans approximated PS (< 30% difference) in 78.3% of perfused tumor volume for Gadomer, but only 37.3% for Gd-DTPA.ConclusionsThe differential contributions of F_p and PS in estimating K^trans values vary with the molecular weight of the contrast agent used. The macromolecular contrast agent resulted in K^trans values that were much less dependent on flow. These findings support the use of macromolecular contrast agents for estimating tumor vessel permeability with DCE-MRI.     

Differentiation of myeloma and metastatic cancer in the spine using dynamic contrast-enhanced MRI

Spinal myeloma and metastatic cancer cause similar symptoms and show similar imaging presentations, thus making them difficult to differentiate. In this study, dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI) was performed to differentiate between 9 myelomas and 22 metastatic cancers that present as focal lesions in the spine. The characteristic DCE parameters, including the peak signal enhancement percentage (SE%), the steepest wash-in SE% during the ascending phase and the wash-out SE%, were calculated by normalizing to the precontrast signal intensity. The two-compartmental pharmacokinetic model was used to obtain K^trans and k_ep. All nine myelomas showed the wash-out DCE pattern. Of the 22 metastatic cancers, 12 showed wash-out, 7 showed plateau, and 3 showed persistent enhancing patterns. The fraction of cases that showed the wash-out pattern was significantly higher in the myeloma group than the metastatic cancer group (9/9 = 100% vs. 12/22 = 55%, P = .03). Compared to the metastatic cancer group, the myeloma group had a higher peak SE% (226% ± 72% vs. 165% ± 60%, P = .044), a higher steepest wash-in SE% (169% ± 51% vs. 111% ± 41%, P = .01), a higher K^trans (0.114 ± 0.036 vs. 0.077 ± 0.028 1/min, P = .016) and a higher k_ep (0.88 ± 0.26 vs. 0.49 ± 0.23 1/min, P = .002). The receiver operating characteristic analysis to differentiate between these two groups showed that the area under the curve was 0.798 for K^trans, 0.864 for k_ep and 0.919 for combined K^trans and k_ep. These results show that DCE-MRI may provide additional information for making differential diagnosis to aid in choosing the optimal subsequent procedures or treatments for spinal lesions.     

Effects of arterial input function selection on kinetic parameters in brain dynamic contrast-enhanced MRI

PurposeKinetic parameters derived from dynamic contrast-enhanced MRI (DCE-MRI) were suggested as a possible instrument for multi-parametric lesion characterization, but have not found their way into clinical practice yet due to inconsistent results. The quantification is heavily influenced by the definition of an appropriate arterial input functions (AIF). Regarding brain tumor DCE-MRI, there are currently several co-existing methods to determine the AIF frequently including different brain vessels as sources. This study quantitatively and qualitatively analyzes the impact of AIF source selection on kinetic parameters derived from commonly selected AIF source vessels compared to a population-based AIF model.Material and methods74 patients with brain lesions underwent 3D DCE-MRI. Kinetic parameters [transfer constants of contrast agent efflux and reflux K^trans and k_ep and, their ratio, v_e, that is used to measure extravascular-extracellular volume fraction and plasma volume fraction v_p] were determined using extended Tofts model in 821 ROI from 4 AIF sources [the internal carotid artery (ICA), the closest artery to the lesion, the superior sagittal sinus (SSS), the population-based Parker model]. The effect of AIF source alteration on kinetic parameters was evaluated by tissue type selective intra-class correlation (ICC) and capacity to differentiate gliomas by WHO grade [area under the curve analysis (AUC)].ResultsArterial AIF more often led to implausible v_e > 100% values (p < 0.0001). AIF source alteration rendered different absolute kinetic parameters (p < 0.0001), except for k_ep. ICC between kinetic parameters of different AIF sources and tissues were variable (0.08–0.87) and only consistent > 0.5 between arterial AIF derived kinetic parameters. Differentiation between WHO III and II glioma was exclusively possible with v_p derived from an AIF in the SSS (p = 0.03; AUC 0.74).ConclusionThe AIF source has a significant impact on absolute kinetic parameters in DCE-MRI, which limits the comparability of kinetic parameters derived from different AIF sources. The effect is also tissue-dependent. The SSS appears to be the best choice for AIF source vessel selection in brain tumor DCE-MRI as it exclusively allowed for WHO grades II/III and III/IV glioma distinction (by v_p) and showed the least number of implausible v_e values.     

Parotid perfusion in nasopharyngeal carcinoma patients in early-to-intermediate stage after low-dose intensity-modulated radiotherapy: Evaluated by fat-saturated dynamic contrast-enhanced magnetic resonance imaging

PurposeTo investigate parotid perfusion in early-to-intermediate stage after parotid-sparing radiation dose using fat-saturated DCE-MRI, and to verify whether the perfusion alteration was related to radiation dose and the PSV.Methods and MaterialsThirty-two parotid glands from 16 consecutive patients with pathologically proven nasopharyngeal carcinoma treated by IMRT were examined. The parotid glands received a radiation dose of 28.9 ± 3.9 Gy with a PSV of 43.1% ± 13.9%. Perfusion parameters were calculated using time-shifted Brix model from fat-saturated DCE-MRI data before (pre-RT) and in early-to-intermediate stage after (post-RT) IMRT. Paired t-test was used to evaluate perfusion changes, while Pearson's correlation test was used to examine perfusion dependency on radiation dose and PSV. For multiple comparisons Bonferroni correction was applied.ResultsSuccessful fat saturation was achieved in 29 of 32 parotid glands. Compared with pre-RT, the post-RT parotid glands showed significantly higher A, peak enhancement, and wash-in slope, plus a lower K_el, suggesting a mixed effect of increased vascular permeability and acinar loss. Linear regression showed that peak enhancement was positively associated with radiation dose in post-RT parotid glands. K_el and slope were negatively associated with PSV, while time-to-peak was positively associated with PSV significantly.ConclusionsOur results suggest that time-shifted Brix model is feasible for quantifying parotid perfusion using DCE-MRI. The perfusion alterations in early-to-intermediate stage after IMRT might be related to a mixed effect of increased vascular permeability and acinar loss with dose and PSV dependencies.     

Intravoxel incoherent motion diffusion-weighted imaging as an adjunct to dynamic contrast-enhanced MRI to improve accuracy of the differential diagnosis of benign and malignant breast lesions

PurposeTo investigate the value of use of intravoxel incoherent motion diffusion-weighted imaging (IVIM-DWI) as an adjunct to dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI) to distinguish benign from malignant breast lesions.Materials and methodsRetrospective analysis of data pertaining to 117 patients with breast lesions who underwent DCE-MRI and IVIM-DWI examination with 3.0 T MRI was conducted. A total of 128 lesions were pathologically confirmed (47 benign and 81 malignant). Between-group differences in DCE-MRI parameters (Morphology, enhancement pattern, maximum slope of increase (MSI) and time–signal curve (TIC) type) and IVIM-DWI parameters (f value, D value and D* value) were assessed. Multivariate logistic regression was performed to identify variables that distinguished benign from malignant breast lesions. The diagnostic performance of DCE-MRI and DCE-MRI plus IVIM-DWI, to distinguish benign from malignant breast lesions, was evaluated using pathology results as the gold standard.ResultsLesion morphology, MSI, and TIC type (P < 0.05), but not the enhancement pattern (P > 0.05), were significantly different between the benign and malignant groups. The f (8.53 ± 2.14) and D* (7.64 ± 2.07) values in the malignant group were significantly higher than those in the benign group (7.68 ± 1.97 and 6.83 ± 2.13, respectively), while the D value (0.99 ± 0.22) was significantly lower than that (1.34 ± 0.17) in the benign group (P < 0.05 for all). On logistic regression analysis, the sensitivity, specificity and accuracy of DCE-MRI were 90.1%, 70.2% and 82.8% respectively; the corresponding figures for the combination of IVIM-DWI and DCE-MRI were 88.8%, 85.1%, and 87.5%respectively.ConclusionIVIM-DWI method as an adjunct to DCE-MRI can improve the specificity and accuracy in differential diagnosis of benign and malignant lesions of breast.     

Interactions between 4-(2-dimethylaminoethyloxy)-N-octadecyl-1,8-naphthalimide and serum albumins: Investigation by spectroscopic approach

A novel 4-(2-dimethylaminoethyloxy)-N-octadecyl-1,8-naphthalimide (DON) has been synthesized as a spectrofluorimetric probe for the determination of proteins. Photophysics of DON in different solvents has been delineated in this paper. Progressive redshift with polarity of solvents in emission and absorption spectra hints at intramolecular charge transfer. The interactions of DON with serum albumins (i.e., human serum albumin (HSA) and bovine serum albumin (BSA)) were studied by fluorescence and absorption spectroscopy. Fluorescence data revealed that the quenching of HSA/BSA by DON were static quenching and the DON–HSA/BSA complexes were formed. The binding constant (K_b) for HSA and was found to be 8.44×10^?4 and 60.26×10^?4 M^?1 and the number of binding sites (n) were 1.00 and 1.40, respectively. The thermodynamic parameters, ΔH and ΔS, for the DON–HSA system was calculated to be ?14.83 kJ mol^?1 and 23.61 J mol^?1 K^?1, indicating the hydrogen bonds and hydrophobic interactions were the dominant intermolecular force. ΔH and ΔS for the binding of DON with BSA was ?60.08 kJ mol^?1 and ?90.7441 mol^?1 K^?1, suggesting the hydrogen bonds and van der Waals force played the main role in the interaction. The results of displacement experiments showed that DON bound HSA/BSA occurred at the Trp-214 proximity, located in subdomain IIA of the serum albumin structure (the warfarin binding pocket). The effect of DON on the conformation of HSA was also analyzed by synchronous and three-dimensional fluorescence spectra. The fluorescence of DON could be quenched by HSA, based on which, a fluorometric method for the determination of microamount protein using DON in the medium of HCl?Tris buffer solution (pH=7.4) was developed. The linear range of the calibration curves was 0.1–10.0 μM for HSA, 0.1–11.2 μM for BSA and 0.2–9.7 μM for egg albumin (EA). The detection limit (3σ) for HSA was 1.12×10^?10 M, for BSA it was 0.92×10^?10 M and for EA it was 4.33×10^?10 M. The effect of metal cations on the fluorescence spectra of DON in ethanol was also investigated. The method has been applied to detect the total proteins in human serum samples and the results were in good agreement with those reported by the hospital.     

High resolution emission spectroscopy of the E2Π–X2Σ+ transition of SrH and SrD

Emission spectra of SrH and SrD have been studied at high resolution using a Fourier transform spectrometer. The molecules have been produced in a high temperature furnace from the reaction of strontium metal vapor with H₂/D₂ in the presence of a slow flow of Ar gas. The spectra observed in the 18 000–19 500 cm^?1 region consist of the 0–0 and 1–1 bands of the E²Π–X²Σ⁺ transition of the two isotopologues. A rotational analysis of these bands has been obtained by combining the present measurements with previously available pure rotation and vibration–rotation measurements for the ground state, and improved spectroscopic constants have been obtained for the E²Π state. The present analysis provides spectroscopic constants for the E²Π state as ΔG(½) = 1166.1011(15) cm^?1, B_e = 3.805503(32) cm^?1, α_e = 0.098880(47) cm^?1, r_e = 2.1083727(89) Å for SrH, and ΔG(½) = 839.1283(23) cm^?1, B_e = 1.918564(15) cm^?1, α_e = 0.034719(23) cm^?1, r_e = 2.1121943(83) Å for SrD.     

Fine structure of far infrared spectrum of ethanol in the lowest OH-torsional vibrational trans-state (e0) of ethanol

In this report the spectroscopic results for far infrared Fourier transform spectrum corresponding to the b-type transitions within the lowest lying trans-substrate (e₀) have been presented. The calculated matrix elements connecting various K-levels suggest that ΔK = 1 transitions within the trans- subs-state should be quite strong but the transitions between the trans state to the gauche states would quite week (practically non-existent). This was also concluded by previous studies using microwave and millimeter wave regions (Pearson et al., 1982; Millar, 1995). The assignments were confirmed by direct observations at the spectrum and the agreement between the observed and calculated spectrum using precise energy levels reported by Pearson et al. (1982). All the strong ^RR and some ^RQ branch lines starting from K = 10 ← 9 through K = 24 ← 23 have been identified. State dependent expansion parameters for all the 15 sub-bands have been presented. These parameters can reproduce the experimental wave numbers within experimental uncertainty. An atlas for about 450 transition lines corresponding to transitions within the e₀ torsional–vibrational species has been prepared. To our knowledge this is the first time the high resolution far infra-red spectral region study for ethanol have been performed.     

Perfusion of the uterine junctional zone in nulliparous and primiparous women assessed by DCE-MRI,as a function of menstrual cycle and hormonal contraception

PurposeTo evaluate the perfusion parameters of inner and outer myometrium in healthy nulliparous and primiparous women who are and who are not currently using hormonal contraceptives by means of dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI).Material and methodsWe performed pelvic 1.5 T DCE-MRI on 98 women: 18 nulliparous non-users, 30 nulliparous users, 12 primiparous non-users and 38 primiparous users of hormonal contraception (mean age respectively 26.4, 25.8, 30.23 and 28.18 years). The nulliparous non-users underwent DCE-MRI investigations during their follicular, ovulatory and luteal phase. Perfusion parameters (iAUC/volume, Ktrans, Kep and Ve) were assessed in the anterior and posterior junctional zone (JZ), outer myometrium and cervix.ResultsIn nulliparous non-users, the mean Ktrans and iAUC/volume showed a decrease from follicular to luteal phase (0.82 vs 0.55 min^− 1 for Ktrans, p = 0/027 and 1.28 vs 0.68 for iAUC/volume, p < 0.001). The anterior JZ demonstrated lower Ktrans (p = 0.050) and higher Kep (p = 0.012), in nulliparous non-users, lower Ktrans in nulliparous users (p < 0.001) and lower Ve in primiparous users (p = 0.012) than the anterior outer myometrium. Ktrans at the anterior and posterior JZ wall in nulliparous users was lower than in non-users (p = 0.001 and p = 0.013) and Ve at the anterior JZ wall in primiparous users was lower than in non-users (p = 0.044).ConclusionThis study provides data on normal perfusion parameters of inner and outer myometrium, which may be potentially useful in assisted reproductive therapy.     

UV–Vis and NMR spectroscopic investigations on effective and selective non-covalent interactions between fullerenes and calix[6]arene

Ground state non-covalent interactions between a macro cyclic calixarene receptor, namely, 4-tert-butylcalix[6]arene (1), and fullerenes (C₆₀ and C₇₀) were studied in toluene medium by absorption spectrophotometric method. Absorption band due to the charge transfer (CT) transition have been observed in the visible region between fullerenes and 1. Utilizing the CT absorption bands, various important physicochemical parameters like oscillator strength, resonance energy, transition dipole strength of the fullerene-1 complexes and ionization potential of 1 is determined in present investigations. From Jobs method of continuous variation, it is observed that both C₆₀ and C₇₀ form stable 1:1 complexes with 1. The most fascinating feature of the present study is that 1 binds selectively C₇₀ compared to C₆₀ as obtained from binding constant (K) data of C₆₀–1 (K_C60–1) and C₇₀–1 (K_C70–1) complexes, i.e., K_C60–1 = 32,400 dm³·mol^? 1 and K_C70–1 = 110,000 dm³.mol^? 1 and selectivity (K_C70–1/K_C60–1) = 3.4. ¹H NMR analysis provides very good support in favor of strong binding between C₇₀ and 1.     

The far infrared spectrum of trans-formic acid: An extension up to 175 cm−1

The far infrared spectrum of HCOOH was recorded at a high resolution (0.0009 cm^?1) and long path length (72 m) at the far-infrared beamline, Canadian Light Source. Spectra were recorded in the region 62–300 cm^?1, showing transitions from the trans-isomer.Ground state rotational transitions with K_a up to 30, were identified up to 175 cm^?1, extending the observation reported in the literature. A total of 3321 transitions were assigned and fitted together with previous (4149) published data. An improved set of rotational parameters was obtained adopting the symmetric top (A) reduction of the rotational Hamiltonian in the I^r representation. The newly measured far infrared transitions allowed the determination of all diagonal and off diagonal 8th order parameters L and of some of the diagonal 10th order parameters P.     

Ionic and electronic conductivities,stability and thermal expansion of La10 − x(Si,Al)6O26 ± δ solid electrolytes

Apatite-type La_10 − xSi_6 − yAl_yO_{27 − 3x/2 − y/2} (x = 0–0.33; y = 0.5–1.5) exhibit predominant oxygen ionic conductivity in a wide range of oxygen partial pressures. The conductivity of silicates containing 26.50–26.75 oxygen atoms per formula unit is comparable to that of gadolinia-doped ceria at 770–870 K. The average thermal expansion coefficients are (8.7–10.8) × 10^− 6 K^− 1 at 373–1273 K. At temperatures above 1100 K, silicon oxide volatilization from the surface layers of apatite ceramics and a moderate degradation of the ionic transport with time are observed under reducing conditions, thus limiting the operation temperature of Si-containing solid electrolytes.     

Growth mode of Pt1−xNix films biased dc-sputter-deposited on MgO(0 0 1)

A study is made by TEM, XRD and by measuring electrical/magnetic properties, of growth mode and properties of Pt_1−xNi_x alloy films deposited on MgO(0 0 1) at 250°C by dc-sputtering at 2.5–2.7 kV in Ar. A bias voltage V_s≤−160 V was applied to the substrate during deposition. It was confirmed that the Pt film was polycrystalline with the texture of Pt(1 1 1)/MgO(0 0 1) while the films of Pt_0.14Ni_0.86 and Pt_0.19Ni_0.81 were epitaxially grown with Pt–Ni(0 0 1)[1 0 0]/MgO(0 0 1)[1 0 0] similarly to the case of Ni/MgO(0 0 1). Thus the growth mode transformation between Pt–Ni(1 1 1)/MgO(0 0 1) and Pt–Ni(0 0 1)/MgO(0 0 1) may be induced at x less than 0.81 for Pt_1−xNi_x alloy films. The temperature coefficient of resistance TCR from 100 to 300 K of Pt_0.14Ni_0.86 films was estimated to be 0.0044–0.0053 K⁻¹ and saturation magnetization at 300 K to be 1.7–3.2 kG, respectively, while TCR of Pt films was estimated to be 0.0035–0.0048 K⁻¹.     

Ionic conductivity of brownmillerite-type calcium ferrite under oxidizing conditions

The thermogravimetric and Mössbauer spectroscopy studies showed that, at atmospheric oxygen pressure, the oxygen content in Ca₂Fe₂O₅ brownmillerite is very close to stoichiometric at 300–1270 K. The orthorhombic lattice of calcium ferrite undergoes a transition from primitive (space group Pnma) to body-centered (I2mb) at 950–1000 K, which is accompanied with decreasing thermal expansion coefficient (TEC) and increasing activation energy for the total conductivity, predominantly p-type electronic. The steady-state oxygen permeation through dense Ca₂Fe₂O₅ ceramics is limited by the bulk ionic conduction. The ion transference numbers in air vary in the range 0.002–0.007 at 1123–1273 K, increasing with temperature. Analysis of stereological factors, which may affect oxygen diffusivity, suggests a dominant role of the ion jumps along octahedral and, possibly, tetrahedral layers of the brownmillerite structure. The ionic conductivity of calcium ferrite is higher than that of Ca₂FeAlO_5+δ, but lower compared to the oxygen-deficient perovskite phases based on SrFeO_3−δ where the diffusion pathways form a three-dimensional network. The average TECs of Ca₂Fe₂O₅ ceramics, calculated from dilatometric data in air, are 13.1 × 10^− 6 K^− 1 at 370–950 K and 11.3 × 10^− 6 K^− 1 at 970–1270 K.     

Structural,vibrational study and superprotonic behavior of a new mixed dipotassium hydrogenselenate dihydrogenphosphate K2(HSeO4)1.5(H2PO4)0.5

Ongoing studies of the KHSeO₄–KH₂PO₄ system aiming at developing novel proton conducting solids resulted in the new compound K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (dipotassium hydrogenselenate dihydrogenphosphate). The crystals were prepared by a slow evaporation of an aqueous solution at room temperature. The structural properties of the crystals were characterized by single-crystal X-ray analysis: K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (denoted KHSeP) crystallizes in the space group P 1¯ with the lattice parameters: a = 7.417(3) Å, b = 7.668(2) Å, c = 7.744(5) Å, α = 71.59(3)°, β = 87.71(4)° and γ = 86.04(6)°. This structure is characterized by HSeO₄⁻ and disordered (H_xSe/P)O₄⁻ tetrahedra connected to dimers via hydrogen bridges. These dimers are linked and stabilized by additional hydrogen bonds (O–H–O) and hydrogen bridges (O–H…O) to build chains of dimers which are parallel to the [0, 1, 0] direction at the position x = 0.5.The differential scanning calorimetry diagram showed two anomalies at 493 and 563 K. These transitions were also characterized by optical birefringence, impedance and modulus spectroscopy techniques. The conductivity relaxation parameters of the proton conductors in this compound were determined in a wide temperature range. The transport properties in this material are assumed to be due to H⁺ protons hopping mechanism.     

Equilibrium of 1:2:3 CLBLCO superconductors with oxygen: reaction equation,thermodynamics and improvement of homogeneity

Equilibrium of 1:2:3 superconductors (Ca_xLa_1−x)(Ba_1.75−xLa_0.25+x)Cu₃O_y (this compound has in the past variously denoted as CLBLCO, CLBCO or CaLaBaCuO) with oxygen was studied for x=0.1 and x=0.4 in the temperature range of 150–950 °C under 1 atm. O₂. The main process is the reversible reaction −Cu₃²⁺O_6.625+0.25O₂=−Cu₂²⁺Cu³⁺O_7.125 which is completed with the formation of one Cu³⁺. The enthalpy (in kJ/mol CLBLCO) and entropy (in J(mol CLBLCO)⁻¹K⁻¹) of this reaction were calculated from the temperature dependence of the equilibrium constant. The values are ΔH=−33.1 and ΔS=−29.9 for x=0.1 and ΔH=−49.4 and ΔS=−42.7 for x=0.4.It was found that the equilibrium of ceramic pellet of CLBLCO with oxygen cannot be practically achieved below 300 °C while the equilibrium for powder is achieved even at 200 °C. Low rate of reaction of CLBLCO with oxygen causes the problem in low temperature equilibration. In contrast, diffusion of oxygen ions in the ceramics is observed even at 200 °C. This diffusion proceeds without the change of the oxygen content and may be applied in order to improve the homogeneity of the distribution of oxygen ions.     

Thermal and chemical expansion of mixed conducting La0.5Sr0.5Fe1−xCoxO3−δ materials

Oxygen deficiency, thermal and chemical expansion of La_0.5Sr_0.5Fe_1−xCo_xO_3−δ (x = 0, 0.5, 1) have been measured by thermogravimetry, dilatometry and high temperature X-ray diffraction. The rhombohedral perovskite materials transformed to a cubic structure at 350 ± 50 °C. The thermal expansion of the materials up to the onset of thermal reduction was 14–18 × 10^− 6 K^− 1. Above 500 °C in air (400 °C in N₂), chemical expansion contributed to the thermal expansion and the linear thermal expansion coefficients were significantly higher, 16–35 × 10^− 6 K^− 1. The chemical expansion, ε_c, showed a maximum of 0.0045 for x = 0.5 and 0.0041 for x = 1 at 800–900 °C. The normalized chemical expansion, ε_c/Δδ, was 0.036 for x = 0.5 and 0.035 for x = 1 at 800 °C. The chemical expansion can be correlated with an increasing ionic radius of the transition metals with decreasing valence state.     

High-pressure dielectric studies of a novel hydrogen-bonded ferroelectric (NH4)2H2P2O6

The hydrostatic pressure effect on the dielectric properties of (NH₄)₂H₂P₂O₆ ferroelectric crystal was studied for pressures from 0.1 MPa to 360 MPa and for temperatures from 100 to 190 K. The pressure–temperature phase diagram obtained is linear with increasing pressure. The paraelectric–ferroelectric phase transition temperature decreases with increasing pressure with the pressure coefficient dT_c/dp=?5.16×10^?2 K MPa^?1. Additionally, the pressure dependences of Curie–Weiss constants for the crystal in paraelectric (C₊) and ferroelectric (C_?) phases are evaluated and discussed. The possible mechanism of paraelectric–ferroelectric phase transition is also discussed.