Electrochemical properties and intermediate-temperature fuel cell performance of dense yttrium-doped barium zirconate with calcium addition

Although BaZr 0.8Y 0.2O 3-δ(BZY) possesses large bulk proton conductivity and excellent chemical stability, its poor sinterability and grain boundaries block proton conduction. In this work, the effect of Ca as a co-dopant and as a sintering aid (as CaO), on the sinterability, proton conductivity, and fuel cell performance of BZY was investigated. The addition of 4 mol% CaO significantly improved the BZY sinterability: BZY pellets with densities of 92.7% and 97.5% with respect to the theoretical density were obtained after sintering at 1500°C and 1600°C, respectively. The improved BZY sinterability by CaO addition resulted also in a large proton conductivity; at 600°C, the total conductivity of BZY-CaO was 2.14 × 10 -3 S/cm, in wet Ar. Anode-supported fuel cells with 25 μm-thick BZY-CaO electrolyte membranes were fabricated by a dual-layer co-firing technique. The peak power density of the fuel cell with a BZY-Ni/BZY-4CaO/BZY-LSCF (La 0.6Sr 0.4Fe 0.8Co 0.2O 3-δ) configuration was 141 mW/cm 2 at 700°C, several times larger than the reported values of BZY electrolyte membrane fuel cells sintered with the addition of CuO or ZnO, demonstrating promising features for practical fuel cell applications.

Detection of renal dysfunction during and after anaesthesia and surgery - evaluation of the influence of inorganic fluoride, ketorolac and clonidine

Drugs and surgical techniques may have harmful renal effects during the perioperative period. Traditional biomarkers are often insensitive to minor renal changes, but novel biomarkers may more accurately detect disturbances in glomerular and tubular function and integrity. The purpose of this study was first, to evaluate the renal effects of ketorolac and clonidine during inhalation anesthesia with sevoflurane and isoflurane, and secondly, to evaluate the effect of tobacco smoking on the production of inorganic fluoride (F-) following enflurane and sevoflurane anesthesia as well as to determine the effect of F- on renal function and cellular integrity in surgical patients. A total of 143 patients undergoing either conventional (n = 75) or endoscopic (n = 68) inpatient surgery were enrolled in four studies. The ketorolac and clonidine studies were prospective, randomized, placebo controlled and double-blinded, while the cigarette smoking studies were prospective cohort studies with two parallel groups. As a sign of proximal tubular deterioration, a similar transient increase in urine N-acetyl-beta-D-glucosaminidase/creatinine (U-NAG/crea) was noted in both the ketorolac group and in the controls (baseline vs. at two hours of anesthesia, p = 0.015) with a 3.3 minimum alveolar concentration hour sevoflurane anesthesia. Uncorrelated U-NAG increased above the maximum concentration measured from healthy volunteers (6.1 units/l) in 5/15 patients with ketorolac and in none of the controls (p = 0.042). As a sign of proximal tubular deterioration, U-glutathione transferase-alpha/crea (U-GST-alpha/crea) increased in both groups at two hours after anesthesia but a more significant increase was noted in the patients with ketorolac. U-GST-alpha/crea increased above the maximum ratio measured from healthy volunteers in 7/15 patients with ketorolac and in 3/15 controls. Clonidine diminished the activation of the renin-angiotensin aldosterone system during pneumoperitoneum; urine output was better preserved in the patients treated with clonidine (1/15 patients developed oliguria) than in the controls (8/15 developed oliguria (p=0.005)). Most patients with pneumoperitoneum and isoflurane anesthesia developed a transient proximal tubular deterioration, as U-NAG increased above 6.1 units/L in 11/15 patients with clonidine and in 7/15 controls. In the patients receiving clonidine treatment, the median of U-NAG/crea was higher than in the controls at 60 minutes of pneumoperitoneum (p = 0.01), suggesting that clonidine seems to worsen proximal tubular deterioration. Smoking induced the metabolism of enflurane, but the renal function remained intact in both the smokers and the non-smokers with enflurane anesthesia. On the contrary, smoking did not induce sevoflurane metabolism, but glomerular function decreased in 4/25 non-smokers and in 7/25 smokers with sevoflurane anesthesia. All five patients with S-F- ≥ 40 micromol/L, but only 6/45 with S-F- less than 40 micromol/L (p = 0.001), developed a S-tumor associated trypsin inhibitor concentration above 3 nmol/L as a sign of glomerular dysfunction. As a sign of proximal tubulus deterioration, U-beta 2-microglobulin increased in 2/5 patients with S-F- over 40 micromol/L compared to 2/45 patients with the highest S-F- less than 40 micromol/L (p = 0.005). To conclude, sevoflurane anesthesia may cause a transient proximal tubular deterioration which may be worsened by a co-administration of ketorolac. Clonidine premedication prevents the activation of the renin-angiotensin aldosterone system and preserves normal urine output, but may be harmful for proximal tubules during pneumoperitoneum. Smoking induces the metabolism of enflurane but not that of sevoflurane. Serum F- of 40 micromol/L or higher may induce glomerular dysfunction and proximal tubulus deterioration in patients with sevoflurane anesthesia. The novel renal biomarkers warrant further studies in order to establish reference values for surgical patients having inhalation anesthesia.

Dielectric properties of Poly(vinylidene fluoride)/CaCu3Ti4O12 composites

The possibility of obtaining relatively high dielectric constant polymer-ceramic composite by incorporating the giant dielectric constant material, CaCu3Ti4O12 (CCTO) in a Poly(vinylidene fluoride) (PVDF) polymer matrix by melt mixing and hot pressing process was demonstrated. The structure, morphology and dielectric properties of the composites were characterized using X-ray diffraction, Thermal analysis. scanning electron microscope, and impedance analyzer. The effective dielectric constant a(epsilon(eff)) of the composite increased with increase in the volume fraction of CCTO at all the frequencies(100 Hz-1 MHz) under study. The dielectric loss did not show any variation up to 40% loading of CCTO, but showed an increasing trend beyond 40%. The room temperature dielectric constant as high as 95 at 100 Hz has been realized for the composite with 55 vol.% of CCTO, which has increased to about 190 at 150 degrees C. Theoretical models like Maxwell's, Clausius-Mossotti, Effective medium theory, logarithmic law and Yamada were employed to rationalize the dielectric behaviour of the composite and discussed. (C) 2010 Published by Elsevier Ltd.

Thiourea based novel chromogenic sensor for selective detection of fluoride and cyanide anions in organic and aqueous media

Novel chromogenic thiourea based sensors 4,4'-bis-[3-(4-nitrophenyl) thiourea] diphenyl ether 1 and 4,4'-bis-[3-(4-nitrophenyl) thiourea] diphenyl methane 2 having nitrophenyl group as signaling unit have been synthesized and characterized by spectroscopic techniques and X-ray crystallography. The both sensors show visual detection, UV-vis and NMR spectral changes in presence of fluoride and cyanide anions in organic solvent as well as in aqueous medium. The absorption spectra indicated the formation of complex between host and guest is in 1:2 stoichiometric ratios. (C) 2010 Elsevier B.V. All rights reserved.

An improved procedure for the synthesis of dehydroamino acids and dehydropeptides from the carbonate derivatives of serine and threonine using tetrabutylammonium fluoride

Dehydroamino acids are important precursors for the synthesis of a number of unnatural amino acids and are structural components in many biologically active peptide derivatives. However, efficient synthetic procedures for their production in large amounts and without side reactions are limited. We report here an improved procedure for the synthesis of dehydroalanine and dehydroamino butyric acid from the carbonate derivatives of serine and threonine using TBAF. The antiselective E-2 elimination of the carbonate derivatives of serine and threonine using TBAF is milder and more efficient than other available procedures. The elimination reaction is completed in less than 10 min with various carbonate derivatives studied and the methodology is very efficient for the synthesis of dehydroamino acids and dehydropeptides. The procedure thus provides an easy access to key synthetic precursors and can be used to introduce interesting structural elements to designed peptides. Copyright

Electron spin resonance in cupric acid fluoride

The electron spin resonance in undiluted single crystals of cupric acid fluoride has been investigated at room temperature with microwaves of frequency 9625 Mc/s. The anisotropy in the g value has been measured in three orthogonal planes. The principal g values gave gshort parallel = 2.410 ± 0.010, gperpendicular = 2.090 ± 0.010. The linewidth shows anisotropy with orientation. The exchange frequency has been estimated to be approximately 0.08 cm-1.The powdered specimen shows asymmetry in the line shape.

Infrared spectra of trichloroacetates of copper, calcium, strontium and barium

Infrared spectra of trichloroacetates of Cu, Ca, Sr and Ba were studied in order to investigate the effect of coordination on the vibration spectra of the ligand. The shifts of the antisymmetric and symmetric COO- stretching frequencies are explained on the basis of the type of co-ordination of the COO- group to the metal ion. From the spectra it is established that the coordination of the COO- group to metal is different for trichloroacetates and monochloroacetates.

Micellar size and shape in solutions of calcium stearate in cetane from optical depolarization data

Observations at a series of temperatures of the changes in viscosities and depolarization factors of 1% and 18% solutions of calcium stearate in cetane to which varying amounts of water have been added can be interpreted in terms of the existence of anisometric micelles. In general, changes in the size of the micelles inferred from values of ρh agree with those deduced from the viscosity data. The correlation between anisometry of micelles from rheological and optical observations is much poorer in the case of ρν, presumably because of the difficulty in differentiating the contribution of anisometry and anisotropy to ρν.

Consideration on thermal decomposition of calcium hydroxide pellets for energy storage

The reversible chemical reaction of Ca(OH)2/CaO appears to be attractive for storage of solar thermal energy, in view of the nonpolluting and nontoxic nature of the reactants. This paper presents some data on thermal decomposition of calcium hydroxide pellets along with its additives of aluminum, aluminum hydroxide, zinc, and copper. The addition of aluminum and zinc powder enhanced the rate of decomposition considerably at 450°C, but copper had no effect. Considerations on the effect of additives are also discussed in some detail, though their effects are not established with certainty. There is some evidence that heat transfer into the pellet, and the number of potential nucleation sites due to thermal stresses, influence the kinetics and mechanism of decomposition.

New family of thallium cuprate superconductors not containing calcium or barium: TlSrn+1−xLnxCunO2n+3+δ (Ln=La, Pr, or Nd)

The first two members of the new TlSrn+1−xLnxCunO2n+3+δ (Ln=La, Pr, or Nd) series of superconducting cuprates possessing 1021 and 1122 type structures are described. The n=1 (1021) members with Tcs around 40 K have electrons or holes as the majority charge carriers depending on x. The n=2 (1122) cuprate (Ln=Pr or Nd) shows a Tc in the 80–90 K range.

Effect of calcium deficiency on the mechanical properties of hydroxyapatite crystals

The deterioration of the mechanical properties of bone with age is related to several factors including the structure, organization and chemistry of the constituent phases; however, the relative contribution of each of these factors is not well understood. In this study, we have investigated the effect of chemistry (calcium deficiency) on the mechanical properties of single crystals of hydroxyapatite. Single crystals of stoichiometric crystals grown by the flux method and calcium-deficient platelet crystals grown using wet chemical methods were used as model systems. Using nanoindentation, we show that calcium deficiency leads to an 80% reduction in the hardness and elastic modulus and at least a 75% reduction in toughness in plate-shaped hydroxyapatite crystals. Measurement of local mechanical properties using nanoindentation and nanoscale chemistry through elemental mapping in a transmission electron microscope points to a direct correlation between the observed spatial variation in composition and the large scatter in the measured hardness and modulus values. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Redistribution of subcellular calcium in rat liver on administration of vanadate

Mitochondria isolated from the livers of rats administered with sodium meta-, ortho-, or polyvanadate, but not vanadyl sulphate, exhibited enhanced Ca2+ — stimulated respiration and uptake of calcium. These effects were shown also by mitochondria isolated from livers perfused with polyvanadate. The concentration of acid-soluble calcium decreased significantly in the mitochondrial fraction on vanadate treatment, while that in the cytosol showed a corresponding increase. Phenoxybenzamine, an antagonist to a-adrenergic receptors, effectively inhibited vanadate-induced Ca2+ mobilization, but surgical sympathectomy was without effect. This is the first demonstration of vanadate mimicking agr-adrenergic agonists in vivo.

Novel organic porous solids with channel and layered structures from 1,3,5-triazine-2,4,6-triaminehexaacetic acid and its calcium salt

Single crystals of a symmetrically substituted molecule, 1,3,5-triazine-2,4,6-triaminehexaacetic acid, (TTHA) and its Ca2+ salt have been synthesized, the analysis of which reveals the existence of novel channel type cavities and helical packing organizations in the crystals.