Investigation of Pr valence and relationship between bond covalency and T-c in Y1-xPrxBa2Cu3O7 (x = 0-1)

The valence of Pr and relationship between bond covalency and T-c in Y1-xPrxBa2Cu3O7 (x = 0-1) have been studied using complex chemical bond theory. The results indicate that the depression of superconductivity in Y1-xPrxBa2Cu3O7 can be reasonably explained by bond covalency difference for the bonds between CuO2 plane and CuO chain. T-c decreases with the decreasing of bond covalency difference and reaches zero when bond covalency difference is zero (or bond covalency in CuO2 exceeds that in CuO chain) at Pr concentration 0.55 and valence +3.30. These are in good agreement with the experiments and meanwhile suggest that the valence of Pr is + 3.30 in Y1-xPrxBa2Cu3O7. The results also indicate that for Pr valence less than +3.15, superconductivity always exists for whatever Pr concentration, whereas for Pr with a valence of +4.0, superconductivity disappears as soon as Pr concentration exceeds 0.19. This supports with the viewpoint that higher valence Pr will contribute more electrons to CuO2 plane, filling the mobile holes responsible for conduction. For PrBa2Cu3O7 with no Ba-site Pr, our calculation suggests that it will be a superconductor if the average valence of Pr is less than +3.15. (C) 1998 Published by Elsevier Science B.V. All rights reserved.

Lanthanide metal complexes for the hydrolysis of ribonucleoside 3',5'-cyclic phosphate and deoxyribonucleoside 3',5'-cyclic phosphate

Ytterbium(III) and praseodymium(III) complexes of 2-carboxyethylgermanium sesquioxide (Ge-132) can hydrolyze the phosphodiester linkage of 3',5'-cyclic adenosine monophosphate (cAMP) and 3',5'-cyclic deoxyadenosine monophosphate (dcAMP). Both cAMP and dcAMP are hydrolyzed with high selectivity, yielding predominantly 3'-monophosphates. The selectivity and activity for hydrolyzing cAMP and dcAMP by lanthanide metal(III) complexes and lanthanide metal ions are compared.

STUDIES ON ORGANOLANTHANIDE COMPLEXES .56. FORMATION OF ION-PAIR COMPLEXES [NA.3PHEN]+[LN(C5H5)3CL]-.PHEN (LN=LA, PR OR ND, PHEN = 1,10-PHENANTHROLINE) AND CRYSTAL-STRUCTURE FOR LN=PR

In the presence of 1,10-phenanthroline (phen), lanthanide chlorides LnCl3 reacted with cyclopentadienylsodium to give the novel complexes [Na.3phen]+[Ln(C5H5)3Cl]-.phen (Ln = La, Pr or Nd). In the praseodymium case, crystal structure analysis showed that

Extension of electrochemically active sites in SOFCs and SOECs

Solid oxide fuel (SOFCs) and electrolyzer (SOECs) cells have been promoted as promising technologies for the stabilization of fuel supply and usage in future green energy systems. SOFCs are devices that produce electricity by the oxidation of hydrogen or hydrocarbon fuels with high efficiency. Conversely, SOECs can offer the reverse reaction, where synthetic fuels can be generated by the input of renewable electricity. Due to this similar but inverse nature of SOFCs and SOECs, these devices have traditionally been constructed from comparable materials. Nonetheless, several limitations have hindered the entry of SOFCs and SOECs into the marketplace. One of the most debilitating is associated with chemical interreactions between cell components that can lead to poor longevities at high working temperatures and/or depleted electrochemcial performance. Normally such interreactions are countered by the introduction of thin, purely ionic conducting, buffer layers between the electrode and electrolyte interface. The objective of this thesis is to assess if possible improvements in electrode kinetics can also be obtained by modifying the transport properties of these buffer layers by the introduction of multivalent cations. The introduction of minor electronic conductivity in the surface of the electrolyte material has previously been shown to radically enhance the electrochemically active area for oxygen exchange, reducing polarization resistance losses. Hence, the current thesis aims to extend this knowledge to tailor a bi-functional buffer layer that can prevent chemical interreaction while also enhancing electrode kinetics.The thesis selects a typical scenario of an yttria stabilized zirconia electrolyte combined with a lanthanide containing oxygen electrode. Gadolinium, terbium and praseodymium doped cerium oxide materials have been investigated as potential buffer layers. The mixed ionic electronic conducting (MIEC) properties of the doped-cerium materials have been analyzed and collated. A detailed analysis is further presented of the impact of the buffer layers on the kinetics of the oxygen electrode in SOFC and SOEC devices. Special focus is made to assess for potential links between the transport properties of the buffer layer and subsequent electrode performance. The work also evaluates the electrochemical performance of different K2NiF4 structure cathodes deposited onto a peak performing Pr doped-cerium buffer layer, the influence of buffer layer thickness and the Pr content of the ceria buffer layer. It is shown that dramatic increases in electrode performance can be obtained by the introduction of MIEC buffer layers, where the best performances are shown to be offered by buffer layers of highest ambipolar conductivity. These buffer layers are also shown to continue to offer the bifunctional role to protect from unwanted chemical interactions at the electrode/electrolyte interface.

Synthesis and Spectral Characterization of Lanthanide Complexes with Sulfamethoxazole and Their Antibacterial Activity

A series of nonelectrolytic lanthanide(III) complexes, [ ML 2 Cl 3 ] · 2 H 2 O, where M is lanthanum(III), praseodymium(III), neodymium(III), samarium(III), gadolinium(III), terbium(III), dysprosium(III), and yttrium(III), containing sulfamethoxazole ligand (L) are prepared. The structure and bonding of the ligand are studied by elemental analysis, magnetic susceptibility measurements, IR, 1 H NMR, TG / DTA , X-ray diffraction studies, and electronic spectra of the complexes. The stereochemistry around the metal ions is a monocapped trigonal prism in which four of the coordination sites are occupied by two each from two chelating ligands, sulfonyl oxygen, and nitrogen of the amide group and the remaining three positions are occupied by three chlorines. The ligand and the new complexes were tested in vitro to evaluate their activity against the bacteria Escherichia coli and Staphylococcus aureus.

A study of the white electroluminescence in ZnS:Cu,Pr,Cl phosphors

The method of preparation of ZnS phosphors doped with praseodymium and copper is given. The electroluminescence (EL) spectrum of ZnS:Pr,Cl has two broad bands at 470 and 570 nm. ZnS:Cu,Pr,Cl gives white emission with spectral peaks at 470, 520, 570 and 640 nm. The EL spectra of both types of phosphor exhibit a conspicuous colour shift as the frequency of the excitation voltage is varied. Detailed investigations show that the relative intensities of spectral peaks are strongly dependent on the frequency of the excitation voltage. The colour shift is explained on the basis of the Schon-Klasens model.

Fabrication of Potentiometric Sensors for the Determination of Lanthanide Ions

In many fields such as earth science biology, environment and electronics, the knowledge about elemental distributions and chemical speciation is important. The determination of metal levels especially the toxic ones both in the environment and in biological materials are increasingly demanded by the society.Ion selective sensors have become one of the most effective ad powerful means for analytical scientists for the trace level monitoring of metal ions. The wide range of applications ,low material requirements and simplicity of analytical procedure have not only brought ion-selective electrodes in to the lime light of analytical chemistry,but have promoted their use as tools for physiologists,medical researchers,biologists,geologists,environmental protection specialists etc.Potentiometric ion-selective sensors have been developed for the determination of lanthanide ions such as La3+,Nd3+,Pr3+,Sm3+, and Gd3+.The sensors fabricated include both PVC membrane sensor and chemically modified carbon paste sensor. A set of 10 sensors have been developed. The response parameters of all the sensors have been studied and the sensors were applied as an indicator electrode in the potentiometric titration and for the determination of metal ions in real samples.

Structural studies on some metal complexes of embelin

This thesis deals with the studies on the synthesis and characterisation of the complexes of embelin with manganese (II), cobalt(II), nickel (II), copper (II), zinc (II), cadmium (II), chromium (III), iron (III) lanthanum(III), praseodymium (III) neodymium (III) Samarium (III), gadolinium (III) dysprosium (III), yttrium (III) thorium (IV) and uranium (VI). Elemental analysis as well as spectral, thermal and magnetic data were used to ascertain the composition of the complexes and to establish the structures of the metal complexes. Wherever possible, the electronic spectra and magnetic data were used to predict the stereochemistry of the complexes.The thesis is divided into four chapters.

Modified rare earth semiconductor oxide as a new nucleotide probe

Recent rapid developments in biological analysis, medical diagnosis, pharmaceutical industry, and environmental control fuel the urgent need for recognition of particular DNA sequences from samples. Currently, DNA detection techniques use radiochemical, enzymatic, fluorescent, or electrochemiluminescent methods; however, these techniques require costly labeled DNA and highly skilled and cumbersome procedure, which prohibit any in-situ monitoring. Here, we report that hybridization of surface-immobilized single-stranded oligonucleotide on praseodymium oxide (evaluated as a biosensor surface for the first time) with complimentary strands in solution provokes a significant shift of electrical impedance curve. This shift is attributed to a change in electrical characteristics through modification of surface charge of the underlying modified praseodymium oxide upon hybridization with the complementary oligonucelotide strand. On the other hand, using a noncomplementary single strand in solution does not create an equivalent change in the impedance value. This result clearly suggests that a new and simple electrochemical technique based on the change in electrical properties of the modified praseodymium oxide semiconductor surface upon recognition and transduction of a biological event without using labeled species is revealed.

[Pr(NO3)3L]: a mononuclear ten-coordinate lanthanide(III) complex with a tetradentate di-Schiff base

The novel praseodymium(III) complex [Pr(NO3)3L] (1), where L=N,N′-bis[1-(pyridin-2-yl)ethylidene]ethane-1,2-diamine, has been obtained by direct reaction of the Schiff base and the metal salt; the gadolinium(III) homologue has also been prepared and so far characterized only spectroscopically. The crystal structure resembles those reported for hexadentate macrocyclic Schiff bases.

Caracterização morfológica e microestrutural da perovskita BaCexPr1-xO3 sintetizada a partir do método de complexação combinando EDTA/Citrato

In this study, binary perovskite (BaCexO3) were doped with praseodymium (Pr) to obtainment of the ternary material BaCexPr1-xO3. This material was synthesized by the complexation method combining EDTA/Citrate with the stoichiometric ratio of the element Praseodymium ranging from x = 0.1 to x = 0.9 in order to determine the influence of this rare earth element on the morphology and microstructure of the final powder. At first the material was synthesized based on the route proposed by literature (Santos, 2010), and then characterized by SEM and XRD, besides being refined by the Rietveld method. In the material that had lowest residual parameter, S, and lowest average size of crystal, pH variation of synthesis solution was made in order to identify the influence of this parameter on the morphology and microscopy of the final powder. The results show that addition of praseodymium did not directly influence the crystallographic and lattice parameters, keeping even the same orthorhombic structure of the binary material BaCexO3, according to Yamanaka et al (2003). Material type BaCe0,2Pr0,8O3 had lowest residual parameter (S=1.4) and lowest average size of crystallite (26.4 nm), being used as reference in the pH variation of synthesis solution for 9, 7, 5 and 3, respectively. Variation of this parameter showed that when the synthesis solution pH was decreased to below 11, there was an increase in the average size of crystals, for pH 9, about 58.3%, for pH 7 (30.3 %), for pH 2 (2.3%) and for pH 3 (42%), indicating that the value initially used and quoted by Santos (2010) was the most coherent

Síntese e Caracterização de Titanatos de Cobalto e Níquel, dopados com Praseodímio, obtidos a partir da decomposição de Nitrilotriacetatos

In recent years, studies about the physicochemical properties of mixed oxides, call attention of the scientific community, properties like as piezoelectricity, photoluminescence, or applications as catalysts, arise in these compounds, when their chemical compositions are modified, in this context some routes are employed in the synthesis of these materials, among which can be cited these methods: ceramic, combustion, co-precipitation, Pechini or polymeric precursor method, hydrothermal, sol-gel; these routes are divided into traditional routes or chemical routes. In this work were synthesized oxides with variable composition, from the thermal decomposition of titanium, cobalt, nickel and praseodymium nitrilotriacetates. The nitrilotriacetates were characterized by IR Spectroscopy (FTIR), Thermogravimetric (TG/ DTG) and Differential Scanning Calorimetry (DSC), while oxides have been characterized by X-ray diffraction (XRD), Spectrofluorimetry and IR Spectroscopy (FTIR). From FTIR data, it was demonstrated that the displacement of the band corresponding to the carboxylate group (νCOOH) at 1712 cm-1, present in nitrilotriacetic acid (H3NTA), for 1680-1545 cm-1, these stretches are characteristics of coordinated nitrilotriacetates, By thermal analysis (TG/DTG /DSC), it was suggested, that in an oxidizing atmosphere (air) oxides are obtained at lower temperatures than in an inert atmosphere N2(g). By results from X-ray Diffraction (XRD), it was determinated that the oxides are crystalline and the predominant phases obtained are summarized titanate phases rutile and ilmenite. By fluorimetry was observed that the intensity of emission bands are directly proportional to the concentration of ions Ni2+, Co2+ and Pr3+, and IR spectroscopy (FTIR) from oxides, demonstrated the disappearance of characteristic bands by nitrilotriacetates, determining the complete decomposition of the nitrilotriacetates in oxides

Sol-gel synthesis and characterization of Fe(2)O(3) center dot CeO(2) doped with Pr ceramic pigments

Undoped x center dot alpha-Fe(2)O(3) y center dot CeO(2) and doped with praseodymium ceramic pigments were obtained by the sol-gel method after heat treatment at 800 degrees C for 2 h. These pigments were characterized by XRD, nitrogen adsorption, scanning electron microscopy, ultraviolet-visible absorption spectroscopy and colorimetrical measurements. Red and brown colors with several tonalities were observed after changes with Ce and Pr concentration.

Structural and Spectroscopic Studies of Pr3+-Doped GdAlO3

In this work, GdAlO3:Pr3+ was successfully prepared by the Pechini method at lower temperatures when compared to others methods such as solid-state synthesis and sol-gel process. In accordance to the XRD data, the fully crystalline single-phase GdAlO3 could be obtained at 900 degrees C. Luminescence measurements indicate Gd -> Pr3+ energy transfer. In the emission spectra, the P-3(0) ->(3) H-4 (blue emission) and D-1(2) ->(3) H-4 (red emission) transitions of Pr3+ ions can be observed and the ratio between their intensities depends on the Pr3+ content due to the cross-relaxation phenomenon.

Ytterbium-induced energy-transfer upconversion enhancement in Nd3+/Pr3+-codoped PbGeO3-PbF2-CdF2 glass excited at 810nm

The effect of ytterbium ions upon energy transfer (ET) excited upconversion emission in Nd3+/Pr3+ -codoped PbGeO3-PbF2-CdF2 glass under 810 nm diode laser excitation is investigated. The results revealed that the presence of Yb3+ ions in the Nd3+/Pr3+-doped sample yields a fourfold enhancement in the visible and near infrared upconversion luminescence. The dependence of the upconversion process upon the excitation power, Nd3+, and Yb3+ concentrations is examined. The results indicated that ytterbium plays a major role in the ET upconversion process by bridging the 810nm neodymium excitation to praseodymium ions. The population of the Pr3+ ions P-3(0) emitting level was accomplished through a multi-ion interaction involving ground-state and excited-state absorption of pump photons at 810 nm by the Nd3+ followed by successive ET involving the Nd3+-Yb3+ and Yb3+-Pr3+ pairs. There is also direct ET Nd3+-Pr3+. (c) 2005 Elsevier B.V. All rights reserved.