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

EFFECT OF CRYSTAL-FIELD AND BONDING PROPERTIES ON SPECTRAL STRUCTURE OF EU-2+

Five Eu~(2+)-doped simple fluorides and six Eu~(2+)-doped complex fluorides are synthesized by solid reactions. The strength of the crystal-field at the sites of Eu~(2+) ion, and the degroe of covalenco of Eu—F bond in these hosts are discussed. The f-f transition emission of Eu~(2+) ion is observed in the hosts which has lower coordination number and strong crystal-field. The f-f transition emission of Eu~(2+) ion is observed for the first time in the simple fluoride AlF_3.

花岗岩-LiF-NaF-H_2O体系液相不混溶的实验研究

Liquid segregation phenomena have been found and explained in the F(Li)-rich granites in south China by Wang Linakui et al. (1979; 1983). A number of experimental investigations into the liquid immiscibilities in the granites systems have been carried out (Anfilogov et al., 1983; Glyuk et al., 1971; Glyuk et al., 1973a; 1973b; kovalenko, 1978; Wang Liangkui et al., 1987). Nevertheless, the detailed scenarios of the liquid immiscibilities in the granitic magmas are much less understood. This experimental study is amide to get access to this problem. Starting materials are biotite granite +LiF(3-10%)+NaF(3-10%)+H_2O(30%). The experimental results have shown that the liquid immiscibilities of melts of different compositions occur at 1 kbar and 840 ℃ when 5wt% (LiF + NaF) are added to the granite samples. three kinds of glasses indicating of three types of coexisting immiscible melts have been observed: light blue matrix glass, melanocratic glass balls and leucocratic glass balls. It is interesting that we have observed various kinds of textures as follows: spherulitic texture, droplets, flow bands, swirls. All these textures can be comparable to those in the natural granitic bodies. Electron microprobe data suggest that these different kinds of glasses are of different chemical compositions respectively; matrix glasses are F-poor silicate melts; melanocratic balls correspond to F-rich silicate melts; and leucocratic balls are the melts consisting mainly of fluorides. Raman spectrometric data have indicated that different glasses have different melt structures. TFM Diagrams at 1000 * 10~5 Pa have been plotted, in which two miscible gaps are found. One of the two gaps corresponds to the immiscibility between F - poor silicate melt and F-rich silicate melt, another to that between the silicate melt and fluoride melt. The experiments at different pressures have suggested that the decreases in pressures are favorable to the liquid immiscibility. Several reversal experiments have indicated that the equilibria in different runs have been achieved. We have applied the experimental results to explain the field evidence of immiscibilities in some of granites associated with W-Sn-Nb-Ta mineralization. These field phenomena include flow structure, globular structures,mineralized globular patche and glass inclusions in topaz. We believe that the liquid immiscibility (liquid segregation) is a possible way of generation of F(Li)-rich granites. During the evolution of the granitic magmas, the contents of Li, F, H_2O and ore-forming elements in the magmas become higher and higher. The granites formed in the extensional tectonic settings commonly bear higher abundences of the above-mentioned elements. the pressures of the granitic magmas are relatively lower during the processes of their emplacements and cooling. The late-staged magmas will produce liquid immiscibilities, leading to the production of several coexisting immiscible melts with different chemical compositions. The flow of immiscible consisting magmas will produce F(Li)-rich granites. It is also considered that liquid immiscibilities are of great significance in the production of rare metal granites. The ore-forming processes and magmatic crystallization and metasomatic processes can be occur at the same time. The mineralisations of rare metals are related to both magmatic and hydrothermal processes.

Tyrosine phosphorylation of G protein alpha subunits by pp60c-src.

A number of lines of evidence suggest that cross-talk exists between the cellular signal transduction pathways involving tyrosine phosphorylation catalyzed by members of the pp60c-src kinase family and those mediated by guanine nucleotide regulatory proteins (G proteins). In this study, we explore the possibility that direct interactions between pp60c-src and G proteins may occur with functional consequences. Preparations of pp60c-src isolated by immunoprecipitation phosphorylate on tyrosine residues the purified G-protein alpha subunits (G alpha) of several heterotrimeric G proteins. Phosphorylation is highly dependent on G-protein conformation, and G alpha(GDP) uncomplexed by beta gamma subunits appears to be the preferred substrate. In functional studies, phosphorylation of stimulatory G alpha (G alpha s) modestly increases the rate of binding of guanosine 5'-[gamma-[35S]thio]triphosphate to Gs as well as the receptor-stimulated steady-state rate of GTP hydrolysis by Gs. Heterotrimeric G proteins may represent a previously unappreciated class of potential substrates for pp60c-src.

Ultracold fluorine production via Doppler cooled BeF

Large parts of the periodic table cannot be cooled by current laser-based methods. We investigate whether zero energy fragmentation of laser cooled fluorides is a potential source of ultracold fluorine atoms. We report new ab initio calculations on the lowest electronic states of the BeF diatomic molecule including spin-orbit coupling, the calculated minima for the valence electronic states being within 1 pm of the spectroscopic values. A four colour cooling scheme based on the A2? ? X2S+ transition is shown to be feasible for this molecule. Multi-Reference Configuration Interaction (MRCI) potentials of the lowest energy Rydberg states are reported for the first time and found to be in good agreement with experimental data. A series of multi-pulse excitation schemes from a single rovibrational level of the cooled molecule are proposed to produce cold fluorine atoms.

From non-porous crystalline to amorphous microporous metal(IV) bisphosphonates

Porous layered hybrid materials have been prepared by the reaction of organo-bisphosphonate ligands, 4-(4'-phosphonophenoxy)phenylphosphonic, 4,4'-biphenylenbisphosphonic and phenylphosphonic acids, with metal(IV) cations (Zr and Sn). Crystalline Zr(IV) and Sn(IV) layered bisphosphonates were also prepared, which were non-porous. The amorphous M(IV) bisphosphonates showed variable compositions and textural properties ranging from mainly mesoporous to highly microporous solids with BET surface areas varying from 300 to 480 m(2) g(-1), micropore volumes ranging 0.10-0.20 cm(3)/g, and narrow porous size distributions for some materials. N-2 isotherms suggest that Sn(IV) derivatives show a comparatively higher micropore contribution than the Zr(IV) analogous at least for the ether-bisphosphonate hybrids. Sn(IV) bisphosphonates exhibit high microporosities without the need of using harmful DMSO as solvent. If ether-bisphosphonic acid is partially replaced by less expensive phenylphosphonic ligand, porous products are also obtained. P-31 and F-17 MAS NMR and XPS data revealed the presence of hydrogen-phosphonate groups and small (F-, Cl- and OH-) anions, which act as spacer ligands within the inorganic layers, in these hybrid materials. The complexity of the inorganic layers is higher for the Sn(IV) bisphosphonates likely due to the larger amount of small bridging anions including fluorides. It is suggested that the presence of these small inorganic ligands may be a key factor influencing both, the interaction of the inorganic layer with the bisphosphonate groups, which bridge the inorganic layers, and the generation of internal voids within a given inorganic layer. Preliminary studies of gases adsorption (H-2 and NO) have been carried out for selected Sn(IV) bisphosphonates. The H-2 adsorption capacity at 77 K and 1 bar was low, 0.26 wt%, but the NO adsorption capacity at similar to 1 bar and 298 K was relatively high, 4.2 wt%. Moreover, the hysteresis in the NO isotherms is indicative of partial strong irreversible adsorption of NO. (C) 2008 Elsevier Inc. All rights reserved.

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.

Medicinal chemistry approaches to malaria drug discovery

Tese de doutoramento, Farmácia (Química Farmacêutica e Terapêutica), Universidade de Lisboa, Faculdade de Farmácia, 2016

Comparative electron impact and fast atom bombardment mass spectrometric studies of some HMPA adducts of phenyltin and phenyllead halides and studies of strong hydrogen bonding by FAB-MS

The fragmentation patterns and mass spectra of some phenyl tin and -lead halide adducts with hexamethylphosphoramide are compared by subjecting them t~ electron impact and fast atom bombardment ionization in a mass spectrometer. This comparison is restricted to the metal-containing ions. Ligand-exchange mechanisms of some of the metal-containing species are explored by FAB-MS. Several moisturesensitive organo-metallics and H-bonded systems have been examined by FAB for attempted characterization, but without any success. Scavenging and trapping of water molecules by complex aggregates in solutions of quaternary ammonium fluorides and hydroxides are investigated by FAB to complement previous NMR-studies.

NMR studies of strong hydrogen bond to fluoride ion

Systems such as MF/diol (M = alkali metal) and }1F/carboxylic acid were subjected to IH, I9F and 13C nmr study to investigate the nature of the very strong H-bonding of fluoride ions with these systems. Evidence indicates a strong H-bond in diol-fluoride systems (~H ~ -(56) kJ mol-I) which is stronger than most 'typical' H-bonds (~H = -(12-40) kJ mol-I), but weaker than that reported for carboxylic acid-fluoride systems (~H ~ -(120) kJ mol-I). Approximate fluoride H-bonded shifts (o(OH)OHF) were evaluated for MF/diol systems from IH chemical shift measurements. No direct correlation was observed between I9F chemical shift and H-bond strength. Thermodynamic parameters were calculated from temperature dependent IH and 19F shifts. Preliminary studies of BUn 4NF-acetylacetone by I9F nmr were conducted at low temperatures and a possible Jmax (ca. 400 Hz) is reported for the fluoride ion H-bonded to acetylacetone. Highfield shift for non-protonated carbons and downfield shift for protonated carbons were observed in carboxylic acid/KF systems. Significant decreas$in I3C TI due to strong H-bonding to fluoride ions were also detected in both diol and carboxylic acid systems. Anomalous results were obtained, such as increasing NOE with increasing temperature in neat 1,2-ethanediol (values above the theoretical maximum of 1.988) and in 1,2-ethanediol/KF. The large 13C NOE's for carboxy carbons in neat carboxylic acids which are. further enhanced by the addition of KF are also unusual.

The importance of hydrogen bonding in the alkylation of phenols

Hydrogen bond assisted alkylation of phenols is compared with the classical base assisted reactions. The influence of solvents on the fluoride assisted reactions is discussed,· with emphasis on the localization of hydrogen bond charge density. Polar aprotic solvents such as DMF favour a-alkylation, and nonpolar aprotic solvents such as toluene favourC-alkylation of phenol. For more reactive and soluble fluorides, such as tetrabu~ylammoniumfluoride, the polar aprotic solvent favours a-alkylation and nonpolar aprotic solvent favours fluorination. Freeze-dried potassium fluoride is a better catalytic agent in hydrogen bond assisted alkylation reactions of phenol than the oven-dried fluoride. The presence of water in the alkylation reactions reduces the expected yield drastically. The tolerance of the reaction to water has also been studied. The use ofa phase transfer catalyst such as tetrabutylammonium bromide in the alkylation reactions of phenol in the presence of potassium fluoride is very effective under anhydrous conditions. Sterically hindered phenols such as 2,6-ditertiarybutyl-4-methyl phenol could not be alkylated even by using the more reactive fluorides, such as tetrabutylammonium fluoride in either polar or nonpolar aprotic solvents. Attempts were also made to alkylate phenols in the presence of triphenylphosphine oxide.

Effets des fluorures sur l'activité antimicrobienne des antibiotiques contre Staphylococcus aureus et Pseudomonas aeruginosa

L’émergence des souches bactériennes résistantes aux antibiotiques est un phénomène inquiétant, qui se répand à travers le monde. Staphylococcus aureus et Pseudomonas aeruginosa sont des bactéries pathogènes opportunistes multi résistantes qui peuvent causer plusieurs maladies. Cependant, ces bactéries deviennent difficiles à traiter avec des antibiotiques sans occasionner de toxicité. Alors pour trouver des solutions, c’est nécessaire de développer de nouvelles molécules afin de combattre les agents pathogènes résistants. Grâce à leur action pharmacologique, les fluorures exercent un certain effet antibactérien au niveau de l'émail des dents; donc, leur association aux antibiotiques pourrait bien a méliorer l’activité antimicrobienne. De ce fait, nous nous sommes proposés d’étudier les activités in vitro de la vancomycine (VAN), l’oxacilline (OXA), la ceftazidime (CFT) et la méropenème (MER) libre ou associée au fluorure de sodium (NaF) et fluorure de lithium (LiF) qui ont été évaluées sur des souches S.aureus et P.aeruginosa sensibles et résistantes, par la méthode de la microdilution en bouillon, déterminant leur concentration minimale inhibitrice (CMI), leur concentration minimale bactéricide (CMB), leur courbe cinétique (Time-Kill). Leur cytotoxicité sur les globules rouges humains, et leur stabilité à la température de 4°C et 22°C ont été étudiées. Les associations des antimicrobiens aux dérivés des fluorures ont montré une amélioration de l’effet des antibiotiques par la réduction des leurs concentrations et toxicité pour traiter correctement ces pathogènes résistants. Par conséquent, des antibiotiques associés aux dérivés de fluorure pourraient devenir une option de traitement contre des souches résistantes afin de diminuer la toxicité causée par de fortes doses des antibiotiques conventionnels.

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.