Synthesis, characterization, and antibacterial activities of some rare Earth metal complexes of pipemidic acid. (17/141)

Eight new solid complexes of pipemidic acid (PPA) with trichlorizated rare earth metals LaCl(3), CeCl(3), PrCl(3), NdCl(3), SmCl(3), TbCl(3), DyCl(3), and YCl(3) have been synthesized. The complexes were characterized by elemental analyses, IR, NMR, and molar conductance measurements. The general formulas of the complexes are [M(PPA)(4)]Cl(3) (M=Ce(III), Pr(III), Nd(III), Sm(III), Tb(III), Dy(III), Y(III)), and [La(PPA)(4)Cl]Cl(2). At the same time, the antibacterial activities of PPA and four of its complexes were tested. The results show that PPA and its complexes all have inhibitory action against bacteria of Escherichia coli, Bacillus subtilis, Streptococcus pneumoniae, and Pseudomonas aeruginosa but not Staphylococcus aureus. We compared their antibacterial activities and found that the antibacterial activity of [La(PPA)(4)Cl]Cl(2) against S. pneumoniae is much stronger than that of PPA and the other complexes.  (+info)

Influence of model and marker on digesta kinetic estimates for sheep. (18/141)

Several models and markers are available for digesta kinetic studies. In this study, kinetic estimates derived from chromium-mordanted hay or pellets were compared to estimates derived from rare earth markers (Yb, Dy, or Er) applied individually to samples. Twelve yearling rams (52 kg) were given ad libitum access to either hay or a commercial pelleted diet in a crossover experiment. Digesta kinetic estimates were obtained both by nonlinear analysis with two age-independent rates (G1G1) or with gamma time dependency in the fast compartment (G2G1 to G4G1) and by linear regression of natural log transformed fecal marker concentrations (LN method of estimate). Model did not influence total tract (P > .21) or ruminal mean retention times (P > .87). Partitioning of total retention time was similar (P > .21) for the LN, G3G1, and G4G1 models, but the G1G1 and G2G1 models did not adequately fit these data. Nonlinear models overestimated, and LN underestimated, fecal DM output by 9% (SEM = 4.7) for the hay diet. All the nonlinear models provided fecal DM output estimates that were within 5% of actual fecal DM output, but the LN model underestimated it by 18% (SEM = 3.3) for the pelleted diet. Ruminal outflow rate was slower (P < .01) and both ruminal and total mean retention time estimates were longer (P < .01) for Cr than for the rare earths. Despite the marker chosen, relative diet effects were similar. The three rare earth markers gave identical results for digesta kinetic estimates, indicating that they are useful for simultaneous study of more than one ingredient or particle, but direct comparison of rare earth and Cr-mordant passage rates is not advisable.  (+info)

Flow paths of plant tissue residues and digesta through gastrointestinal segments in Spanish goats and methodological considerations. (19/141)

A sequence of eight twice-daily meals, each marked with different rare earth elements, was fed to 24 Spanish goats (BW = 20.6 +/- 1.94 kg) to produce meal-based profiles of rare earth markers within segments of the gastrointestinal digesta on subsequent slaughter. Accumulative mean residence time and time delay of rare earths and segmental and accumulative mean residence times of indigestible NDF (IDF) were estimated for each sampled segment. Diets consisted of ad libitum access to bermudagrass hay with a limit feeding of one of four supplements: 1) minerals (basal, B); 2) B + energy (E); 3) B + CP (CP); or 4) B + E + CP for 84 d. Mean daily intake (g/kg of BW) during the 5 d before slaughter differed (P < 0.05) via diet for DM but not for IDF (8.0 +/- 0.35 g/kg of BW). Larger estimates of cumulative mean residence time for IDF vs. rare earths were suggested to be the consequence of a meal-induced bias in the single measurement of IDF pool size by anatomical site. The rare earth compartment method was considered more reliable than the IDF pool dilution method because it yielded flow estimates based on the flux of eight meal-dosed rare earth markers over 4 d and was independent of anatomical definitions of pool size. Statistically indistinguishable estimates for gastrointestinal mean residence times for IDF and rare earths conform to assumed indelibility for the specifically applied rare earths and indigestibility of IDF. The potentially digestible NDF (PDF):IDF ratio of dietary fragments (0.8) progressively decreased in the following order: caudodorsal reticulorumen (0.390) > crainodorsal reticulorumen (0.357) approximately reticulum (0.354) > mid-dorsal reticulorumen (0.291) approximately ventral reticulorumen (0.286), to that within the omasal folds and in the abomasum (0.259). Such a gradient of progressively aging mixture of plant tissue fragments is consistent with age-dependent flow paths established in the reticulorumen and flowing to the omasum and abomasum. Such heterogeneity of fragment ages within the reticulorumen is also indicated by the superior fit of marker dose site double dagger marker sampling site model assumptions. Additionally, cyclic meal- and rumination-induced variations in escape rate occur. Estimates of mean escape rates over days, needed for the practice of ruminant nutrition, must consider the complex interactions among plant tissues and the dynamics of their ruminal digestion of PDF.  (+info)

Pinpointing the source of a lunar meteorite: implications for the evolution of the Moon. (20/141)

The lunar meteorite Sayh al Uhaymir 169 consists of an impact melt breccia extremely enriched with potassium, rare earth elements, and phosphorus [thorium, 32.7 parts per million (ppm); uranium, 8.6 ppm; potassium oxide, 0.54 weight percent], and adherent regolith. The isotope systematics of the meteorite record four lunar impact events at 3909 +/- 13 million years ago (Ma), approximately 2800 Ma, approximately 200 Ma, and <0.34 Ma, and collision with Earth sometime after 9.7 +/- 1.3 thousand years ago. With these data, we can link the impact-melt breccia to Imbrium and pinpoint the source region of the meteorite to the Lalande impact crater.  (+info)

The metal sites on sarcoplasmic reticulum membranes that bind lanthanide ions with the highest affinity are not the ATPase Ca2+ transport sites. (21/141)

We attempted to establish whether lanthanide ions, when added to sarcoplasmic reticulum (SR) membranes in the absence of nucleotide, compete with Ca2+ for binding to the transport sites of the Ca(2+)-ATPase in these membranes, or whether they bind to different sites. Equilibrium measurements of the effect of lanthanide ions on the intrinsic fluorescence of SR ATPase and on 45Ca2+ binding to it were performed either at neutral pH (pH 6.8), i.e. when endogenous or contaminating Ca2+ was sufficient to nearly saturate the ATPase transport sites, or at acid pH (pH 5.5), which greatly reduced the affinity of calcium for its sites on the ATPase. These measurements did reveal apparent competition between Ca2+ and the lanthanide ions La3+, Gd3+, Pr3+, and Tb3+, which all behaved similarly, but this competition displayed unexpected features: lanthanide ions displaced Ca2+ with a moderate affinity and in a noncooperative way, and the pH dependence of this displacement was smaller than that of the Ca2+ binding to its own sites. Simultaneously, we directly measured the amount of Tb3+ bound to the ATPase relative to the amount of Ca2+ and found that Tb3+ ions only reduced significantly the amount of Ca2+ bound after a considerable number of Tb3+ ions had bound. Furthermore, when we tested the effect of Ca2+ on the amount of Tb3+ bound to the SR membranes, we found that the Tb3+ ions which bound at low Tb3+ concentrations were not displaced when Ca2+ was added at concentrations which saturated the Ca2+ transport sites. We conclude that the sites on SR ATPase to which lanthanide ions bind with the highest affinity are not the high affinity Ca2+ binding and transport sites. At higher concentrations, lanthanide ions did not appear to be able to replace Ca2+ ions and preserve the native structure of their binding pocket, as evaluated in rapid filtration measurements from the effect of moderate concentrations of lanthanide ions on the kinetics of Ca2+ dissociation. Thus, the presence of lanthanide ions slowed down the dissociation from its binding site of the first, superficially bound 45Ca2+ ion, instead of specifically preventing the dissociation of the deeply bound 45Ca2+ ion. These results highlight the need for caution when interpreting, in terms of calcium sites, experimental data collected using lanthanide ions as spectroscopic probes on SR membrane ATPase.  (+info)

Identification of intrinsic high-level resistance to rare-earth oxides and oxyanions in members of the class Proteobacteria: characterization of tellurite, selenite, and rhodium sesquioxide reduction in Rhodobacter sphaeroides. (22/141)

We have identified intrinsic high-level resistance (HLR) to tellurite, selenite, and at least 15 other rare-earth oxides and oxyanions in the facultative photoheterotroph Rhodobacter sphaeroides grown either chemoheterotrophically or photoheterotrophically. Other members of the class Proteobacteria, including members of the alpha-2 and alpha-3 phylogenetic subgroups, were also shown to effect the reduction of many of these compounds, although genera from the alpha-1, beta-1, and gamma-3 subgroups did not express HLR to the oxyanions examined. Detailed analyses employing R. sphaeroides have shown that HLR to at least one class of these oxyanions, the tellurite class (e.g., tellurate, tellurite, selenate, selenite, and rhodium sesquioxide), occurred via intracellular oxyanion reduction and resulted in deposition of metal in the cytoplasmic membrane. The concomitant evolution of hydrogen gas from cells grown photoheterotrophically in the presence of these oxyanions was also observed. HLR to tellurite class oxyanions in R. sphaeroides was not affected by exogenous methionine or phosphate but was reduced 40-fold by the addition of cysteine to growth media. In contrast HLR to the periodate class oxyanions (e.g., periodate, siliconate, and siliconite) was inhibited by extracellular PO4(3-) but did not result in metal deposition or gas evolution. Finally, we observed that HLR to arsenate class oxyanions (e.g., arsenate, molybdate, and tungstate) occurred by a third, distinct mechanism, as evidenced by the lack of intracellular metal deposition and hydrogen gas evolution and an insensitivity to extracellular PO4(3-) or cysteine. Examination of a number of R. sphaeroides mutants has determined the obligate requirement for an intact CO2 fixation pathway and the presence of a functional photosynthetic electron transport chain to effect HLR to K2TeO3 under photosynthetic growth conditions, whereas functional cytochromes bc1 and c2 were required under aerobic growth conditions to facilitate HLR. Finally, a purification scheme to recover metals from intact bacterial cells was developed.  (+info)

Accumulation and fractionation of rare earth elements (REEs) in wheat: controlled by phosphate precipitation, cell wall absorption and solution complexation. (23/141)

Previous studies on rare earth element (REE) bioaccumulation have focused on their accumulation rate and fractionation, but the processes involved remain unclear. In this study, the accumulation and fractionation of REEs in wheat (Triticum aestivum L.) were investigated using solution culture with exogenous mixed REEs. A decrease in REE contents was observed from the roots to the tops of wheat. Significant fractionations of REEs were found in wheat organs as compared to the exogenous mixed REEs. Middle REE (MREE, the elements from Sm to Gd) enrichment and an M-type tetrad effect (an effect that can cause a split of REE patterns into four consecutive convex segments) were observed in the roots, which were probably caused by phosphate precipitation of REEs in/on the roots and absorption of REEs to root cell walls. Light REE (LREE, the elements from La to Eu) and heavy REE (HREE, the elements from Gd to Lu) enrichments were observed in the stems and leaves, respectively, accompanied by conspicuous W-type tetrad effects (an opposite effect to the M-type tetrad effect) in the REE patterns. HREE enrichment decreased from the older to the younger leaves and increased upwards within a single leaf. It is suggested that the solution complexation that occurred in the xylem vessels plays an important role in REE fractionations in the above-ground parts of wheat.  (+info)

Preconcentration of rare earth elements on silica gel loaded with 1-phenyl-3-methyl-4-benzoylpyrazol-5-one prior to their determination by ICP-AES. (24/141)

A new chelating resin, silica gel loaded with 1-phenyl-3-methyl-4-benzoylpyrazol-5-one (PMBP), was prepared and used for the preconcentration of trace amounts of rare earth elements (REEs) in water samples prior to their determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). REEs (La, Eu, Yb and Y) were quantitatively retained on the column packed with modified silica gel in the pH range 5 - 8 and separated from the matrix, and then recovered by eluting with 2.0 mol L(-1) HNO3. The adsorption capacity of modified silica gel for La, Eu, Yb and Y was 0.208, 0.249, 0.239 and 0.224 mmol g(-1), respectively. The method has been successfully applied for the determination of La, Eu, Yb and Y in geological and environmental samples with satisfactory results.  (+info)