Although exposed to similar allergic and environmental stimuli, not all humans develop asthma. Similarly, mouse strains vary in the degree of pathophysiology seen following induction of experimental asthma. Three mouse strains (CBA/Ca, BALB/c, and C57BL/6) were used to determine if the extent and duration of inflammation influenced the degree of lung tissue damage in an OVA-induced allergic asthma model. Airways obstruction, leukocyte infiltration, edema, eosinophil accumulation, and degranulation were less severe in wild-type (wt) CBA/Ca mice than wt BALB/c and C57BL/6 mice. F1 hybrids of CBA/Ca mice crossed with BALB/c or C57BL/6 mice had bronchoalveolar lavage leukocyte (BAL) and cell-free protein profiles similar to those of the respective disease-susceptible parental strain. IL-5 transgene expression on each of the three genetic backgrounds accentuated the difference between CBA/Ca and the other two strains. Importantly, even when overexpressing IL-5, CBA/Ca mice did not develop substantial airways obstruction. Eosinophils recovered from the airways of allergic wt and IL-5 transgenic (Tg) CBA/Ca mice entered apoptosis at a faster rate than eosinophils from the other parental strains and F1 hybrids. In contrast, eosinophils harvested from the peritoneal cavities of untreated CBA/Ca IL-5 Tg mice had a relatively low rate of apoptosis in vitro. The CBA/Ca mouse strain is therefore relatively resistant to experimental asthma, and this may be a consequence of a propensity for apoptosis of eosinophils recruited into the allergic lung. Restricting survival of a key effector cell may thus limit pathogenesis in this experimental model and in humans.
Zirconium / Hafnium / Crown ether / Liquid-liquid extraction / Distribution ratio / Separation factor SummaryThe extraction of zirconium and hafnium from hydrochloric acid media was studied using the crown ethers dibenzo-18-crown-6 (DB18C6), dicyclohexano-18-crown-6 (DC18C6) and dicyclohexano-24-crown-8 (DC24C8) as extractants. The goal was to find an extraction system that exhibits a high selectivity between the members of group 4 of the periodic table and is suitable for the study of rutherfordium. It was found Rf.
We have carried out both time-resolved laser fluorescence spectroscopic and computational studies on the complexes of curium(III) with multidentate Phosphonopropionic (PPA) acid ligands. A number of complexes of Cm(III) with these ligands, such as CmH(2)PPA(2+), CmHPPA(+), Cm[H(2)PPA](2)(+), and Cm[HPPA](2)(-) have been studied. Our computational studies focused on all possible isomers in the gas phase and aqueous solution so that the relative binding strengths of carboxylic versus phosphoric groups can be assessed in these multidentate systems. The solvation effects play an important role in the determination of the preferred configurations and binding propensities of carboxylate versus phosphate sites of the ligands. Our computations assess the relative strengths of single and multidentate complexes in solutions for these systems. The computed free energies of solvation explain the experimentally observed fluorescence spectra and the lifetimes of these complexes in that as more water molecules are displaced from the first hydration sphere by the ligands that bind to Cm(III), the fluorescence lifetime increases. We have found that the most stable complex for CmH(2)PPA(2+) in the aqueous phase exhibits a monodentate complex where the curium(III) is bound to the deprotonated phosphate oxygen atom. Our computations support the observed longer fluorescence lifetime of CmH(2)PPA(2+) (112 mus) compared to the free Cm(III) aquo ion (65 mus), suggesting a greater degree of H(2)O displacement from the hydration sphere. For the Cm-HPPA(+) complex, we find a tridentate form as the most stable structure which supports the observed fluorescence lifetime for the CmHPPA(+) complex (172 mus), confirming the removal of up to six water molecules from the inner hydration sphere. The relative stabilities of the complexes are found to vary substantially between the gas phase and solution, indicating a major role of solvation in the relative stabilities of these complexes.
The extraction of niobium (Nb) and tantalum (Ta) from hydrochloric acid media by bis(2-ethylhexyl) hydrogen phosphate (HDEHP) and bis(2-ethylhexyl) hydrogen phosphite (BEHP) was studied. The goal of the experiments is to find a system that demonstrates selectivity between the members of group five of the Periodic Table and is also suitable for the study of dubnium (Db, Z = 105). Experiments were performed at the trace level (10 -16 M Nb or Ta) using hydrochloric acid with concentrations ranging from 1 -11 M and short-lived isotopes of Nb and Ta produced in nuclear reactions. When HDEHP was used as the extractant, the Nb extraction yield decreased with increasing acid concentrations above 6 M, while the amount of Ta extracted remained over 75% for all acid concentrations studied. Tantalum was found to be extracted by BEHP at acid concentrations above 6 M, while niobium was not significantly extracted. The data obtained are used as the basis to discuss the speciation of Nb and Ta under the conditions studied and to evaluate possible extraction mechanisms.
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