Plutonium is a toxic synthetic element with no natural biological function, but it is strongly retained by humans when ingested. Using small-angle X-ray scattering, receptor binding assays and synchrotron X-ray fluorescence microscopy, we find that rat adrenal gland (PC12) cells can acquire plutonium in vitro through the major iron acquisition pathway--receptor-mediated endocytosis of the iron transport protein serum transferrin; however, only one form of the plutonium-transferrin complex is active. Low-resolution solution models of plutonium-loaded transferrins derived from small-angle scattering show that only transferrin with plutonium bound in the protein's C-terminal lobe (C-lobe) and iron bound in the N-terminal lobe (N-lobe) (Pu(C)Fe(N)Tf) adopts the proper conformation for recognition by the transferrin receptor protein.
View Article and Find Full Text PDFSeveral methods for rapid sequestration, fluorometric detection, and the subsequent mass spectroscopic analysis of lanthanide ions using surface modified polystyrene magnetic microspheres are demonstrated. Mixed-ligand antenna complexes of Eu(3+) in which one of the ligands is attached to the surface of the microspheres have been used as a means for the sequestration, immobilization, and detection of these ions. Using the ion-exchange properties of these microspheres, this scheme has been extended to the detection of nonluminescent ions.
View Article and Find Full Text PDFPairing of a Keggin or Lindqvist polyoxometalate (POM) anion with an appropriate tetraalkylphosphonium cation is shown to yield the first members of a new family of ionic liquids (ILs). Detailed characterization of one of them, an ambient-temperature "liquid POM" comprising the Lindqvist salt of the trihexyl(tetradecyl) phosphonium cation, by voltammetry, viscometry, conductimetry, and thermal analysis indicates that it exhibits conductivity and viscosity comparable to those of the one previously described inorganic-organic POM-IL hybrid but with substantially improved thermal stability.
View Article and Find Full Text PDFSignificant solubilization of ostensibly water-immiscible ionic liquids (ILs) in acidic aqueous phases is induced by the presence of any of a variety of neutral extractants, the apparent result of the formation of the protonated form of the extractant and its subsequent exchange for the cationic component of the IL. The extent of this solubilization is shown to diminish with increasing hydrophobicity of the IL cation and decreasing extractant basicity. These observations raise concerns as to the viability of ILs as "drop in replacements" for traditional organic solvents in the solvent extraction of metal ions.
View Article and Find Full Text PDFThe pairing of selected polyoxometalate (POM) anions with appropriate tetraalkylphosphonium cations is shown to yield an original family of ionic liquids, among them an ambient-temperature "liquid POM".
View Article and Find Full Text PDFSmall-angle neutron scattering (SANS) data for the tri-n-butyl phosphate (TBP)-n-octane, HNO(3)-Zr(NO(3))(4) solvent extraction system, obtained under a variety of experimental conditions, have been interpreted using the Baxter model for hard spheres with surface adhesion. The increase in scattering intensity in the low Q range observed when increasing amounts of Zr(NO(3))(4) were extracted into the organic phase was interpreted as arising from interactions between small reverse micelle-like particles containing two to three TBP molecules. Upon extraction of Zr(NO(3))(4), the particles interact through attractive forces between their polar cores with a potential energy that exceeds 2 k(B)T.
View Article and Find Full Text PDFThe synthesis and purification of a poly(N-isopropylacrylamide)-lipid conjugate and its use in the preparation of a thermoresponsive lipid mesophase is described. Specifically, poly(N-isopropylacrylamide) with a single carboxyl group at one end was activated with dicyclohexylcarbodiimide/N-hydroxysuccinimide to form an active ester. This N-hydroxysuccinimide ester was then used to form a dimyristoyl-sn-glycero-3-phosphoethanolamine conjugate with poly(N-isopropylacrylamide) via an amide bond, rendering the conjugate amphiphilic.
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