Probing Cation and Vacancy Ordering in the Dry and Hydrated Yttrium-Substituted BaSnO(3) Perovskite by NMR Spectroscopy and First Principles Calculations: Implications for Proton Mobility

Hydrated BaSn(1-x)Y(x)O(3-x/2) is a protonic conductor that, unlike many other related perovskites, shows high conductivity even at high substitution levels. A joint multinuclear NMR spectroscopy and density functional theory (total energy and GIPAW NMR calculations) investigation of BaSn(1-x)Y(x)O(3-x/2) (0.10 ≤ x ≤ 0.50) was performed to investigate cation ordering and the location of the oxygen vacancies in the dry material. The DFT energetics show that Y doping on the Sn site is favored over doping on the Ba site. The (119)Sn chemical shifts are sensitive to the number of neighboring Sn and Y cations, an experimental observation that is supported by the GIPAW calculations and that allows clustering to be monitored: Y substitution on the Sn sublattice is close to random up to x = 0.20, while at higher substitution levels, Y-O-Y linkages are avoided, leading, at x = 0.50, to strict Y-O-Sn alternation of B-site cations. These results are confirmed by the absence of a "Y-O-Y" (17)O resonance and supported by the (17)O NMR shift calculations. Although resonances due to six-coordinate Y cations were observed by (89)Y NMR, the agreement between the experimental and calculated shifts was poor. Five-coordinate Sn and Y sites (i.e., sites next to the vacancy) were observed by (119)Sn and (89)Y NMR, respectively, these sites disappearing on hydration. More five-coordinated Sn than five-coordinated Y sites are seen, even at x = 0.50, which is ascribed to the presence of residual Sn-O-Sn defects in the cation-ordered material and their ability to accommodate O vacancies. High-temperature (119)Sn NMR reveals that the O ions are mobile above 400 °C, oxygen mobility being required to hydrate these materials. The high protonic mobility, even in the high Y-content materials, is ascribed to the Y-O-Sn cation ordering, which prevents proton trapping on the more basic Y-O-Y sites.     

Photoreduction de la benzophenone par des thioethers etudiee par pnic

CIDNP (Chemically Induced Dynamic Nuclear Polarization) studies of the photoreduction of benzophenone by R-CH₂-S-R' show evidence for the $\text{formation of vinylic}$ deratives and adducts. The central intermediate in the reaction scheme is the radical pair R-CH-S-R' φ₂-C-OH^t. A study with selenides shows a different behaviour for these compounds.     

Reanalysis of the mass difference ofB_d^0 - \bar B_d^0 within the Minimal Supersymmetric Standard Modelwithin the Minimal Supersymmetric Standard Model

We present a detailed and complete calculation of the loop corrections to the mass difference $\Delta {{m_{B_d^0 } } \mathord{\left/ {\vphantom {{m_{B_d^0 } } {m_{B_d^0 } }}} \right. \kern-0em} {m_{B_d^0 } }}$ . We include charginos and scalar up quarks as well as gluinos and scalar down quarks on the relevant loop diagrams. We include the mixings of the charginos and of the scalar partners of the left and right handed quarks. We find that the gluino contribution to this quantity is important with respect to the chargino contribution only in a small part of phase space: mainly when the gluino mass is small (～100 GeV) and the symmetry-breaking parameterm _S is below 300 GeV. This contribution is also important for very large values of tanβ (～50) irrespective of the other parameters. Otherwise, the chargino contribution dominates vastly and can be roughly as large as that of the Standard Model. We also present the contribution of the charged Higgs to the mass difference $\Delta {{m_{B_d^0 } } \mathord{\left/ {\vphantom {{m_{B_d^0 } } {m_{B_d^0 } }}} \right. \kern-0em} {m_{B_d^0 } }}$ in the casem _b tanβ?m _t cotβ. This last contribution can be larger than the Standard Model contribution for small values of the Higgs mass and small values of tanβ.     

Determination of intracellular prolyl/glycyl proteases in intact living human cells and protoporphyrin IX production as a reporter system

The determination of enzyme activity or inhibition in intact living cells is a problem in the development of inhibitors for intracellular proteases. The production of fluorescent protoporphyrin IX (PpIX) from the nonfluorescent (N)-Gly/Pro-5-aminolevulinic acid (ALA) substrates was used to evaluate the prolyl/glycyl-specific dipeptidylpeptidase IV (DPPIV)-like and prolyloligopeptidase (POP)-like activities of human cells. The results demonstrated that whereas POP-like activity could be attributed to the actual POP, the DPPIV-like activity could be related to actual DPPIV only in one colon cell line. In the other breast and colon cell lines, DPPIV-like activity was intracellular and displayed by other prolyl-specific aminopeptidases. Our experiments also demonstrated the involvement of glycyl-specific proteases in the processing of ALA precursors. These observations have important consequences for the development and evaluation of selective inhibitors for these enzymes.     

Synthesis and Anticancer Activity of Long-Chain Isonicotinic Ester Ligand-Containing Arene Ruthenium Complexes and Nanoparticles

Arene ruthenium complexes containing long-chain N-ligands L¹ = NC₅H₄–4-COO–C₆H₄–4-O–(CH₂)₉–CH₃ or L² = NC₅H₄–4-COO–(CH₂)₁₀–O–C₆H₄–4-COO–C₆H₄–4-C₆H₄–4-CN derived from isonicotinic acid, of the type [(arene)Ru(L)Cl₂] (arene = C₆H₆, L = L¹: 1; arene = p-MeC₆H₄Pr ⁱ , L = L¹: 2; arene = C₆Me₆, L = L¹: 3; arene = C₆H₆, L = L²: 4; arene = p-MeC₆H₄Pr ⁱ , L = L²: 5; arene = C₆Me₆, L = L²: 6) have been synthesized from the corresponding [(arene)RuCl₂]₂ precursor with the long-chain N-ligand L in dichloromethane. Ruthenium nanoparticles stabilized by L¹ have been prepared by the solvent-free reduction of 1 with hydrogen or by reducing [(arene)Ru(H₂O)₃]SO₄ in ethanol in the presence of L¹ with hydrogen. These complexes and nanoparticles show a high anticancer activity towards human ovarian cell lines, the highest cytotoxicity being obtained for complex 2 (IC₅₀ = 2 μM for A2780 and 7 μM for A2780cisR).     

Functionalized bismuth ferrite harmonic nanoparticles for cancer cells labeling and imaging

Journal of Nanoparticle Research - Nanoparticles form the fundamental building blocks for many exciting applications in various scientific disciplines. However, the problem of the large-scale...     

Radiometric detector options to aid in DOE high activity waste tank in situ characterization efforts

Radioactive waste cleanup and subsequent closure of waste storage tanks is currently underway at the Savannah river site, prompting the need to characterize the residual contents (heels) of the tanks. Occasionally, results from laboratory analyses indicate alternative sub-sampling strategies are needed, resulting in repetitive efforts to sample and analyze tank bottoms. The development of a system for in situ tank analyses using a radiometric probe, which could be lowered into a waste tank, could aid in identifying waste structures on tank bottoms requiring further sampling and characterization. Ideally, the probe would provide information for determining which structures were higher in concentrations of actinides and fission products characteristic of DOE high level waste (HLW) heels. Although only a limited set of isotopes can be measured directly without extensive radiochemical separations, the low-energy photon spectra of HLW do offer some intriguing possibilities for characterization using a radiometric probe. One possibility for obtaining a low-energy photon spectrum in the presence of high levels of interfering radiation would be to design a probe primarily based upon recently developed technology from Amptek Inc. Such a detector would be relatively insensitive to the high photon background, which would paralyze conventional gamma probes (i.e. sodium iodide) subjected to the same radiological conditions. The prototype detector is capable of successfully obtaining high resolution measurements at very high count rates (in excess of 500,000 counts per second). An overview of measurements obtained from various HLW samples using the prototype Amptek detector, as well as some additional detector technologies, which could enhance this prototype, will be discussed.