1,712 research outputs found

    The cytotoxic activity of diiron bis-cyclopentadienyl complexes with bridging c3-ligands

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    Diiron bis-cyclopentadienyl bis-carbonyl cationic complexes with a bridging vinylim-inium ligand, [Fe2Cp2 (CO)(µ-CO){µ-η1:η3-C3 (R′)C2HC1NMe(R′′)}]CF3SO3 (R = Xyl = 2,6-C6H3Me2, R′ = Ph, R′′ = H, 2a; R = Xyl, R′ = R′′ = Me, 2b; R = R′ = Me, R′′ = H, 2c; R = Me, R′ = 2-naphthyl, R′′ = H, 2d; R = Me, R′ = R′′ = Ph, 2e), are easily available from commercial chemicals, robust in aqueous media and exert a variable in vitro cytotoxicity against cancer cell lines depending on the nature of the substituents on the vinyliminium ligand. The anticancer activity is, at least in part, associated to fragmentation reactions, leading to iron oxidation and active neutral and well-defined monoiron species. We report an innovative synthetic procedure for the preparation of 2a,c,d, and a facile method to access the monoiron derivative of 2a, i.e., [FeCp(CO){C1 (NMeXyl)C2HC3 (Ph)C(O)}] (3a). According to IC50 analyses at different times of incubation of the complexes, 3a is significantly faster in inhibiting cell viability compared to its diiron precursor 2a. The neutral complexes [Fe2Cp2 (CO)(µ-CO){µ-k1N:k1C:k1C-C3 (R′)C2 (Se)C1 (NMe2)C4 (CO2Y)C5 (CO2Y)}] (R′ = Y = Me, 4a; R′ = Pr, Y =tBu, 4b; R′ = Y = Et, 4c) are obtained via the two-step modification of the vinyliminium moiety and comprise a bridging selenophene-decorated alkylidene ligand. The antiproliferative activity exhibited by 4a-c is moderate but comparable on the ovarian cancer cell line A2780 and the corresponding cisplatin resistant cell line, A2780cisR. Complexes 4a-c in aqueous solutions undergo progressive release of the alkylidene ligand as a functionalized selenophene, this process being slower in cell culture medium. Since the released selenophenes SeC1 {C(O)R′ }C2 (NMe2)C3 (CO2Y)C4 (CO2Y) (R′ = Y = Me, 5a; R′ = Pr, Y =tBu, 5b) are substantially not cytotoxic, it is presumable that the activity of 4a-c is largely ascribable to the {Fe2Cp2 (CO)2 } scaffold

    Effect of grain refinement on enhancing critical current density and upper critical field in undoped MgB2 ex-situ tapes

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    Ex-situ Powder-In-Tube MgB2 tapes prepared with ball-milled, undoped powders showed a strong enhancement of the irreversibility field H*, the upper critical field Hc2 and the critical current density Jc(H) together with the suppression of the anisotropy of all of these quantities. Jc reached 104 A/cm2 at 4.2 K and 10 T, with an irreversibility field of about 14 T at 4.2 K, and Hc2 of 9 T at 25 K, high values for not-doped MgB2. The enhanced Jc and H* values are associated with significant grain refinement produced by milling of the MgB2 powder, which enhances grain boundary pinning, although at the same time also reducing the connectivity from about 12% to 8%. Although enhanced pinning and diminished connectivity are in opposition, the overall influence of ball milling on Jc is positive because the increased density of grains with a size comparable with the mean free path produces strong electron scattering that substantially increases Hc2, especially Hc2 perpendicular to the Mg and B planes.Comment: 26 pages, 9 figures, submitted to J. Appl. Phy

    Magnetic field dependence of vortex activation energy: a comparison between MgB2, NbSe2 and Bi2Sr2Ca2Cu3O10 superconductors

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    The dissipative mechanism at low current density is compared in three different classes of superconductors. This is achieved by measurement of resistance as a function of temperature and magnetic field in clean polycrystalline samples of NbSe2, MgB2 and Bi2Sr2Ca2Cu3O10 superconductors. Thermally activated flux flow behavior is clearly identified in bulk MgB2. While the activation energy at low fields for MgB2 is comparable to Bi2Sr2Ca2Cu3O10, its field dependence follows a parabolic behavior unlike a power law dependence seen in Bi2Sr2Ca2Cu3O10. We analyze our results based on the Kramer's scaling for grain boundary pinning in MgB2and NbSe2

    Quantification of 37Ar emanation fractions from irradiated natural rock samples and field applications.

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    Underground-produced 37Ar can be used for underground nuclear explosions (UNE) detection and for groundwater dating. The quantification of the emanation, that is the fraction of activity produced in the rock that escapes to the pore space, is essential for predicting the background activity expected in natural environments. We propose an experiment in which artificial CaCO3 powder and natural rock particles are irradiated with neutrons in a routinely operated medical cyclotron, whose energy spectrum is experimentally measured. The produced activity was quantified and compared with the emanated activity to determine the emanating fraction. The results showed consistent and reproducible patterns with a dominance of the recoil process at small scales (<2 mm). We observed emanation values ≤1% with a dependency on the grain size and the inner geometry of particles. Soil weathering and the presence of water increased the recoil emanation. The atoms produced that were instantaneously recoiled in the intra- or inter-granular pore space left macroscopic samples by diffusion on timescales of days to weeks (Deff = 10-12 - 10-16 m2 s-1). This diffusive transport determines the activity that prevails in the fluid-filled pore space accessible for groundwater or soil gas sampling

    Neutron Irradiation of Mg11B2 : From the Enhancement to the Suppression of Superconducting Properties

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    In this letter we present the effect of neutron irradiation up to fluences of 3.9 1019 n/cm2 on the superconducting properties of MgB2. In order to obtain a disorder structure homogeneously distributed, the experiment was carried out on bulk samples prepared with the 11B isotope. Up to fluences of 1018 n/cm2 the critical temperature is slightly diminished (36 K) and the superconducting properties are significantly improved; the upper critical field is increased from 13.5 T to 20.3 T at 12 K and the irreversibility field is doubled at 5 K. For larger neutron fluences the critical temperature is suppressed down to 12 K and the superconducting properties come out strongly degraded.Comment: 13 pages, 4 figures. Submitted to Appl.Phys.Let
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