NMR relaxation and magnetic properties of superparamagnetic nanoworms

in Contrast Media & Molecular Imaging (2010), 5(6), 318-322

Maghemite particles are used as T-2 contrast agents for magnetic resonance imaging, especially for molecular and cellular imaging. Linear clusters of particles - called nanoworms - were recently developed ... [more ▼]

Maghemite particles are used as T-2 contrast agents for magnetic resonance imaging, especially for molecular and cellular imaging. Linear clusters of particles - called nanoworms - were recently developed to enhance the targeting efficiency. In this work, the magnetic and NMR relaxation properties of these nanoworms are studied at multiple magnetic fields. After the usual saturation at 0.5 T, the magnetization of the worms is still increasing, which results in an appreciable increase of the transverse relaxivity at high magnetic fields. The obtained relaxivities are typical of superparamagnetic particles of iron oxide (SPIOs). The transverse relaxation of the worms is clearly more efficient than for the isolated grains, which is confirmed by computer simulations. At high field, the longitudinal relaxation of the worms is less pronounced than for the grains, as expected for SPIOs. The nanoworms thus constitute a promising T-2 agent for cellular and molecular imaging. Copyright (C) 2010 John Wiley Sons, Ltd. [less ▲]

Nuclear forward and inelastic spectroscopy on 125Te and Sb2 125Te3 2

in Europhysics Letters [=EPL] (2010)

We report on the observation of nuclear forward and nuclear inelastic scattering of synchrotron radiation by Te-125 and the application of both spectroscopic methods to tellurium compounds by using a high ... [more ▼]

We report on the observation of nuclear forward and nuclear inelastic scattering of synchrotron radiation by Te-125 and the application of both spectroscopic methods to tellurium compounds by using a high-resolution backscattering sapphire monochromator in combination with fast detection electronics. The lifetime of the nuclear resonance and the energy of the transition were determined to be 2.131(12) ns and 35493.12(30) eV, respectively. As applications, the nuclear inelastic spectrum in Sb2Te3 and the nuclear forward scattering by Te metal were measured. These measurements open the field of nuclear resonance spectroscopy on tellurium compounds such as thermoelectric and superconducting materials. [less ▲]

Influence of the rare-earth element on the effects of the structural and magnetic phase transitions in CeFeAsO, PrFeAsO and NdFeAsO

in New Journal of Physics (2009), 11

We present results of transport and magnetic properties and heat capacity measurements on polycrystalline CeFeAsO, PrFeAsO and NdFeAsO. These materials undergo structural phase transitions, spin density ... [more ▼]

We present results of transport and magnetic properties and heat capacity measurements on polycrystalline CeFeAsO, PrFeAsO and NdFeAsO. These materials undergo structural phase transitions, spin density wave-like magnetic ordering of small moments on iron and antiferromagnetic ordering of rare-earth moments. The temperature dependence of the electrical resistivity, Seebeck coefficient, thermal conductivity, Hall coefficient and magnetoresistance are reported. The magnetic behavior of the materials have been investigated using Mossbauer spectroscopy and magnetization measurements. Transport and magnetic properties are affected strongly by the structural and magnetic transitions, suggesting significant changes in the band structure and/or carrier mobilities occur, and phonon-phonon scattering is reduced upon transformation to the low-temperature structure. Results are compared with recent reports for LaFeAsO, and systematic variations in properties as the identity of Ln is changed are observed and discussed. As Ln progresses across the rare-earth series from La to Nd, an increase in the hole contributions to the Seebeck coefficient and increases in magnetoresistance and the Hall coefficient are observed in the low-temperature phase. Analysis of hyperfine fields at the iron nuclei determined from Mossbauer spectra indicates that the moment on Fe in the orthorhombic phase is nearly independent of the identity of Ln, in apparent contrast to reports of powder neutron diffraction refinements. [less ▲]

Syntheses, structure, and a Mossbauer and magnetic study of Ba4Fe2I5S4

in Inorganic Chemistry (2008), 47(1), 94-100

The compound Ba4Fe2I5S4 has been prepared at 1223-1123 K by the "U-assisted" reaction of FeS, BaS, S, and U with BaI2 as a flux. A more rational synthesis was also found; however, the presence of U ... [more ▼]

The compound Ba4Fe2I5S4 has been prepared at 1223-1123 K by the "U-assisted" reaction of FeS, BaS, S, and U with BaI2 as a flux. A more rational synthesis was also found; however, the presence of U appears to be essential for the formation of single crystals suitable for X-ray diffraction studies. Ba4Fe2I5S4 crystallizes in a new structure type with two formula units in space group 14/m of the tetragonal system. The structure consists of a Ba-I network penetrated by (1)(infinity) [Fe2S4] chains. Each Fe atom, which is located on a site with 4 symmetry, is tetrahedrally coordinated to four S atoms. The FeS4 tetrahedra edge-share to form linear (1)(infinity)[Fe2S4] chains in the [001] direction. The Fe-Fe interatomic distance in these chains is 2.5630(4) angstrom, only about 3 % longer than the shortest Fe-Fe distance in alpha-Fe metal. Charge balance dictates that the average formal oxidation state of Fe in these chains is +2.5. The Mossbauer spectra obtained at 85 and 270 K comprise a single quadrupole doublet that has hyperfine parameters consistent with an average Fe oxidation state of +2.5. The Mossbauer spectrum obtained at 4.2 K consists of a single magnetic sextet with a small hyperfine field of -15.5 T. This spectrum is also consistent with rapid electron delocalization and an average Fe oxidation state of +2.5. The molar magnetic susceptibility of Ba4Fe2I5S4, obtained between 3.4 and 300 K, qualitatively indicates the presence of weak pseudo-one-dimensional ferromagnetic exchange within a linear chain above 100 K and weak three-dimensional ordering between the chains at lower temperatures. [less ▲]

Charge Order, Dynamics, and Magnetostructural Transition in Multiferroic LuFe2O4

in Physical Review Letters (2008), 101(22),

We investigated the series of temperature and field-driven transitions in LuFe2O4 by optical and Mossbauer spectroscopies, magnetization, and x-ray scattering in order to understand the interplay between ... [more ▼]

We investigated the series of temperature and field-driven transitions in LuFe2O4 by optical and Mossbauer spectroscopies, magnetization, and x-ray scattering in order to understand the interplay between charge, structure, and magnetism in this multiferroic material. We demonstrate that charge fluctuation has an onset well below the charge ordering transition, supporting the "order by fluctuation" mechanism for the development of charge order superstructure. Bragg splitting and large magneto-optical contrast suggest a low-temperature monoclinic distortion that can be driven by both temperature and magnetic field. [less ▲]

Phase transitions in LaFeAsO: Structural, magnetic, elastic, and transport properties, heat capacity and Mossbauer spectra

in Physical Review. B (2008), 78(9),

We present results from a detailed experimental investigation of LaFeAsO, the parent material in the series of "FeAs" based oxypnictide superconductors. Upon cooling, this material undergoes a tetragonal ... [more ▼]

We present results from a detailed experimental investigation of LaFeAsO, the parent material in the series of "FeAs" based oxypnictide superconductors. Upon cooling, this material undergoes a tetragonal-orthorhombic crystallographic phase transition at similar to 160 K followed closely by an antiferromagnetic ordering near 145 K. Analysis of these phase transitions using temperature dependent powder x-ray and neutron-diffraction measurements is presented. A magnetic moment of similar to 0.35 mu(B) per iron is derived from Mossbauer spectra in the low-temperature phase. Evidence of the structural transition is observed at temperatures well above the transition temperature (up to near 200 K) in the diffraction data as well as the polycrystalline elastic moduli probed by resonant ultrasound spectroscopy measurements. The effects of the two phase transitions on the transport properties (resistivity, thermal conductivity, Seebeck coefficient, and Hall coefficient), heat capacity, and magnetization of LaFeAsO are also reported, including a dramatic increase in the magnitude of the Hall coefficient below 160 K. The results suggest that the structural distortion leads to a localization of carriers on Fe, producing small local magnetic moments which subsequently order antiferromagnetically upon further cooling. Evidence of strong electron-phonon interactions in the high-temperature tetragonal phase is also observed. [less ▲]

Weak ferromagnetism in Fe1-xCoxSb2

in Physical Review b (2007), 76(22),

Weak ferromagnetism in Fe1-xCoxSb2 is studied by magnetization and Mossbauer measurements. A small spontaneous magnetic moment of the order of similar to 10(-3)mu(B) appears along the b axis for 0.2 <= x ... [more ▼]

Weak ferromagnetism in Fe1-xCoxSb2 is studied by magnetization and Mossbauer measurements. A small spontaneous magnetic moment of the order of similar to 10(-3)mu(B) appears along the b axis for 0.2 <= x <= 0.4. Based on a structural analysis, we argue against extrinsic sources of weak ferromagnetism. We discuss our results in the framework of the nearly magnetic electronic structure of the parent compound FeSb2. [less ▲]

Antimony-121 Mossbauer spectral study of the Eu14MnSb11 and Yb14MnSb11 Zintl compounds

in Inorganic Chemistry (2007), 46(25), 10736-10740

The antimony-121 Mossbauer spectra of the Yb14MnSb11 and Eu14MnSb11 Zintl compounds have been measured between 2 or 5 and 300 K. The resulting three-dimensional arrays of the spectral counts, velocity ... [more ▼]

The antimony-121 Mossbauer spectra of the Yb14MnSb11 and Eu14MnSb11 Zintl compounds have been measured between 2 or 5 and 300 K. The resulting three-dimensional arrays of the spectral counts, velocity, and temperature have been simultaneously fit with a minimum number of free parameters. These fits yield a 0 Kelvin transferred hyperfine field of 2.9(2) T, a Curie temperature of 57(3) K, and a Mossbauer temperature of 182(2) K for Yb14MnSb11; in this case the transferred field arises solely from the ordering of Mn2+. Because Eu14MnSb11 has both Eu2+ and Mn2+ ions that are magnetically ordered, its antimony-121 Mossbauer spectra are more complex and reveal two magnetic transitions, the first at 92(1) K resulting from the ordering of the Mn 2+ ions and the second at 9.5(1.0) K resulting from the ordering of the Eu2+ ions; the corresponding 0 Kelvin transferred hyperfine fields are 1.3(1) and 3.7(1) T. The antimony-121 isomer shifts yield electronic configurations of 5s(1.74)5p(4.28) and 5s(1.74)5p(4.19) for the average antimony anion in Yb14MnSb11 and Eu14MnSb11, respectively. [less ▲]

A Mossbauer spectral study of the GdCo4-xFexB compounds

in Journal of Applied Physics (2007), 101(2),

The iron-57 Mossbauer spectra of the GdCo4-xFexB compounds, where x is 0.10, 0.15, 0.20, 0.25, 1, 2, 2.5, and 2.6, have been measured at room temperature and reveal relatively small iron hyperfine fields ... [more ▼]

The iron-57 Mossbauer spectra of the GdCo4-xFexB compounds, where x is 0.10, 0.15, 0.20, 0.25, 1, 2, 2.5, and 2.6, have been measured at room temperature and reveal relatively small iron hyperfine fields of approximately 12-18 T, relatively large quadrupole interactions of approximately +0.9 and -1 mm/s, and three very different types of spectra for x=0.10 and 0.15, x=0.25, 1, and 2, and x=2.5 and 2.6. The differences result from both the different easy magnetization directions in these compounds and the different cobalt and/or iron occupancies of the crystallographic 2c and 6i sites. The spectra have been fitted by calculating the spectral absorption with the complete iron-57 nuclear excited state Hamiltonian for the iron 2c and 6i sites. The fits have used an asymmetry parameter eta and Euler angles theta and phi that relate the hyperfine field to the iron electric field gradient axes of each crystallographic site in an orientation that is consistent with the structural and magnetic properties of the site. The results of the fits indicate both that the full Hamiltonian approach is required for physically reasonable spectral fits and that the small observed fields result from the presence of large orbital contributions which subtract from the Fermi contact contributions to the magnetic hyperfine fields of the two sites. The iron 2c occupancy obtained from the Mossbauer spectral area has been used to model the compositional dependence of the magnetic anisotropy constant in the GdCo4-xFexB compounds. (c) 2007 American Institute of Physics. [less ▲]

Fe-57 Mossbauer spectral and muon spin relaxation study of the magnetodynamics of monodispersed gamma-Fe2O3 nanoparticles

in Physical Review b (2007), 76(17),

The Mossbauer spectra of monodispersed iron oxide nanoparticles with diameters of 4, 7, 9, and 11 nm have been measured between 4.2 and 315 K and fitted within the formalism for stochastic fluctuations of ... [more ▼]

The Mossbauer spectra of monodispersed iron oxide nanoparticles with diameters of 4, 7, 9, and 11 nm have been measured between 4.2 and 315 K and fitted within the formalism for stochastic fluctuations of the hyperfine Hamiltonian. In this model, the hyperfine field is assumed to relax between the six +/- x, +/- y, and +/- z directions in space with a distribution of relaxation rates that is temperature dependent. Muon spin relaxation measurements have been carried out on the 9 nm particles between 4.2 and 295 K. Both techniques reveal three regimes in the magnetic dynamics of these nanoparticles. In the low-temperature regime, between 4.2 and similar to 30 K, the nanoparticle magnetic moments are blocked and a spin-glass-like state is observed with nearly static hyperfine fields, as is indicated by the well resolved magnetic Mossbauer spectra and the slow exponential decay of the muon asymmetry functions. In the high-temperature regime, above similar to 125 K, the nanoparticle magnetic moments and, hence, the hyperfine fields, relax rapidly and a typical thermally activated superparamagnetic behavior is observed, as is indicated by the Mossbauer doublet line shape and the muon asymmetry functions that are unquestionably characteristic of monodispersed nanoparticles. In the intermediate regime between similar to 30 and 125 K, the Mossbauer spectra are the superposition of broad sextets and doublets and the muon asymmetry functions have been fitted with a sum of two terms, one relaxing term similar to that observed at and above 125 K and one term characteristic of static local fields. Hence, in this intermediate regime, the sample is magnetically inhomogeneous and composed of nanoparticles rapidly and slowly relaxing as a result of interparticle interactions. The magnetic anisotropy constants determined from both the Mossbauer spectral and magnetic susceptibility results decrease by a factor similar to 4 with increasing diameter from 4 to 22 nm and increase linearly with the percentage of iron(III) ions present at the surface of the nanoparticles. The interparticle interaction energy is estimated to be between 89 and 212 K from the temperature dependence of the magnetic hyperfine field measured on the 9 nm nanoparticles. [less ▲]