Mössbauer studies of the ultrafine antiferromagnetic cores of ferritin

The ultrafine iron cores found within the iron-storage protein ferritin are of interest to both the molecular biologist and physicist. The manner in which the protein shell (apoferritin) takes up, releases and sequesters iron is of great biological importance. Also, due to their nano-size (8 nm), the magnetically ordered cores are singly domained. Such particles possess interesting magnetic relaxation and dynamic properties for which Mössbauer spectroscopy is an ideal analytic tool. Horse ferritin molecules iron-loaded artificially contain ferrihydrite-like cores which behave as superparamagnets due to their nano-size. An anomalous decrease in thef-factor occurs above the blocking temperature of the superparamagnetic particles. This has been attributed to a magnetostriction effect resulting from superparamagnetic switching.     

Magnetism in plant and mammalian ferritin

A rich variety of magnetic phenomena is observed in Mössbauer studies of ferritin. Depending on the amount of iron in the horse spleen ferritin core, a paramagnetic relaxation spectrum, or quadrupole split doublet or a magnetically split sextet showing superpara-magnetism, are obtained a 4.1 K. Mössbauer studies of the recently prepared iron loaded concanavalin A yield hyperfine parameters identical to those found previously in mammalian ferritin, yet show the existence of larger iron aggregates. Due to the larger particle size it is possible to follow the magnetic hyperfine field and to obtain the magnetic ordering temperature as 240 K. This is exactly the Neél temperature of ferrihydrite, thus establishing that this is indeed the iron compound in the ferritin core.     

On the kinetics of anomalous muonium in silicon

The spin relaxation rate of anomalous muonium in a longitudinal magnetic field was measured in a silicon single crystal. The results are treated as the diffusion of anomalous muonium in a silicon crystal.     

Proton NMR and susceptibility measurements on the magnetic core of ferritin

We report an investigation of the magnetic core of the biomolecule ferritin by means of proton nuclear magnetic resonance (NMR) and relaxation, magnetic susceptibility and scanning electron microscope (SEM) measurements. SEM images show that the outer protein shell is taken out completely by an appropriate chemical treatment and indicate particle sizes ranging from 10² to 10⁴ nm. Susceptibility measurements show a maximum in the zero-field-cooled data which is strongly field-dependent and can be ascribed to superparamagnetic behavior, whereas the hysteresis curve is different from normal ferritin. Proton NMR and spin-lattice relaxation data as a function of temperature at 4.7 T suggest the presence of an antiferromagnetic transition around 100 K.     

A study of the parameterisation of the uniaxial model of superparamagnetic relaxation

Mössbauer spectra of the iron storage protein ferritin taken over a range of temperatures exhibit the characteristic behaviour of superparamagnetic relaxation, and can be used to investigate a model for the superparamagnetic relaxation of a sample of small magnetic particles. A computer program is used to calculate a series of Mössbauer spectra based on the relaxation model, and these theoretical spectra are then fitted simultaneously to all the variable temperature experimental spectra, with the parameters of the uniaxial anisotropy model as the only variables.     

Deuterium NMR lineshape and relaxation study of a hydrated cross-linked polymer

A combined study of²H nuclear magnetic resonance lineshape and spin-lattice and spin-spin relaxation times as functions of temperature and the amount of hydration water in a cross-linked copolymer of sucrose and 1,4-butadienol diglycidyl ether in the hydrogel phase is reported. The results show strong evidence that the onset of the relaxation mechanisms is driven by anomalous water molecule diffusion depending on both temperature and the hydration degree of the hydrogel. In addition, these results are correlated with the transitions observed by differential thermal analysis.     

Relaxationserscheinungen in Elektronenstrahlen

In electron beams with high charge density there are observed anomalous shiftings and broadenings as well as symmetrizations of the energy distribution (Boersch 1954). Continuing former work, where these phenomena were ascribed to a relaxation process changing the energy distribution to a new equilibrium distribution, quantitative expressions are derived for the energy spread and the shape of this new energy distribution. Furthermore a relaxation degree is defined which measures the progress of relaxation. Measurements are described with the highest relaxation degrees reached up to now. In addition to the verification of former results up to these new limits the shape of the measured energy-distributions can be fitted to the derived one with suitable choice of a single parameter. Peculiarities of measurements with superposed axial magnetic fields are discussed.     

Variation of superparamagnetic properties with iron loading in mammalian ferritin

The average blocking temperatures of ferritin molecules containing differing amounts of iron were determined by Mossbauer spectroscopy. The results imply that the magnetic anisotropy of the ferritin core particles is a function of particle volume. By addition of⁵⁷Fe to ferritin core particles it was determined that, at a given temperature within the superpara-magnetic temperature region, the “last-in” ferric ions have average relaxation times that are shorter than those of the bulk ferric ions.     

Mössbauer spectra of a paramagnetic ion in an axial crystal field in the presence of spin-lattice relaxation

The influence of spin-lattice relaxation on the Mössbauer hyperfine spectra of the Fe³⁺ ion is investigated in the case of an axial crystal field. All the various influences of the relaxation process on the spectra can be explicitly described using two relaxation parameters. A detailed analysis of the Mössbauer relaxation spectra for the various temperatures, relations between the relaxation parameters and external magnetic field directions is carried out. When the magnetic field direction is nearly collinear with the symmetry axis and one of the relaxation parameters is small, the dynamics of Mössbauer spectra is shown to have anomalous features. The influence of random magnetic fields is shown to give an unconventional development of patterns as a function of the relaxation parameters.     

Relaxivities of human liver and spleen ferritin

Ferritin, the iron-storing protein of mammals, is known to darken T₂-weighted magnetic resonance images. This darkening can be used to noninvasively measure an organ's iron content. Significant discrepancies exist between T₂ data obtained with ferritin-containing tissues and with aqueous solutions of horse spleen ferritin (HSF). The NMR properties of stable human ferritin have never been studied in aqueous solutions. Relaxometry results on human liver and spleen ferritin are reported here, showing that the relaxation induced in aqueous solutions by human ferritins is comparable to that induced by HSF. As a consequence, the differences between ferritin-containing human tissues and ferritin solutions cannot be attributed to different NMR properties of human and horse ferritins, but probably to a clustering of the protein in vivo.     

Cesium adsorption in hydrated iron oxide particles suspensions: an NMR study

137Cs is an important component of nuclear waste which may pollute water. Its migration in natural environments is slowed down by adsorption on minerals. Cesium adsorption on akaganeite (beta-FeOOH) particles, dextran-coated ferrihydrite (5 Fe(2)O(3)-9H(2)O) particles, and ferritin in aqueous solutions is studied with (133)Cs nuclear magnetic resonance measurements. The longitudinal relaxation time (T(1)) of (133)Cs in the presence of such magnetic particles depends on whether the ions bind to the particle or not. T(1) of (133)Cs ions in aqueous solutions containing the same amount of magnetized particles will not depend on cesium concentration if relaxation is governed by diffusion (when cesium is not able to bind), but it will depend on cesium concentration if exchange governs relaxation (when cesium is able to bind). The method is successfully tested using TEMPO, a nitroxide stable free radical whose relaxation is due to diffusion. (133)Cs relaxation in solutions of ferritin, akaganeite, and dextran-coated ferrihydrite particles is found to result from a cationic exchange of cesium ions between particles surface and bulk ions, owing to adsorption. The effect of pH on (133)Cs relaxation in solutions of the particles is consistent with the adsorption properties of cations on hydrated iron oxides.     

Paramagnetische Relaxation von CeCl3·7H2O im Temperaturbereich von 1,1 bis 4,2°K

The paramagnetic relaxation of a single crystal of CeCl₃·7H₂O has been studied by the dispersion-absorption-method at temperatures between 1,1 and 4,2°K. Alternating magnetic fields with frequencies between 5 and 2660 Hz and parallel magnetic fields up to 4000 Oe have been used. The spin lattice relaxation time has been determined as a function of temperature. At two special rangesH ₁ andH ₄ of the magnetic field a second, temperature-independent dispersion-absorption region has been observed besides the temperature-dependent spin-lattice relaxation (double relaxation). At two other special magnetic fieldsH ₂ andH ₃ the anomalous field dependence of the high frequency adiabatic susceptibility suggests a second dispersion-absorption-region ocurring at frequencies, which we cannot attain experimentally. In all cases cross relaxation processes are combined with the spin lattice relaxation.     

Rotational dynamics of Di-tert-butyl-nitroxide in normal and supercooled water: an electron paramagnetic resonance study

In order to obtain dynamical information on the water solvent, which is characterized by a strong anomalous behavior in its structural and transport properties especially in the supercooled region, low concentration di-tert-butyl-nitroxide (DTBN) aqueous solutions were studied by Electron Paramagnetic Resonance spectroscopy in the temperature range from 28 down to ?17°C. The accurate spectra reconstruction, achieved by a multi-parameters Monte Carlo fitting algorithm, allowed us to reliably extract some relevant spectral parameters of the spin probe, which were connected to the probe dynamics in the framework of the motional narrowing magnetic relaxation theory. The observed trend with the temperature showed however a significant deviation from what expected from the magnetic relaxation model. This anomalous behavior is discussed in terms of the influence upon the probe motion of solvent-induced local fluctuating structures which, very likely, are connected to the water hydrogen bond network dynamics.     

Effets comparés des impuretés de terres rares sur la résonance ferrimagnétique et la relaxation nucléaire dans le grenat de fer et d’yttrium

The anomalous properties of impure yttrium iron garnet are related to the susceptibilities of the rare earth ions which it contains. The susceptibilities are calculated assuming a slow relaxation. It is shown that the success of the theory of “slow relaxation” requires the existence of a coupling between the transverse magnetization of the iron lattice on the one hand, and components of the magnetic moments of the rare earth ions, with non zero diagonal matrix elements, on the other hand. The temperature variations of the ferrimagnetic linewidth and the nuclear relaxation time are compared.     

Resonant spin tunneling in small magnetic particles

A new macroscopic test of spin tunneling in single-domain magnetic particles is proposed. It is shown that quantization of spin, even in particles of a considerable size, may lead to a detectable zero-field maximum in the dependence of the rate of the magnetic relaxation on the magnetic field. This effect must be especially pronounced in antiferromagnetic particles. It is argued that recent observation by several groups of the non-monotonic field dependence of the blocking temperature in ferritin may, in fact, present the experimental evidence of this effect.     

Non-Arrhenius relaxation of the Heisenberg model with dipolar and anisotropic interactions

The dynamical properties of a 2D Heisenberg model with dipolar interactions and perpendicular anisotropy are studied using Monte Carlo simulations in two different ordered regions of the equilibrium phase diagram. We find a temperature defining a dynamical transition below which the relaxation suddenly slows down and the system apart from the typical Arrhenius relaxation to a Vogel-Fulcher-Tamann law. This anomalous behavior is observed in the scaling of the magnetic relaxation and may eventually lead to a freezing of the system. Through the analysis of the domain structures we explain this behavior in terms of the domains dynamics. Moreover, we calculate the energy barriers distribution obtained from the data of the magnetic viscosity. Its shape supports our comprehension of both, the Vogel-Fulcher-Tamann dynamical slowing down and the freezing mechanism.     

Quasielastic electron-electron scattering and anomalous magnetoresistance

Wave function phase relaxation due to the quasielastic electron-electron collisions is shown to depend essentially on the external magnetic field. Additional contribution to anomalous magnetoresistance connected with this deoendence is discussed and found to be important in two dimensional case.     

Ferromagnetic resonance of horse spleen ferritin: core blocking and surface ordering temperatures.

In nature, ferritin, an iron-storage molecule, is found in species ranging from bacteria to man. In the past 50 years its chemical, physical, and magnetic properties have been studied, searching to relate function and structure. Horse spleen ferritin has been investigated by EPR at temperatures between 7 and 290 K. These spectra change from an isotropic line at 290 K to an anisotropic one at 19 K, with a behavior consistent with a system of particles that undergoes superparamagnetic relaxation. A blocking temperature of (116+/-9) K is obtained. A new temperature-dependent signal is observed in the low field region at temperatures higher than 80 K. At 7 K no EPR signal appears, suggesting (14+/-5) K as the Néel temperature of surface spins. Analysis of the temperature dependence of the distance between EPR lines extrema, under the view of two theoretical models, allowed the evaluation of magnetic parameters. These parameters are 2K/M=2.7 x 10(3) Oe and MV=1.9 x 10(-17) emu or K/M=1.3 x 10(3) Oe and MV=2.0 x 10(-17) emu, where K is the anisotropy energy per unit volume, M is the sample magnetization, and V is the superparamagnetic core volume. The results are also discussed, and some structural models in the literature are considered.     

Nuclear spin-lattice relaxation in heavily doped silicon

The anomalous temperature and magnetic field dependences of spin-lattice relaxation time were observed in heavily phosphorus doped silicon. These anomalies should be attributed to the dynamical nature of the highly correlated electron gas which contributes to metallic impurity conduction.     

Applied field Mössbauer studies of the iron storage proteins ferritin and haemosiderin

Applied field Mössbauer spectra obtained from ferritin and haemosiderin have been fitted using a spin-Hamiltonian model, to determine the effect of the applied field on the direction of the iron magnetic moments. The results of these fits indicate that the ordering of magnetic moments within the ferrihydrite core of these proteins is antiferromagnetic. The values of the anisotropy field obtained from these fits correspond to much higher values of the superparamagnetic blocking temperatures than those actually observed. This anomaly has implications for our understanding of the superparamagnetic relaxation processes in these materials.