Quadrupole Doublet Research Articles

An electrostatic quadrupole doublet focusing system for MeV heavy ions in MeV-SIMS

The importance of imaging mass spectrometry (MS) for visualizing the spatial distribution of molecular species in biological tissues and cells is growing. In conventional SIMS with keV-energy ion beams, elastic collisions occur between projectiles and atoms in constituent molecules. The collisions produce fragments, making acquisition of molecular information difficult. In contrast, MeV-energy ion beams excite electrons near the surface and enhance the ionization of high-mass molecules, hence, fragment suppressed SIMS spectrum of ionized molecules can be obtained. This work is a further step on our previous report on the successful development of a MeV secondary ion mass spectrometry (MeV-SIMS) for biological samples. We have developed an electrostatic quadrupole doublet (EQ doublet) focusing system, made of two separate lenses, Q1 and Q2, to focus the MeV heavy ion beam and reduce measurement time. A primary beam of 6MeV Cu4+ was focused with this EQ doublet. We applied 1120V to the Q1 lens and 1430V to the Q2 lens, and the current density increased by a factor of about 60. Using this arrangement, we obtained an MeV-SIMS image of 100×100pixels of cholesterol-OH+ of cerebellum (m/z=369.3) over a 4mm×4mm field of view, with a pixel size of 40μm within 5min, showing that our EQ doublet reduces the measurement time of current imaging by a factor of about 30.

Experimental verification of resonance instability bands in quadrupole doublet focusing channels

The tabletop plasma trap experiment named “S-POD” is employed to explore the stability of intense charged-particle beams focused by a series of quadrupole doublet cells. S-POD is a compact linear Paul-trap, where we generate a single-species non-neutral ion plasma that can approximately reproduce the collective motion of an intense beam focused by periodic linear forces. Unlike conventional beam-dynamics experiments relying on large-scale transport channels and accelerators, it is straightforward in S-POD to control the functional form of quadrupole beam focusing over a wide range of variation to explore a variety of quadrupole focusing lattices. We systematically measure the loss rate of trapped particles as a function of bare betatron tune to locate resonance bands in which the plasma becomes unstable. It is confirmed that a few bands of coherent resonances appear depending on the beam intensity. When there is an imbalance between the horizontal and vertical focusing, those instability bands split. Experimental results indicate that the instability band is relatively insensitive to the phase of quadrupole focusing element placement within the doublet configuration over a significant range of parameters. Experimental observations are compared with transverse slice particle-in-cell simulations carried out using the Warp code.

Compact Superconducting High Gradient Quadrupole Magnets for the Interaction Regions of High Luminosity Colliders

Recent developments in the high luminosity <i xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">e</i> <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">+</sup> <i xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">e</i> <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-</sup> colliders are based on a collision scheme with a large Piwinski angle, a vertical beta function β <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">y</sub> much smaller than the bunch length, and a crab waist transformation. This scheme is being adopted in the SuperB asymmetric collider, to be built in Italy, with a design peak luminosity of 10 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">36</sup> cm <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-2</sup> sec <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-1</sup> . A crucial role is played by the quadrupole doublets QD0/QF1, which are placed close to the interaction point and generate gradients close to 100 T/m. The available space for the doublets is very small, causing the magnets to be operated with a high engineering current density (2000 A/mm <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sup> ). Starting from the helical coil concept, an advanced design of the quadrupole has been developed. The paper discusses the basic design concepts and the development of a coil model aimed at assessing the design criteria and demonstrating the feasibility of the quadrupole. The successful test of the coil model opens the way to new compact superconducting high gradient quadrupole magnets for the interaction regions of high luminosity colliders.

Function of the diiron cluster of Escherichia coli class Ia ribonucleotide reductase in proton-coupled electron transfer.

The class Ia ribonucleotide reductase (RNR) from Escherichia coli employs a free-radical mechanism, which involves bidirectional translocation of a radical equivalent or "hole" over a distance of ~35 Å from the stable diferric/tyrosyl-radical (Y122(•)) cofactor in the β subunit to cysteine 439 (C439) in the active site of the α subunit. This long-range, intersubunit electron transfer occurs by a multistep "hopping" mechanism via formation of transient amino acid radicals along a specific pathway and is thought to be conformationally gated and coupled to local proton transfers. Whereas constituent amino acids of the hopping pathway have been identified, details of the proton-transfer steps and conformational gating within the β sununit have remained obscure; specific proton couples have been proposed, but no direct evidence has been provided. In the key first step, the reduction of Y122(•) by the first residue in the hopping pathway, a water ligand to Fe1 of the diferric cluster was suggested to donate a proton to yield the neutral Y122. Here we show that forward radical translocation is associated with perturbation of the Mössbauer spectrum of the diferric cluster, especially the quadrupole doublet associated with Fe1. Density functional theory (DFT) calculations verify the consistency of the experimentally observed perturbation with that expected for deprotonation of the Fe1-coordinated water ligand. The results thus provide the first evidence that the diiron cluster of this prototypical class Ia RNR functions not only in its well-known role as generator of the enzyme's essential Y122(•), but also directly in catalysis.

Iron oxide nanoparticles in NaA zeolite cages

Zeolite NaA samples with varying concentration of Fe3+ ions have been prepared by wet chemical method. Based on powder X-ray diffraction, 29Si and 27Al MAS NMR and Fe3+ EPR investigations, the formation of nano-sized ferric oxide particles inside the larger α-cages of zeolite NaA has been established. Both Mössbauer effect and magnetization measurements carried out down to 4.5 K established the superparamagnetic behaviour of these Fe2O3 particles with a blocking temperature of ≈20 K, where the magnetization values showed deviation for the zero field cooled and field cooled samples and the appearance of a very narrow magnetic hysteresis loop below this temperature. For all Fe3+ containing samples the room temperature Mössbauer spectrum is a broad quadrupole doublet with chemical shift, δ ≈ 0.33 mm/s and quadrupole splitting, ΔEq ≈ 0.68 mm/s. Variable temperature 57Fe Mössbauer effect measurements exhibited magnetic features below the blocking temperature and at 4.5 K, the observed spectrum is a broad magnetic sextet characterized by an internal hyperfine field value of ≈504 kOe along with a very weak central superparamagnetic quadrupole doublet.

Luminosity studies in a traveling waist regime in the Compact Linear Collider

The final focus system of the Compact Linear Collider (CLIC) features a crab cavity just before the final quadrupole doublet to ensure head-on collisions at the interaction point. A decrease in the expected luminosity with respect to the case without crossing angle has been recently observed in simulations for the CLIC baseline configuration. This effect is explained from the aberrations induced due to a $z$-dependent off-center horizontal orbit in the final focus sextupoles produced by the crab cavity. Three options to recover from this loss are explored. The effect of the longitudinal $E\mathrm{\text{\ensuremath{-}}}z$ correlation of the incoming beam from the linac is taken into account and its effect on the expected luminosity is evaluated.

Crystallographic and Magnetic Properties of Nickel Substituted Manganese Ferrites Synthesized by Sol-gel Method

Nickel substituted manganese ferrites, Mn 1-x Ni x Fe₂O₄ (0.0 ≤ x ≤ 0.6), were fabricated by sol-gel method. The effects of sintering and substitution on their crystallographic and magnetic properties were studied. X-ray diffractometry of Mn 0.6 Ni 0.4 Fe₂O₄ ferrite sintered above 523 K indicated a spinel structure; particles increased in size with hotter sintering. The Mossbauer spectrum of this ferrite sintered at 523 K could be fitted as a single quadrupole doublet, indicative of a superparamagnetic phase. Sintering at 573 K led to spectrum fitted as the superposition of two Zeeman sextets and a single quadrupole doublet, indicating both ferrimagnetic and paramagnetic phase. Sintering at 673 K and at 773 K led to spectra fitted as two Zeeman sextets due to a ferrimagnetic phase. The saturation magnetization and the coercivity of Mn 0.6 Ni 0.4 Fe₂O₄ ferrite sintered at 773 K were 53.05 emu/g and 142.08 Oe. In Mn 1-x Ni x Fe₂O₄ (0.0 ≤ x ≤ 0.6) ferrites, sintering of any composition at 773 K led to a single spinel structure. Increased Ni substitution decreased the ferrites’ lattice constants and increased their particle sizes. The Mossbauer spectra could be fitted as the superposition of two Zeeman sextets due to the tetrahedral and the octahedral sites of the Fe³? ions. The variations of saturation magnetization and coercivity with changing Ni content could be explained using the changes of particle size.

Properties of the static NMR response of a confined thin nematic film of 5CB-d2under crossed electric and magnetic fields: Theory and experiments

This work describes an investigation of the static (or quasistatic) nuclear magnetic resonance (NMR) response in a nematic liquid crystal confined between two planar conducting plates and subject to a magnetic field and an electric field produced by a difference of voltage applied on the plates. Deuterium NMR spectroscopy of 4-pentyl-d(2)-4'-cyanobiphenyl (5CB-d(2)) under these conditions has revealed a voltage dependent inhomogeneous director distribution for a particular narrow range of voltages and for a fixed magnetic field (that of the spectrometer). In the ideal setup the two plates are assumed to be rigorously parallel, so that a difference of voltage applied on the plates leads to a constant electric field normal to them. When the magnetic field is parallel to the plates (orthogonal geometry) there exists a threshold value of the electric field for which the effect of both fields exactly compensate; moreover, for stronger electric field the director aligns with the electric field while for weaker electric field the director aligns with the magnetic field. If there is a lack of parallelism between the two plates, the electric field becomes inhomogeneous so that it may be larger than the threshold value in some region of the sample and smaller in the remaining part of the sample. In that case the director will adopt essentially two orientations within the sample, namely, parallel or perpendicular to the magnetic field, and the position of the frontier between the two domains depends on the voltage. This feature is clearly shown by deuterium NMR spectra that exhibit a transfer of intensity between two quadrupolar doublets with increase in the applied voltage. The coexistence of two director populations occurs for a range of voltages that depends on the degree of nonparallelism; accordingly, an estimation of this range by NMR yields an experimental estimation of the lack of parallelism. A tiny tilt of the magnetic field (nonorthogonal geometry) entrains a notably different behavior since a single doublet with voltage dependent splitting is observed in this case. In a first stage (simple model) of this work, the main features observed for the orthogonal and nonorthogonal geometries are interpreted within the framework of Leslie-Ericksen theory by employing the concept of a single effective field replacing the two real fields. However, the spectra reveal an additional director distribution, especially for the orthogonal geometry, that cannot be interpreted by this simple approach. In a second stage (advanced model), these less clear features have been investigated by numerical simulations of a two-dimensional model which includes the effects of inversion walls and of the high relative dielectric anisotropy of 5CB.

A compact beam focusing and steering element using quadrupoles with independently excited poles

Beam steering elements for accelerator beam transport are conventionally and conveniently incorporated into beamlines by fitting magnetic dipole elements around the vacuum tube of the line. Two steerers in each plane (X and Y) together with a quadrupole doublet constitute a module providing full control of the direction, position and focus of the beam. In some installations however, there may be insufficient space on the beamline to mount separate steerer elements. To provide steering capabilities in such a situation we have used a magnetic quadrupole doublet with the coils of each pole independently excited to synthesise the desired combination of quadrupole, horizontal dipole and vertical dipole fields. This paper describes the quadrupole steerer and its multichannel power supply and presents calculated magnetic field distributions together with raytracing simulation of its performance.

The New Peruvian Meteorite Carancas: Mössbauer Spectroscopy and X-Ray Diffraction Studies

The Carancas meteorite fell on 15 September 2007 approximately 10 km south of Desaguadero, near Lake Titicaca, Peru, producing bright lights, clouds of dust in the sky and intense detonations. The Carancas meteorite is classified as a H4–5 ordinary chondrite with shock stage S3 and a degree of weathering W0. The Carancas meteorite is characterized by well defined chondrules composed either of olivine or pyroxene. The Mossbauer spectra show an overlapping of paramagnetic and magnetic phases. The spectra show two quadrupole doublets associated to olivine and pyroxene; and two magnetic sextets, associated with the primary phases kamacite/taenite and Troilite (Fe2+). Metal particles were extracted from the bulk powdered samples exhibit only kamacite and small amounts of the intergrowth tetrataenite/antitaenite. X-Ray diffractogram shows the primary phases olivine, pyroxene, troilite, kamacite, diopside and albite. Iron oxides has not been detected by Mossbauer spectroscopy or XRD as can be expected for a meteorite immediately recovered after its fall.

Mössbauer spectroscopic study of FeII-doped sulphonated poly(ether-urethane)—styrene-acrylate copolymer

Thermoplastic linear ionomer based on sulphonated poly(ether-urethane)—styrene-acrylate copolymer, doped with natural Fe2 + , was studied by Mossbauer spectroscopy at T = 78 and 290 K to monitor the chemical state of Fe species. The Fe2 + added to aqueous suspension of the system was only partly oxidised in the course of polymer film preparation and drying in air. The oxidised part comprised a magnetic phase (~19 % of total Fe both at T = 78 and 298 K) and a quadrupole doublet (~40 %), while FeII (over 40 %) stabilised in two types of microenvironments.

Biophysical Investigation of the Ironome of Human Jurkat Cells and Mitochondria

The speciation of iron in intact human Jurkat leukemic cells and their isolated mitochondria was assessed using biophysical methods. Large-scale cultures were grown in medium enriched with (57)Fe citrate. Mitochondria were isolated anaerobically to prevent oxidation of iron centers. 5 K Mössbauer spectra of cells were dominated by a sextet due to ferritin. They also exhibited an intense central quadrupole doublet due to S = 0 [Fe(4)S(4)](2+) clusters and low-spin (LS) Fe(II) heme centers. Spectra of isolated mitochondria were largely devoid of ferritin but contained the central doublet and features arising from what appear to be Fe(III) oxyhydroxide (phosphate) nanoparticles. Spectra from both cells and mitochondria contained a low-intensity doublet from non-heme high-spin (NHHS) Fe(II) species. A portion of these species may constitute the "labile iron pool" (LIP) proposed in cellular Fe trafficking. Such species might engage in Fenton chemistry to generate reactive oxygen species. Electron paramagnetic resonance spectra of cells and mitochondria exhibited signals from reduced Fe/S clusters, and HS Fe(III) heme and non-heme species. The basal heme redox state of mitochondria within cells was reduced; this redox poise was unaltered during the anaerobic isolation of the organelle. Contributions from heme a, b, and c centers were quantified using electronic absorption spectroscopy. Metal concentrations in cells and mitochondria were measured using inductively coupled plasma mass spectrometry. Results were collectively assessed to estimate the concentrations of various Fe-containing species in mitochondria and whole cells - the first "ironome" profile of a human cell.

Development of the Superconducting Quadrupole Magnet for the SuperKEKB Final Focusing System

We have developed the superconducting final-focus quadrupoles for SuperKEKB, the next generation B-factory experiment in Japan. The system consists of four quadrupole doublets for incoming and outgoing electron and positron beams, respectively. A R&D superconducting quadrupole magnet was fabricated. In this paper, we describe the results on the excitation test and the magnetic field measurements of this R&D magnet.

Low-temperature Mössbauer study of heterosite, (Fe, Mn)PO4

The heterosite phase occurring in a pegmatitic rock sample was characterized by X-ray diffraction, by energy-dispersive X-ray spectroscopy and by Mössbauer spectroscopy. The orthorhombic unit-cell parameters, expressed in Å, were found as a=9.733 (1), b=5.837 (1) and c=4.776 (1). The composition was determined to be (Fe0.54Mn0.43Mg0.04)PO4. Mössbauer spectra recorded at temperatures T of 65K and higher consist of two broadened quadrupole doublets. Their isomer shifts δ are both diagnostic for the ferric state. The dominant doublet (∼60% of total area) exhibits an average quadrupole splitting ΔEQ,av of 1.62mm/s at room temperature, while the weaker broader doublet has ΔEQ,av=0.68mm/s. For temperatures T≤60K the spectra are composed of a broad sextet and a central quadrupole doublet. The doublet persists down to the lowest applied temperature of 17K. It is concluded that this doublet is due to an Fe-bearing phase other than heterosite and which gives rise to the inner doublet appearing in the spectra recorded at T≥65K. The broad sextets, attributable to the heterosite phase, were fitted with model-independent hyperfine-field distributions. However, it was consistently experienced that using the common Lorentzian-shaped elementary sextets composing the distribution, could not adequately reproduce the observed line shapes. Instead, the calculations had to be based on the diagonalization of the complete hyperfine-interaction Hamiltonian. This is due to the unusually strong quadrupole interaction. The as-such calculated hyperfine parameters of the heterosite phase at 17K may be summarized as follows: maximum-probability hyperfine field Bhf,m=473kOe, isomer shift δFe=0.54mm/s, average quadrupole coupling constant ½e2qQ=1.50mm/s, asymmetry parameter of the EFG η=0.80, and polar angles of the hyperfine field with respect to the EFGs principal axes frame Ω=40° and Ψ=90°. The temperature variation of the hyperfine field was interpreted in terms of the Bean–Rodbell (BR) model. The BR parameter, ηBR, was found to be 0.90, indicating a first-order magnetic transition at TN=59.7K. The temperature variation of the isomer shift is explained by the second-order Doppler shift δSOD. Using the Debye model for the lattice vibrational spectrum for calculating δSOD, the characteristic Mössbauer temperature ΘM was found to be 400K, which is unusually low for a ferric compound.

Anisotropic mean-squared-displacement tensor in cubic almandine garnet: a single crystal 57Fe Mössbauer study

This paper describes single-crystal measurements on a crystal plate cut from a naturally-occurring almandine-rich single crystal (Alm69Pyr19Spe8Gro4) from Wrangell Alaska. The objective was to measure the mean-squared-displacement (msd) tensor precisely using Mossbauer spectroscopy. Parallel quantum-mechanical calculations based on X-ray determined atomic displacement parameters and Mossbauer parameters from polycrystalline measurements indicated that the msd tensor should display significant anisotropy, easily measurable within the precision of the Mossbauer experiment. For each single-crystal orientation the observed Mossbauer spectrum represents a macroscopic quantity that is the average over six symmetry-related (local) dodecahedral sites in which the high-spin Fe2+ ions reside. The anisotropy in the measured msd tensor is, nevertheless, unequivocal. Furthermore, the magnitudes of the Mossbauer-determined msd principal values exceed those of the corresponding X-ray-determined quantities by a factor 3.7. The equivalent recoilless fractions are also anisotropic and consequently one observes the Gol’danskii–Karyagin Effect (GKE), as manifested by an asymmetric quadrupole doublet in polycrystalline absorbers. Moreover, the line widths of the two quadrupole lines are markedly different but angle invariant. This is interpreted as implying that, in addition to anisotropy in the msd tensor, differential spin–spin relaxation is present in the \( m = \pm 3/2 \leftrightarrow \pm 1/2 \) and \( m = \pm 1/2 \leftrightarrow \pm 1/2,\, \mp 1/2 \) nuclear transitions. While both effects contribute to the quadrupole asymmetries observed in Mossbauer spectra of polycrystalline almandine, the GKE is apparently predominant.

Temperature-dependent 57Fe Mössbauer spectroscopy and local structure of mullite-type Bi2(Fe x Al1 – x )4O9 (0.1≤x≤1) solid solutions

Abstract Oxides of the chemical composition Bi2(Fe x Al1 – x )4O9 (0.1≤x≤1) possessing a mullite-type structure have been investigated using 57Fe Mössbauer spectroscopy in the temperature range between room temperature and 1073K. The spectra have been fitted with two quadrupole doublets for Fe3 + ions in octahedral and tetrahedral oxygen coordination. The distribution of iron on the two inequivalent structural sites has been determined from the relative areas of the subspectra. The site occupancy is found to be random within experimental error: it does not exhibit any preference of iron for the octahedral or tetrahedral sites, either as a function of temperature or with a dependence on the composition of the solid solutions.

Electronic spin states of ferric and ferrous iron in the lower-mantle silicate perovskite

The electronic spin and valence states of iron in lower-mantle silicate perovskite have been previously investigated at high pressures using various experimental and theoretical techniques. However, experimental results and their interpretation remain highly debated. Here we have studied a wellcharacterized silicate perovskite starting sample [(Mg0.9,Fe0.1)SiO3] in a chemically inert Ne pressure medium at pressures up to 120 GPa using synchrotron Mössbauer spectra. Analyses of the Mössbauer spectra explicitly show a high-spin to low-spin transition of the octahedral-site Fe3+ occurring at ~13-24 GPa, as evidenced from a significant increase in the hyperfine quadrupole splitting. Two quadrupole doublets of the A-site Fe2+, with extremely high-QS values of 4.1 and 3.1 mm/s, occur simultaneously with the spin transition of the octahedral-site Fe3+ and continue to develop to 120 GPa. It is conceivable that the spin-pairing transition of the octahedral-site Fe3+ causes a volume reduction and a change in the local atomic-site configurations that result in a significant increase of the quadrupole splitting in the dodecahedral-site Fe2+ at 13-24 GPa. Our results here provide a coherent explanation for recent experimental and theoretical results on the spin and valence states of iron in perovskite, and assist in comprehending the effects of the spin and valence states of iron on the properties of the lower-mantle minerals.

Studies on Structural, Magnetic and Thermal Properties of xFe2TiO4-(1−x)Fe3O4 (0≤x≤1) Pseudo-binary System

The xFe2TiO4-(1−x)Fe3O4 pseudo-binary systems (0≤x≤1) of ulvöspinel component were synthesized by solid-state reaction between ulvöspinel Fe2TiO4 precursors and commercial Fe3O4 powders in stochiometric proportions. Crystalline structures were determined by X-ray powder diffraction (XRD) and it was found that the as-obtained titanomagnetites maintain an inverse spinel structure. The lattice parameter a of synthesized titanomagnetite increases linearly with the increase in the ulvöspinel component. 57Fe room temperature Mössbauer spectra were employed to evaluate the magnetic properties and cation distribution. The hyperfine magnetic field is observed to decrease with increasing Fe2TiO4 component. The fraction of Fe2+ in both tetrahedral and octahedral sites increases with the increase in Ti4+ content, due to the substitution and reduction of Fe3+ by Ti4+ that maintains the charge balance in the spinel structure. For x in the range of 0 ≤x≤0.4, the solid solution is ferrimagnetic at room temperature. However, it shows weak ferrimagnetic and paramagnetic behavior for x in the range of 0.4<x≤0.7. When x>0.70, it only shows paramagnetic behavior, with the appearance of quadrupole doublets in the Mössbauer spectra. Simultaneous differential scanning calorimetry and thermogravimetric analysis (DSC–TGA) studies showed that magnetite is not stable, and thermal decomposition of magnetite occurs with weight losses accompanying with exothermic processes under heat treatment in inert atmosphere.

Salen-Based Coordination Polymers of Iron and the Rare Earth Elements

Reaction of N,N'-bis(4-carboxysalicylidene)ethylenediamine (H(4)L) with iron(III) chloride and lanthanide nitrates resulted in the coordination polymers of composition {[Ln(2)(FeLCl)(2)(NO(3))(2)(DMF)(5)]·(DMF)(4)}(n) (Ln = Y, Eu, Gd, Tb, Dy). The polymers consist of iron-salen-based moieties having carboxylate linkers connected to rare earth atoms in a 1D chain structure. Thus, the iron-salen complex acts as a "metalloligand". Because of the twisting of the chains, porous structures are formed and possess large free void space. The magnetic studies of selected compounds exhibit weak intramolecular antiferromagnetic interactions of Ln-Ln. At 3, 30, and 80 K, the Mössbauer spectra of the iron-dysprosium compound show a strongly asymmetric quadrupole doublet with isomer shift and quadrupole splitting values typical for Fe(III) ions in high spin state. In addition, an anomalous temperature dependence of both isomer shift and quadrupole splitting has been observed.

Mössbauer and EPR Study of Iron in Vacuoles from Fermenting Saccharomyces cerevisiae

Vacuoles were isolated from fermenting yeast cells grown on minimal medium supplemented with 40 μM (57)Fe. Absolute concentrations of Fe, Cu, Zn, Mn, Ca, and P in isolated vacuoles were determined by ICP-MS. Mössbauer spectra of isolated vacuoles were dominated by two spectral features: a mononuclear magnetically isolated high-spin (HS) Fe(III) species coordinated primarily by hard/ionic (mostly or exclusively oxygen) ligands and superparamagnetic Fe(III) oxyhydroxo nanoparticles. EPR spectra of isolated vacuoles exhibited a g(ave) ~ 4.3 signal typical of HS Fe(III) with E/D ~ 1/3. Chemical reduction of the HS Fe(III) species was possible, affording a Mössbauer quadrupole doublet with parameters consistent with O/N ligation. Vacuolar spectral features were present in whole fermenting yeast cells; however, quantitative comparisons indicated that Fe leaches out of vacuoles during isolation. The in vivo vacuolar Fe concentration was estimated to be ~1.2 mM while the Fe concentration of isolated vacuoles was ~220 μM. Mössbauer analysis of Fe(III) polyphosphate exhibited properties similar to those of vacuolar Fe. At the vacuolar pH of 5, Fe(III) polyphosphate was magnetically isolated, while at pH 7, it formed nanoparticles. This pH-dependent conversion was reversible. Fe(III) polyphosphate could also be reduced to the Fe(II) state, affording similar Mössbauer parameters to that of reduced vacuolar Fe. These results are insufficient to identify the exact coordination environment of the Fe(III) species in vacuoles, but they suggest a complex closely related to Fe(III) polyphosphate. A model for Fe trafficking into/out of yeast vacuoles is proposed.