T. G. St. Pierre

Deformation of a hydrophobic ferrofluid droplet suspended in a viscous medium under uniform magnetic fields

The effect of applied magnetic fields on the deformation of a biocompatible hydrophobic ferrofluid drop suspended in a viscous medium is investigated numerically and compared with experimental data. A numerical formulation for the time-dependent simulation of magnetohydrodynamics of two immiscible non-conducting fluids is used with a volume-of-fluid scheme for fully deformable interfaces. Analytical formulae for ellipsoidal drops and near-spheroidal drops are reviewed and developed for code validation. At low magnetic fields, both the experimental and numerical results follow the asymptotic small deformation theory. The value of interfacial tension is deduced from an optimal fit of a numerically simulated shape with the experimentally obtained drop shape, and appears to be a constant for low applied magnetic fields. At high magnetic fields, on the other hand, experimental measurements deviate from numerical results if a constant interfacial tension is implemented. The difference can be represented as a dependence of apparent interfacial tension on the magnetic field. This idea is investigated computationally by varying the interfacial tension as a function of the applied magnetic field and by comparing the drop shapes with experimental data until a perfect match is found. This estimation method provides a consistent correlation for the variation in interfacial tension at high magnetic fields. A conclusion section provides a discussion of physical effects which may influence the microstructure and contribute to the reported observations.

Low-frequency low-field magnetic susceptibility of ferritin and hemosiderin

Low-frequency low-field magnetic susceptibility measurements were made on four samples of mammalian tissue iron oxide deposits. The samples comprised: (1) horse spleen ferritin; (2) dugong liver hemosiderin; (3) thalassemic human spleen ferritin; and (4) crude thalassemic human spleen hemosiderin. These samples were chosen because Mössbauer spectroscopic measurements on the samples indicated that they exemplified the variation in magnetic and mineral structure found in mammalian tissue iron oxide deposits. The AC-magnetic susceptometry yielded information on the magnetization kinetics of the four samples indicating samples 1, 2, and 3 to be superparamagnetic with values of around 10(11) s(-1) for the pre-exponential frequency factor in the Néel-Arrhenius equation and values for characteristic magnetic anisotropy energy barriers in the range 250-400 K. Sample 4 was indicated to be paramagnetic at all temperatures above 1.3 K. The AC-magnetic susceptometry data also indicated a larger magnetic anisotropy energy distribution in the dugong liver sample compared with samples 1 and 3 in agreement with previous Mössbauer spectroscopic data on these samples. At temperatures below 200 K, samples 1-3 exhibited Curie-Weiss law behavior, indicating weak particle-particle interactions tending to favor antiparallel alignment of the particle magnetic moments. These interactions were strongest for the dugong liver hemosiderin, possibly reflecting the smaller separation between mineral particles in this sample. This is the first magnetic susceptometry study of hemosiderin iron deposits and demonstrates that the AC-magnetic susceptometry technique is a fast and informative method of studying such tissue iron oxide deposits.

A magnetic resonance imaging based method for measurement of tissue iron concentration in liver arterially embolized with ferrimagnetic particles designed for magnetic hyperthermia treatment of tumors

Rabbit liver was loaded with ferrimagnetic particles of gamma -Fe2 O3 (designed for magnetic hyperthermia treatment of liver tumors) by injecting various doses of a suspension of the particles into the hepatic artery in vivo. Proton transverse relaxation rate (R(2)) images of the livers in vivo, excised, and dissected were generated from a series of single spin-echo images. Mean R(2) values for samples of ferrimagnetic-particle-loaded liver dissected into approximate 1 cm cubes were found to linearly correlate with tissue iron concentration over the range from approximately 0.1 to at least 2.7 mg Fe/g dry tissue when measured at room temperature. Changing the temperature of ferrimagnetic-particle-loaded samples of liver from 1 degrees C to 37 degrees C had no observable effect on tissue R(2) values. However, a small but significant decrease in R(2) was found for control samples containing no ferrimagnetic material on raising the temperature from 1 degrees C to 37 degrees C. Both chemically measured iron concentrations and mean R(2) values for rabbit livers with implanted tumors tended to be higher than those measured for tumor-free liver. This study indicates that tissue R(2) measurement and imaging by nuclear magnetic resonance may have a useful role in magnetic hyperthermia therapy protocols for the treatment of liver cancer.

Synthesis, structure and magnetic properties of ferritin cores with varying composition and degrees of structural order: models for iron oxide deposits in iron-overload diseases

The cage-like protein ferritin was used to form nanoscale iron-containing mineral particles in vitro with different structures and compositions by reconstituting the metal-free protein (apoferritin) with iron at different temperatures and in the presence of different quantities of phosphate. The products of reconstitution were studied with inductively coupled plasma spectrometry, transmission electron microscopy, electron diffraction, extended X-ray absorption fine structure analysis, and Mossbauer spectroscopy. Reconstitution at 4°C resulted in poorly ordered core structures while reconstitution at 55°C resulted in more ordered structures based on that of the mineral ferrihydrite. The more ordered structure of the 55°C ferritin resulted in stronger magnetic exchange interactions between the iron atoms within each core and a larger magnetic anisotropy energy per core. Incorporation of phosphate within the core structure reduced the core density. This also reduced the strength of the magnetic exchange interactions between the iron atoms. High levels of phosphate within the core resulted in cores with no measurable periodicity within their structure. This in turn caused a reduction in the magnetic anisotropy energy per core. The ability to tailor the degree of structural order and phosphate content of ferritin cores in vitro makes available a range of model materials for a more comprehensive study of the structural and magnetic correlations found in nanoscale iron biominerals in vivo such as native ferritins and haemosiderins deposited in iron-overloaded tissues.

Formation of cobalt nanoparticle dispersions in the presence of polysiloxane block copolymers

Abstract Stable suspensions of superparamagnetic cobalt nanoparticles have been prepared in poly(dimethysiloxane) (PDMS) carrier fluids in the presence of poly[dimethylsiloxane- b -(3-cyanopropyl)methylsiloxane- b -dimethylsiloxane] (PDMS–PCPMS–PDMS) triblock copolymers as steric stabilizers. A series of the polysiloxane triblock copolymers with systematically varied molecular weights were prepared via anionic polymerization using LiOH as an initiator. These copolymers formed micelles in toluene and served as ‘nanoreactors’ for thermal decomposition of the Co 2 (CO) 8 precursor. The nitrile groups on the PCPMS central blocks are thought to adsorb onto the particle surface, while the PDMS endblocks protrude into the reaction medium to provide steric stability. The particle size can be controlled by adjusting the cobalt to copolymer ratio. TEM shows non-aggregated cobalt nanoparticles with narrow size distributions which are evenly surrounded with copolymer sheaths. However, some degree of surface oxidation was observed over time, resulting in a decrease in magnetic susceptibility.

Field-induced motion of ferrofluid droplets through immiscible viscous media

The motion of a hydrophobic ferrofluid droplet placed in a viscous medium and driven by an externally applied magnetic field is investigated numerically in an axisymmetric geometry. Initially, the drop is spherical and placed at a distance away from the magnet. The governing equations are the Maxwell equations for a non-conducting flow, momentum equation and incompressibility. A numerical algorithm is derived to model the interface between a magnetized fluid and a non-magnetic fluid via a volume-of-fluid framework. A continuum-surface-force formulation is used to model the interfacial tension force as a body force, and the placement of the liquids is tracked by a volume fraction function. Three cases are studied. First, where inertia is dominant, the magnetic Laplace number is varied while the Laplace number is fixed. Secondly, where inertial effects are negligible, the Laplace number is varied while the magnetic Laplace number is fixed. In the third case, the magnetic Bond number and inertial effects are both small, and the magnetic force is of the order of the viscous drag force. The time taken by the droplet to travel through the medium and the deformations in the drop are investigated and compared with a previous experimental study and accompanying simpler model. The transit times are found to compare more favourably than with the simpler model.

Magnetic susceptibility of iron in malaria-infected red blood cells

During intra-erythrocytic maturation, malaria parasites catabolize up to 80% of cellular haemoglobin. Haem is liberated inside the parasite and converted to haemozoin, preventing haem iron from participating in cell-damaging reactions. Several experimental techniques exploit the relatively large paramagnetic susceptibility of malaria-infected cells as a means of sorting cells or investigating haemoglobin degradation, but the source of the dramatic increase in cellular magnetic susceptibility during parasite growth has not been unequivocally determined. Plasmodium falciparum cultures were enriched using high-gradient magnetic fractionation columns and the magnetic susceptibility of cell contents was directly measured. The forms of haem iron in the erythrocytes were quantified spectroscopically. In the 3D7 laboratory strain, the parasites converted approximately 60% of host cell haemoglobin to haemozoin and this product was the primary source of the increase in cell magnetic susceptibility. Haemozoin iron was found to have a magnetic susceptibility of (11.0+/-0.9)x10(-3) mL mol(-1). The calculated volumetric magnetic susceptibility (SI units) of the magnetically enriched cells was (1.88+/-0.60)x10(-6) relative to water while that of uninfected cells was not significantly different from water. Magnetic enrichment of parasitised cells can therefore be considered dependent primarily on the magnetic susceptibility of the parasitised cells.

A comparison of methods for the measurement of the particle-size distribution of magnetic nanoparticles

Recently, interest in magnetic particles, particularly in the nanometre-size range, has increased significantly. The main driving forces behind this interest are both the development of improved synthesis techniques and an increase in the number of potential applications for suitable magnetic nanoparticles. A critical factor of interest in both the synthesis and the development of applications is the particle-size distribution. In this paper, we investigate three common techniques for determining the particle-size distribution of magnetic nanoparticles (electron microscopy, magnetic measurements and small-angle neutron scattering). We compare the distributions determined by each technique for two standard samples and discuss their advantages, disadvantages and limitations.

Detection limits for ferrimagnetic particle concentrations using magnetic resonance imaging based proton transverse relaxation rate measurements

A clinical magnetic resonance imaging (MRI) system was used to measure proton transverse relaxation rates (R2) in agar gels with varying concentrations of ferrimagnetic iron oxide nanoparticles in a field strength of 1.5 T. The nanoparticles were prepared by coprecipitation of ferric and ferrous ions in the presence of either dextran or polyvinyl alcohol. The method of preparation resulted in loosely packed clusters (dextran) or branched chains (polyvinyl alcohol) of particles containing of the order of 600 and 400 particles, respectively. For both methods of particle preparation, concentrations of ferrimagnetic iron in agar gel less than 0.01 mg ml(-1) had no measurable effect on the value of R2 for the gel. The results indicate that MRI-based R2 measurements using 1.5 T clinical scanners are not quite sensitive enough to detect the very low concentrations of nanoparticulate biogenic magnetite reported in human brain tissue.

Organ-specific crystalline structures of ferritin cores in β-thalassemia/hemoglobin E

SummaryThe cores of ferritins isolated from different organs of human subjects withβ-thalassemia/hemoglobin E (β-thal/HbE) disease have different size distributions and crystallinities depending on the source organ. These patients have not been treated by hypertransfusion regimen or iron chelation therapy.β-Thal/HbE spleens and livers yield ferritin cores which are less crystalline than those isolated from normal spleens and livers, reflecting the more rapid deposition of iron in the diseased state. Ferritins isolated from the hearts and pancreases ofβ-thal/HbE subjects were found to have larger, more crystalline cores than those from theβ-thal/HbE livers and spleens, possibly as a consequence of the role of the heart and pancreas as long-term iron deposition sites in this iron overload pathology.