Small Oxide Particles Research Articles

Correlation between chemical composition and size of very small oxide particles in the MA957 ODS ferritic alloy

ODS (oxide dispersion strengthened) alloys have superior creep properties. As it is well known, these excellent creep properties result from very fine oxide particles dispersed with the matrix. However, there is no common understanding about the nature of the very small oxide particles. Two hypotheses arise from the literature, 1: non-stoichiometric Y-, Ti-, O-enriched clusters and 2: stoichiometric Y 2Ti 2O 7. In this work, both chemically extracted residue method and extraction replica method were applied to the commercial ODS ferritic alloy, MA957. These samples were then observed using XRD (X-ray diffractometry) and FEG–STEM (field emission gun–scanning transmission electron microscopy) with EDS (energy dispersive X-ray spectrometer). From the results, it was concluded that the composition of small particles is related to the particle size. They exhibit at least two types of phase, 1: non-stoichiometric Y-, Ti-, O-enriched clusters from ∼2 to ∼15 nm (Y/Ti < 1) and 2: stoichiometric Y 2Ti 2O 7 from ∼15 to ∼35 nm. Based on the result, it is suggested that the appropriate increase of titanium content compared to yttrium content in oxide particles by modifying the chemical compositions of ODS alloys could be an effective way to obtain a finer dispersion of oxide particles.

Protease-Specific Nanosensors for Magnetic Resonance Imaging

Imaging of enzyme activity is a central goal of molecular imaging. With the introduction of fluorescent smart probes, optical imaging has become the modality of choice for experimental in vivo detection of enzyme activity. Here, we present a novel high-relaxivity nanosensor that is suitable for in vivo imaging of protease activity by magnetic resonance imaging. Upon specific protease cleavage, the nanoparticles rapidly switch from a stable low-relaxivity stealth state to become adhesive, aggregating high-relaxivity particles. To demonstrate the principle, we chose a cleavage motif of matrix metalloproteinase 9 (MMP-9), an enzyme important in inflammation, atherosclerosis, tumor progression, and many other diseases with alterations of the extracellular matrix. On the basis of clinically tested very small iron oxide particles (VSOP), the MMP-9-activatable protease-specific iron oxide particles (PSOP) have a hydrodynamic diameter of only 25 nm. PSOP are rapidly activated, resulting in aggregation and increased T2*-relaxivity.

Magnetic labeling of non‐phagocytic adherent cells with iron oxide nanoparticles: a comprehensive study

Small particles of iron oxide (SPIO) and ultrasmall particles of iron oxide (USPIO), inducing a strong negative contrast on T(2) and T(2)*-weighted MR images, are the most commonly used systems for the magnetic labeling of cultured cells and their subsequent detection by magnetic resonance imaging (MRI). The purpose of this work is to study the influence of iron incubation concentration, nanoparticle size and nanoparticle coating on the magnetic labeling and the viability of non-phagocytic adherent cells in culture. The magnetic labeling of 3T6 fibroblasts was studied by T(2)-weighted MRI at 4.7 T and by dosing-or cytochemical revealing-of iron through methods based on Perl's Prussian blue staining. Cells were incubated for 48 h with increasing iron concentrations of SPIO (25-1000 microg Fe/ml Endorem. Sinerem, a USPIO (20-40 nm) coated with neutral dextran, and Resovist (65 nm), a SPIO bearing an anionic carboxydextran coating, were compared with Endorem (dextran-coated, 80-150 nm) as magnetic tags. The iron loading of marrow stromal cell primary cultures (MSCs) isolated from rat femurs was compared with that of 3T6 fibroblasts. The SPIO-labeling of cells with Endorem was found to be dependent on the iron incubation concentration. MSCs, more sparsely distributed in the culture, exhibited higher iron contents than more densely populated 3T6 fibroblast cultures. A larger iron loading was achieved with Resovist than with Endorem, which in turn was more efficient than Sinerem as a magnetic tag. The magnetic labeling of cultured non-phagocytic adherent cells with iron oxide nanoparticles was thus found to be dependent on the relative concentration of the magnetic tag and of the cells in culture, on the nanoparticle size, and on the coating type. The viability of cells, estimated by methods assessing cell membrane permeability, was not affected by magnetic labeling in the conditions used in this work.

Influence of oxygen on the growth of carbon nanotubes

The influence of oxygen on the growth of carbon nanotubes (CNTs) using plasma-enhanced chemical vapour deposition has been studied. The cobalt catalyst film and CNTs were characterized by scanning electron microscopy, transmission electron microscopy, high resolution transmission electron microscope, x-ray photoelectron spectroscopy and Raman spectroscopy. The results showed that small cobalt oxide particles obtained by O2-etching were deoxidized back to Co catalyst particles with small size in the CH4/H2 atmosphere for the growth of CNTs. Small Co particles and the inlet of oxygen in the stage of CNT growth enhanced the yield rate and purity of aligned CNTs.

Pain fMRI in rat cervical spinal cord: An echo planar imaging evaluation of sensitivity of BOLD and blood volume-weighted fMRI

Objective measure of pain is valuable in drug discovery research and development of analgesics. Spinal cord is an important relay of the pain pathway, and fMRI offers an excellent opportunity to quantify pain using activation in the spinal cord induced by painful stimuli. fMRI literature of cervical spinal cord with regard to the spatial extent, in both longitudinal and cross-sectional directions, of neuronal activation induced by noxious stimulation is ambiguous. This study investigates the feasibility of developing a robust pain assay using fMRI in the cervical spinal cord in α-chloralose anesthetized rats subjected to transcutaneous noxious electrical stimulation of the forepaw. Blood oxygenation level dependent (BOLD) and blood volume (BV)-weighted fMRI data were acquired without and with intravenous injection of ultra small superparamagnetic iron oxide particles (USPIO), respectively. BOLD data were acquired by gradient-echo (GE) and spin-echo (SE) echo planar imaging (EPI), while BV-weighted fMRI data were acquired only by GE EPI. Cervical spinal cord activity was robustly detected by all three fMRI techniques. The sensitivity of the fMRI signal was highest in GE BV-weighted fMRI followed in order by GE BOLD, and SE BOLD, respectively. Spatially, the fMRI signal extended ∼ 9 mm in the longitudinal direction, covering C 4–C 8 segments, coinciding with the synapse location of afferent terminals from the stimulated site. In the cross-sectional direction, the signal change is localized predominantly to the ipsilateral dorsal region. This study demonstrates that cervical spinal cord fMRI can be performed reliably in anesthetized rats offering it as a potential tool for analgesic drug development.

The Use of Clinically Approved Small Particles of Iron Oxide (SPIO) for Labeling of Mesenchymal Stem Cells Aggravates Clinical Symptoms in Experimental Autoimmune Encephalomyelitis and Influences Their In Vivo Distribution

Multiple sclerosis (MS) is an inflammatory and demyelinating disease of the central nervous system (CNS). Mesenchymal stem cells (MSC) have been shown to ameliorate symptoms in experimental autoimmune encephalomyelitis (EAE), a model of MS. Using cloned MSC labeled with clinically approved small particles of iron oxide (SPIO) for treatment of EAE we analyzed the tissue localization of transferred cells. Treatment with unlabeled MSC led to disease amelioration compared to controls. In contrast, treatment with SPIO-labeled MSC lead to increase in disease severity. Treatment with SPIO alone did not alter disease course. After transplantation labeled and nonlabeled MSC were detected in the CNS and the liver with significantly more SPIO-labeled cells present in the CNS. Iron deposition was present in the group treated with SPIO-labeled MSC, indicating that in vivo the initially cell surface-bound iron detached from the MSC. These results could be of great importance for imaging of patients in the clinical setting, indicating that in vivo application of SPIO-labeled MSC needs to be performed with caution because the cell-derived exposure of iron can lead to disease aggravation.

Carbon-templated hexaaluminates with enhanced surface area and catalytic performance

Carbon templating was used to synthesize high-surface area LaFeAl 11O 19 hexaaluminates leading to improved catalytic performance. The oxide precursor–template composites were prepared by impregnation, complexation with citric acid, and coprecipitation routes varying the amounts of acetylene black incorporated. Calcination in static air at 1473 K led to single-phased hexaaluminates. The samples were characterized at different stages of the synthetic protocol by ICP–OES, in situ and ex situ XRD, TEM, N 2 adsorption, He pycnometry, TGA, H 2-TPR, and XPS. The templating effect of carbon originates fine oxide particles. Consequently, the specific surface area of the non-templated hexaaluminates (1–11 m 2 g −1 depending on the preparation method) increased up to a factor of 25 upon incorporation of carbon in the synthesis. The stabilization of small particles occurs despite the temperature difference between the elimination of carbon (973 K) and the attainment of the hexaaluminate phase above 1373 K. The morphology of the oxide obtained upon carbon removal determines the textural properties of the hexaaluminate particles. Our results demonstrate that the confined space synthesis is not exclusively responsible for small oxide particles. The stabilization of small crystallites on the carbon surface in the composite and breakage of the oxide layer caused by template combustion are key aspects for attaining finely dispersed particles when the carbon is macroporous. The enhanced catalytic activity and time-on-stream stability of the templated hexaaluminates was demonstrated in the direct N 2O decomposition using model and simulated feed mixtures. In this application, a quasi-linear relation between the reaction rate and the specific surface area of the samples was obtained. Characterization by H 2-TRP and XPS indicated that the nature of iron in LaFeAl 11O 19 was not altered by carbon incorporation in the synthesis.

Correlation of Carotid Atheromatous Plaque Inflammation Using USPIO-Enhanced MR Imaging With Degree of Luminal Stenosis

Inflammation is a recognized risk factor for the vulnerable atherosclerotic plaque. The study explores the relationship between the degree of Magnetic Resonance (MR)-defined inflammation using Ultra Small Super-Paramagnetic Iron Oxide (USPIO) particles and the severity of luminal stenosis in asymptomatic carotid plaques. Seventy-one patients with an asymptomatic carotid stenosis of > or = 40% underwent multi-sequence USPIO-enhanced MR imaging. Stenosis severity was measured according to the NASCET and ECST methods. No demonstrable relationship between inflammation as measured by USPIO-enhanced signal change and the degree of luminal stenosis was found. Inflammation and stenosis are likely to be independent risk factors, although this needs to be further validated.

Linking Proteins with Anionic Nanoparticles via Protamine: Ultrasmall Protein‐Coupled Probes for Magnetic Resonance Imaging of Apoptosis

Magnetic resonance imaging (MRI) of a target in vivo depends on the surface, size, and particle relaxivity of the target-specific nanoparticles for MRI. Here a new method for decorating very small iron oxide particles (VSOPs) with target-specific ligands is described. The method is based on the electrostatic attraction of the strongly positively charged peptide protamine to the anionic citrate shell of the electrostatically stabilized VSOPs. The protamine coat allows linkage chemistry and chimera technology to functionalize VSOPs or other negative charged surfaces with biologics. Annexin A5 (anxA5)-VSOP utilizing thiol chemistry was generated to couple biologically active anxA5 to VSOPs for in vivo MRI of apoptosis. Annexin A5-VSOP comprises five anxA5 molecules per iron oxide nanoparticle with a high R2 particle relaxivity of 180 000 mM(-1) s(-1) yet small hydrodynamic diameter of only 14.7+/-2.9 nm beneficial for in vivo MRI of extravascular targets.

Visualisation of the kinetics of macrophage infiltration during experimental autoimmune encephalomyelitis by magnetic resonance imaging

Macrophages are considered to be the predominant effector cells in multiple sclerosis (MS) and its animal model experimental autoimmune encephalomyelitis (EAE). Ultra small particles of iron oxide (USPIO) can be used to detect macrophage infiltrates in the CNS with magnetic resonance imaging (MRI). Here, we investigated whether the kinetics of lesion formation in EAE can be visualised by altering the time point of USPIO injection and the time interval between particle injection and MRI. When USPIO are systemically injected 24 h before MRI, hypo intense regions are detected in different brain regions depending on the disease stage. These regions correspond to sites of macrophage infiltration. A more complete visualisation of sites of inflammation is accomplished by USPIO injection at disease onset and postponing MRI to top of disease. This study demonstrates that the distribution pattern and amount of inflammatory lesions detected with USPIO, depends on timing of USPIO administration and subsequent MRI. These findings are important for a correct application and interpretation of USPIO dependent contrast imaging of CNS inflammation.

Comparison of the Inflammatory Burden of Truly Asymptomatic Carotid Atheroma with Atherosclerotic Plaques in Patients with Asymptomatic Carotid Stenosis Undergoing Coronary Artery Bypass Grafting: An Ultrasmall Superparamagnetic Iron Oxide Enhanced Magnetic Resonance Study

Inflammation is a recognized risk factor for the vulnerable atherosclerotic plaque. The aim of this study was to explore whether there is a difference in the degree of Magnetic Resonance (MR) defined inflammation using Ultra Small Super-Paramagnetic Iron Oxide (USPIO) particles, within carotid atheroma in completely asymptomatic individuals and the asymptomatic carotid stenosis in a cohort of patients undergoing coronary artery bypass grafting (CABG). 10 patients awaiting CABG with asymptomatic carotid disease and 10 completely asymptomatic individuals with no documented coronary artery disease underwent multi-sequence MR imaging before and 36 hours post USPIO infusion. Images were manually segmented into quadrants and signal change in each quadrant, normalised to adjacent muscle signal, was calculated following USPIO administration. The mean percentage of quadrants showing signal loss was 94% in the CABG group, compared to 24% in the completely asymptomatic individuals (p<0.001). The carotid plaques from the CABG patients showed a significant mean signal intensity decrease of 16.4% after USPIO infusion (95% CI 10.6% to 22.2%; p<0.001). The truly asymptomatic plaques showed a mean signal intensity increase (i.e. enhancement) after USPIO infusion of 8.4% (95% CI 2.6% to 14.2%; p=0.007). The mean signal difference between the two groups was 24.9% (95% CI 16.7% to 33.0%; p<0.001). These findings are consistent with the hypothesis that inflammatory atheroma is a systemic disease. The carotid territory is more likely to take up USPIO if another vascular territory is symptomatic.

Iron oxide labelling of human mesenchymal stem cells in collagen hydrogels for articular cartilage repair

For the development of new therapeutical cell-based strategies for articular cartilage repair, a reliable cell monitoring technique is required to track the cells in vivo non-invasively and repeatedly. We present a systematic and detailed study on the performance and biological impact of a simple and efficient labelling protocol for human mesenchymal stem cells (hMSCs). Commercially available very small superparamagnetic iron oxide particles (VSOPs) were used as magnetic resonance (MR) contrast agent. Iron uptake via endocytosis was confirmed histologically with prussian blue staining and quantified by mass spectrometry. Compared with unlabelled cells, VSOP-labelling did neither influence the viability nor the proliferation potential of hMSCs. Furthermore, iron incorporation did not affect hMSCs in undergoing adipogenic, osteogenic or chondrogenic differentiation, as demonstrated histologically and by gene expression analyses. The efficiency of the labelling protocol was assessed with high-resolution MR imaging at 11.7 T. VSOP-labelled hMSCs were visualised in a collagen type I hydrogel, which is in clinical use for matrix-based articular cartilage repair. The presence of VSOP-labelled hMSCs was indicated by distinct hypointense spots in the MR images, as a result of iron specific loss of signal intensity. In summary, this labelling technique has great potential to visualise hMSCs and track their migration after transplantation for articular cartilage repair with MR imaging.

Transmission electron microscopic observation on reduction process of copper–iron spinel catalyst for steam reforming of dimethyl ether

The reduction process of copper–iron spinel oxide, which is active for steam reforming of dimethyl ether after mixing with alumina, has been investigated by a transmission electron microscope (TEM), scanning TEM (STEM), and energy dispersive X-ray (EDX) analyzer. The catalyst preparation was started from formation of well-sintered CuFe2O4 by calcination in air at 900°C. After reduction of CuFe2O4 with hydrogen at 250°C, metallic copper grains were developed on reduced spinel surface by the phase separation from the oxide. Strong chemical interaction between deposited Cu and reduced spinel oxide was expected from their intimate interfacial contact and lattice matching. The reduced sample contained metallic Cu, reduced spinel, and spinel oxide with super-lattice structure. Partial elimination of Cu and lattice oxygen resulted in formation of pores in and between the oxide grains. The size of the deposited Cu particle and Cu grain was largely distributed. After heating at higher temperature of 350°C, the large spinel oxide particles are decomposed into small particles via formation of cracks. The resultant catalyst powder was very porous and consisted of very small particles of Cu, iron oxide, and spinel oxide. STEM–EDX analyses clarified the phase separation process of metallic Cu and iron oxide from host CuFe2O4 upon reduction.

BOLD and blood volume-weighted fMRI of rat lumbar spinal cord during non-noxious and noxious electrical hindpaw stimulation

Spinal cord fMRI is a useful tool for studying spinal mechanisms of pain, hence for analgesic drug development. Its technical feasibility in both humans and rats has been demonstrated. This study investigates the reproducibility, robustness, and spatial accuracy of fMRI of lumbar spinal cord activation due to transcutaneous noxious and non-noxious electrical stimulation of the hindpaw in α-chloralose-anesthetized rats. Blood oxygenation level-dependent (BOLD) and blood volume-weighted fMRI data were acquired without and with intravenous injection of ultra small superparamagnetic iron oxide particles (USPIO), respectively, using a gradient echo (GE) echo planar imaging (EPI) technique at 4.7 T. Neuronal activation in the spinal cord induced by noxious stimulation to the hindpaw (2 ms wide, 5 mA amplitude, known to activate C-fibers) can be robustly detected by both fMRI techniques with excellent reproducibility and peaked at the stimulus frequency of 40 Hz. However, both fMRI techniques were not sensitive to neuronal activation in spinal cord induced by non-noxious stimulation (0.3 ms, 1.5 mA, known only to activate A-fibers). Spatially, the fMRI signal extended ∼ 5 mm in the longitudinal direction, covering L 3–L 5 segments. In the cross-sectional direction, the highest signal change of blood volume-weighted fMRI was in the middle of the ipsilateral dorsal horn, which roughly corresponds to laminae V and VI, while the highest signal change of BOLD fMRI was in the ipsilateral dorsal surface. This study demonstrates that spinal cord fMRI can be performed in anesthetized rats reliably and reproducibly offering it as a potential tool for analgesic drug discovery.

Nano-scale oxide dispersoids by internal oxidation of Fe–Ti–Y intermetallics

The processing of high-temperature alloys containing nano-scale oxide dispersoids usually involves mechanical alloying, but dispersoid formation by internal oxidation is also an option. In this work, the internal oxidation of the intermetallics Fe 17Y 2 and Fe 11YTi was studied. Internal oxidation resulted in small (∼20 nm) oxide particles in an iron solid solution matrix. Oxides such as Y 2O 3, YFeO 3, Y 2Ti 2O 7, and Fe 2TiO 4 were observed. Hardness values as high as those of the original intermetallics were observed. However, the oxide particles coarsened quickly during annealing at 1000 °C. In order to reduce the coarsening rates, oxides more similar to those in mechanically alloyed steels need to be synthesized.

Whole-Heart Coronary Magnetic Resonance Angiography

To test the feasibility and performance of a 4D magnetic resonance coronary angiography sequence compared with conventional inversion recovery (IR) prepared gradient echo imaging. A 4D sequence with 100 milliseconds temporal resolution was implemented on a 1.5 T system. Five minipigs were examined after administration of very small superparamagnetic iron oxide particles. Coronary angiographies with an isotropic resolution of 0.82 mm were performed in the pigs using 4D and IR sequences. The 4D sequence allowed visualization of the coronary arteries, the effect of their movement and that of the entire heart without prolonging scan time. The contrast-to-noise ratio of the IR images was on average 38% higher than that of the corresponding 4D phase. 4D magnetic resonance imaging is superior in that no trigger delay time needs to be determined and an additional whole-heart cine study can be obtained.

Mouse model mimics multiple sclerosis in the clinico‐radiological paradox

The value of experimental autoimmune encephalomyelitis (EAE), an animal model of multiple sclerosis, in deriving novel diagnostic and therapeutic input has been subject to recent debate. This study is the first to report a disseminated distribution of plaques including cranial nerves, prior to or at early stages of disease in murine adoptive transfer EAE, irrespective of the development of clinical symptoms. We induced EAE by adoptive proteolipid protein-specific T-cell transfer in 26 female SJL/J mice, and applied high-field-strength magnetic resonance imaging (MRI) scans longitudinally, assessing blood-brain barrier (BBB) disruption by gadopentate dimeglumine enhancement. We visualized inflammatory nerve injury by gadofluorine M accumulation, and phagocytic cells in inflamed tissue by very small anionic iron oxide particles (VSOP-C184). MRI was correlated with immunohistological sections. In this study, we discovered very early BBB breakdown of white and grey brain matter in 25 mice; one mouse developed exclusively spinal cord inflammation. Widely disseminated contrast-enhancing lesions preceded the onset of disease in 10 animals. Such lesions were present despite the absence of any clinical disease formation in four mice, and coincided with the first detectable symptoms in others. Cranial nerves, predominantly the optic and trigeminal nerves, showed signal intensity changes in nuclei and fascicles of 14 mice. At all sites of MRI lesions we detected cellular infiltrates on corresponding histological sections. The discrepancy between the disease burden visualized by MRI and the extent of disability indeed mimics the human clinico-radiological paradox. MRI should therefore be implemented into evaluational in vivo routines of future therapeutic EAE studies.

A comparative study of the water-gas shift activity of Pt catalysts supported on single (MO x) and composite (MO x/Al 2O 3, MO x/TiO 2) metal oxide carriers

The water-gas shift (WGS) activity of platinum catalysts dispersed on a variety of single metal oxides as well as on composite MO x /Al 2O 3 and MO x /TiO 2 supports (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, La, Ce, Nd, Sm, Eu, Gd, Ho, Er, Tm) has been investigated in the temperature range of 150–500 °C, using a feed composition consisting of 3% CO an 10% H 2O. For Pt catalysts supported on single metal oxides, it has been found that both the apparent activation energy of the reaction and the intrinsic rate depend strongly on the nature of the support. In particular, specific activity of Pt at 250 °C is 1–2 orders of magnitude higher when supported on “reducible” compared to “irreducible” metal oxides. For composite Pt/MO x /Al 2O 3 and Pt/MO x /TiO 2 catalysts, it is shown that the presence of MO x results in a shift of the CO conversion curve toward lower reaction temperatures, compared to that obtained for Pt/Al 2O 3 or Pt/TiO 2, respectively. The specific reaction rate is in most cases higher for composite catalysts and varies in a manner which depends on the nature, loading, and primary crystallite size of dispersed MO x . Results are explained by considering that reducibility of small oxide particles increases with decreasing crystallite size, thereby resulting in enhanced WGS activity. Therefore, evidence is provided that the metal oxide support is directly involved in the WGS reaction mechanism and determines to a significant extent the catalytic performance of supported noble metal catalysts. Results of catalytic performance tests obtained under realistic feed composition, consisting of 3% CO, 10% H 2O, 20% H 2 and 6% CO 2, showed that certain composite Pt/MO x /Al 2O 3 and Pt/MO x /TiO 2 catalysts are promising candidates for the development of active WGS catalysts suitable for fuel cell applications.

Comparison of the inflammatory burden of truly asymptomatic carotid atheroma with atherosclerotic plaques contralateral to symptomatic carotid stenosis: an ultra small superparamagnetic iron oxide enhanced magnetic resonance study

Background:Inflammation is a recognised risk factor for the vulnerable atherosclerotic plaque. The aim of this study was to explore whether there is a difference in the degree of magnetic resonance...

Electrochemical hydrogen storage in LaNi 4.25Al 0.75 alloys: A comparative study between film and powder materials

A comparison is made of the electrochemical and structural properties of LaNi 4.25Al 0.75 alloys in thin film and powder forms. X-ray diffraction (XRD) revealed that both the LaNi 4.25Al 0.75 thin film and powder materials are crystalline. Atomic force microscopy (AFM) and focused ion beam microscopy (FIB) proved that the film appeared to have a hill-like surface morphology, but was rather dense with a thickness of about 4.2 μm. Simulated battery tests indicate that both exhibit similar electrochemical behavior, possibly due to their crystal structure, as it requires a primary activation to reach its fully active state. However it took a longer activation period for the film to be activated; an apparent initial decrease of charging voltage with cycle number was observed, as were abnormal discharge processes during activation. After 30 charge/discharge cycles, small needle-shaped aluminium oxide particles were formed on both the powder and film surfaces.