Surfactant-controlled morphology and magnetic property of manganese ferrite nanocrystal contrast agent

MnFe(2)O(4) nanocrystals (NCs) coated with three different surfactants (oleic acid, oleylamine or 1,2-hexadecanediol) and their mixtures, with sizes in range 6-12 nm, were synthesized by high-temperature decomposition of organometallic precursors. The effects of morphology and surface chemistry of MnFe(2)O(4) NCs on the magnetic properties were systematically investigated by comparing their saturation magnetization values and their capability to improve the negative contrast for magnetic resonance imaging (MRI) after converting the hydrophobic NCs to hydrophilic ones by a ligand exchange protocol. An important finding is that the magnetization values and proton relaxivity rates of MnFe(2)O(4) NCs are strongly dependent on the size and surface state of the particles that covalently bonded with different hydrophobic ligands before ligand exchange. In particular, monodisperse cubic MnFe(2)O(4) NCs could be obtained when oleylamine and 1,2-hexadecanediol were used as mixed stabilizers, and showed excellent morphology and magnetic properties. Furthermore, the low cytotoxicity and good cell uptake MR imaging of the dopamine capped MnFe(2)O(4) NCs make them promising candidates for use as bio-imaging probes.     

Biocompatible nanotemplate-engineered nanoparticles containing gadolinium: stability and relaxivity of a potential MRI contrast agent

In this article, we use a nanotemplate engineering approach to prepare biodegradable nanoparticles composed of FDA-approved materials and possessing accessible gadolinium (Gd) atoms and demonstrate their potential as a Magnetic Resonance Imaging (MRI) contrast agent. Nanoparticles containing dimyristoyl phosphoethanolamine diethylene triamine penta acetate (PE-DTPA) were prepared using 3.5 mg of Brij 78, 2.0 mg of emulsifying wax and 0.5 mg of PE-DTPA/ml from a microemulsion precursor. After the addition of GdCl3, the presence of Gd on the surface of nanoparticles was characterized using inductively coupled plasma atomic emission spectroscopy and Scanning Transmission Electron Microscopy (STEM). The in vitro relaxivities of the PE-DTPA-Gd nanoparticles in different media were assessed at different field strengths. The conditional stability constant of Gd binding to the nanoparticles was determined using competitive spectrophotometric titration. Transmetallation kinetics of the gadolinium ion from PE-DTPA-Gd nanoparticles with zinc as the competing ionic was measured using the relaxivity evolution method. Nanoparticles with a diameter of approximately 130 nm possessing surface chelating functions were made from GRAS (Generally Regarded As Safe) materials. STEM demonstrated the uniform distribution of Gd3+ on the surface of the nanoparticles. The thermodynamic binding constant for Gd3+ to the nanoparticles was approximately 10(18) M(-1) and transmetallation studies with Zn2+ yielded kinetic constants K1 and K(-1) of 0.033 and 0.022 1/h, respectively, with an equilibrium constant of 1.5. A payload of approximately 10(5) Gd/nanoparticle was achieved; enhanced relaxivities were observed, including a pH dependence of the transverse relaxivity (r2). Nanoparticles composed of materials that have been demonstrated to be hemocompatible and enzymatically metabolized and possessing accessible Gd ions on their surface induce relaxivities in the bulk water signal that make them potentially useful as next-generation MRI tumor contrast enhancement agents.     

In situ synthesis of manganese zinc ferrite nanoparticle/polymer hybrid nanocomposite from metal organics

A manganese zinc ferrite nanoparticle/polymer hybrid nanocomposite was synthesized in situ from metal acetylacetonates at 80 °C. A mixture of manganese(II) acetylacetonate (MA), zinc(II) acetylacetonate (ZA), and iron(III) 3-allylacetylacetonate (IAA) was hydrolyzed and polymerized, yielding a spinel oxide nanoparticle/organic hybrid. The crystallite size of the spinel particles was dependent upon the hydrolysis conditions of MA–ZA–IAA. Crystalline manganese zinc ferrite nanoparticles less than 5 nm in size were uniformly dispersed in the organic matrix. The magnetization of the hybrid increased as the amount of water for hydrolysis increased. The magnetization versus field curve for the manganese zinc ferrite nanoparticle/organic hybrid showed neither remanence nor coercivity above 11 K. The magnetization versus H/T curves from 50 to 200 K were superimposed on the same curve described by the Langevin equation. The remanent magnetization and coercive field of the hybrid were 2.1 emu/g and 20 Oe, respectively, at 4.2 K. The absorption edge of the hybrid film was blue-shifted as compared to that of bulk ferrite.     

Synthesis of nanoparticle CT contrast agents: in vitro and in vivo studies

Water-soluble and biocompatible D-glucuronic acid coated Na₂WO₄ and BaCO₃ nanoparticles were synthesized for the first time to be used as x-ray computed tomography (CT) contrast agents. Their average particle diameters were 3.2 ± 0.1 and 2.8 ± 0.1 nm for D-glucuronic acid coated Na₂WO₄ and BaCO₃ nanoparticles, respectively. All the nanoparticles exhibited a strong x-ray attenuation. In vivo CT images were obtained after intravenous injection of an aqueous sample suspension of D-glucuronic acid coated Na₂WO₄ nanoparticles, and positive contrast enhancements in the kidney were clearly shown. These findings indicate that the nanoparticles reported in this study may be promising CT contrast agents.     

Synthesis of nanoparticle CT contrast agents: in vitro and in vivo studies

Abstract

Water-soluble and biocompatible D-glucuronic acid coated Na₂WO₄ and BaCO₃ nanoparticles were synthesized for the first time to be used as x-ray computed tomography (CT) contrast agents. Their average particle diameters were 3.2 ± 0.1 and 2.8 ± 0.1 nm for D-glucuronic acid coated Na₂WO₄ and BaCO₃ nanoparticles, respectively. All the nanoparticles exhibited a strong x-ray attenuation. In vivo CT images were obtained after intravenous injection of an aqueous sample suspension of D-glucuronic acid coated Na₂WO₄ nanoparticles, and positive contrast enhancements in the kidney were clearly shown. These findings indicate that the nanoparticles reported in this study may be promising CT contrast agents.     

Optical and acoustical observations of the effects of ultrasound on contrast agents

Optimal use of encapsulated microbubbles for ultrasound contrast agents and drug delivery requires an understanding of the complex set of phenomena that affect the contrast agent echo and persistence. With the use of a video microscopy system coupled to either an ultrasound flow phantom or a chamber for insonifying stationary bubbles, we show that ultrasound has significant effects on encapsulated microbubbles. In vitro studies show that a train of ultrasound pulses can alter the structure of an albumin-shelled bubble, initiate various mechanisms of bubble destruction or produce aggregation that changes the echo spectrum. In this analysis, changes observed optically are compared with those observed acoustically for both albumin and lipid-shelled agents. We show that, when insonified with a narrowband pulse at an acoustic pressure of several hundred kPa, a phospholipid-shelled bubble can undergo net radius fluctuations of at least 15%; and an albumin-shelled bubble initially demonstrates constrained expansion and contraction. If the albumin shell contains air, the shell may not initially experience surface tension; therefore, the echo changes more significantly with repeated pulsing. A set of observations of contrast agent destruction is presented, which includes the slow diffusion of gas through the shell and formation of a shell defect followed by rapid diffusion of gas into the surrounding liquid. These observations demonstrate that the low-solubility gas used in these agents can persist for several hundred milliseconds in solution. With the transmission of a high-pulse repetition rate and a low pressure, the echoes from, contrast agents can be affected by secondary radiation force. Secondary radiation force is an attractive force for these experimental conditions, creating aggregates with distinct echo characteristics and extended persistence. The scattered echo from an aggregate is several times stronger and more narrowband than echoes from individual bubbles.     

Arsenic adsorption on cobalt and manganese ferrite nanoparticles

The adsorption of As(III) on cobalt and manganese ferrite nanoparticles (NPs) was studied. The ferrite NPs were synthesized using the Massart-assisted microwave hydrothermal treatment. All the NPs exhibited the spinel structure with a formula such as M _x Fe_3?x O₄, where M = Co or Mn, and x runs from 0.21 to 1.14. The changes in the stoichiometry caused different effects on the physical properties as well on the As(III) adsorption capacity of the NPs. The adsorption data were fitted in very good agreement with the Freundlich model. It was concluded that As(III) was better attracted to ferrimagnetic cobalt ferrite NPs, given that the arsenic removal was significantly higher than that exhibited by superparamagnetic manganese-substituted ferrite NPs.     

Size variation and magnetic dilution effects on the structure and magnetic properties of cobalt zinc ferrite

Nanocrystalline cobalt zinc ferrites Co_1?xZn_xFe₂O₄ (x?=?0.0, 0.2, 0.4, 0.5, 0.6, 0.8, 1.0), have been prepared by employing a precursor combustion method via decomposition of the metal carboxylato hydrazinate precursors. This synthesis technique yields nanoparticles with particle size between 12 and 15 nm as determined from transmission electron microscopy (TEM) studies. The nanoferrites were then sintered at 1000 °C for 15 h to obtain micrometer size ‘bulk’ ferrites in the range of 0.3–0.8 μm. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) Spectroscopy confirmed the formation of the mixed ferrites without any impurities. Addition of non-magnetic ion like Zn²⁺ into the crystal structure of cobalt ferrite leads to a prominent change in the size, structure and properties. The saturation magnetization values (M_S) increases upto x?=?0.4 and then decreases with further increase in Zn concentration. A maximum M_S value of 90.85 emu/g and 79.59 emu/g for x?=?0.4 was obtained for the sintered and nanoferrite sample, respectively. The lower M_S and higher coercivity (H_C) values for nanoferrites than the sintered ferrites exhibited a strong dependence on the particle size due to the cation distribution and surface effects. The Curie temperature (T_C) was found to decrease appreciably with the reduction in particle size and with increasing concentration of Zn. The room temperature Mössbauer spectra showed a transition from ferrimagnetic to a paramagnetic state with increasing zinc concentration along with superparamagnetic features which was in corroboration with VSM studies.

     

Processing effects on in-flight particle state and functional coating properties of plasma-sprayed manganese zinc ferrite

Magnetic properties of manganese zinc ferrite (MZF) coatings deposited by atmospheric dc plasma spraying largely depend on zinc and oxygen loss during particle flight. The temperature and velocity of in-flight MZF particles were widely varied by changing plasma spray conditions to examine these chemistry changes and resultant magnetic properties. Zn loss increases with increased particle temperature or decreased particle velocity. Meanwhile, wüstite (FeO) formation, related to the oxygen loss, is more complicated, partly because oxygen, which is lost during flight in the high-temperature zone of the plasma jet, can be recovered at longer spray distances. As a result, the saturation magnetization of MZF coatings decreases and the coercivity increases with increased particle temperature or decreased particle velocity.     

Effect of proton irradiation on the magnetic properties of manganese ferrite

Cubic-spinel MnFe2O4 magnetic nanoparticles (NPs) were prepared, with an average particle size of about 4 nm determined from a high-resolution transmission electron microscope. When the NPs were proton-irradiated, the lattice constants decreased with increasing proton irradiation. Before the proton irradiation, the NPs exhibited 36.2 +/- 0.1 emu/g magnetization (M(S)) and 11.1 +/- 0.1 Oe coercivity (H(C)). After the irradiation of the samples with 5 and 10 pC/microm2 doses, the M(S) changed to 35.6 and 35.1 +/- 0.1 emu/g, and the H(C) to 11.3 and 12.9 +/- 0.1 Oe, respectively. The room-temperature M?ssbauer spectra of the NPs showed superparamagnetic characteristics, with the single-absorption line of two sites and a large relaxation frequency. During the proton irradiation, the relaxation frequency decreased to 156.02 and 134.29 +/- 0.01 Gamma/? from the unirradiated sample's 164.02 +/- 0.01 Gamma/?. It is suggested that the proton irradiation induced the increase in the anisotropy energy of the MnFe2O4 NPs. Moreover, from the external-field-induced M?ssbauer spectra at 4.2 K, an increase in the canted angle of the hyperfine field between sites A (tetrahedral) and B (octahedral) was observed with proton irradiation.     

Safety assessment of nanoparamagnetic contrast agents with different coatings for molecular MRI

Despite the wide application of gadolinium as a contrast agent for magnetic resonance imaging (MRI), there is a serious lack of information on its toxicity. Gadolinium and gadolinium oxide (Gd-oxide) are used as contrast agents for magnetic resonance imaging (MRI). There are methods for reducing toxicity of these materials, such as core nanoparticles coating or conjugating. Therefore, for toxicity evaluation, we compared the viability of commercial contrast agents in MRI (Gd-DTPA) and three nanoparticles with the same core Gd₂O₃ and small particulate gadolinium oxide or SPGO (< 40 nm) but different coatings of diethyleneglycol (DEG) as Gd₂O₃-DEG and methoxy polyethylene glycol-silane (mPEG-silane: 550 and 2000 Dalton) as SPGO-mPEG-silane550 and SPGO-mPEG-silane2000, respectively, in the SK-MEL3 cell line, by light microscopy, MTT assay using 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl tetrazolium bromide, and the LDH assay detecting lactate dehydrogenase activity. The viability values were not statistically different between the three nanoparticles and Gd-DTPA. The MTT and LDH assay results showed that Gd₂O₃-DEG nanoparticles were more toxic than Gd-DTPA and other nanoparticles. Also, SPGO-mPEG-silane2000 was more biocompatible than other nanoparticles. The obtained results did not show any significant increase in cytotoxicity of the nanoparticles and Gd-DTPA, neither dose-dependent nor time-dependent. Therefore, DEG and PEG, due to their considerable properties and irregular sizes (different molecular weights), were selected as the useful surface covering materials of nanomagnetic particles that could reveal noticeable relaxivity and biocompatibility characteristics.     

A preliminary evaluation of the effects of primary and secondaryradiation forces on acoustic contrast agents

Primary and secondary radiation forces result from pressure gradients in the incident and scattered ultrasonic fields. These forces and their dependence on experimental parameters are described, and the theory for primary radiation force is extended to consider a pulsed traveling wave. Both primary and secondary radiation forces are shown to have a significant effect on the flow of microbubbles through a small vessel during insonation. The primary radiation force produces displacement of microspheres across a 100 micron vessel radius for a small transmitted acoustic pressure. The displacement produced by primary radiation force is shown to display the expected linear dependence on the pulse repetition frequency and a nonlinear dependence on transmitted pressure. The secondary radiation force produces a reversible attraction and aggregation of microspheres with a significant attraction over a distance of approximately 100 microns. The magnitude of the secondary radiation force is proportional to the inverse of the squared separation distance, and thus two aggregates accelerate as they approach one another. We show that this force is sufficient to produce aggregates that remain intact for a physiologically appropriate shear rate. Brief interruption of acoustic transmission allows an immediate disruption of the aggregate     

Modification of dielectric and mechanical properties of rubber ferrite composites containing manganese zinc ferrite

Spinel ferrites constitute an important class of magnetic materials. Polycrystalline ferrites are a complex system composed of crystallite grain boundaries and pores. Manganese zinc ferrites have resistivities between 0.01 and 10 Ω m. Making composite materials of ferrites with either natural rubber or plastics will modify the electrical properties of ferrites. Composite materials are ideally suited for many modern applications where ceramic materials have some drawbacks. The mouldability and flexibility of these composites find wide use in industrial and other scientific applications. Mixed ferrites belonging to the series Mn_(1−x)Zn_xFe₂O₄ (MZF) were synthesized for different ‘x’ values in steps of 0.2. These pre-characterized ceramic ferrites were then incorporated in a natural rubber matrix. The dielectric properties of the ceramic manganese zinc ferrite and RFC were also studied. A program based on G programming was developed with the aid of LabVIEW package to automate the dielectric measurements. The dielectric permittivity of the RFC were then correlated with that of the corresponding dielectric permittivity of the magnetic filler and matrix by a mixture equation, which helps to tailor properties of the composites.     

Size and surface effects on the mechanical behavior of nanotubes in first gradient elasticity

First gradient elasticity theory considering surface energy is employed to investigate the axisymmetric deformation of circular nanotubes, in which the microstructural and surface effects are taken into account. The governing equilibrium equation is derived and the corresponding analytical solutions are obtained. It is demonstrated that the total stress decreases with the increase of the intrinsic bulk size, while it increases with the increase of the directional surface energy length parameter. These parameters have strong influences on the mechanical behavior of the embedded nanotubes and thus should be considered in the practical analysis of nanostructures.     

Size and surface modification effects on the pH response of Si nanowire field-effect transistors

We investigated the effects of Si nanowire (SiNW) dimensions and their surface modifications on the pH-dependent electronic transport characteristics of SiNW Electrolyte-insulator-Semiconductor Field-Effect Transistors (EISFETs). The threshold voltages, Vth's, of all devices were extracted from the Id-Vg characteristics with Vg applied to the reference electrode immersed in different pH solutions, and their pH-dependences were analyzed for various devices. We found that our devices produce the systematic pH-dependence of Vth with respect to the SiNW's length and show significant changes in a linear pH region and a pH sensitivity upon the Si surface modifications. Particularly in the case of the APTES-treated surface, the linear variation was observed in the wide region of pH = 2 to approximately 11 with the sensitivity of 54.7 +/- 0.6 mV/pH. Also we compared our data to a theoretical result based on the Gouy-Chapmam-Stern-Graham model and found a reasonable agreement between them.     

Assessing the environmental footprints of the manganese recovery process from low-grade ore to synthesize manganese ferrite

Clean Technologies and Environmental Policy - Increasing demand for manganese and rapid depletion of high-grade manganese ores grow attention to other resources. However, environmental impacts and...     

Biocompatible magnetite/gold nanohybrid contrast agents via green chemistry for MRI and CT bioimaging

Magnetite/gold (Fe(3)O(4)/Au) hybrid nanoparticles were synthesized from a single iron precursor (ferric chloride) through a green chemistry route using grape seed proanthocyanidin as the reducing agent. Structural and physicochemical characterization proved the nanohybrid to be crystalline, with spherical morphology and size ~35 nm. Magnetic resonance imaging and magnetization studies revealed that the Fe(3)O(4) component of the hybrid provided superparamagnetism, with dark T(2) contrast and high relaxivity (124.2 ± 3.02 mM(-1) s(-1)). Phantom computed tomographic imaging demonstrated good X-ray contrast, which can be attributed to the presence of the nanogold component in the hybrid. Considering the potential application of this bimodal nanoconstruct for stem cell tracking and imaging, we have conducted compatibility studies on human Mesenchymal Stem Cells (hMSCs), wherein cell viability, apoptosis, and intracellular reactive oxygen species (ROS) generation due to the particle-cell interaction were asessed. It was noted that the material showed good biocompatibility even for high concentrations of 500 μg/mL and up to 48 h incubation, with no apoptotic signals or ROS generation. Cellular uptake of the nanomaterial was visualized using confocal microscopy and prussian blue staining. The presence of the nanohybrids were clearly visualized in the intracytoplasmic region of the cell, which is desirable for efficient imaging of stem cells in addition to the cytocompatible nature of the hybrids. Our work is a good demonstrative example of the use of green aqueous chemistry through the employment of phytochemicals for the room temperature synthesis of complex hybrid nanomaterials with multimodal functionalities.