Multifunctional, multicompartment polyorganosiloxane magnetic nanoparticles for biomedical applications

We present the synthesis and characterization of maghemite nanoparticles (average size 6±1.5 nm) and their incorporation into the core of polyorganosiloxane core-shell nanospheres (total average diameter 35±10 nm). The nanoparticles are easily redispersable in organic solvents and can subsequently be modified by grafting of end-functionalized poly(ethylene oxide) to obtain water soluble nanospheres. The network structure of the nanospheres allows the diffusion of small molecules into the nanospheres, and consequently the nanospheres can be employed as nanocontainers and nanoreactors for potential biomedical applications.     

Quadrupole magnetic field-flow fractionation: A novel technique for the characterization of magnetic nanoparticles

Quadrupole magnetic field-flow fractionation (MgFFF) is an analytical separation and characterization technique for nano- and micro-sized magnetic particles. It fractionates particles according to their content of magnetite or other magnetic material. The potential and versatility of MgFFF for separation and characterization of magnetic nanoparticles, such as those used for immunospecific labeling of biological cells for magnetic separation, is demonstrated. A broadly polydisperse sample of dextran-coated magnetite nanoparticles was eluted under programmed field decay conditions, and quantitative data concerning the distribution of magnetite content were determined from the elution profile using a data reduction method.     

Synthesis and characterization of core-shell europium(III)-silica nanoparticles

Luminescent core-shell europium(III)-silica nanoparticles were prepared using europium(III) chelate core structure and polyvinylpyrrolidone synthesis strategy for silica shell. Europium(III):naphtoyltrifluoroacetone:trioctylphosphineoxide complex was spontaneously agglomerated from organic solvent to water. Polyvinylpyrrolidone was adsorbed onto the core structure and stable silica shell was synthesized using tetraethylorthosilicate. Nanosized particles with a diameter of 71 ± 5 nm and 11 nm shell thickness were obtained with fluorescence decay rate of 517 μs and excitation and emission wavelengths of 334 and 614 nm, respectively.     

磁性核壳纳米粒子的制备及其在分离和光谱检测中的应用

磁性及其核壳复合纳米粒子由于在不同领域中具有广泛应用而受到研究者的极大关注,总结了磁性及磁性核壳纳米粒子常见的制备方法及各自的特点,并重点讨论了其在磁分离及光谱检测方面的应用,也介绍了本课题组在纳米粒子合成及应用方面所做的一部分工作。最后对磁性纳米粒子中存在的问题进行了探讨,并对其应用前景进行了展望。     

Synthesis and characterization of manganese ferrite nanoparticles by thermal treatment method

Cubic structured manganese ferrite nanoparticles were synthesized by a thermal treatment method followed by calcination at various temperatures from 723 to 873 K. In this investigation, we used polyvinyl pyrrolidon (PVP) as a capping agent to control the agglomeration of the nanoparticles. The characterization studies were conducted by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The average particle sizes of manganese ferrite nanoparticles were determined by TEM, which increased with the calcination temperature from 12 to 22 nm and they had good agreement with XRD results. Fourier transform infrared spectroscopy confirmed the presence of metal oxide bands at all temperatures and the absence of organic bands at 873 K. Magnetic properties were demonstrated by a vibrating sample magnetometer, which showed a super-paramagnetic behavior for all samples and also saturation magnetization (M_s) increases from 3.06 to 15.78 emu/g by increasing the calcination temperature. The magnetic properties were also confirmed by the use of electron paramagnetic resonance spectroscopy, which revealed the existence of unpaired electrons and also measured peak-to-peak line width, resonant magnetic field and the g-factor.     

Synthesis and characterization of noscapine loaded magnetic polymeric nanoparticles

The delivery of noscapine therapies directly to the site of the tumor would ultimately allow higher concentrations of the drug to be delivered, and prolong circulation time in vivo to enhance the therapeutic outcome of this drug. Therefore, we sought to design magnetic based polymeric nanoparticles for the site directed delivery of noscapine to invasive tumors. We synthesized Fe₃O₄ nanoparticles with an average size of 10±2.5 nm. These Fe₃O₄ NPs were used to prepare noscapine loaded magnetic polymeric nanoparticles (NMNP) with an average size of 252±6.3 nm. Fourier transform infrared (FT-IR) spectroscopy showed the encapsulation of noscapine on the surface of the polymer matrix. The encapsulation of the Fe₃O₄ NPs on the surface of the polymer was confirmed by elemental analysis. We studied the drug loading efficiency of polylactide acid (PLLA) and poly (l-lactide acid-co-gylocolide) (PLGA) polymeric systems of various molecular weights. Our findings revealed that the molecular weight of the polymer plays a crucial role in the capacity of the drug loading on the polymer surface. Using a constant amount of polymer and Fe₃O₄ NPs, both PLLA and PLGA at lower molecule weights showed higher loading efficiencies for the drug on their surfaces.     

Magnetic characterization of surface-coated magnetic nanoparticles for biomedical application

The influence of the oleic acid surface coating on Fe₃O₄ and NiFe₂O₄ nanoparticles on their magnetic and calorimetric characterization was investigated. Fe₃O₄ nanoparticles (particle sizes of 15-20 and 20-30 nm) and NiFe₂O₄ nanoparticles (particle sizes of 20-30 nm) were dispersed in oleic acid. The surface coating resulted in a decrease in the dipole-dipole interaction between the particles, which in turn affected the coercivity and heat dissipation of the nanoparticles. The coercivity of the oleic-acid-coated nanoparticles was found to be lower than that of the uncoated nanoparticles. The temperature rise in the oleic-acid-coated nanoparticles was greater than that of the uncoated nanoparticles; this temperature rise was associated with the relaxation losses. The viscosity dependence on the self-heating temperature of Fe₃O₄ nanoparticles (15-20 and 20-30 nm) under an ac magnetic field was measured. The temperature rise for both the Fe₃O₄ nanoparticles (15-20 and 20-30 nm) exhibited a strong dependence on viscosity at each magnetic field frequency, and the contribution of Brownian relaxation loss to the temperature rise was revealed. Moreover, an in vitro cytotoxicity test of Fe₃O₄ and NiFe₂O₄ was performed using human cervical carcinoma cells (HeLa), and the cytotoxicity of NiFe₂O₄ nanoparticles was compared to that of Fe₃O₄ nanoparticles.     

Magnetic nanoparticles separation based on nanostructures

This study describes a magnetic array, which consists of depositing Fe nanowires on a porous alumina membrane. Such a device can be used as a planar magnetic separator. Its performance for the collection of Fe₃O₄ nanoparticles is experimentally shown. For magnetization of such iron nanowires in the vertical direction, we propose equations to calculate the theoretical absorption ratio.     

Synthesis and magnetic characterization of Zn0.6Ni0.4Fe2O4 nanoparticles via a polyethylene glycol-assisted hydrothermal route

Zn-doped nickel ferrite nanoparticles (Zn_0.6Ni_0.4Fe₂O₄) have been prepared via a surfactant, polyethylene glycol assisted hydrothermal route. X-ray powder diffractometry (XRD), Fourier transform infrared spectroscopy, transmission electron microscopy (TEM), and vibrating scanning magnetometry (VSM) were used for the structural, morphological, and magnetic characterizations of the product, respectively. TEM analysis revealed that the nanoparticles have a narrow size distribution, with average particle size of 15±1 nm, which agrees well with the XRD based estimate of 14±2 nm. The absence of saturation and remanent magnetization, and coercivity in the high temperature region of the M-H curve and non-zero magnetic moments indicate superparamagnetism of the nanoparticles with a canted spin structure. The appearance of a peak on the temperature-dependent zero-field cooling magnetization curve at ∼190 K indicates the blocking temperature of the sample.     

Size-dependant heating rates of iron oxide nanoparticles for magnetic fluid hyperthermia

Using the thermal decomposition of organometallics method we have synthesized high-quality, iron oxide nanoparticles of tailorable size up to ∼15 nm and transferred them to a water phase by coating with a biocompatible polymer. The magnetic behavior of these particles was measured and fit to a log-normal distribution using the Chantrell method and their polydispersity was confirmed to be very narrow. By performing calorimetry measurements with these monodisperse particles we have unambiguously demonstrated, for the first time, that at a given frequency, heating rates of superparamagnetic particles are dependent on particle size, in agreement with earlier theoretical predictions.     

Synthesis and characterization of CoxZn1−xFe2O4 magnetic nanoparticles via a PEG-assisted route

We present an investigation of properties of Co_xZn_1−xFe₂O₄ (x=0.0-1.0) nanoparticles synthesized by a polyethylene glycol (PEG)-assisted hydrothermal route. X-ray powder diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and vibrating scanning magnetometry (VSM) were used to characterize the structural, morphological and magnetic properties. The particle size obtained from TEM and XRD are consistent with each other. It was observed that the lattice constant for each composition decreases with increasing Co substitution and follows Vegard's law. Magnetization measurements show that while the materials with high Zn substitution are superparamagnetic at room temperature, they are ferromagnetic at temperatures lower than the blocking temperature. The materials with less Zn substitution are ferromagnetic below room temperature. Magnetizations and the coercivities of the samples decrease with the Zn substitution. The resultant overall magnetic behavior of the superparamagnetic samples are found to be considerably different than that of conventional superparamagnetic systems due to the antiferromagnetic interactions both in intra- and inter-cluster spins, and size (effective moment) distribution of the particles.     

Synthesis and self-assembly of magnetic nanoparticles

We report the synthesis and self-assembly of different shapes and sizes of FePt nanoparticles. Our study shows that surfactants and solvent play an important role in the synthesis of different shapes and sizes of FePt nanoparticles. Higher boiling point solvents lead to the formation of spherical nanoparticles and low boiling point solvents form cubic nanoparticles. Our studies also indicate that self-assembly of FePt nanoparticles on substrates is a complex process that is sensitive to the concentration of excess surfactant in the nanoparticle solution.     

Fabrication of water-soluble magnetic nanoparticles by ligand-exchange with thermo-responsive polymers

We report the use of thermo-responsive polymers in the synthesis of Co and γ-Fe₂O₃ nanoparticles using a two-step method involving thermal decomposition of the organometallic complexes in the presence of oleic acid and then followed by ligand-exchange process with thermo-responsive polymer. Among different thermo-responsive polymers investigated, it was found that the polymer based on poly(N-isopropylacrylamide) with a co-monomer component of acrylic acid and acrylamide can be used in the ligand-exchange to coat Co and γ-Fe₂O₃ nanoparticles, respectively. The nanoparticles are found to be water-soluble at temperatures below coil-to-globule phase transition of the coating polymer.     

Synthesis and magnetic properties of size-selected CoPt nanoparticles

CoPt nanoparticles are widely studied, in particular for their potentially very high magnetic anisotropy. However, their magnetic properties can differ from the bulk ones and they are expected to vary with the particle size. In this paper, we report the synthesis and characterization of well-defined CoPt nanoparticle samples produced in ultrahigh vacuum conditions following a physical route: the mass-selected low energy cluster beam deposition technique. This approach relies on an electrostatic deviation of ionized clusters which allows us to easily adjust the particle size, independently from the deposited equivalent thickness (i.e. the surface or volume particle density in a sample). Diluted samples made of CoPt particles, with different diameters, embedded in amorphous carbon are studied by transmission electron microscopy and superconducting interference device magnetometry, which gives access to the magnetic anisotropy energy distribution. We then compare the magnetic properties of two different particle sizes. The results are found to be consistent with an anisotropy constant (including its distribution) which does not evolve with the particle size in the range considered.     

Synthesis and characterization of iron-based alloy nanoparticles for magnetorheological fluids

The borohydride reduction method was used to synthesize the Fe-based alloy nanoparticles in an aqueous medium for MR fluids. The effect of ethanol content in the reaction medium on the synthesis of Fe–Co–B nanoparticles was studied first. With increasing the ethanol content from 0 to 40 vol%, the average diameters of Fe–Co–B nanoparticles were decreased from 170 to 35 nm. The possible mechanism for the effect of ethanol has been proposed. Among the four types of Fe-based alloys particles synthesized in this work, Fe–B had the highest magnetization saturation M_s, while M_s decreased in an order of Fe–B>Fe–Co–B>Fe–Cr–B>Fe–Ni–B. A magnetic field of 3000 Oe was able to increase M_s by about 5–6% for each type of iron-based alloy. Under a magnetic field, chain structures of nanoparticles were always formed. When a strong magnetic field such as 3000 Oe was applied, the particles were “squeezed” into chains.     

Ionic magnetic fluid based on cobalt ferrite nanoparticles: Influence of hydrothermal treatment on the nanoparticle size

Magnetic fluid based on cobalt ferrite nanoparticles was obtained using a hydrothermal treatment added to the Massart procedure. This treatment increases the average size of the nanoparticles from 11.9 to 18.7 nm and also improves the dispersity and crystallinity of the cobalt ferrite particles. The nanoparticles obtained after the hydrothermal treatment were dispersed in aqueous solvent by the classical procedure for ionic magnetic fluids. The ferrofluid thus obtained is stable at pH 7 and may be useful for hyperthermia applications.     

Size-controlled magnetic nanoparticles with lecithin for biomedical applications

Lecithin-adsorbed magnetic nanoparticles were prepared by three-step process that the thermal decomposition was combined with ultrasonication. Experimental parameters were three items—molar ratio between Fe(CO)₅ and oleic acid, keeping time at decomposition temperature and lecithin concentration. As the molar ratio between Fe(CO)₅ and oleic acid, and keeping time at decomposition temperature increased, the particle size increased. However, the change of lecithin concentration did not show the remarkable particle size variation.     

PtCo/Au nanocomposite: Synthesis, characterization, and magnetic properties

Magnetic PtCo/Au nanocomposites with narrow size distribution were synthesized in a reverse micelle, followed by a post-synthesis handling of the stabilizer-exchange technique. The PtCo/Au nanocomposites were characterized by ultraviolet visible spectroscopy, X-ray diffraction and transmission electron microscopy, respectively. Superconducting quantum interference device studies revealed that the nanocomposites were superparamagnetic above the blocking temperature (T_B=69 K), while the samples were ferromagnetic with Hc (628 Oe) and Ms (2.97 emu/g) at 5 K.     

Synthesis and characterization of Ni magnetic nanoparticles in AlMCM41 host

Superparamagnetic nickel nanoparticles were prepared by incorporating nickel ion into AlMCM41 as a nanoreactor and then reduced with sodium borohydride or H₂ gas. Products were characterized by elemental analysis, transmission electron microscopy, X-ray powder diffraction, and magnetic susceptibility. The nickel particle size and blocking temperature depend on the reduction method.