Superparamagnetic Microspheres Research Articles

A magnetic phantom technique for investigating structural effects on quantitative ultrasound parameters.

Media that contain ultrasound scatterers arranged in a regular spatial distribution can be considered as structured. Structural effects affect quantitative ultrasound parameters that reflect the microstructure properties. Prior studies examined structural effects using simulations or phantoms with fixed microarchitecture, focusing on a limited set of ultrasound parameters, with limited attention given to their underlying physical significance. This study aims to investigate the concordance of the physical interpretations of multiple quantitative ultrasound parameters experimentally by introducing a phantom type with an adjustable microarchitecture. The phantom consists of an aqueous solution containing superparamagnetic microspheres, acting as scatterers. The spatial arrangement of the magnetic particles is modified by applying an external magnetic field, therefore changing the degree of structure of the phantom. Quantitative ultrasound parameters are estimated in three different configurations: the magnetic field intensity is varied over time, strength, and orientation. In each experiment, the backscatter coefficient and the envelope quantitative ultrasound parameters are successfully extracted (R2 ≈ 0.94). Their physical interpretations are supported by microphotographs and geometrical considerations through concordant hypotheses. This study paves the way for the use of magnetic phantoms. This methodology could be followed to validate theoretical scattering models and the physical meanings of quantitative ultrasound parameters.

Video-microscopy-based automated trajectory determination

We present a method for tracking densely clustered, high-velocity, indistinguishable objects being spawned at a high rate and moving in a directed force field using only object centroids as inputs and no other image information. The algorithm places minimal restrictions on the velocities or accelerations of the objects being tracked and uses a methodology based on a scoring function and a backtracking refinement process. This combination leads to successful tracking of hundreds of particles in challenging environments even when the displacement of the individual objects at successive times approaches the separation between neighboring objects in any one frame. We note that these cases can be particularly difficult to handle by existing methods. The performance of the algorithm is methodically examined by comparison to simulated trajectories, which vary the temporal and spatial densities, velocities, and accelerations of the objects in motion, as well as the signal/noise ratio. Also, we demonstrate its capability by analyzing data from experiments with superparamagnetic microspheres moving in an inhomogeneous magnetic field in aqueous buffer at room temperature. Our method should be widely applicable since trajectory determination problems are ubiquitous in video microscopy applications in biology, materials science, physics, and engineering.

Propulsion of Homonuclear Colloidal Chains Based on Orientation Control under Combined Electric and Magnetic Fields

The remarkable efficiency and dynamics of micromachines in living organisms have inspired researchers to make artificial microrobots for targeted drug delivery, chemical sensing, cargo transport, and waste remediation applications. While several self- and directed-propulsion mechanisms have been discovered, the phoretic force has to be generated via either asymmetric surface functionalization or sophisticated geometric design of microrobots. As a result, many symmetric structures assembled from isotropic colloids are ruled out as viable microrobot possibilities. Here, we propose to utilize orientation control to actuate axially symmetric micro-objects with homogeneous surface properties, such as linear chains assembled from superparamagnetic microspheres. We demonstrate that the fore-and-aft symmetry of a horizontal chain can be broken by tilting it with an angle relative to the substrate under a two-dimensional magnetic field. A superimposed alternating current electric field propels the tilted chains. Our experiments and numerical simulation confirm that the electrohydrodynamic flow along the electrode is unbalanced surrounding the tilted chain, generating hydrodynamic stresses that both propel the chain and reorient it slightly toward the substrate. Our work takes advantage of external fields, where the magnetic field, as a driving wheel and brake, controls chain orientation and direction, while the electric field, as an engine, provides power for locomotion. Without the need to create complex-shaped micromotors with intricate building blocks, our work reveals a propulsion mechanism that breaks the symmetry of hydrodynamic flow by manipulating the orientation of a microscopic object.

Induction heating enables efficient heterogeneous catalytic reactions over superparamagnetic nanocatalysts

Most catalytic processes are achieved by heating the whole reaction systems including the entire reactor, substrate and solvent, which leads to energy loss and obvious heat transfer limits. In this study, induction heating was employed to boost the catalytic Suzuki-Miyaura cross-coupling reactions by using conductive superparamagnetic microspheres with loaded Pd nanoparticles as heterogeneous catalysts. It was found that, at the same apparent reaction temperatures, the reactions by adopting the induction heating all exhibit better catalytic performance with higher conversion and yield, as compared to the reactions using conventional joule heating. The improvement is mainly attributed to the localized heating effect endowed by high efficiency of the heat transfer from the heat source to catalytic sites, which dissipates the electromagnetic energy through Néel relaxation mechanism. Moreover, it has be found that the reactions have been largely accelerated, resulting in much shorter reaction time required to approach a given value of reactant conversion. These results indicate that the unique heating method based on the superparamagnetic nanomaterials as both the inductive component and catalyst support holds a promising application for fast and efficient heterogeneous catalytic process, and exhibits potential for improving energy transfer efficiency and reducing the side reactions attributed to the uneven temperature profile.

Construction of a Microfluidic Platform With Core-Shell CdSSe@ZnS Quantum Dot-Encoded Superparamagnetic Iron Oxide Microspheres for Screening and Locating Matrix Metalloproteinase-2 Inhibitors From Fruits of Rosa roxburghii.

The microfluidic platform is a versatile tool for screening and locating bioactive molecules from functional foods. Here, a layer-by-layer assembly approach was used to fabricate core-shell CdSSe@ZnS quantum dot encoded superparamagnetic iron oxide microspheres, which served as a carrier for matrix metalloproteinase-2. The matrix metalloproteinase-2 camouflaged magnetic microspheres was further incorporated into a homemade microfluidic platform and incubated with extracts of fruits of Rosa roxburghii. The flow rate of the microfluidic platform was tuned. The major influencing parameters on ligand binding, such as dissociate solvents, incubation pH, ion strength, temperature, and incubation time were also optimized by using ellagic acid as a model compound. The specific binding ligands were sent for structure elucidation by mass spectrometry. The absolute recovery of ellagic acid ranged from 101.14 to 102.40% in the extract of R. roxburghii under the optimal extraction conditions. The linearity was pretty well in the range of 0.009–1.00 mg·ml−1 (R2 = 0.9995). The limit of detection was 0.003 mg·ml−1. The relative SDs of within-day and between-day precision were <1.91%. A total of thirteen ligands were screened out from fruits of R. roxburghii, which were validated for their inhibitory effect by enzyme assay. Of note, eleven new matrix metalloproteinase-2 inhibitors were identified, which may account for the antitumor effect of fruits of R. roxburghii.

Highly efficient extraction of uranium from aqueous solution using imidazole functionalized core–shell sunflower-like superparamagnetic polymer microspheres: understanding adsorption and binding mechanisms

The core–shell sunflower-like magnetic polymer adsorbent Fe3O4/P (MBA-VIM) prepared by distillation–precipitation polymerization not only showed an outstanding adsorption efficiency for uranium, but also could be facilely isolated by using magnetic force.

Highly efficient extraction of uranium from strong HNO3 media achieved on phosphine oxide functionalized superparamagnetic composite polymer microspheres

The magnetic adsorbent Fe3O4@SiO2/P(TRIM–VPA) developed by distillation–precipitation polymerization not only shows good adsorption efficiency for uranium in strong HNO3 media, but also has strong acid resistance in strong HNO3 solution.

Bio-inspired polymeric iron-doped hydroxyapatite microspheres as a tunable carrier of rhBMP-2

Hybrid superparamagnetic microspheres with bone-like composition, previously developed by a bio-inspired assembling/mineralization process, are evaluated for their ability to uptake and deliver recombinant human bone morphogenetic protein-2 (rhBMP-2) in therapeutically-relevant doses along with prolonged release profiles. The comparison with hybrid non-magnetic and with non-mineralized microspheres highlights the role of nanocrystalline, nanosize mineral phases when they exhibit surface charged groups enabling the chemical linking with the growth factor and thus moderating the release kinetics. All the microspheres show excellent osteogenic ability with human mesenchymal stem cells whereas the hybrid mineralized ones show a slow and sustained release of rhBMP-2 along 14 days of soaking into cell culture medium with substantially bioactive effect, as reported by assay with C2C12 BRE-Luc cell line. It is also shown that the release extent can be modulated by the application of pulsed electromagnetic field, thus showing the potential of remote controlling the bioactivity of the new micro-devices which is promising for future application of hybrid biomimetic microspheres in precisely designed and personalized therapies.

Click chemical assembly and validation of bio-functionalized superparamagnetic hybrid microspheres

Surface derivatized magnetic nanoparticles have been commonly used for magnetic separation. Facile mechanisms are needed to be developed for the design of bio-functionalized magnetic hybrid materials, where the surfaces can be re-generated for the re-use of the developed platforms. Superparamagnetic iron oxide nanoparticles with a diameter below 10 nm were synthesized via a novel microwave-assisted hydrothermal method in the presence of citrate ions, which allowed to obtain uniform and negatively charged nanoparticles. These were then coupled with Poly-l-lysine (PLL), forming micrometer-sized self-assembled spherical entities. Cross-linking the PLL within these microspheres with glutaraldehyde stabilized them chemically and mechanically. The active bio-functionality was introduced by a protein grafting methodology, using m-maleimidobenzoyl-N-hydroxysulfosuccinimide ester (SMBS). The Moringa oleifera Coagulant Protein (MOCP) from a seed extract was employed for its characteristic coagulation activity. The performance of the MOCP functionalized microspheres was evaluated as a function of turbidity removal of problematic colloidal clay from water via magnetic separation, resulting in over 80% of activity within 15 min. Surface of these hybrid materials can be re-generated by treatment with alcohol, allowing their easy magnetic separation and re-use. The rapid and strong response with tunable magnetic property makes these hybrid microspheres a powerful tool for many potential applications, due to the general applicability of the developed methodology.

Orthogonal test design for the optimization of superparamagnetic chitosan plasmid gelatin microspheres that promote vascularization of artificial bone.

The optimal conditions for the preparation of superparamagnetic chitosan plasmid (pReceiver‐M29‐VEGF165/DH5a) gelatin microspheres (SPCPGMs) were determined. Then, the performance of the SPCPGMs during neovascularization was evaluated in vivo. The SPCPGMs were prepared through a cross‐linking curing method and then filled into the hollow scaffold of an artificial bone. Neovascularization at the bone defect position was histologically examined in samples collected 2, 4, 6, and 8 weeks after the operation. The cellular magnetofection rate of superparamagnetic chitosan nanoparticles/plasmid (pReceiver‐M29‐VEGF165/DH5a) complexes reached 1–3% under static magnetic field (SMF). Meanwhile, the optimal conditions for SPCPGM fabrication were 20% Fe3O4 (w/v), 4 mg of plasmid, 5.3 mg of glutaraldehyde, and 500 rpm of emulsification rotate speed. Under oscillating magnetic fields (OMFs), 4–6 μg of plasmids was released daily for 21 days. Under the combined application of SMF and OMF, evident neovascularization occurred at the bone defect position 6 weeks after the operation. This result is expected to provide a new type of angiogenesis strategy for the research of bone tissue engineering.

Superparamagnetic NiO-doped mesoporous silica flower-like microspheres with high nickel content

Morphology oriented synthesis of metal oxide doped silica structures have fascinating properties which needed to be explored extensively. In this work, NiO doped silica microsphere with beautiful flower-like morphology has been achieved by adopting a facile surfactant-assisted synthetic route using CTAB-ammonia in H2O–ethanol mixed solvent media. The sol–gel synthesis with effective variations of Ni/Si ratios up to 7.0, followed by a simple hydrothermal treatment and subsequent calcination leads to the formation of NiO–silica mesostructures with high nickel content. Detailed structural and elemental characterizations by using powder X-ray analysis (XRD), scanning electron (SEM) and transmission electron microscopy (TEM), N2 adsorption–desorption, X-ray photoelectron spectroscopy (XPS) revealed that single cubic phase NiO doped mesoporous silica microspheres (for Ni/Si=5:1 and 7:1) with good surface area (169 and 205m2g−1 for sample with Ni/Si=7:1 and 5:1, respectively) and pore width 3–5nm, have been formed with 3D flower-like shape and 500–600nm particle size. These NiO–silica microspheres containing high Ni content up to 76wt% have shown excellent paramagnetic properties at room temperature.

A quantitative study of magnetic interactions between a micro-magnet array and individual magnetic micro-particles by scanning particle force microscopy

Magnetic particle force microscopy has been used to measure magnetic interactions between an array of thermomagnetically patterned hard micro-magnets and both hard magnetic and superparamagnetic microspheres. Maximum interaction forces are experienced when the microspheres scan over the interface between reversed and non-reversed zones, where the stray magnetic field produced by the micro-magnet array is maximum. Comparison of experimental and simulated force maps of the hard spheres is used to validate assumptions concerning the remanent magnetisation and depth of the reversed zones. This information is in turn used to deduce the content of magnetic nanoparticles in the superparamagnetic spheres. Asymmetries in the experimental force maps of hard spheres are attributed to (i) the existence of a weak in-plane component of the force and (ii) the fact that the transition between two regions with opposite magnetization direction is not abrupt.

Superparamagnetic hybrid microspheres affecting osteoblasts behaviour

The present work describes biomimetic hybrid microspheres made of collagen type I-like peptide matrix (RCP) mineralised with Fe2+/Fe3+ doping hydroxyapatite (RCPFeHA) by a bio-inspired process. Superparamagnetic RCPFeHA microspheres are obtained by emulsification of the hybrid slurries in the presence of citrate ions, to achieve a biomimetic surface functionalisation improving the bioactivity and the dispersion ability in cell culture medium. A biological in vitro study correlates the osteoblast cells behaviour to calcium and iron ions released by the hybrid microspheres in culture media mimicking physiological or inflammatory environment, evidencing a clear triggering of cell activity and bio-resorption ability. In presence of the microspheres, the osteoblast cells maintain their typical morphology and no cell damage were detected, whereas also showing up-regulation of osteogenic markers. The ability of the hybrid microspheres to undergo bio-resorption and release bioactive ions in response to different environmental stimuli without harmful effects opens new perspectives in bone regeneration, as magnetically active bone substitute with potential ability of drug carrier and smart response in the presence of inflammatory states.

A Trisymmetric Magnetic Microchip Surface for Free and Two‐Way Directional Movement of Magnetic Microbeads

AbstractThe guidance of labeled microcarriers in microfluidic environments is a prerequisite to the development of magnetic pattern assisted lab‐on‐chip technology. Square wave modulations of in‐plane applied magnetic fields enable the forward and backward locomotion of superparamagnetic microspheres on discrete hexagonally arranged ferromagnetic structures in a flowless microfluidic environment at a single bead level. By using distinct magnetic field sequences, selective directional transportation and two‐way separational motion of different ensembles of beads across a varying stray magnetic field pattern is achieved. Microbeads can be moved along different directions along spatial microcorridors. The demonstrated realization of multifunctional patterned magnetic surfaces enables the controlled positioning and sorting of mixed populations of functionalized microcarriers for biodiagnostic applications.

Microfluidic approaches for the production of monodisperse, superparamagnetic microspheres in the low micrometer size range

The preparation of small, monodispersed magnetic microparticles through microfluidic approaches has been consistently challenging due to the high energy input needed for droplet break-off at such small diameters. In this work, we show the microfluidic production of 1–3 μm magnetic nanoparticle-loaded poly(d, l-lactide) (PLA) microspheres. We describe the use of two approaches, using a conventional flow-focusing microfluidic geometry. The first approach is the separation of target size satellite particles from the main droplets; the second approach is the direct production using high flow rate jetting regimes. The particles were produced using a polymeric thiol-ene microfluidic chip platform, which affords the straightforward production of multiple chip copies for single-time use, due to large feature sizes and replica molding approaches. Through the encapsulation of magnetite/maghemite nanoparticles, and their characterization with scanning electron microscopy (SEM) and vibrating sample magnetometry (VSM) measurements, we show that the resulting particles are monosized, highly spherical and exhibit superparamagnetic properties. The particle size regime and their magnetic response show potential for in vivo intravenous applications of magnetic targeting with maximum magnetic response, but without blocking an organ’s capillaries.

A novel strategy for in vivo angiogenesis and osteogenesis: magnetic micro-movement in a bone scaffold

Angiogenesis and osteogenesis in tissue-engineered bone are the key factors in the clinical application of tissue-engineering technology to repair large bone defects. In vivo cells that are farther than 200 μm from capillaries cannot survive due to lack of nutrients and oxygen, and thus, the tissue-engineered bone is not suitable for repairing large bone defects. In this study, we constructed a novel artificial bone scaffold loaded with superparamagnetic plasmid gene microspheres. Magnetic micro-movement of the magnetic microspheres in the scaffold was generated by an oscillating magnetic field and a static magnetic field to promote the release of plasmid genes from microspheres for transfection of surrounding cells, resulting in protein expression of vascular endothelial growth factor, thus promoting angiogenesis and osteogenesis in the scaffold, internal vascularization of the artificial bone scaffold and repair of large bone defects.

Self-Template Etching Synthesis of Urchin-Like Fe3O4 Microspheres for Enhanced Heavy Metal Ions Removal

Hierachical Fe3O4 microspheres with superparamagnetic properties are attractive for their superior structural, water-dispersible, and magnetic separation merits. Here self-template etching route was developed to create optimal porous structure in superparamagnetic Fe3O4 microspheres by using the oxalic acid (H2C2O4) as etching agent. A plausible formation mechanism of the urchin-like Fe3O4 microspheres was proposed based on systematic investigation of the etching process, which involved two stages including pore-forming step based on size-selective etching and pore-expanding step based on further etching. The as-synthesized Fe3O4 microspheres exhibited urchin-like structure with specific surface area and pore-size tunable, water-dispersible, and superparamagnetic properties. The optimal urchin-like Fe3O4 microspheres demonstrated superior performance including fast magnetic separation and high removal capabilities for the heavy metals ions like Pb2+ (112.8 mg g-1) and Cr(VI) (68.7 mg g-1). This work will shed new light on the synthesis of urchin-like microspheres for superior performance.

Fabrication of superparamagnetic nanofibrous poly(l-lactic acid)/γ-Fe2 O3 microspheres for cell carriers.

Nanofibrous poly(l-lactic acid) (PLLA) microspheres are extensively studied to be used as cell carriers in the field of tissue engineering because the unique structure can promote cell proliferation and migration. But as injectable scaffold materials, PLLA microspheres easily run off to the soft tissue space because of the lack of cohesive force. It will affect the treatment efficiency and even cause additional inflammatory response. In order to overcome this disadvantage, superparamagnetic γ-Fe2 O3 nanoparticles assisted with oxidative polymerization of dopamine were used for surface modification of PLLA microspheres in this study. The results showed that this surface modification had no obvious cytotoxicity, and the modified microspheres possessed the ability to carry seed cells to controllably move to the defect sites with the guidance of magnetic field, which may be able to increase the repair efficiency. Moreover, the characteristic nanofibrous structure was not destroyed after modification, which was able to promote biological activity of cells. This work provides a novel way to produce superparamagnetic nanofibrous microspheres designed for cell microcarriers. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2018. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 107B: 511-520, 2019.

Superparamagnetic Mo-containing core-shell microspheres for catalytic oxidative desulfurization of fuel

Magnetic core-shell structured materials as carriers have received extensive attention in heterogeneous catalysis due to their unique magnetic responsively properties. Herein, we report a synthetic route to obtain magnetic core-shell microspheres by a sol–gel approach. The Fe3O4 (ca. 8nm) is completely coated with SiO2 (ca. 15nm) to prevent Fe3O4 from being oxidized in the reaction and the microspheres also show superparamagnetism, which allows the catalyst easy to separate. To explore their application, Mo-containing compound is loaded to their surface by impregnating and then calcined at different temperatures (100–800°C). The obtained catalysts are used in oxidative desulfurization (ODS). The removal of DBT from model oil can reach 100% with calcination temperature at 400°C and be recycled for at least five times without obvious decrease.

Ultrasonic assisted rapid synthesis of high uniform super-paramagnetic microspheres with core-shell structure and robust magneto-chromatic ability

Super-paramagnetic core-shell microspheres were synthesized by ultrasonic assisted routine under low ultrasonic irradiation powers. Compared with conventional routine, ultrasonic effect could not only improve the uniformity of the core-shell structure of Fe3O4@SiO2, but shorten the synthesis time in large scale. Owing to their hydrophilicity and high surface charge, the Fe3O4@SiO2 microspheres could be dispersed well in distilled water to form homogeneous colloidal suspension. The suspensions have favorable magneto-chromatic ability that they sensitively exhibit brilliant colorful ribbons by magnetic attraction. The colorful ribbons, which distributed along the magnetic lines, make morphology of the magnetic fields become “visible” to naked eyed. Those colorful ribbons originate from strong magnetic interaction between the microspheres and magnetic fields. Furthermore, the magneto-chromatic performance is reversible as the colorful ribbons vanished rapidly with the removing of magnetic fields. The silica layer effectively enhanced the acid resistance and surface-oxidation resistance of theFe3O4@SiO2 microspheres, so they could exhibit stable magnetic nature and robust magneto-chromatic property in acid environment.