Magnetic Nanoparticle Clusters Research Articles

Photoacoustic and photothermal cytometry using photoswitchable proteins and nanoparticles with ultrasharp resonances

Photoswitchable fluorescent proteins (PSFPs) with controllable spectral shifts in emission in response to light have led to breakthroughs in cell biology. Conventional photoswitching, however, is not applicable to weakly fluorescent proteins. As an alternative, photothermal (PT) and photoacoustic (PA) spectroscopy have demonstrated a tremendous potential for studying absorbing nonfluorescent proteins and nanoparticles. However, little progress has been made in the development of switchable PT and PA probes with controllable spectral shifts in absorption. Here, we introduce the concept of photothermally switchable nanoparticles (PTSNs). To prove the concept, we demonstrated fast, reversible magnetic-PT switching of conventional and gold-coated magnetic nanoparticle clusters in cancer cells in vitro and PT switching of nonlinear ultrasharp plasmonic resonances in gold nanorods molecularly targeted to circulating cells in vivo. We showed that genetically encoded PSFPs with relatively slow switching can serve as triple-modal fluorescent, PT, and PA probes under static conditions, while PTSNs with ultrafast switching may provide higher PA sensitivity in the near-infrared window of tissue transparency under dynamic flow conditions. Application of nonlinear phenomena for super-resolution spectral PT and PA cytometry, microscopy, and spectral burning beyond the diffraction and spectral limits are also proposed.

Field-dependent motion of bio-functionalized magnetic nanoparticle clusters under a rotating magnetic field

In this paper, we investigated the behavior of biofunctionalized, magnetic nanoparticle clusters under rotating magnetic fields in an aqueous solution to facilitate the use of such nanoparticles in biomedical applications. We found that two modes of motion for clusters of the nanoparticles exist. These two modes of motion exhibited by the clusters were rotation and oscillation, depending on the size of the cluster. Due to the interaction between the rotating magnetic field and the net magnetic dipole moment, the clusters were subjected to a forced vibration. A critical diameter range for the magnetic clusters was defined that may be used to distinguish between the rotation and oscillation of clusters. Furthermore, the characteristics of size dependence of the clusters’ motion were also investigated.

The Establishment of Sensitive and Rapid Pathogenic Bacteria Detection Method Using Magnetic Nanoparticle Clusters and Optical Nanoparticle Probes

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A facile and sensitive method for detecting pathogenic bacteria using personal glucose meters

We report a facile and sensitive method for the detection of Salmonella bacteria in milk using a personal glucose meter (PGM). Monoclonal antibody-functionalized magnetic nanoparticle clusters (MNCs) were used to capture Salmonella bacteria in milk, and MNC–Salmonella complexes were magnetically separated from the sample using a permanent magnet. The complexes were further conjugated to polyclonal antibody-functionalized invertase and dispersed in a 0.5M sucrose solution. After the hydrolysis of sucrose to glucose and fructose, the concentration of glucose was measured using the PGM. The hydrolysis reaction was conducted at various temperatures, and the optimal temperature and activation energy were determined. The detection limit of Salmonella in milk was found to be 10cfu/mL.

Magnetophoretic Chromatography for the Detection of Pathogenic Bacteria with the Naked Eye

A facile and sensitive analytical method that uses gold-coated magnetic nanoparticle clusters (Au/MNCs) and magnetophoretic chromatography with a precision pipet has been developed for the detection of Salmonella bacteria. Antibody-conjugated Au/MNCs are used to capture the Salmonella bacteria in milk and are then separated from the milk by applying an external magnetic field. The Salmonella-containing solution is sucked into a precision pipet tip to which a viscous polymer solution is then added. Once the magnetophoretic chromatography process has been carried out for 10 min, the presence of 100 cfu/mL Salmonella bacteria can be detected with the naked eye because the bacteria have become concentrated at the narrow pipet tip. The performance of this method was evaluated by using dynamic light scattering and light absorption spectroscopy.

An NMR-relaxation study of the effect of albumin on aggregation of magnetic iron oxide nanoparticles

The dependence of the aggregation of magnetic iron oxide nanoparticles in aqueous suspensions under the action of human serum albumin is analyzed based on the data of proton magnetic relaxation. It is shown that albumin adsorption on magnetic nanoparticles gives rise to the formation of a protein corona and clusters of magnetic nanoparticles, decreasing the aggregation stability of the suspension in a 7.1-T magnetic field. Clustering of magnetic iron oxide nanoparticles enhances the relaxation efficiency of magnetic suspensions during NMR measurements.

Self-organization of magnetite nanoparticles in providing Saccharomyces cerevisiae Yeasts with magnetic properties

The compared analyze of four methods of the magnetic nanoparticles clusters parameters estimation were developed and performed, such as, method, which takes into account two magneto-force scans of surface for calculation, geometry distance measurement between two centers of clusters in chains using the functions of NOVA-program, which is the standard computer equipment for scanning probe microscopy SOLVER PRO-M and the model, which takes into account the table meaning of magnetite magnetization and atomic-force microscopy. The magnetically-controllable biosorbent based on the culture of Saccharomyces cerevisiae was used as a model object for adequacy analyze of these models. As the result of the work we get the information about the depth of clusters penetration inside biomembrane, the typical sizes of clusters and the dispersion of magnetic clusters sizes. This analyze shows that all four methods can be used for single magnetic clusters, but for clusters, which lay in chains with small distance between their centers, the mode, which takes into account the table meaning of magnetite magnetization, cannot be used, because this model does not take into account the nearest neighbors contribution of interaction of magnetic fields dipole with magnetic probe.

Soft Polymer Magnetic Nanocomposites: Microstructure Patterning by Magnetophoretic Transport and Self-Assembly.

A method to produce and pattern magnetic microstructure in a soft-polymer matrix is demonstrated. An externally applied magnetic field is used to influence the dynamics of magnetophoretic transport and dipolar self-assembly of magnetic nanoparticle clusters in the liquid precursor of poly-dimethylsiloxane (PDMS). Magnetic nanoparticles agglomerate by an interplay of van der Waals forces and dipolar interactions to form anisotropic clusters. These clusters are concentrated on a substrate by magnetophoresis, wherein they self-organize by dipolar interactions to form microscopic filaments. The polymer is cured in the presence of the magnetic field to preserve the microstructure shape. The externally applied magnetic field and its gradient are the two main control variables of interest when considering magnetic control during nanoparticle self-assembly. Their influence on microstructure geometry is investigated through correlations with the height of a characteristic self-assembled filament, fraction of the substrate area covered by the microstructure and its shape anisotropy. These relations enable a priori design.

Motion of bio-functionalized magnetic nanoparticle clusters under a rotating magnetic field

Motion of bio-functionalized magnetic nanoparticle clusters under a rotating magnetic field

Size-dependent motion of bio-functionalized magnetic nanoparticle clusters under a rotating magnetic field

Size-dependent motion of bio-functionalized magnetic nanoparticle clusters under a rotating magnetic field

Uniform growth of clusters of magnetic nanoparticles in a rotating magnetic field

It was recently shown that the exposure of magnetic microbeads to a homogeneous magnetic field, which rotates around the axis perpendicular to the field direction, generates highly ordered two-dimensional particle arrays. In this work, the impact of downscaling such systems is analyzed. Dilutions of cobalt nanoparticles with an average diameter of 6 nm were brought into a rotating homogeneous magnetic field. A strong localization of the number of particles within a certain cluster size can be observed if the rotation frequency is adjusted to a specific particle concentration. In particular, we obtain an increase of 85 % of the maximum of the cluster size distribution, when changing the rotation frequency of the magnetic field from 300 to 750 rpm for a cobalt concentration of 35.95 mmol/l. We propose a heuristic model to explain the observed frequency dependence.

Effects of Superparamagnetic Nanoparticle Clusters on the Polymerase Chain Reaction

The polymerase chain reaction (PCR) method is widely used for the reproduction and amplification of specific DNA segments, and a novel PCR method using nanomaterials such as gold nanoparticles has recently been reported. This paper reports on the effects of superparamagnetic nanoparticles on PCR amplification without an external magnetic field, and clarifies the mechanism behind the effects of superparamagnetic particle clusters on PCR efficiency by estimating the structures of such clusters in PCR. It was found that superparamagnetic nanoparticles tend to inhibit PCR amplification depending on the structure of the magnetic nanoparticle clusters. The paper also clarifies that Taq polymerase is captured in the spaces formed among magnetic nanoparticle clusters, and that it is captured more efficiently as a result of their motion from heat treatment in PCR thermal cycles. Consequently, Taq polymerase that should be used in PCR is reduced in the PCR solution. These outcomes will be applied to novel PCR techniques using magnetic particles in an external magnetic field.

Anomalous magnetism in noble metal (nano)particles

In a previous article published in Langmuir 27 (2011) 7783–7787, we reported on a novel synthesis route to make magnetic noble metal nanoparticles and nanoparticle clusters. In this article we demonstrate an enhanced method of recovering the magnetic particles after synthesis and give an insight into the temperature dependence of their magnetization. Based on our findings, we conclude that the magnetism induced by our method has a dominant contribution from the surface instead of the bulk as is common for classical magnetism.

Hierarchically Structured Free-Standing Hydrogels with Liquid Crystalline Domains and Magnetic Nanoparticles as Dual Physical Cross-Linkers

Here we report a modular strategy for preparing physically cross-linked and mechanically robust free-standing hydrogels comprising unique thermotropic liquid crystalline (LC) domains and magnetic nanoparticles both of which serve as the physical cross-linkers resulting in hydrogels that can be used as magnetically responsive soft actuators. A series of amphiphilic LC pentablock copolymers of poly(acrylic acid) (PAA), poly(5-cholesteryloxypentyl methacrylate) (PC5MA), and poly(ethylene oxide) (PEO) blocks in the sequence of PAA-PC5MA-PEO-PC5MA-PAA were prepared using reversible addition-fragmentation chain transfer polymerization. These pentablock copolymers served as macromolecular ligands to template Fe(3)O(4) magnetic nanoparticles (MNPs), which were directly anchored to the polymer chains through the coordination bonds with the carboxyl groups of PAA blocks. The resulting polymer/MNP nanocomposites comprised a complicated hierarchical structure in which polymer-coated MNP clusters were dispersed in a microsegregated pentablock copolymer matrix that further contained LC ordering. Upon swelling, the hierarchical structure was disrupted and converted to a network structure, in which MNP clusters were anchored to the polymer chains and LC domains stayed intact to connect solvated PEO and PAA blocks, leading to a free-standing LC magnetic hydrogel (LC ferrogel). By varying the PAA weight fraction (f(AA)) in the pentablock copolymers, the swelling degrees (Q) of the resulting LC ferrogels were tailored. Rheological experiments showed that these physically cross-linked free-standing LC ferrogels exhibit good mechanical strength with storage moduli G' of around 10(4)-10(5) Pa, similar to that of natural tissues. Furthermore, application of a magnetic field induced bending actuation of the LC ferrogels. Therefore, these physically cross-linked and mechanically robust LC ferrogels can be used as soft actuators and artificial muscles. Moreover, this design strategy is a versatile platform for incorporation of different types of nanoparticles (metallic, inorganic, biological, etc.) into multifunctional amphiphilic block copolymers, resulting in unique free-standing hybrid hydrogels of good mechanical strength and integrity with tailored properties and end applications.

Ferri-liposomes as an MRI-visible drug-delivery system for targeting tumours and their microenvironment

The tumour microenvironment regulates tumour progression and the spread of cancer in the body. Targeting the stromal cells that surround cancer cells could, therefore, improve the effectiveness of existing cancer treatments. Here, we show that magnetic nanoparticle clusters encapsulated inside a liposome can, under the influence of an external magnet, target both the tumour and its microenvironment. We use the outstanding T2 contrast properties (r2=573-1,286 s(-1) mM(-1)) of these ferri-liposomes, which are ∼95 nm in diameter, to non-invasively monitor drug delivery in vivo. We also visualize the targeting of the tumour microenvironment by the drug-loaded ferri-liposomes and the uptake of a model probe by cells. Furthermore, we used the ferri-liposomes to deliver a cathepsin protease inhibitor to a mammary tumour and its microenvironment in a mouse, which substantially reduced the size of the tumour compared with systemic delivery of the same drug.

Template-assisted self-assembly of individual and clusters of magnetic nanoparticles

The deliberate control over the spatial arrangement of nanostructures is the desired goal formany applications such as, for example, in data storage, plasmonics or sensor arrays. Herewe present a novel method to assist the self-assembly process of magnetic nanoparticles.The method makes use of nanostructured aluminum templates obtained after anodizationof aluminum discs and the subsequent growth and removal of the newly formedalumina layer, resulting in a regular honeycomb-type array of hexagonally shapedvalleys. The iron oxide nanoparticles, 20 nm in diameter, are spin-coated onto thesurface of honeycomb nanostructured Al templates. Depending on the size, eachhexagon site can host up to 30 nanoparticles. These nanoparticles form clusters ofdifferent arrangements within the valleys, such as collars, chains and hexagonallyclosed islands. Ultimately, it is possible to isolate individual nanoparticles. Thestrengths of the magnetic interaction between particles in a cluster are probedusing the memory effect known from the coupled state in superspin glass systems.

Regulation of PCR efficiency with magnetic nanoparticles in a rotating magnetic field

The polymerase chain reaction (PCR) method is widely used for the reproduction and amplification of specific DNA segments in vitro, and a novel PCR method using nanomaterials such as gold nanoparticles has recently been reported. This paper reports on the regulation of PCR efficiency with superparamagnetic nanoparticles in a rotating magnetic field. The level of efficiency was successfully regulated in a rotating magnetic field by the authors, and decreased with increasing frequency of the field. The results obtained show that simply controlling the structure and dynamics of magnetic nanoparticle clusters in a rotating magnetic field can regulate PCR efficiency.

The Assembly State between Magnetic Nanosensors and Their Targets Orchestrates Their Magnetic Relaxation Response

The target-induced clustering of magnetic nanoparticles is typically used for the identification of clinically relevant targets and events. A decrease in the water proton transverse NMR relaxation time, or T(2), is observed upon clustering, allowing the sensitive and accurate detection of target molecules. We have discovered a new mechanistically unique nanoparticle-target interaction resulting in a T(2) increase and demonstrate herein that this increase, and its associated r(2) relaxivity decrease, are also observed upon the interaction of the nanoparticles with ligands or molecular entities. Small molecules, proteins, and a 15-bp nucleic acid sequence were chemically conjugated to polyacrylic-acid-coated iron oxide nanoparticles, and all decreased the original nanoparticle r(2) value. Further experiments established that the r(2) decrease was inversely proportional to the number of ligands bound to the nanoparticle and the molecular weight of the bound ligand. Additional experiments revealed that the T(2)-increasing mechanism was kinetically faster than the conventional clustering mechanism. Most importantly, under conditions that result in T(2) increases, as little as 5.3 fmol of Bacillus anthracis plasmid DNA (pX01 and pX02), 8 pmol of the cholera toxin B subunit (Ctb), and even a few cancer cells in blood were detected. Transition from the binding to the clustering mechanism was observed in the carbohydrate-, Ctb-, and DNA-sensing systems, simply by increasing the target concentration significantly above the nanoparticle concentration, or using Ctb in its pentameric form as opposed to its monomer. Collectively, these results demonstrate that the molecular architectures resulting from the interaction between magnetic nanosensors and their targets directly govern water proton NMR relaxation. We attribute the observed T(2) increases to the bound target molecules partially obstructing the diffusion of solvent water molecules through the superparamagnetic iron oxide nanoparticles' outer relaxation spheres. Finally, we anticipate that this novel interaction can be incorporated into new clinical and field detection applications, due to its faster kinetics relative to the conventional nanoparticle-clustering assays.

Hierarchical Gold-Decorated Magnetic Nanoparticle Clusters with Controlled Size

We present a new route to stable magnetic-plasmonic nanocomposite materials with exceptional control over composite size and very high monodispersity. The method involves the assembly of magnetic iron oxide nanoparticles, of any size in the superparamagnetic size range, whose steric repulsion is gradually reduced by competitive stabilizer desorption arising from the presence of a tertiary silica phase. Subsequent addition of gold nanoparticles results in hierarchical assemblies in the form of gold-decorated magnetic nanoparticle clusters, in a range of possible sizes from 20 to 150 nm, selected by the timing of the addition. This approach adds plasmonic and chemical functionality to the magnetic clusters and improves the physical robustness and processability of the suspensions. Most critically, detailed NMR relaxation analysis demonstrates that the effect of the gold NPs on the interaction between bulk solvent and the magnetic moments of the cluster is minimal and that the clusters remain superparamagnetic in nature. These advantages enhance the potential of the materials as size-selected contrast agents for magnetic resonance imaging. The possibility of generalizing the approach for the production of hierarchical assemblies of variable composition is also demonstrated.

Self-assembly and flux closure studies of magnetic nanoparticle rings

Thermoremanent magnetic nanoparticles (MNPs) can self-assemble into rings through dipolar interactions, when dispersed under appropriate conditions. Analysis of individual MNP rings and clusters by off-axis electron holography reveals bistable flux closure (FC) states at ambient temperatures, and their reversible switching by magnetic field gradients. We introduce a line-bond formalism to describe the coupling between MNPs.