Analytical methods for separating and isolating magnetic nanoparticles.

Despite the large body of literature describing the synthesis of magnetic nanoparticles, few analytical tools are commonly used for their purification and analysis. Due to their unique physical and chemical properties, magnetic nanoparticles are appealing candidates for biomedical applications and analytical separations. Yet in the absence of methods for assessing and assuring their purity, the ultimate use of magnetic particles and heterostructures is likely to be limited. In this review, we summarize the separation techniques that have been initially used for this purpose. For magnetic nanoparticles, it is the use of an applied magnetic flux or field gradient that enables separations. Flow based techniques are combined with applied magnetic fields to give methods such as magnetic field flow fractionation and high gradient magnetic separation. Additional techniques have been explored for manipulating particles in microfluidic channels and in mesoporous membranes. Further development of these and new analytical tools for separation and analysis of colloidal particles is critically important to enable the practical use of these, particularly for medicinal purposes.

Purification and magnetic interrogation of hybrid Au-Fe3O4 and FePt-Fe3O4 nanoparticles.

Purifying heterodimers: differential magnetic catch and release separation is used to purify two important hybrid nanocrystal systems, Au-Fe(3)O(4) and FePt-Fe(3)O(4). The purified samples have substantially different magnetic properties compared to the as-synthesized materials: the magnetization values are more accurate and magnetic polydispersity is identified in morphologically similar hybrid nanoparticles.

Diffusive flux of nanoparticles through chemically modified alumina membranes.

Surface chemistry plays an important role in determining flux through porous media such as in the environment. In this paper diffusive flux of nanoparticles through alkylsilane modified porous alumina is measured as a model for understanding transport in porous media of differing surface chemistries. Experiments are performed as a function of particle size, pore diameter, attached hydrocarbon chain length and chain terminus, and solvent. Particle fluxes are monitored by the change in absorbance of the solution in the receiving side of a diffusion cell. In general, flux increases when the membranes are modified with alkylsilanes compared to untreated membranes, which is attributed to the hydrophobic nature of the porous membranes and differences in wettability. We find that flux decreases, in both hexane and aqueous solutions, when the hydrocarbon chain lining the interior pore wall increases in length. The rate and selectivity of transport across these membranes is related to the partition coefficient (K(p)) and the diffusion coefficient (D) of the permeating species. By conducting experiments as a function of initial particle concentration, we find that K(p)D increases with increasing particle size, is greater in alkylsilane-modified pores, and larger in hexane solution than water. The impact of the alkylsilane terminus (-CH(3), -Br, -NH(2), -COOH) on permeation in water is also examined. In water, the highest K(p)D is observed when the membranes are modified with carboxylic acid terminated silanes and lowest with amine terminated silanes as a result of electrostatic effects during translocation.

Differential magnetic catch and release: experimental parameters for controlled separation of magnetic nanoparticles.

Differential magnetic catch and release (DMCR) has been used as a method for the purification and separation of magnetic nanoparticles. DMCR separates nanoparticles in the mobile phase by magnetic trapping of magnetic nanoparticles against the wall of an open tubular capillary wrapped between two narrowly spaced electromagnetic poles. Using Au and CoFe(2)O(4) nanoparticles as model systems, the loading capacity of the 250 µm diameter capillary is determined to be ∼130 µg, and is scalable to higher quantities with larger bore capillary. Peak resolution in DMCR is externally controlled by selection of the release time (R(t)) at which the magnetic flux density is removed, however, longer capture times are shown to reduce the capture yield. In addition, the magnetic nanoparticle capture yields are observed to depend on the nanoparticle diameter, mobile phase viscosity and velocity, and applied magnetic flux. Using these optimized parameters, three samples of CoFe(2)O(4) nanoparticles whose diameters are different by less than 10 nm are separated with excellent resolution and capture yield, demonstrating the capability of DMCR for separation and purification of magnetic nanoparticles.

The use of magnetic nanoparticles in analytical chemistry.

Magnetic nanoparticles uniquely combine superparamagnetic behavior with dimensions that are smaller than or the same size as molecular analytes. The integration of magnetic nanoparticles with analytical methods has opened new avenues for sensing, purification, and quantitative analysis. Applied magnetic fields can be used to control the motion and properties of magnetic nanoparticles; in analytical chemistry, use of magnetic fields provides methods for manipulating and analyzing species at the molecular level. In this review, we describe applications of magnetic nanoparticles to analyte handling, chemical sensors, and imaging techniques.

Diffusive flux and magnetic manipulation of nanoparticles through porous membranes.

Measurement of transport of nanometer scale particles through porous media is important to begin to understand the potential environmental impacts of nanomaterials. Using a diffusion cell with two compartments separated by either a porous alumina or polycarbonate membrane as a model system, diffusive flux through mesoporous materials is examined. Experiments are performed as a function of particle size, pore diameter, and solvent, and the particle fluxes are monitored by the change in absorbance of the solution in the receiving cell. Using the measured extinction coefficient and change in absorbance of the solution as a function of time, the fluxes of 3, 8, and 14 nm diameter CoFe(2)O(4) particles are determined as they are translocated across pores with diameters 30, 50, 100, and 200 nm in hexane and aqueous solutions. In general, flux decreases with increasing particle size and increases with pore diameter. We find that fluxes are faster in aqueous solutions than in hexane, which is attributed to the hydrophilic nature of the porous membranes and differences in wettability. The impact of an applied magnetic flux gradient, which induces magnetization and motion, on permeation is also examined. For larger membrane pore diameters, applied magnetic fluxes increase the rate of transport of 14 nm CoFe(2)O(4) particles more than that of 3 or 8 nm diameter particles, reflecting their differences in susceptibility. However, larger particles are excluded from membranes with small diameter pores, consistent with magnetic interparticle attractions that reversibly induce magnetic aggregation.

Differential magnetic catch and release: analysis and separation of magnetic nanoparticles.

This article reports the purification and separation of magnetic nanoparticle mixtures using differential magnetic catch and release (DMCR). This method applies a variable magnetic flux orthogonal to the flow direction in an open tubular capillary to trap and controllably release magnetic nanoparticles. Magnetic moments of 8, 12, and 17 nm diameter CoFe2O4 nanoparticles are calculated using the applied magnetic flux and experimentally determined force required to trap 50% of the particle sample. Balancing the relative strengths of the drag and magnetic forces enables separation and purification of magnetic CoFe2O4 nanoparticle samples with <20 nm diameters. Samples were characterized by transmission electron microscopy to determine the average size and size dispersity of the sample population. DMCR is further demonstrated to be useful for separation of a magnetic nanoparticle mixture, resulting in samples with narrowed size distributions.