Measuring and controlling the transport of magnetic nanoparticles.

摘要

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. 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. This thesis further describes 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.;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 CoFe2O4 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.;Surface chemistry plays an important role in determining flux through porous media such as in the environment. 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 (Kp) and the diffusion coefficient (D) of the permeating species. By conducting experiments as a function of initial particle concentration, we find that KpD increases with increasing particle size, is greater in alkylsilane--modified pores, and larger in hexane solution than water. The impact of the alkylsilane terminus (--CH3, --Br, --NH2, --COOH) on permeation in water is also examined. In water, the highest KpD 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.;Finally, the manipulation of magnetic nanoparticles for the controlled formation of linked nanoparticle assemblies between microfluidic channels by the application of an external magnet is discussed. Two orthogonal channels were prepared using standard PDMS techniques with pressure-driven flow used to deliver the Fe3O4 and Au nanoparticle reactants. Nanoparticle assembly formation is based upon locally confined surface modification of Fe3O4 nanoparticles interacting with Au nanoparticles bridging the two particles together. For the magnetic particles, transfer between flow streams is greatly increased by placing a permanent magnet above and below the channel intersections. Multiple configurations of Fe3O 4 and Au nanoparticle assemblies are observed as a function of flow rate and interaction time of the individual nanoparticle components. We observe the formation of higher order assemblies by increasing the concentration of Fe3O4 nanoparticles introduced to the microfluidic device. This technique demonstrates the ability to form nanoparticle linked assemblies and could be easily linked to other analytical techniques developed in our lab to further isolate and separate a particular product. (Abstract shortened by UMI.).