Michael R. Bockstaller

Evaluation of iron-cobalt/ferrite core-shell nanoparticles for cancer thermotherapy

Magnetic nanoparticles (MNPs) offer promise for local hyperthermia or thermoablative cancer therapy. Magnetic hyperthermia uses MNPs to heat cancerous regions in an rf field. Metallic MNPs have larger magnetic moments than iron oxides, allowing similar heating at lower concentrations. By tuning the magnetic anisotropy in alloys, the heating rate at a particular particle size can be optimized. Fe–Co core-shell MNPs have protective CoFe2O4 shell which prevents oxidation. The oxide coating also aids in functionalization and improves biocompatibility of the MNPs. We predict the specific loss power (SLP) for FeCo (SLP ∼450W∕g) at biocompatible fields to be significantly larger in comparision to oxide materials. The anisotropy of Fe-Co MNPs may be tuned by composition and/or shape variation to achieve the maximum SLP at a desired particle size.

Rapid uptake of gold nanorods by primary human blood phagocytes and immunomodulatory effects of surface chemistry.

Nanoparticle-based in vivo applications should consider the omnipresence of the phagocytes in the bloodstream and tissue. We have studied the nanoparticle uptake capacities of the most important human primary leukocyte populations using a nanoparticle library encompassing both rod-shaped and spherical gold nanoparticles with diameters between 15 and 50 nm and a variety of surface chemistries. Cetyltrimethylammoniumbromide (CTAB)-stabilized nanoparticles were internalized rapidly within 15 min and in large amounts by macrophages and to a lower extent also by monocytes. Interestingly, we found that the uptake of nanorods by macrophages was more efficient than that of nanospheres. Blocking experiments and electron microscopic studies revealed macropinocytosis as the major uptake mechanism. Grafting of poly(ethylene oxide) (PEO) onto the nanorods was found to significantly delay their internalization for several hours. The long-term uptake of PEO-coated nanoparticles with positively or negatively charged end groups was almost identical. Particle surface chemistry strongly influenced the expression of inflammation-related genes within 1 day. Furthermore, the macrophage phenotype was significantly affected after 7 days of culture with nanorods depending on the surface chemistry. Thus, in vivo application of nanoparticles with certain surface functionalities may lead to inflammation upon particle accumulation. However, our data also suggest that chemical modifications of nanoparticles may be useful for immunomodulation.

Imidazolium-based ionic liquids as efficient shape-regulating solvents for the synthesis of gold nanorods.

Herein we present an alternate synthetic strategy based onionic liquid solvents that alleviates the need for shape-regulating surfactants.Ionic liquids (ILs) have attracted interest as benignsolvent systems for the synthesis of nanomaterials as theycombine several attractive characteristics, for example inher-ent conductivity, stability over a broad range of electro-chemical potentials, and environmental benefits derivingfrom the low vapor pressure and straightforward separationprocedures.

Flexible particle array structures by controlling polymer graft architecture.

Surface-initiated atom-transfer radical polymerization is used to synthesize particle brushes with controlled fraction of extended and relaxed conformations of surface-grafted chains. In the semidilute brush limit, the grafting of polymeric ligands is shown to facilitate the formation of ordered yet plastic-compliant particle array structures in which chain entanglements give rise to fracture through a polymer-like crazing process that dramatically increases the toughness and flexibility of the particle assembly.

Toughening fragile matter: mechanical properties of particle solids assembled from polymer-grafted hybrid particles synthesized by ATRP

The effect of polymer-graft modification on the structure formation and mechanical characteristics of inorganic (silica) nanoparticle solids is evaluated as a function of the degree of polymerization of surface-grafted chains. A transition from ‘hard-sphere-like’ to ‘polymer-like’ mechanical characteristics of particle solids is observed for increasing degree of polymerization of grafted chains. The elastic modulus of particle solids increases by about 200% and levels off at intermediate molecular weights of surface-grafted chains, a trend that is rationalized as a consequence of the elastic modulus being determined by dispersion interactions between the polymeric grafts. A pronounced increase (of about one order of magnitude) of the fracture toughness of particle solids is observed as the degree of polymerization of grafted chains exceeds a threshold value that is similar for both polystyrene and poly(methyl methacrylate) grafts. The increased resistance to fracture is interpreted as a consequence of the existence of entanglements between surface-grafted chains that give rise to energy dissipation during fracture through microscopic plastic deformation and craze formation. Within the experimental uncertainty the transition to polymer-like deformation characteristics is captured by a mean field scaling model that interprets the structure of the polymer shell of polymer-grafted particles as effective ‘two-phase’ systems consisting of a stretched inner region and a relaxed outer region. The model is applied to predict the minimum degree of polymerization needed to induce polymer-like mechanical characteristics and thus to establish ‘design criteria’ for the synthesis of polymer-modified particles that are capable of forming mechanically robust and formable particle solid structures.

Effect of Matrix Molecular Weight on the Coarsening Mechanism of Polymer-Grafted Gold Nanocrystals

A systematic evaluation of the effect of polymer matrix molecular weight on the coarsening kinetics of uniformly dispersed polystyrene-grafted gold nanoparticles is presented. Particle coarsening is found to proceed via three stages (i.e., atomic-diffusion-based Ostwald ripening (OR), particle-migration-based collision-coalescence, and the subsequent reshaping of particle assemblies). The relative significance of each stage and hence the evolution of particle size and shape have been found to depend sensitively upon time, temperature, and the molecular weight of the host polymer. At temperatures close to the matrix glass-transition temperature, Ostwald ripening has been observed to be dominant on all experimental timescales. With increasing annealing temperature, collision coalescence becomes the dominant mode of coarsening, leading to rapid particle growth. The onset of the latter process is found to be increasingly delayed with increasing molecular weight of the polymer host. Particle coalescence is observed to proceed via two fundamental modes (i.e., diffusion-limited aggregation and growth resulting in the formation of fractal particle clusters and the subsequent recrystallization into more spherical monolithic aggregate structures). Interestingly, particle coarsening in high-molecular-weight matrix polymers is found to proceed significantly faster than predicted on the basis of the bulk polymer viscosity; this acceleration is interpreted to be a consequence of the network characteristics of high-molecular-weight polymers by analogy to the phenomenon of nanoviscosity that has been reported in the context of nanoparticle diffusion within high-molecular-weight polymers.

Strategies for the Synthesis of Thermoplastic Polymer Nanocomposite Materials with High Inorganic Filling Fraction

The governing parameters controlling the miscibility of particle additives within polymeric host media are analyzed for the particular case of silica particle fillers embedded within a poly(methyl methacrylate) (PMMA) matrix. For athermal polymer-graft modification of particles (corresponding to equal chemical composition of graft and matrix polymer), compatibility is found to be a sensitive function of the degree of polymerization of graft and host polymer chains as well as the particle radius. In agreement with theoretical predictions, uniform particle dispersion is observed if the degree of polymerization of grafted chains is comparable to (or exceeds) the corresponding value of the polymer matrix. The resulting restriction to high degree of polymerization limits the accessible inorganic fraction that is attainable in athermal particle/polymer blends. In contrast, favorable interaction between grafted polymer chains and the polymeric host (as realized in the case of poly(styrene-r-acrylonitrile)-grafted particles embedded within PMMA matrix) is shown to facilitate thermodynamically stable and uniform particle dispersion across the entire compositional range even in the limit of large particle size, short grafted chains, and high molecular matrix chains. The synthesis of thermoplastic composite materials with inorganic fraction exceeding 50 vol % combining quantitative optical limiting within the UV frequency range and polymer-like mechanical properties is demonstrated.

Understanding ligand distributions in modified particle and particlelike systems.

Chemical modification of nanoparticles or particlelike systems is ubiquitously being used to facilitate specific pharmaceutical functionalities or physicochemical attributes of nanocrystals, proteins, enzymes, or other particlelike systems. Often the modification process is incomplete and the functional activity of the product depends upon the distribution of functional ligands among the different particles in the system. Here, the distribution function describing the spread of ligands in particlelike systems undergoing partial modification reactions is derived and validated against a conjugated enzyme model system by use of matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF). The distribution function is shown to be applicable to describe the distribution of ligands in a wide range of particlelike systems (such as enzymes, dendrimers, or inorganic nanocrystals) and is used to establish guidelines for the synthesis of uniformly modified particle systems even at low reaction efficiencies.

Performance of Dielectric Nanocomposites: Matrix-Free, Hairy Nanoparticle Assemblies and Amorphous Polymer–Nanoparticle Blends

Demands to increase the stored energy density of electrostatic capacitors have spurred the development of materials with enhanced dielectric breakdown, improved permittivity, and reduced dielectric loss. Polymer nanocomposites (PNCs), consisting of a blend of amorphous polymer and dielectric nanofillers, have been studied intensely to satisfy these goals; however, nanoparticle aggregates, field localization due to dielectric mismatch between particle and matrix, and the poorly understood role of interface compatibilization have challenged progress. To expand the understanding of the inter-relation between these factors and, thus, enable rational optimization of low and high contrast PNC dielectrics, we compare the dielectric performance of matrix-free hairy nanoparticle assemblies (aHNPs) to blended PNCs in the regime of low dielectric contrast to establish how morphology and interface impact energy storage and breakdown across different polymer matrices (polystyrene, PS, and poly(methyl methacrylate), PMMA) and nanoparticle loadings (0-50% (v/v) silica). The findings indicate that the route (aHNP versus blending) to well-dispersed morphology has, at most, a minor impact on breakdown strength trends with nanoparticle volume fraction; the only exception being at intermediate loadings of silica in PMMA (15% (v/v)). Conversely, aHNPs show substantial improvements in reducing dielectric loss and maintaining charge/discharge efficiency. For example, low-frequency dielectric loss (1 Hz-1 kHz) of PS and PMMA aHNP films was essentially unchanged up to a silica content of 50% (v/v), whereas traditional blends showed a monotonically increasing loss with silica loading. Similar benefits are seen via high-field polarization loop measurements where energy storage for ∼15% (v/v) silica loaded PMMA and PS aHNPs were 50% and 200% greater than respective comparable PNC blends. Overall, these findings on low dielectric contrast PNCs clearly point to the performance benefits of functionalizing the nanoparticle surface with high-molecular-weight polymers for polymer nanostructured dielectrics.

Nanoparticle-regulated phase behavior of ordered block copolymers

Although block copolymer motifs have received considerable attention as supramolecular templates for inorganic nanoparticles, experimental observations of a nanostructured diblock copolymer containing inorganic nanoparticles-supported by theoretical trends predicted from a hybrid self-consistent field/density functional theory-confirm that nanoparticle size and selectivity can likewise stabilize the copolymer nanostructure by increasing its order-disorder transition temperature.