Theoretical study of the photothermal behaviour of self-assembled magnetic-plasmonic chain structures.

We study the field-directed self-assembly and photothermal behavior of one-dimensional (1D) chains of core-shell Fe3O4@Au magnetic-plasmonic nanoparticles. Monte Carlo analysis is used to predict the self-assembly of the nanoparticles when they are subjected to a uniform magnetic field and confined to a fluidic nanochannel. A coupled photonic and thermodynamic analysis is performed to analyze the optical and photothermal properties of the 1D chain structures. We show for the first time that the assembled chain structures exhibit a pronounced dip in their absorption spectrum at a wavelength that is strongly sensitive to changes in the refractive index of the surrounding medium. The plasmon enhanced features of these structures are well suited for a variety of theranostic modalities as we discuss.

Optimization of Optical Absorption of Colloids of SiO2@Au and Fe3O4@Au Nanoparticles with Constraints.

We study the optical response of monodisperse colloids of core-shell plasmonic nanoparticles and introduce a computational approach to optimize absorption for photothermal applications that require dilute colloids of non-interacting particles with a prescribed volume fraction. Since the volume fraction is held constant, the particle concentration is size-dependent. Optimization is achieved by comparing the absorption spectra of colloids as a function of particle size and structure. We demonstrate the approach via application to colloids of core-shell SiO2@Au and Fe3O4@Au nanoparticles with particle sizes that range from 5-100 nm and with the incident wavelength varying from 600-1200 nm. The absorption spectra are predicted using Mie theory and the analysis shows that there is a unique mix of parameters (core radius, shell thickness, wavelength) that maximize absorption, independent of the value of volume fraction. We show that lossy Fe3O4 cores produce a much broader absorption peak with much less sensitivity to variations in particle structure and wavelength than lossless SiO2 cores. This approach can be readily adapted to colloids of nanoparticles with arbitrary materials, shapes and structure using appropriate numerical methods to compute the absorption spectra. As such, it is useful for the rational design of colloids and process variables for a broad range of photothermal applications.

Theoretical Comparison of Optical Properties of Near-Infrared Colloidal Plasmonic Nanoparticles.

We study optical properties of near-infrared absorbing colloidal plasmonic nanostructures that are of interest for biomedical theranostic applications: SiO2@Au core-shell particles, Au nanocages and Au nanorods. Full-wave field analysis is used to compare the absorption spectra and field enhancement of these structures as a function of their dimensions and orientation with respect to the incident field polarization. Absorption cross-sections of structures with the same volume and LSPR wavelength are compared to quantify differential performance for imaging, sensing and photothermal applications. The analysis shows that while the LSPR of each structure can be tuned to the NIR, particles with a high degree of rotational symmetry, i.e. the SiO2@Au and nanocage particles, provide superior performance for photothermal applications because their absorption is less sensitive to their orientation, which is random in colloidal applications. The analysis also demonstrates that Au nanocages are advantaged with respect to other structures for imaging, sensing and drug delivery applications as they support abundant E field hot spots along their surface and within their open interior. The modeling approach presented here broadly applies to dilute colloidal plasmonic nanomaterials of arbitrary shapes, sizes and material constituents and is well suited for the rational design of novel plasmon-assisted theranostic applications.

Magnetic levitation-based electromagnetic energy harvesting: a semi-analytical non-linear model for energy transduction.

Magnetic levitation has been used to implement low-cost and maintenance-free electromagnetic energy harvesting. The ability of levitation-based harvesting systems to operate autonomously for long periods of time makes them well-suited for self-powering a broad range of technologies. In this paper, a combined theoretical and experimental study is presented of a harvester configuration that utilizes the motion of a levitated hard-magnetic element to generate electrical power. A semi-analytical, non-linear model is introduced that enables accurate and efficient analysis of energy transduction. The model predicts the transient and steady-state response of the harvester a function of its motion (amplitude and frequency) and load impedance. Very good agreement is obtained between simulation and experiment with energy errors lower than 14.15% (mean absolute percentage error of 6.02%) and cross-correlations higher than 86%. The model provides unique insight into fundamental mechanisms of energy transduction and enables the geometric optimization of harvesters prior to fabrication and the rational design of intelligent energy harvesters.

Self-Assembly of Crystalline Structures of Magnetic Core-Shell Nanoparticles for Fabrication of Nanostructured Materials.

A theoretical study is presented of the template-assisted formation of crystalline superstructures of magnetic-dielectric core-shell particles. The templates produce highly localized gradient fields and a corresponding magnetic force that guides the assembly with nanoscale precision in particle placement. The process is studied using two distinct and complementary computational models that predict the dynamics and energy of the particles, respectively. Both mono- and polydisperse colloids are studied, and the analysis demonstrates for the first time that although the particles self-assemble into ordered crystalline superstructures, the particle formation is not unique. There is a Brownian motion-induced degeneracy in the process wherein various distinct, energetically comparable crystalline structures can form for a given template geometry. The models predict the formation of hexagonal close packed (HCP) and face centered cubic (FCC) structures as well as mixed phase structures due to in-plane stacking disorders, which is consistent with experimental observations. The polydisperse particle structures are less uniform than the monodisperse particle structures because of the irregular packing of different-sized particles. A comparison of self-assembly using soft- and hard-magnetic templates is also presented, the former being magnetized in a uniform field. This analysis shows that soft-magnetic templates enable an order-of-magnitude more rapid assembly and much higher spatial resolution in particle placement than their hard-magnetic counterparts. The self-assembly method discussed is versatile and broadly applies to arbitrary template geometries and multilayered and multifunctional mono- and polydisperse core-shell particles that have at least one magnetic component. As such, the method holds potential for the bottom-up fabrication of functional nanostructured materials for a broad range of applications. This work provides unprecedented insight into the assembly process, especially with respect to the viability and potential fundamental limitations of realizing structure-dependent material properties for applications.

Magnetofection Mediated Transient NANOG Overexpression Enhances Proliferation and Myogenic Differentiation of Human Hair Follicle Derived Mesenchymal Stem Cells.

We used magnetofection (MF) to achieve high transfection efficiency into human mesenchymal stem cells (MSCs). A custom-made magnet array, matching well-to-well to a 24-well plate, was generated and characterized. Theoretical predictions of magnetic force distribution within each well demonstrated that there was no magnetic field interference among magnets in adjacent wells. An optimized protocol for efficient gene delivery to human hair follicle derived MSCs (hHF-MSCs) was established using an egfp-encoding plasmid, reaching approximately ∼50% transfection efficiency without significant cytotoxicity. Then we applied the optimized MF protocol to express the pluripotency-associated transcription factor NANOG, which was previously shown to reverse the effects of organismal aging on MSC proliferation and myogenic differentiation capacity. Indeed, MF-mediated NANOG delivery increased proliferation and enhanced the differentiation of hHF-MSCs into smooth muscle cells (SMCs). Collectively, our results show that MF can achieve high levels of gene delivery to MSCs and, therefore, may be employed to moderate or reverse the effects of cellular senescence or reprogram cells to the pluripotent state without permanent genetic modification.

Template-assisted nano-patterning of magnetic core-shell particles in gradient fields.

A method is proposed for controlling the assembly of colloidal magnetic core-shell nanoparticles into patterned monolayer structures with nanoscale feature resolution. The method is based on magnetic field-directed self-assembly that is enhanced using soft-magnetic template elements. The elements are embedded in a nonmagnetic substrate and magnetized using a uniform bias field. A key feature of this approach is the combined use of a uniform field with induced gradient-fields produced by the template elements. This enables the customization of a force field with localized regions of attractive and repulsive magnetic forces that provide extraordinary control of particle motion during assembly. The method is demonstrated using a computational model that simulates the assembly process taking into account magnetic and hydrodynamic forces including interparticle interactions, Brownian diffusion, van der Waals force and effects of surfactants. The analysis shows that extended geometric patterns of particles can be assembled with nanoscale resolution, beyond that of the template elements, within milliseconds. This is achieved by tailoring key parameters including the template geometry to produce a force field that focuses the particles into prescribed patterns; the thickness of the dielectric particle shell to control the magnetic dipole-dipole force upon contact and the particle volume fraction to suppress undesired aggregation during assembly. The proposed method broadly applies to arbitrary template geometries and multi-layered core-shell particles with at least one magnetic component. It can enable the self-assembly of complex patterns of nanoparticles and open up opportunities for the scalable fabrication of multifunctional nanostructured materials for a broad range of applications.

A model for predicting field-directed particle transport in the magnetofection process.

PURPOSE: To analyze the magnetofection process in which magnetic carrier particles with surface-bound gene vectors are attracted to target cells for transfection using an external magnetic field and to obtain a fundamental understanding of the impact of key factors such as particle size and field strength on the gene delivery process. METHODS: A numerical model is used to study the field-directed transport of the carrier particle-gene vector complex to target cells in a conventional multiwell culture plate system. The model predicts the transport dynamics and the distribution of particle accumulation at the target cells. RESULTS: The impact of several factors that strongly influence gene vector delivery is assessed including the properties of the carrier particles, the strength of the field source, and its extent and proximity relative to the target cells. CONCLUSIONS: The study demonstrates that modeling can be used to predict and optimize gene vector delivery in the magnetofection process for novel and conventional in vitro systems.