Thermosensitivity through Exchange Coupling in Ferrimagnetic/Antiferromagnetic Nano-Objects for Magnetic-Based Thermometry.

Temperature is a fundamental physical quantity important to the physical and biological sciences. Measurement of temperature within an optically inaccessible three-dimensional (3D) volume at microscale resolution is currently limited. Thermal magnetic particle imaging (T-MPI), a temperature variant of magnetic particle imaging (MPI), hopes to solve this deficiency. For this thermometry technique, magnetic nano-objects (MNOs) with strong temperature-dependent magnetization (thermosensitivity) around the temperature of interest are required; here, we focus between 200 K and 310 K. We demonstrate that thermosensitivity can be amplified in MNOs consisting of ferrimagnetic (FiM) iron oxide (ferrite) and antiferromagnetic (AFM) cobalt oxide (CoO) through interface effects. The FiM/AFM MNOs are characterized by X-ray diffraction (XRD), (scanning) transmission electron microscopy (STEM/TEM), dynamic light scattering (DLS), and Raman spectroscopy. Thermosensitivity is evaluated and quantified by temperature-dependent magnetic measurements. The FiM/AFM exchange coupling is confirmed by field-cooled (FC) hysteresis loops measured at 100 K. Magnetic particle spectroscopy (MPS) measurements were performed at room temperature to evaluate the MNOs MPI response. This initial study shows that FiM/AFM interfacial magnetic coupling is a viable method to increase thermosensitivity in MNOs for T-MPI.

Solution-Phase Magnetic Mechanistic Study of Ni-Seamed Pyrogallol[4]arene Nanocapsules Reveal Presence of Novel Cylindrical and Spherical Species.

The magnetic properties of nickel-seamed C-pyrogallol[4]arene (PgC3 Ni) hexamers and dimers are studied for the first time in solution. The combination of small-angle neutron scattering and superconducting quantum interference device magnetometer measurements of the solution species reveal their paramagnetic and weakly antiferromagnetic behaviour. Surprisingly, the magnetic results indicated the presence of an unprecedented 13 Å-radius species, larger than both the dimeric and hexameric nanocapsules with both octahedral and square-planar metal centers. To confirm the presence of this novel species, we performed a mechanistic study of PgC3 Ni as a function of temperature and solvent and deduced the presence of two additional new species: a) an 11 Šcylinder with Ni atoms seaming the tubular framework and b) an 8 Å-radius sphere with non-interacting Ni centers located within the internal cavity. Select parameters that shift the equilibrium towards desired species are also identified.

Advanced characterization of magnetization dynamics in iron oxide magnetic nanoparticle tracers.

Characterization of the magnetization dynamics of single-domain magnetic nanoparticles (MNPs) is important for magnetic particle imaging (MPI), magnetic resonance imaging (MRI), and emerging medical diagnostic/therapeutic technologies. Depending on particle size and temperature, nanoparticle magnetization relaxation time constants span from nanoseconds to seconds. In solution, relaxation occurs via coupled Brownian and Néel relaxation mechanisms. Even though their coexistence complicates analysis, the presence of two timescales presents opportunities for more direct control of magnetization behavior if the two processes can be understood, isolated, and tuned. Using high frequency coils and sample temperature tunability, we demonstrate unambiguous determination of the specific relaxation processes for iron oxide nanoparticles using both time and frequency domain techniques. Furthermore, we study the evolution of the fast dynamics at ≈ 10 nanosecond timescales, for magnetic field amplitudes relevant to MPI.

The effects of intraparticle structure and interparticle interactions on the magnetic hysteresis loop of magnetic nanoparticles.

Technologically relevant magnetic nanoparticles for biomedicine are rarely noninteracting single-domain nanoparticles; instead, they are often interacting, with complex physical and magnetic structures. In this paper, we present both experimental and simulated magnetic hysteresis loops of a system of magnetic nanoparticles with significant interparticle interactions and a well-defined intraparticle structure which are used for magnetic nanoparticle hyperthermia cancer treatment. Experimental measurements were made at 11 K on suspensions of magnetic nanoparticles dispersed in H2O which have been frozen in a range of applied magnetic fields to tune the interparticle interactions. Micromagnetic simulations of hysteresis loops investigated the roles of particle orientation with respect to the field and of particle chaining in the shape of the hysteresis loops. In addition, we present an analysis of the magnetic anisotropy arising from the combination of magnetocrystalline and shape anisotropy, given the well-defined internal structure of the nanoparticles. We find that the shape of the experimental hysteresis loops can be explained by the internal magnetic structure, modified by the effects of interparticle interactions from chaining.

Improvement of Reproducibility of Magnetic Moment Detected by a SQUID Magnetometer Through Radial Offset Measurement on a YIG Sphere.

We report here on the reproducibility of measurements on a second-order gradiometer superconducting quantum interference device magnetometer of two different yttrium iron garnet spheres, both having a diameter of 1 mm: 1) the National Institute of Standards and Technology magnetic moment standard reference material (SRM) and 2) a commercial sample. It has been suggested that rotating the sample rod around its axis can move the sample center toward the center of the second-order gradiometer coil. The observed value of the magnetic moment will be theoretically a minimum when the radial offset is 0, and this value will increase in a "quadratic" manner with the radial offset. When the magnetic moment of the SRM was repeatedly measured as a function of rotation angle φ from 0° to 360°, we observed a sinusoidal variation in the measured values. The radial offset dependence of the observed magnetic moment was experimentally confirmed by the measurements of the commercial sphere placed in a hole in several cylindrical containers, wherein the distance between the center of the hole and the center of the container was r. The r-dependence of the minimum from each φ-dependent measurement series is qualitatively consistent with the theoretical curve. When the φ-dependent measurements for the SRM in a capsule were repeated 12× over 21 months, the relative standard deviation of the minimums improved up to 0.1%. Knowledge of these facts will be necessary for the accurate measurement of the magnetic moment of other sample forms (e.g., powders).

Nanoparticle architecture preserves magnetic properties during coating to enable robust multi-modal functionality.

Magnetic iron oxide nanoparticles (MIONs) have established a niche as a nanomedicine platform for diagnosis and therapy, but they present a challenging surface for ligand functionalization which limits their applications. On the other hand, coating MIONs with another material such as gold to enhance these attachments introduces other complications. Incomplete coating may expose portions of the iron oxide core, or the coating process may alter their magnetic properties. We describe synthesis and characterization of iron oxide/silica/gold core-shell nanoparticles to elucidate the effects of a silica-gold coating process and its impact on the resulting performance. In particular, small angle neutron scattering reveals silica intercalates between iron oxide crystallites that form the dense core, likely preserving the magnetic properties while enabling formation of a continuous gold shell. The synthesized silica-gold-coated MIONs demonstrate magnetic heating properties consistent with the original iron oxide core, with added x-ray contrast for imaging and laser heating.

Measurement and modeling of polarized specular neutron reflectivity in large magnetic fields.

The presence of a large applied magnetic field removes the degeneracy of the vacuum energy states for spin-up and spin-down neutrons. For polarized neutron reflectometry, this must be included in the reference potential energy of the Schrödinger equation that is used to calculate the expected scattering from a magnetic layered structure. For samples with magnetization that is purely parallel or antiparallel to the applied field which defines the quantization axis, there is no mixing of the spin states (no spin-flip scattering) and so this additional potential is constant throughout the scattering region. When there is non-collinear magnetization in the sample, however, there will be significant scattering from one spin state into the other, and the reference potentials will differ between the incoming and outgoing wavefunctions, changing the angle and intensities of the scattering. The theory of the scattering and recommended experimental practices for this type of measurement are presented, as well as an example measurement.

Bio-Nano-Magnetic Materials for Localized Mechanochemical Stimulation of Cell Growth and Death.

Magnetic nanoparticles are promising new tools for therapeutic applications, such as magnetic nanoparticle hyperthermia therapy and targeted drug delivery. Recent in vitro studies have demonstrated that a force application with magnetic tweezers can also affect cell fate, suggesting a therapeutic potential for magnetically modulated mechanical stimulation. The magnetic properties of nanoparticles that induce physical responses and the subtle responses that result from mechanically induced membrane damage and/or intracellular signaling are evaluated. Magnetic particles with various physical, geometric, and magnetic properties and specific functionalization can now be used to apply mechanical force to specific regions of cells, which permit the modulation of cellular behavior through the use of spatially and time controlled magnetic fields. On one hand, mechanochemical stimulation has been used to direct the outgrowth on neuronal growth cones, indicating a therapeutic potential for neural repair. On the other hand, it has been used to kill cancer cells that preferentially express specific receptors. Advances made in the synthesis and characterization of magnetic nanomaterials and a better understanding of cellular mechanotransduction mechanisms may support the translation of mechanochemical stimulation into the clinic as an emerging therapeutic approach.

Chloride-bridged, defect-dicubane {Ln4} core clusters: syntheses, crystal structures and magnetic properties.

Three chloride-bridged lanthanide compounds, [Ln4Cl6(CH3OH)12(OH)2]·4Cl·2CH3OH [Ln = Gd (), Dy () and Er ()], have been unexpectedly isolated by the reactions of LnCl3·6H2O and N,N'-bis(salicylidene)-1,2-(phenylene-diamine) (H2L). X-ray crystallographic analysis reveals a triclinic cell with a unique defect-dicubane {Ln4} core and the structure across this series is nominally isomorphic. Measurements of direct current magnetic susceptibility and isothermal magnetization give insight into the relevant cluster Hamiltonians for , , and , and alternating current susceptibility shows slow relaxation in , but not in or down to 2 K and up to 1 kHz.

Physics of heat generation using magnetic nanoparticles for hyperthermia.

Magnetic nanoparticle hyperthermia and thermal ablation have been actively studied experimentally and theoretically. In this review, we provide a summary of the literature describing the properties of nanometer-scale magnetic materials suspended in biocompatible fluids and their interactions with external magnetic fields. Summarised are the properties and mechanisms understood to be responsible for magnetic heating, and the models developed to understand the behaviour of single-domain magnets exposed to alternating magnetic fields. Linear response theory and its assumptions have provided a useful beginning point; however, its limitations are apparent when nanoparticle heating is measured over a wide range of magnetic fields. Well-developed models (e.g. for magnetisation reversal mechanisms and pseudo-single domain formation) available from other fields of research are explored. Some of the methods described include effects of moment relaxation, anisotropy, nanoparticle and moment rotation mechanisms, interactions and collective behaviour, which have been experimentally identified to be important. Here, we will discuss the implicit assumptions underlying these analytical models and their relevance to experiments. Numerical simulations will be discussed as an alternative to these simple analytical models, including their applicability to experimental data. Finally, guidelines for the design of optimal magnetic nanoparticles will be presented.

Magnetic differentiation of pyrogallol[4]arene tubular and capsular frameworks.

The differences in magnetic properties of metal-based nanometric assemblies are due to distinct contributions from host-guest interactions, structural integrity, and magnetic interactions. To disentangle these contributions, it is necessary to control the self-assembly process that forms these entities. Herein we study the effect of host-to-guest ratios to identify remarkably different structural-magnetic contributions of C-methylpyrogallol[4]arene⊂ferrocene/(PgC1)2⊂Fc dimers vs (PgC1)3⊂Fc nanotubes. At low temperature, a weak anti-ferromagnetic alignment is observed, suggesting a weak dipolar interaction between Fc guest moieties within adjacent dimers or tubes. Also, differences are observed between magnetic atom occupancy as a function of guest (PgC1⊂Fc tube/dimer) versus magnetic atom occupancy within the framework wall (PgC3Ni hexamer/dimer). Identification of the role of the framework shape and metal-metal distances in the crystal lattice opens up unparalleled prospects for materials engineering.

Exploring the magnetic behavior of nickel-coordinated pyrogallol[4]arene nanocapsules.

The magnetic behavior of nickel-seamed C-propylpyrogallol[4]arene dimeric and hexameric nanocapsular assemblies has been investigated in the solid state using a SQUID magnetometer. These dimeric and hexameric capsular entities show magnetic differentiation both in terms of moment per nanocapsule and potential antiferromagnetic interactions within individual nanocapsules. The weak antiferromagnetic behavior observed at low temperatures indicates dipolar interactions between neighboring nickel atoms; however, this effect is higher in the hexameric nickel-seamed assembly. The differences in magnetic behavior of dimer versus hexamer can be attributed to different coordination environments and metal arrangements in the two nanocapsular assemblies.

Thin-film solid-state proton NMR measurements using a synthetic mica substrate: polymer blends.

Solid-state proton nuclear magnetic resonance (NMR) measurements are performed successfully on polymer blend thin films through the use of synthetic mica as a substrate. When used as a substrate, synthetic fluorophlogopite mica with its proton-free, diamagnetic character, allows for adequate measurement sensitivity while minimally perturbing the proton thin-film spectra, especially relative to more commonly available natural micas. Specifically, we use multiple-pulse techniques in the presence of magic-angle spinning to measure the degree of mixing in two different polymer blend thin films, polystyrene/poly(xylylene ether) and poly(1-methyladamantyl methacrylate) (PMAdMA)/triphenylsulfonium perfluorobutanesulfonate (TPS-PFBS), spin-coated onto mica substrates. Our earlier studies had focused on bulk systems where NMR signals are stronger, but may not be representative of thin films of the same systems that are relevant to many applications such as photoresist formulations in the electronics industry. The superiority of synthetic over natural paramagnetic mica is demonstrated by the maintenance of resolution and spinning sideband intensities (relative to bulk samples) for the synthetic mica samples. In contrast, degraded resolution and large spinning sidebands are shown to typify spectra of the natural mica samples. This approach can be applied to many other proton measurements of solid thin films, thereby greatly extending the types of systems to be investigated. Magnetic susceptibility measurements are also reported for all micas used.

Optical and electron microscopy studies of Schiller layer formation and structure.

Iridescent Schiller layers were prepared by centrifugation of beta-FeOOH sols with an initial particle concentration of 10(14) particles/mL, reducing the Schiller layer formation time from over 2 months to 3 weeks. The formation and structure of the Schiller layers were investigated using optical and transmission electron microscopy. Microscopy studies revealed the self-assembly to proceed by the formation of two-dimensional particle arrays followed by the stacking of these arrays to form the final iridescent state. Varying the pH showed that Schiller layer formation occurs only in the pH range 1.4-2.0, indicating that electrostatic interactions play a pivotal role in the self-assembly. Decreasing the particle concentration of the sols was found to inhibit the assembly. DLVO theory and order-disorder phase transition models were found to be insufficient to accurately model the experimental behavior. Several approaches were investigated in an attempt to make ferrimagnetic arrays from the Schiller layers. The most promising was via electron beam irradiation, which transforms the beta-FeOOH into gamma-Fe(2)O(3) without altering the shape of the nanorods.

Influence of the colloidal environment on the magnetic behavior of cobalt nanoparticles.

The magnetic properties of 10 nm diameter surfactant-coated cobalt (Co) nanoparticles in 1,2-dichlorobenzene (DCB) are investigated by a series of sequential magnetic moment (m) vs temperature (T) measurements. A rapid rise in magnetic moment around 250 K during warming and an abrupt drop at 234 K during cooling are observed when a nonsaturating external magnetic field is applied. Differential scanning calorimetry (DSC) measurements demonstrate that the rapid rise and abrupt drop in magnetization are associated with the melting and freezing of the solvent. Magnetic measurements of these Co nanoparticles in DCB are also used to probe their aging over a period of 70 days. The saturation magnetic moment of Co nanoparticles in DCB stored in air at room temperature decreases by nearly 40% over 70 days. Transmission electron microscopy (TEM) characterizations are reported to show the time evolution in the size, shape, and crystalline structures of DCB-immersed nanoparticles.