We have studied the growth of ordered arrays by evaporation-induced self-assembly of iron oxide nanocubes with edge lengths of 6.8 and 10.1 nm using video microscopy (VM) and quartz crystal microbalance with dissipation monitoring (QCM-D). Ex situ electron diffraction of the ordered arrays demonstrates that the crystal axes of the nanocubes are coaligned and confirms that the ordered arrays are mesocrystals. Time-resolved video microscopy shows that growth of the highly ordered arrays at slow solvent evaporation is controlled by particle diffusion and can be described by a simple growth model. The growth of each mesocrystal depends only on the number of nanoparticles within the accessible region irrespective of the relative time of formation. The mass of the dried mesocrystals estimated from the analysis of the bandwidth-shift-to-frequency-shift ratio correlates well with the total mass of the oleate-coated nanoparticles in the deposited dispersion drop.

In this study we investigate the magnetic behavior of magnetic multi-core particles and the differences in the magnetic properties of multi-core and single-core nanoparticles and correlate the results with the nanostructure of the different particles as determined from transmission electron microscopy (TEM). We also investigate how the effective particle magnetic moment is coupled to the individual moments of the single-domain nanocrystals by using different measurement techniques: DC magnetometry, AC susceptometry, dynamic light scattering and TEM. We have studied two magnetic multi-core particle systems BNF Starch from Micromod with a median particle diameter of 100 am and FeraSpin R from nanoPET with a median particle diameter of 70 nm - and one single-core particle system - SHP25 from Ocean NanoTech with a median particle core diameter of 25 nm. (C) 2014 Elsevier B.V. All rights reserved.

We investigated, in depth, the interrelations among structure, magnetic properties, relaxation dynamics and magnetic hyperthermia performance of magnetic nanoflowers. The nanoflowers are about 39 nm in size, and consist of densely packed iron oxide cores. They display a remanent magnetization, which we explain by the exchange coupling between the cores, but we observe indications for internal spin disorder. By polarized small-angle neutron scattering, we unambiguously confirm that, on average, the nano flowers are preferentially magnetized along one direction. The extracted discrete relaxation time distribution of the colloidally dispersed particles indicates the presence of three distinct relaxation contributions. We can explain the two slower processes by Brownian and classical Neel relaxation, respectively. The additionally observed very fast relaxation contributions are attributed by us to the relaxation of disordered spins within the nanoflowers. Finally, we show that the intrinsic loss power (ILP, magnetic hyperthermia performance) of the nanoflowers measured in colloidal dispersion at high frequency is comparatively large and independent of the viscosity of the surrounding medium. This concurs with our assumption that the observed relaxation in the high frequency range is primarily a result of internal spin relaxation, and possibly connected to the disordered spins within the individual nanoflowers.

The assembly of magnetic cores into regular structures may notably influence the properties displayed by a magnetic colloid. Here, key synthesis parameters driving the self-assembly process capable of organizing colloidal magnetic cores into highly regular and reproducible multi-core nanoparticles are determined. In addition, a self-consistent picture that explains the collective magnetic properties exhibited by these complex assemblies is achieved through structural, colloidal, and magnetic means. For this purpose, different strategies to obtain flower-shaped iron oxide assemblies in the size range 25-100 nm are examined. The routes are based on the partial oxidation of Fe(OH)(2), polyol-mediated synthesis or the reduction of iron acetylacetonate. The nanoparticles are functionalized either with dextran, citric acid, or alternatively embedded in polystyrene and their long-term stability is assessed. The core size is measured, calculated, and modeled using both structural and magnetic means, while the Debye model and multi-core extended model are used to study interparticle interactions. This is the first step toward standardized protocols of synthesis and characterization of flower-shaped nanoparticles.

The manuscript reports the investigation of spin disorder in maghemite nanoparticles of different shape by a combination of polarized small -angle neutron scattering (SANSPOL) and nuclear forward scattering (NFS) techniques. Both methods are sensitive to magnetization on the nanoscale. SANSPOL allows for investigation of the particle morphology and spatial magnetization distribution and NFS extends this nanoscale information to the atomic scale, namely the orientation of the hyperfine field experienced by the iron nuclei. The studied nanospheres and nanocubes with diameters of 7.4nm and 10.6 nm, respectively, exhibit a significant spin disorder. This effect leads to a reduction of the magnetization to 44 % and 58% of the theoretical maghemite bulk value, observed consistently by both techniques.

Understanding the assembly of nanoparticles into superlattices with well-defined morphology and structure is technologically important but challenging as it requires novel combinations of in-situ methods with suitable spatial and temporal resolution. In this study, we have followed evaporation-induced assembly during drop casting of superparamagnetic, oleate-capped gamma-Fe2O3 nanospheres dispersed in toluene in real time with Grazing Incidence Small Angle X-ray Scattering (GISAXS) in combination with droplet height measurements and direct observation of the dispersion. The scattering data was evaluated with a novel method that yielded time-dependent information of the relative ratio of ordered (coherent) and disordered particles (incoherent scattering intensities), superlattice tilt angles, lattice constants, and lattice constant distributions. We find that the onset of superlattice growth in the drying drop is associated with the movement of a drying front across the surface of the droplet. We couple the rapid formation of large, highly ordered superlattices to the capillary-induced fluid flow. Further evaporation of interstitital solvent results in a slow contraction of the superlattice. The distribution of lattice parameters and tilt angles was significantly larger for superlattices prepared by fast evaporation compared to slow evaporation of the solvent.

Antiphase boundaries (APBs) normally form as a consequence of the initial growth conditions in all spinel ferrite thin films. These boundaries result from the intrinsic nucleation and growth mechanism, and are observed as regions where the periodicity of the crystalline lattice is disrupted. The presence of APBs in epitaxial films of the inverse spinel Fe3O4 alters their electronic and magnetic properties due to strong antiferromagnetic (AF) interactions across these boundaries. We explore the effect of using in-plane in situ electric-field-assisted growth on the formation of APBs in heteroepitaxial Fe3O4(100)/MgO(100) thin films. The electric-field-assisted growth is found to reduce the AF interactions across APBs and, as a consequence, APB-free thin-film-like properties are obtained, which have been probed by electronic, magnetic, and structural characterization. The electric field plays a critical role in controlling the density of APBs during the nucleation process by providing an electrostatic force acting on adatoms and therefore changing their kinetics. This innovative technique can be employed to grow epitaxial spinel thin films with controlled AF interactions across APBs.

Silica (SiO2)-derived nanoadsorbents are a powerful and attractive tool for the extraction and separation of rare earth elements (REE) from many perspectives such as reusability, efficiency and minimum impact on the environment. In the present work, we investigated two different methods of adsorption down to the molecular level: (1) the mechanism of the coordination of different groups of REE (light, medium, heavy) with iminodiacetic acid (IDA) was revealed by exploiting models obtained from X-ray crystallography, explaining the selectivity of this type of ligand, and (2) the mechanism of the seeding of RE(OH)(3) initiated by SiO2-based nanoadsorbents was investigated by EXAFS, both individually and in combination with mechanism (1), showing the coexistence of both mechanisms. The REE loaded nanoadsorbents possess a high magnetic susceptibility. This property was studied by magnetometry to quantify the REE adsorption efficiency and compared with the values obtained from complexometry.

We have measured and analyzed three different commercial magnetic nanoparticle systems, both multi-core and single-core in nature, with the particle (core) size ranging from 20 to 100 nm. Complementary analysis methods and same characterization techniques were carried out in different labs and the results are compared with each other. The presented results primarily focus on determining the particle size-both the hydrodynamic size and the individual magnetic core size-as well as magnetic and structural properties. The used analysis methods include transmission electron microscopy, static and dynamic magnetization measurements, and Mossbauer spectroscopy. We show that particle (hydrodynamic and core) size parameters can be determined from different analysis techniques and the individual analysis results agree reasonably well. However, in order to compare size parameters precisely determined from different methods and models, it is crucial to establish standardized analysis methods and models to extract reliable parameters from the data.

Extended exposure to sunlight or artificial UV sources is a major cause of serious skin and eye diseases such as cancer. There is thus a great need for convenient materials for the easy monitoring of UV doses. While organic photochromic molecules are tunable for responses under different wavelengths of UV radiation, they suffer from rather poor durability because the color changes involve drastic changes in molecular structure. Inorganic materials, on the other hand, are durable, but they have lacked tunability. Here, by combining computational and empirical data, we confirm the mechanism of coloration in the hackmanites, nature-based materials, and introduce a new technique called thermotenebrescence. With knowledge of the mechanism, we show that we can control and thus tune the energy of electronic states of synthetic hackmanites (Na,M)(8)Al6Si6O24(Cl,S)(2) so that their body color is sensitive to the solar UV index as well as UVA, UVB or UVC radiation levels. Finally, we demonstrate that it is possible to use images taken with an inexpensive cell phone to quantify the radiation dose or UV index. The hackmanite materials thus show great potential for use in portable healthcare both in everyday life and in laboratories.

DNA-assembled nanoparticle superstructures offer numerous bioresponsive properties that can be utilized for point-of-care diagnostics. Functional DNA sequences such as deoxyribozymes (DNAzymes) provide novel bioresponsive strategies and further extend the application of DNA-assembled nanoparticle superstructures. In this work, we describe a microRNA detection biosensor that combines magnetic nanoparticle (MNP) assemblies with DNAzyme-assisted target recycling. The DNA scaffolds of the MNP assemblies contain substrate sequences for DNAzyme and can form cleavage catalytic structures in the presence of target DNA or RNA sequences, leading to rupture of the scaffolds and disintegration of the MNP assemblies. The target sequences are preserved during the cleavage reaction and release into the suspension to trigger the digestion of multiple DNA scaffolds. The high local concentration of substrate sequences in the MNP assemblies reduces the diffusion time for target recycling. The concentration of released MNPs, which is proportional to the concentration of the target, can be quantified by a 405 nm laser-based optomagnetic sensor. For the detection of let-7b in 10% serum, after 1 h of isothermal reaction at 50 degrees C, we found a linear detection range between 10 pM and 100 nM with a limit of detection of 6 pM. For the quantification of DNA target in buffer solution, a limit of detection of 1.5 pM was achieved. Compared to protein enzyme-based microRNA detection methods, the proposed DNAzyme-based biosensor has an increased stability, a reduced cost and a possibility to be used in living cells, all of which are valuable features for biosensing applications.

The ability to detect and analyze the state ofmagnetic labels with high sensitivity is of crucial importance fordeveloping magnetic biosensors. In this work, we demonstrate, forthefirst time, a ferromagnetic resonance (FMR) basedhomogeneous and volumetric biosensor for magnetic labeldetection. Two different isothermal amplification methods, i.e.,rolling circle amplification (RCA) and loop-mediated isothermalamplification (LAMP), are adopted and combined with a standardelectron paramagnetic resonance (EPR) spectrometer for FMRbiosensing. For the RCA-based FMR biosensor, binding of RCAproducts of a syntheticVibrio choleraetarget DNA sequence givesrise to the formation of aggregates of magnetic nanoparticles.Immobilization of nanoparticles within the aggregates leads to adecrease of the net anisotropy of the system and a concomitant increase of the resonancefield. A limit of detection of 1 pM isobtained with a linear detection range between 7.8 and 250 pM. For the LAMP-based sensing, a synthetic Zika virus targetoligonucleotide is amplified and detected in 20% serum samples. Immobilization of magnetic nanoparticles is induced by theircoprecipitation with Mg2P2O7(a byproduct of LAMP) and provides a detection sensitivity of 100 aM. The fast measurement,high sensitivity, and miniaturization potential of the proposed FMR biosensing technology makes it a promising candidate fordesigning future point-of-care devices.

We demonstrate a homogeneous biosensor for the detection of multivalent targets by combination of magnetic nanoparticle (MNP) chains and a low-cost 405 nm laser-based optomagnetic system. The MNP chains are assembled in a rotating magnetic field and stabilized by multivalent target molecules. The number of chains remaining in zero field is proportional to the target concentration, and can be quantified by optomagnetic measurements. The shape anisotropy of the MNP chains enhances the biosensor system in terms of providing efficient mixing, reduction of depletion effects (via magnetic shape anisotropy), and directly increasing the optomagnetic signal (via optical shape anisotropy). We achieve a limit of detection (LOD) of 5.5 pM (0.82 ng/mL) for the detection of a model multivalent molecule, biotinylated anti-streptavidin, in PBS. For the measurements of prostate-specific antigen (PSA) in 50% serum using the proposed method, we achieve an LOD of 21.6 pM (0.65 ng/mL) and a dynamic detection range up to 66.7 nM (2 µg/mL) with a sample-to-result time of approximately 20 min. The performance for PSA detection therefore well meets the clinical requirements in terms of LOD (the threshold PSA level in blood is 4 ng/mL) and detection range (PSA levels span from < 0.1–10⁴ ng/mL in blood), thus showing great promise for routine PSA diagnostics and for other in-situ applications.

Here we demonstrate how monodisperse iron oxide nanocubes and nanospheres with average sizes between 5 and 27 nm can be synthesized by thermal decomposition. The relative importance of the purity of the reactants, the ratio of oleic acid and sodium oleate, the maximum temperature, and the rate of temperature increase, on robust and reproducible size and shape-selective iron oxide nanoparticle synthesis are identified and discussed. The synthesis conditions that generate highly monodisperse iron oxide nanocubes suitable for producing large ordered arrays, or mesocrystals are described in detail.

The widespread use of magnetic nanoparticles in the biotechnical sector puts new demands on fast and quantitative characterization techniques for nanoparticle dispersions. In this work, we report the use of asymmetric flow field-flow fractionation (AF4) and ferromagnetic resonance (FMR) to study the properties of a commercial magnetic nanoparticle dispersion. We demonstrate the effectiveness of both techniques when subjected to a dispersion with a bimodal size/magnetic property distribution: i.e., a small superparamagnetic fraction, and a larger blocked fraction of strongly coupled colloidal nanoclusters. We show that the oriented attachment of primary nanocrystals into colloidal nanoclusters drastically alters their static, dynamic, and magnetic resonance properties. Finally, we show how the FMR spectra are influenced by dynamical effects; agglomeration of the superparamagnetic fraction leads to reversible line-broadening; rotational alignment of the suspended nanoclusters results in shape-dependent resonance shifts. The AF4 and FMR measurements described herein are fast and simple, and therefore suitable for quality control procedures in commercial production of magnetic nanoparticles.

One of the ultimate goals of nanocrystal self-assembly is to transform nanoscale building blocks into a material that displays enhanced properties relative to the sum of its parts. Herein, we demonstrate that 1D needle shaped assemblies composed of Fe3-delta O4 nanocubes display a significant augmentation of the magnetic susceptibility and dissipation as compared to OD and 2D systems. The performance of the nanocube needles is highlighted by a colossal anisotropy factor defined as the ratio of the parallel to the perpendicular magnetization components. We show that the origin of this effect cannot be ascribed to shape anisotropy in its classical sense; as such, it has no analogy in bulk magnetic materials. The temperature-dependent anisotropy factors of the in- and out-of-phase components of the magnetization have an extremely strong particle size dependence and reach values of 80 and 2500, respectively, for the largest nanocubes in this study. Aided by simulations, we ascribe the anisotropy of the magnetic susceptibility, and its strong particle-size dependence to a synergistic coupling between the dipolar interaction field and a net anisotropy field resulting from a partial texture in the 1D nanocube needles.