Exploring the Magnetic Properties of Individual Barcode Nanowires using Wide-Field Diamond Microscopy.

A barcode magnetic nanowire typically comprises a multilayer magnetic structure in a single body with more than one segment type. Interestingly, due to selective functionalization and novel interactions between the layers, it has attracted significant attention, particularly in bioengineering. However, analyzing the magnetic properties at the individual nanowire level remains challenging. Herein, the characterization of a single magnetic nanowire is investigated at room temperature under ambient conditions based on magnetic images obtained via wide-field quantum microscopy with nitrogen-vacancy centers in diamond. Consequently, critical magnetic properties of a single nanowire can be extracted, such as saturation magnetization and coercivity, by comparing the experimental result with that of micromagnetic simulation. This study opens up the possibility for a versatile in situ characterization method suited to individual magnetic nanowires.

Interwire and Intrawire Magnetostatic Interactions in Fe-Au Barcode Nanowires with Alternating Ferromagnetically Strong and Weak Segments.

Metallic barcode nanowires (BNWs) composed of repeating heterogeneous segments fabricated by template-assisted electrodeposition can offer extended functionality in magnetic, electrical, mechanical, and biomedical applications. The authors consider such nanostructures as a 3D system of magnetically interacting elements with magnetic behavior strongly affected by complex magnetostatic interactions. This study discusses the influence of geometrical parameters of segments on the character of their interactions and the overall magnetic behavior of the array of BNWs having alternating magnetization, because the Fe and Au segments are made of Fe-Au alloys with high and low magnetizations. By controlling the applied current densities and the elapsed time in the electrodeposition, the dimension of the Fe-Au BNWs can be regulated. This study reveals that the influence of the length of magnetically weak Au segments on the interaction field between nanowires is different for samples with magnetically strong 100 and 200 nm long Fe segments using the first-order reversal curve (FORC) diagram method. With the help of micromagnetic simulations, three types of magnetostatic interactions in the BNW arrays are discovered and analy. This study demonstrates that the dominating type of interaction depends on the geometric parameters of the Fe and Au segments and the interwire and intrawire distances.

Inorganic Hollow Nanocoils Fabricated by Controlled Interfacial Reaction and Their Electrocatalytic Properties.

The fabrication of 3D hollow nanostructures not only allows the tactical provision of specific physicochemical properties but also broadens the application scope of such materials in various fields. The synthesis of 3D hollow nanocoils (HNCs), however, is limited by the lack of an appropriate template or synthesis method, thereby restricting the wide-scale application of HNCs. Herein, a strategy for preparing HNCs by harnessing a single sacrificial template to modulate the interfacial reaction at a solid-liquid interface that allows the shape-regulated transition is studied. Furthermore, the triggering of the Kirkendall effect in 3D HNCs is demonstrated. Depending on the final state of the transition metal ions reduced during the electrochemical preparation of HNCs, the surface states of the binding anions and the composition of the HNCs can be tuned. In a single-component CrPO4 HNC with a clean surface, the Kirkendall effect of the coil shape is analyzed at various points throughout the reaction. The rough-surface multicomponent MnOx P0.21 HNCs are complexed with ligand-modified BF4 -Mn3 O4 nanoparticles. The fabricated nanocomposite exhibits an overpotential decrease of 25 mV at neutral pH compared to pure BF4 -Mn3 O4 nanoparticles because of the increased active surface area.

Magnetic Control and Real-Time Monitoring of Stem Cell Differentiation by the Ligand Nanoassembly.

Native extracellular matrix (ECM) exhibits dynamic change in the ligand position. Herein, the ECM-emulating control and real-time monitoring of stem cell differentiation are demonstrated by ligand nanoassembly. The density of gold nanoassembly presenting cell-adhesive Arg-Gly-Asp (RGD) ligand on Fe3 O4 (magnetite) nanoparticle in nanostructures flexibly grafted to material is changed while keeping macroscale ligand density invariant. The ligand nanoassembly on the Fe3 O4 can be magnetically attracted to mediate rising and falling ligand movements via linker stretching and compression, respectively. High ligand nanoassembly density stimulates integrin ligation to activate the mechanosensing-assisted stem cell differentiation, which is monitored via in situ real-time electrochemical sensing. Magnetic control of rising and falling ligand movements hinders and promotes the adhesion-mediated mechanotransduction and differentiation of stem cells, respectively. These rising and falling ligand states yield the difference in the farthest distance (≈34.6 nm) of the RGD from material surface, thereby dynamically mimicking static long and short flexible linkers, which hinder and promote cell adhesion, respectively. Design of cytocompatible ligand nanoassemblies can be made with combinations of dimensions, shapes, and biomimetic ligands for remotely regulating stem cells for offering novel methodologies to advance regenerative therapies.

Large and Externally Positioned Ligand-Coated Nanopatches Facilitate the Adhesion-Dependent Regenerative Polarization of Host Macrophages.

Macrophages can associate with extracellular matrix (ECM) demonstrating nanosequenced cell-adhesive RGD ligand. In this study, we devised barcoded materials composed of RGD-coated gold and RGD-absent iron nanopatches to show various frequencies and position of RGD-coated nanopatches with similar areas of iron and RGD-gold nanopatches that maintain macroscale and nanoscale RGD density invariant. Iron patches were used for substrate coupling. Both large (low frequency) and externally positioned RGD-coated nanopatches stimulated robust attachment in macrophages, compared with small (high frequency) and internally positioned RGD-coated nanopatches, respectively, which mediate their regenerative/anti-inflammatory M2 polarization. The nanobarcodes exhibited stability in vivo. We shed light into designing ligand-engineered nanostructures in an external position to facilitate host cell attachment, thereby eliciting regenerative host responses.

In Situ Magnetic Control of Macroscale Nanoligand Density Regulates the Adhesion and Differentiation of Stem Cells.

Developing materials with remote controllability of macroscale ligand presentation can mimic extracellular matrix (ECM) remodeling to regulate cellular adhesion in vivo. Herein, we designed charged mobile nanoligands with superparamagnetic nanomaterials amine-functionalized and conjugated with polyethylene glycol linker and negatively charged RGD ligand. We coupled negatively a charged nanoligand to a positively charged substrate by optimizing electrostatic interactions to allow reversible planar movement. We demonstrate the imaging of both macroscale and in situ nanoscale nanoligand movement by magnetically attracting charged nanoligand to manipulate macroscale ligand density. We show that in situ magnetic control of attracting charged nanoligand facilitates stem cell adhesion, both in vitro and in vivo, with reversible control. Furthermore, we unravel that in situ magnetic attraction of charged nanoligand stimulates mechanosensing-mediated differentiation of stem cells. This remote controllability of ECM-mimicking reversible ligand variations is promising for regulating diverse reparative cellular processes in vivo.

Multi-Component Mesocrystalline Nanoparticles with Enhanced Photocatalytic Activity.

Mesocrystals, consisting of small subunits, have gained research interests owing to their ability to simultaneously modify material-specific properties and interactions among subunits. However, despite these unique characteristics, most mesocrystals are composed of a single material, and there is a disjunction between academic discovery and practical application. In this study, the synthesis of multi-component mesocrystalline nanoparticles composed of Fe3 O4 , ZnFe2 O4 , and ZnO subunits using a polymerization induced heterogeneous nucleation method is reported. The structure has small ZnFe2 O4 and ZnO nanocrystals covering the Fe3 O4 crystallites. It exhibits not only magnetic and catalytic properties determined by the size of each subunit nanocrystal, but also enhances photocatalytic and colloidal properties that originates because of its crowded arrangement. The magnetically recoverable catalysts exhibit remarkable photodegradation of organic molecules under the irradiation of visible light for 1 h; thus, improving its applicability in purifying a large amount of wastewater during the daytime.

One-Step Electrochemical Synthesis of Multiyolk-Shell Nanocoils for Exceptional Photocatalytic Performance.

Multiyolk-shell (mYS) nanostructures have garnered significant interest in various photocatalysis applications such as water splitting and waste treatment. Nonetheless, the complexity and rigorous conditions for the synthesis have hindered their widespread implementation. This study presents a one-step electrochemical strategy for synthesizing multiyolk-shell nanocoils (mYSNC), wherein multiple cores of noble metal nanoparticles, such as Au, are embedded within the hollow coil-shaped FePO4 shell structures, mitigating the challenges posed by conventional methods. By capitalizing on the dissimilar dissolution rates of bimetallic alloy nanocoils in an electrochemically programmed solution, nanocoils of different shapes and materials, including two variations of mYSNCs are successfully fabricated. The resulting Au-FePO4 mYSNCs exhibit exceptional photocatalytic performance for environmental remediation, demonstrating up to 99% degradation of methylene blue molecules within 50 min and 95% degradation of tetracycline within 100 min under ultraviolet-visible (UV-vis) light source. This remarkable performance can be attributed to the abundant electrochemical active sites, internal voids facilitating efficient light harvesting with coil morphology, amplified localized surface plasmon resonance (LSPR) at the plasmonic nanoparticle-semiconductor interface, and effective band engineering. The innovative approach utilizing bimetallic alloys demonstrates precise geometric control and design of intricate multicomponent hybrid composites, showcasing the potential for developing versatile hollow nanomaterials for catalytic applications.

Submolecular Ligand Size and Spacing for Cell Adhesion.

Cell adhesion occurs when integrin recognizes and binds to Arg-Gly-Asp (RGD) ligands present in fibronectin. In this work, submolecular ligand size and spacing are tuned via template-mediated in situ growth of nanoparticles for dynamic macrophage modulation. To tune liganded gold nanoparticle (GNP) size and spacing from 3 to 20 nm, in situ localized assemblies of GNP arrays on nanomagnetite templates are engineered. 3 nm-spaced ligands stimulate the binding of integrin, which mediates macrophage-adhesion-assisted pro-regenerative polarization as compared to 20 nm-spaced ligands, which can be dynamically anchored to the substrate for stabilizing integrin binding and facilitating dynamic macrophage adhesion. Increasing the ligand size from 7 to 20 nm only slightly promotes macrophage adhesion, not observed with 13 nm-sized ligands. Increasing the ligand spacing from 3 to 17 nm significantly hinders macrophage adhesion that induces inflammatory polarization. Submolecular tuning of ligand spacing can dominantly modulate host macrophages.

Remote Control of Time-Regulated Stretching of Ligand-Presenting Nanocoils In Situ Regulates the Cyclic Adhesion and Differentiation of Stem Cells.

Native extracellular matrix (ECM) can exhibit cyclic nanoscale stretching and shrinking of ligands to regulate complex cell-material interactions. Designing materials that allow cyclic control of changes in intrinsic ligand-presenting nanostructures in situ can emulate ECM dynamicity to regulate cellular adhesion. Unprecedented remote control of rapid, cyclic, and mechanical stretching ("ON") and shrinking ("OFF") of cell-adhesive RGD ligand-presenting magnetic nanocoils on a material surface in five repeated cycles are reported, thereby independently increasing and decreasing ligand pitch in nanocoils, respectively, without modulating ligand-presenting surface area per nanocoil. It is demonstrated that cyclic switching "ON" (ligand nanostretching) facilitates time-regulated integrin ligation, focal adhesion, spreading, YAP/TAZ mechanosensing, and differentiation of viable stem cells, both in vitro and in vivo. Fluorescence resonance energy transfer (FRET) imaging reveals magnetic switching "ON" (stretching) and "OFF" (shrinking) of the nanocoils inside animals. Versatile tuning of physical dimensions and elements of nanocoils by regulating electrodeposition conditions is also demonstrated. The study sheds novel insight into designing materials with connected ligand nanostructures that exhibit nanocoil-specific nano-spaced declustering, which is ineffective in nanowires, to facilitate cell adhesion. This unprecedented, independent, remote, and cytocompatible control of ligand nanopitch is promising for regulating the mechanosensing-mediated differentiation of stem cells in vivo.

Heat-Generating Iron Oxide Multigranule Nanoclusters for Enhancing Hyperthermic Efficacy in Tumor Treatment.

The development of heat-generating magnetic nanostructures is critical for the effective management of tumors using magnetic hyperthermia. Herein, we demonstrate that polyethylene glycol (PEG)-coated iron oxide (magnetite, Fe3O4) multigranule nanoclusters (PEG-MGNCs) can enhance the efficiency of hyperthermia-based tumor suppression in vitro and in vivo. MGNCs consisting of granules (crystallites) measuring 22.9 nm in diameter were prepared via the hydrothermal polyol method, followed by the surface modification of MGNCs with PEG-dopamine. The freshly prepared PEG-MGNCs exhibit 145.9 ± 10.2 nm diameter on average under aqueous conditions. The three-dimensional structures of PEG-MGNCs enhance the hyperthermic efficacy compared with PEGylated single iron-oxide nanoparticles (NPs), resulting in severe heat damage to tumor cells in vitro. In the SCC7 tumor-bearing mice, near-infrared fluorescence dye (Cy5.5)-labeled PEG-MGNCs are successfully accumulated in the tumor tissues because of NP-derived enhanced permeation and retention effect. Finally, the tumor growth is significantly suppressed in PEG-MGNC-treated mice after two-times heat generation by using a longitudinal solenoid, which can generate an alternating magnetic field under high-frequency (19.5 kA/m, 389 kHz) induction. This study shows for the first time that the PEG-MGNCs greatly enhance the hyperthermic efficacy of tumor treatment both in vitro and in vivo.

Independent Tuning of Nano-Ligand Frequency and Sequences Regulates the Adhesion and Differentiation of Stem Cells.

The native extracellular matrix (ECM) can exhibit heterogeneous nano-sequences periodically displaying ligands to regulate complex cell-material interactions in vivo. Herein, an ECM-emulating heterogeneous barcoding system, including ligand-bearing Au and ligand-free Fe nano-segments, is developed to independently present tunable frequency and sequences in nano-segments of cell-adhesive RGD ligand. Specifically, similar exposed surface areas of total Fe and Au nano-segments are designed. Fe segments are used for substrate coupling of nanobarcodes and as ligand-free nano-segments and Au segments for ligand coating while maintaining both nanoscale (local) and macroscale (total) ligand density constant in all groups. Low nano-ligand frequency in the same sequences and terminally sequenced nano-ligands at the same frequency independently facilitate focal adhesion and mechanosensing of stem cells, which are collectively effective both in vitro and in vivo, thereby inducing stem cell differentiation. The Fe/RGD-Au nanobarcode implants exhibit high stability and no local and systemic toxicity in various tissues and organs in vivo. This work sheds novel insight into designing biomaterials with heterogeneous nano-ligand sequences at terminal sides and/or low frequency to facilitate cellular adhesion. Tuning the electrodeposition conditions can allow synthesis of unlimited combinations of ligand nano-sequences and frequencies, magnetic elements, and bioactive ligands to remotely regulate numerous host cells in vivo.

Metallic Fe-Au Barcode Nanowires as a Simultaneous T Cell Capturing and Cytokine Sensing Platform for Immunoassay at the Single-Cell Level.

Barcode nanowires (BNWs) composed of multiple layered segments of different materials are attractive to bioengineering field due to their characteristics that allow the adjustment of physicochemical properties and conjugation with two or more types of biomolecules to facilitate multiple tasks. Here, we report a metallic Fe (iron)-Au (gold) BNW-based platform for capturing CD8 T cells and the interferon-γ (γ) they secrete, both of which play key roles in controlling infectious diseases such as tuberculosis, at the single-cell level. We also describe an efficient approach for conjugating distinct antibodies, which recognize different epitopes to appropriate materials. The platform achieved detection even with 4.45-35.6 µg mL-1 of BNWs. The T cell capture efficiency was close to 100% and the detection limit for interferon-γ was 460 pg mL-1. This work presents a potential guideline for the design of single-cell immunoassay platforms for eliminating diagnostic errors by unambiguously identifying disease-relevant immune mediators.

MnO2 Nanowire-CeO2 Nanoparticle Composite Catalysts for the Selective Catalytic Reduction of NO x with NH3.

MnO x-based catalysts have been applied to the selective catalytic reduction of NO x with ammonia (NH3) owing to their high NO x removal efficiency and catalytic stability. In general, the fabrication of a variety of nanomaterials in a complex structure requires complicated processes, including heat treatment and a series of cleaning steps. In addition, MnO2 which has diverse polymorphs, exhibits different catalytic effects depending on its crystalline structure. Among them, synthesizing the ε-MnO2 phase, which functions as a nanocatalyst, has been the most difficult and has hardly been reported. Here, we report the synthesis of heterostructured composite nanocatalysts consisting of ε-MnO2 nanowires (NWs) and CeO2 nanoparticles (NPs) by applying pulsed currents sequentially. This method drastically simplifies the overall process compared to the conventional techniques. Through X-ray diffraction and transmission electron microscopy, it was confirmed that 2-3 nm of CeO2 NPs were formed on the surfaces of the ε-MnO2 NWs. The de-NO x efficiency of the nanocatalysts was analyzed in terms of content variation, specific surface area, and the elemental chemical state of the surface. A ceramic filter containing the nanocatalysts shows a high catalytic activity over the broad operating temperature range 100-400 °C. In the low-temperature region, ε-MnO2 plays a major role in determining the catalytic property, which is consistent with the Brunauer-Emmett-Teller (BET), H2 temperature-programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS) results. On the other hand, in the high-temperature region, the efficiency increases gradually as the content of CeO2 increases. The H2 TPR, NH3-temperature-programmed desorption, and XPS patterns reveal why the composite exhibits such superior characteristics in the temperature range mentioned above.

Magnetization reversal of ferromagnetic nanosprings affected by helical shape.

Helicity, a natural property of macro-, micro-, and nano-objects, potentially offers a new dimension to mechanical and electromagnetic applications for creating emerging nanodevices, such as nanorobots, nanomagnets, nanosensors, and high-density magnetic memory. Helical magnetic nanosprings are unique objects with remarkable magnetic properties, including the absence of stray fields in remanence owing to the chiral geometry, which makes them promising for data storage devices, nanoelectromechanical systems, and biomedical usage. Here, we investigated Co and CoFe nanospring arrays electrodeposited in highly ordered nanoporous templates. We report helical-shape-driven magnetization reversal of the nanosprings in comparison with the behavior of dipolarly coupled nanowires. We reveal two magnetization reversal modes depending on the orientation of the external magnetic field: coherent rotation of magnetization in the longitudinal geometry and three-dimensional vortex domain wall motion in the transverse geometry. The experimental findings are supported by analytical calculations and micromagnetic simulations that help to explain the field-dependent spin configurations observed by magnetic force microscopy.

Synthesis of Co nanotubes by nanoporous template-assisted electrodeposition via the incorporation of vanadyl ions.

We report a facile fabrication concept for nanotubes (NTs) based upon template-assisted electrodeposition, which is widely applied for metallic nanowire (NW) synthesis. Co NTs have been synthesized into nanoporous anodized aluminum oxide (AAO) templates via electrodeposition by simply adding a small amount of chemicals including vanadyl ions (VO2+).

Synthesis of Fe Doped ZnO Nanowire Arrays that Detect Formaldehyde Gas.

Owing to their chemical and thermal stability and doping effects on providing electrons to the conduction band, doped ZnO nanowires have generated interest for use in electronic devices. Here we report hydrothermally grown Fe-doped ZnO nanowires and their gas-sensing properties. The synthesized nanowires have a high crystallinity and are 60 nm in diameter and 1.7 µm in length. Field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) are employed to understand the doping effects on the microstructures and gas sensing properties. When the Fe-doped ZnO nanowire arrays were evaluated for gas sensing, responses were recorded through changes in temperature and gas concentration. Gas sensors consisting of ZnO nanowires doped with 3-5 at.% Fe showed optimum formaldehyde (HCHO) sensing performance at each working temperature.