Heterometallic Gd-Dy Formate Frameworks for Enhanced Magnetocaloric Properties.

Lanthanide-based metal-organic frameworks (MOFs) have great potential as magnetic refrigerants under cryogenic conditions and are comparable to conventional alloys and magnetic nanoparticles. In particular, MOFs with Gd3+ ions behave as excellent magnetic refrigerants because of their large spin ground states. However, the major drawback of Gd3+-based MOFs is that they are not affected by the ligand material owing to the excessively large spin-only magnetic moment; therefore, their application is limited to the cryogenic region in the magnetic cooling field. In this study, we report the magnetic properties and magnetocaloric effect (MCE) resulting from heterogenized MOFs obtained from the reaction of Gd3+ and Dy3+ ions and their varied molar composition with the formate ligand. For GdxDy1-x-(HCOO)3, where 0 ≤ x ≤ 1, the isothermal magnetic entropy change (ΔSm) increased with the increase in the fraction of Gd in the heterogenized MOFs. Meanwhile, with increasing Dy contents, the maximum peak temperature of ΔSm is shifted to a higher temperature while preserving a relatively high ΔSm value of 22.35 J·kg-1 K-1 at T = 7 K for an applied field change (ΔH) of 7 T despite the anisotropy and crystalline electric field effects. Furthermore, it was confirmed that the samples with a Dy content of 75% or more maintained the ΔSm operating temperature longer. Therefore, the current approach of including Dy3+ ions in lanthanide compounds provides the possibility of further extending the operating temperature of magnetic cooling materials from cryogenic temperatures.

Light- and magnetically actuated FePt microswimmers.

Externally controlled microswimmers offer prospects for transport in biological research and medical applications. This requires biocompatibility of the swimmers and the possibility to tailor their propulsion mechanisms to the respective low Reynolds number environment. Here, we incorporate low amounts of the biocompatible alloy of iron and platinum (FePt) in its [Formula: see text] phase in microstructures by a versatile one-step physical vapor deposition process. We show that the hard magnetic properties of [Formula: see text] FePt are beneficial for the propulsion of helical micropropellers with rotating magnetic fields. Finally, we find that the FePt coatings are catalytically active and also make for Janus microswimmers that can be light-actuated and magnetically guided.

Superior Magnetic Performance in FePt L10 Nanomaterials.

The discovery of the high maximum energy product of 59 MGOe for NdFeB magnets is a breakthrough in the development of permanent magnets with a tremendous impact in many fields of technology. This value is still the world record, for 40 years. This work reports on a reliable and robust route to realize nearly perfectly ordered L10 -phase FePt nanoparticles, leading to an unprecedented energy product of 80 MGOe at room temperature. Furthermore, with a 3 nm Au coverage, the magnetic polarization of these nanomagnets can be enhanced by 25% exceeding 1.8 T. This exceptional magnetization and anisotropy is confirmed by using multiple imaging and spectroscopic methods, which reveal highly consistent results. Due to the unprecedented huge energy product, this material can be envisaged as a new advanced basic magnetic component in modern micro and nanosized devices.

Coordinated Molecule-Modulated Magnetic Phase with Metamagnetism in Metal-Organic Frameworks.

Most well-known metal-organic frameworks (MOFs) possessing the magnetic Ni2O2(CO2)2 chains, called Ni-MOF-74, have been investigated with regard to magnetic properties at open-metal sites. We present the modulation of their magnetic phase and metamagnetism via imidazole molecule coordination.

Hybrids of Pd Nanoparticles and Metal-Organic Frameworks for Enhanced Magnetism.

Nonmagnetic Pd exhibits ferromagnetism in the nanosize regime. Various stabilization agents, including surfactants, metal oxide supports, polymers, and porous materials (e.g., metal-organic frameworks (MOFs)), have been employed to prevent the agglomeration of metal nanoparticles. However, magnetic properties are greatly affected by the structural and electronic changes imposed by these stabilizing agents. In particular, metal-MOF hybrids (NPs@MOFs) have reduced magnetic properties, as reported by several authors. Herein, we report the enhancement in magnetic properties resulting from the combination of magnetic Pd NPs with UiO-66(Hf), which exhibits ferromagnetism, and the corresponding modifications in the hybridized structures. These hybridized structures are found to be strongly ferromagnetic, showing high magnetization and coercivity. We observed that the magnetic property is enhanced by 2 to 3 times upon including the Pd NPs on the surface of a UiO-66(Hf) shell support. For a fundamental understanding, the magnetization (M-H data) of the hybridized structure is analyzed with a modified Langevin function.

Biocompatible Magnetic Micro- and Nanodevices: Fabrication of FePt Nanopropellers and Cell Transfection.

The application of nanoparticles for drug or gene delivery promises benefits in the form of single-cell-specific therapeutic and diagnostic capabilities. Many methods of cell transfection rely on unspecific means to increase the transport of genetic material into cells. Targeted transport is in principle possible with magnetically propelled micromotors, which allow responsive nanoscale actuation and delivery. However, many commonly used magnetic materials (e.g., Ni and Co) are not biocompatible, possess weak magnetic remanence (Fe3 O4 ), or cannot be implemented in nanofabrication schemes (NdFeB). Here, it is demonstrated that co-depositing iron (Fe) and platinum (Pt) followed by one single annealing step, without the need for solution processing, yields ferromagnetic FePt nanomotors that are noncytotoxic, biocompatible, and possess a remanence and magnetization that rival those of permanent NdFeB micromagnets. Active cell targeting and magnetic transfection of lung carcinoma cells are demonstrated using gradient-free rotating millitesla fields to drive the FePt nanopropellers. The carcinoma cells express enhanced green fluorescent protein after internalization and cell viability is unaffected by the presence of the FePt nanopropellers. The results establish FePt, prepared in the L10 phase, as a promising magnetic material for biomedical applications with superior magnetic performance, especially for micro- and nanodevices.

Highly nonlinear magnetoelectric effect in buckled-honeycomb antiferromagnetic Co4Ta2O9.

Strongly correlated materials with multiple order parameters provide unique insights into the fundamental interactions in condensed matter systems and present opportunities for innovative technological applications. A class of antiferromagnetic honeycomb lattices compounds, A4B2O9 (A = Co, Fe, Mn; B = Nb, Ta), have been explored owing to the occurrence of linear magnetoelectricity. From our investigation of magnetoelectricity on single crystalline Co4Ta2O9, we discovered strongly nonlinear and antisymmetric magnetoelectric behavior above the spin-flop transition for magnetic fields applied along two orthogonal in-plane directions. This observation suggests that two types of inequivalent Co2+ sublattices generate magnetic-field-dependent ferroelectric polarization with opposite signs. The results motivate fundamental and applied research on the intriguing magnetoelectric characteristics of these buckled-honeycomb lattice materials.

Corrosion-Protected Hybrid Nanoparticles.

Nanoparticles composed of functional materials hold great promise for applications due to their unique electronic, optical, magnetic, and catalytic properties. However, a number of functional materials are not only difficult to fabricate at the nanoscale, but are also chemically unstable in solution. Hence, protecting nanoparticles from corrosion is a major challenge for those applications that require stability in aqueous solutions and biological fluids. Here, this study presents a generic scheme to grow hybrid 3D nanoparticles that are completely encapsulated by a nm thick protective shell. The method consists of vacuum-based growth and protection, and combines oblique physical vapor deposition with atomic layer deposition. It provides wide flexibility in the shape and composition of the nanoparticles, and the environments against which particles are protected. The work demonstrates the approach with multifunctional nanoparticles possessing ferromagnetic, plasmonic, and chiral properties. The present scheme allows nanocolloids, which immediately corrode without protection, to remain functional, at least for a week, in acidic solutions.

Selectable Nanopattern Arrays for Nanolithographic Imprint and Etch-Mask Applications.

A parallel nanolithographic patterning method is presented that can be used to obtain arrays of multifunctional nanoparticles. These patterns can simply be converted into a variety of secondary nanopatterns that are useful for nanolithographic imprint, plasmonic, and etch-mask applications.