A. Urtizberea

Origin of slow magnetic relaxation in Kramers ions with non-uniaxial anisotropy

Transition metal ions with long-lived spin states represent minimum size magnetic bits. Magnetic memory has often been associated with the combination of high spin and strong uniaxial magnetic anisotropy. Yet, slow magnetic relaxation has also been observed in some Kramers ions with dominant easy-plane magnetic anisotropy, albeit only under an external magnetic field. Here we study the spin dynamics of cobalt(II) ions in a model molecular complex. We show, by means of quantitative first-principles calculations, that the slow relaxation in this and other similar systems is a general consequence of time-reversal symmetry that hinders direct spin-phonon processes regardless of the sign of the magnetic anisotropy. Its magnetic field dependence is a subtle manifestation of electronuclear spin entanglement, which opens relaxation channels that would otherwise be forbidden but, at the same time, masks the relaxation phenomenon at zero field. These results provide a promising strategy to synthesize atom-size magnetic memories.

Synthesis and magnetic behavior of ultra-small bimetallic FeCo/graphite nanoparticles

FeCo-alloy graphite-coated nanoparticles with mean particle diameter under 8 nm have been synthesized following a CVD carbon-deficient method. The superior magnetic properties of FeCo-alloy nanoparticles makes them good candidates to be used as magnetic filler in magneto-polymer composites. Thanks to the protective effect of the graphite shell, FeCo nanoparticles are stable under oxygen atmosphere up to 200 ° C. The as-prepared nanoparticles presented a highly long range chemically ordered core being ferromagnetic at room temperature with a saturation magnetization at room temperature close to the bulk value. After annealing at 750 K the saturation magnetization and the coercive field increase. To investigate the processes involved in the thermal treatment, the temperature dependence of the magnetization and the particle composition, size and structure have been characterized before and after annealing. Besides powder x-ray diffraction (XRD) and x-ray photoelectron spectroscopy (XPS), a detailed study by means of advanced transmission electron microscopy (TEM) techniques has been carried out. In particular, aberration corrected scanning transmission electron microscopy (STEM), has shown that nanoparticles became faceted after the thermal treatment, as a mechanism to reach the thermodynamic equilibrium within the metastable phase. This outstanding feature, not previously reported, leads to an increase of the shape anisotropy, which in turn might be the origin of the observed increase of the coercive field after annealing.

Shifted loops and coercivity from field-imprinted high-energy barriers in ferritin and ferrihydrite nanoparticles

We show that the coercive field in ferritin and ferrihydrite depends on the maximum magnetic field in a hysteresis loop and that coercivity and loop shifts depend both on the maximum and cooling fields. In the case of ferritin we show that the time dependence of the magnetization also depends on the maximum and previous cooling fields. This behavior is associated to changes in the intra-particle energy barriers imprinted by these fields. Accordingly, the dependence of the coercive and loop shift fields with the maximum field in ferritin and ferrihydrite can be described within the frame of a uniform-rotation model considering a dependence of the energy barrier with the maximum and the cooling fields.

Biomimetic Phospholipid Membrane Organization on Graphene and Graphene Oxide Surfaces: A Molecular Dynamics Simulation Study

Supported phospholipid membrane patches stabilized on graphene surfaces have shown potential in sensor device functionalization, including biosensors and biocatalysis. Lipid dip-pen nanolithography (L-DPN) is a method useful in generating supported membrane structures that maintain lipid functionality, such as exhibiting specific interactions with protein molecules. Here, we have integrated L-DPN, atomic force microscopy, and coarse-grained molecular dynamics simulation methods to characterize the molecular properties of supported lipid membranes (SLMs) on graphene and graphene oxide supports. We observed substantial differences in the topologies of the stabilized lipid structures depending on the nature of the surface (polar graphene oxide vs nonpolar graphene). Furthermore, the addition of water to SLM systems resulted in large-scale reorganization of the lipid structures, with measurable effects on lipid lateral mobility within the supported membranes. We also observed reduced lipid ordering within the supported structures relative to free-standing lipid bilayers, attributed to the strong hydrophobic interactions between the lipids and support. Together, our results provide insight into the molecular effects of graphene and graphene oxide surfaces on lipid bilayer membranes. This will be important in the design of these surfaces for applications such as biosensor devices.

Multiple-length-scale small-angle X-ray scattering analysis on maghemite nanocomposites

Small-angle X-ray scattering (SAXS) analysis has been performed on maghemite–poly(4-vinylpyridine) nanocomposites prepared by in situ precipitation from iron–polymer coordination compounds. According to electron microscopy observations, the nanocomposites contain isolated spherical particles with a narrow size distribution, uniformly distributed throughout the polymer matrix. The scattering intensity of nanocomposites has relevant contributions from both the polymer and the nanocomposites, showing features characteristic of multiscale structured systems, namely two power laws and a Guinier regime. The data have been analysed in terms of Beaucages unified approach and it is found that the maghemite particle size increases with the iron/polymer weight ratio used in the preparation of the nanocomposites. SAXS curves also feature a bump that was analysed as arising from a second particle population or from interactions. Magnetization and transmission electron microscopy results give arguments favouring the latter interpretation. It is found that the maghemite particle sizes vary linearly with the iron weight ratio used in the preparation of the nanocomposites.

Ink transport modelling in Dip-Pen Nanolithography and Polymer Pen Lithography

Abstract Dip-pen nanolithography (DPN) and Polymer pen lithography (PPL) are powerful lithography techniques being able to pattern a wide range of inks. Transport and surface spreading depend on the ink physicochemical properties, defining its diffusive and fluid character. Structure assembly on surface arises from a balance between the entanglement of the ink itself and the interaction with the substrate. According to the transport characteristics, different models have been proposed. In this article we review the common types of inks employed for patterning, the particular physicochemical characteristics that make them flow following different dynamics as well as the corresponding transport mechanisms and models that describe them.

Texture-induced magnetic interactions in ferrofluids

We report a method for reversibly controlling the strength of dipole-dipole interactions in maghemite ferrofluids. In order to induce some magnetic texture, the ferrofluid is exposed to a strong magnetic field while it is cooled from room temperature to below its freezing temperature. The experimental data show that the average strength of dipolar interactions increases with increasing texture and that the magnetic relaxation becomes slower.

Note: A sample holder design for sensitive magnetic measurements at high temperatures in a magnetic properties measurement system

A sample holder design for high temperature measurements in a commercial MPMS SQUID magnetometer from Quantum Design is presented. It fulfills the requirements for the simultaneous use of the oven and reciprocating sample option (RSO) options, thus allowing sensitive magnetic measurements up to 800 K. Alternating current susceptibility can also be measured, since the holder does not induce any phase shift relative to the ac driven field. It is easily fabricated by twisting Constantan© wires into a braid nesting the sample inside. This design ensures that the sample be placed tightly into a tough holder with its orientation fixed, and prevents any sample displacement during the fast movements of the RSO transport, up to high temperatures.

Polymer Pen Lithography with Lipids for Large-Area Gradient Patterns

Gradient patterns comprising bioactive compounds over comparably (in regard to a cell size) large areas are key for many applications in the biomedical sector, in particular, for cell screening assays, guidance, and migration experiments. Polymer pen lithography (PPL) as an inherent highly parallel and large area technique has a great potential to serve in the fabrication of such patterns. We present strategies for the printing of functional phospholipid patterns via PPL that provide tunable feature size and feature density gradients over surface areas of several square millimeters. By controlling the printing parameters, two transfer modes can be achieved. Each of these modes leads to different feature morphologies. By increasing the force applied to the elastomeric pens, which increases the tip-surface contact area and boosts the ink delivery rate, a switch between a dip-pen nanolithography (DPN) and a microcontact printing (μCP) transfer mode can be induced. A careful inking procedure ensuring a homogeneous and not-too-high ink-load on the PPL stamp ensures a membrane-spreading dominated transfer mode, which, used in combination with smooth and hydrophilic substrates, generates features with constant height, independently of the applied force of the pens. Ultimately, this allows us to obtain a gradient of feature sizes over a mm2 substrate, all having the same height on the order of that of a biological cellular membrane. These strategies allow the construction of membrane structures by direct transfer of the lipid mixture to the substrate, without requiring previous substrate functionalization, in contrast to other molecular inks, where structure is directly determined by the printing process itself. The patterns are demonstrated to be viable for subsequent protein binding, therefore adding to a flexible feature library when gradients of protein presentation are desired.