Size-Specific Magnetic Configurations in Electrodeposited Epitaxial Iron Nanocuboids: From Landau Pattern to Vortex and Single Domain States.

As the size of magnetic devices continuously decreases, the creation of three-dimensional nanomagnets and the understanding of their magnetic configurations become increasingly important for modern applications. Here, by progressive nucleation during epitaxial nanoelectrodeposition, we synthesize single-crystal iron nanocuboids with sizes ranging 10 to 200 nm on one sample. The size-dependent magnetic configurations of these nanocuboids are studied by quantitative magnetic force microscopy and electron holography. In conjunction, a "magnetic configuration versus size" phase diagram is established via micromagnetic simulations. Both experiment and theory reveal a sequential transition from Landau pattern to vortex and finally single domain when decreasing the sizes of the nanocuboids. The combinatorial-like approach leads to a quantitative understanding of the magnetic configurations of the nanomagnets in a broad size range. It can be transferred to other materials and shapes and thereby presents an advanced route to enrich the material library for future nanodevice design.

Creating Ferroic Micropatterns through Geometrical Transformation.

The functionality of a ferroic device is intimately coupled to the configuration of domains, domain boundaries, and the possibility for tailoring them. Exemplified with a ferromagnetic system, we present a novel approach which allows the creation of new, metastable multidomain patterns with tailored wall configurations through a self-assembled geometrical transformation. By preparing a magnetic layer system on a polymeric platform including swelling layer, a repeated self-assembled rolling into a multiwinding tubular structure and unrolling of the functional membrane is obtained. When polarizing the rolled-up 3D structure in a simple homogeneous magnetic field, the imprinted configuration translates into a regularly arranged multidomain configuration once the tubular structure is unwound. The process is linked to the employed magnetic anisotropy with respect to the surface normal, and the geometrical transformation connects the angular with the lateral degrees of freedom. This combination offers unparalleled possibilities for designing new magnetic or other ferroic micropatterns.

Modal Frustration and Periodicity Breaking in Artificial Spin Ice.

Here, an artificial spin ice lattice is introduced that exhibits unique Ising and non-Ising behavior under specific field switching protocols because of the inclusion of coupled nanomagnets into the unit cell. In the Ising regime, a magnetic switching mechanism that generates a uni- or bimodal distribution of states dependent on the alignment of the field is demonstrated with respect to the lattice unit cell. In addition, a method for generating a plethora of randomly distributed energy states across the lattice, consisting of Ising and Landau states, is investigated through magnetic force microscopy and micromagnetic modeling. It is demonstrated that the dispersed energy distribution across the lattice is a result of the intrinsic design and can be finely tuned through control of the incident angle of a critical field. The present manuscript explores a complex frustrated environment beyond the 16-vertex Ising model for the development of novel logic-based technologies.

Stress-Actuated Spiral Microelectrode for High-Performance Lithium-Ion Microbatteries.

Miniaturization of batteries lags behind the success of modern electronic devices. Neither the device volume nor the energy density of microbatteries meets the requirement of microscale electronic devices. The main limitation for pushing the energy density of microbatteries arises from the low mass loading of active materials. However, merely pushing the mass loading through increased electrode thickness is accompanied by the long charge transfer pathway and inferior mechanical properties for long-term operation. Here, a new spiral microelectrode upon stress-actuation accomplishes high mass loading but short charge transfer pathways. At a small footprint area of around 1 mm2 , a 21-fold increase of the mass loading is achieved while featuring fast charge transfer at the nanoscale. The spiral microelectrode delivers a maximum area capacity of 1053 µAh cm-2 with a retention of 67% over 50 cycles. Moreover, the energy density of the cylinder microbattery using the spiral microelectrode as the anode reaches 12.6 mWh cm-3 at an ultrasmall volume of 3 mm3 . In terms of the device volume and energy density, the cylinder microbattery outperforms most of the current microbattery technologies, and hence provides a new strategy to develop high-performance microbatteries that can be integrated with miniaturized electronic devices.

Comparison and Validation of Different Magnetic Force Microscopy Calibration Schemes.

The future of consumer electronics depends on the capability to reliably fabricate nanostructures with given physical properties. Therefore, techniques to characterize materials and devices with nanoscale resolution are crucial. Among these is magnetic force microscopy (MFM), which transduces the magnetic force between the sample and a magnetic oscillating probe into a phase shift, enabling the locally resolved study of magnetic field patterns down to 10 nm. Here, the progress done toward making quantitative MFM a common tool in nanocharacterization laboratories is shown. The reliability and ease of use of the calibration method based on a magnetic reference sample, with a calculable stray field, and a deconvolution algorithm is demonstrated. This is achieved by comparing two calibration approaches combined with numerical modeling as a quantitative link: measuring the probe's effect on the voltage signal when scanning above a nanosized graphene Hall sensor, and recording the MFM phase shift signal when the probe scans across magnetic fields produced by metallic microcoils. Furthermore, in the case of the deconvolution algorithm, it is shown how it can be applied using the open-source software package Gwyddion. The estimated magnetic dipole approximation for the most common probes currently in the market is also reported.

Self-assembly of Co/Pt stripes with current-induced domain wall motion towards 3D racetrack devices.

Modification of the magnetic properties under the induced strain and curvature is a promising avenue to build three-dimensional magnetic devices, based on the domain wall motion. So far, most of the studies with 3D magnetic structures were performed in the helixes and nanowires, mainly with stationary domain walls. In this study, we demonstrate the impact of 3D geometry, strain and curvature on the current-induced domain wall motion and spin-orbital torque efficiency in the heterostructure, realized via a self-assembly rolling technique on a polymeric platform. We introduce a complete 3D memory unit with write, read and store functionality, all based on the field-free domain wall motion. Additionally, we conducted a comparative analysis between 2D and 3D structures, particularly addressing the influence of heat during the electric current pulse sequences. Finally, we demonstrated a remarkable increase of 30% in spin-torque efficiency in 3D configuration.

Development and characterization of a capillary gap sampler as new microfluidic device for fast and direct analysis of low sample amounts by ESI-MS.

Direct hyphenation of miniaturized sampling devices to electrospray ionization-mass spectrometry (ESI-MS) is attractive because ESI-MS is compatible with microfluidics and allows comprehensive sample analysis, yielding information that is orthogonal to that available from optical methods. We present a "capillary gap sampler" as a platform for directly connecting microfluidics to µ-ESI-MS. The sampler was designed to be robust, light and compact, and to allow precise and fast liquid handling. Sample introduction in the range of a few nanoliters is performed via an open liquid bridge as a new microfluidic element. This allows minimum contact of the sample with system surfaces during the infusion process. The system shows good performance characteristics such as symmetrical peak shapes, low sample carryover (below 1%), and total injection cycle times of less than 15 s. This new device thus has the potential for rapid analysis of biomedical and pharmaceutical samples with limited sample amounts in a high-throughput mode.

Investigation of reaction mechanisms of drug degradation in the solid state: a kinetic study implementing ultrahigh-performance liquid chromatography and high-resolution mass spectrometry for thermally stressed thyroxine.

A reaction scheme was derived for the thermal degradation of thyroxine in the solid state, using data obtained from ultrahigh-performance liquid chromatography and high-resolution mass spectrometry (UHPLC-HRMS). To study the reaction mechanism and kinetics of the thermal degradation of the pharmaceutical in the solid state, a workflow was developed by generating compound-specific, time-dependent degradation or formation curves of at least 13 different degradation products. Such curves allowed one to distinguish between first- and second-generation degradation products, as well as impurities resulting from chemical synthesis. The structures of the degradation products were derived from accurate molecular masses and multistage mass spectrometry. Deiodination and oxidative side chain degradation were found to be the major degradation reactions, resulting in the formation of deiodinated thyroxines, as well as acetic acid, benzoic acid, formaldehyde, acetamide, hydroxyacetic acid, oxoacetic acid, hydroxyacetamide, or oxoacetamide derivatives of thyroxine or deiodinated thyroxine. Upon additional structural verification of mass spectrometric data using nuclear magnetic resonance spectroscopy, this comprehensive body of data sheds light on an elaborate, radical-driven reaction scheme, explaining the presence or formation of impurities in thermally stressed thyroxine.

Rapid and comprehensive impurity profiling of synthetic thyroxine by ultrahigh-performance liquid chromatography-high-resolution mass spectrometry.

Rapid and efficient quality control according to the public authority regulations is mandatory to guarantee safety of the pharmaceuticals and to save resources in the pharmaceutical industry. In the case of so-called "grandfather products" like the synthetic thyroid hormone thyroxine, strict regulations enforce a detailed chemical analysis in order to characterize potentially toxic or pharmacologically relevant impurities. We report a straightforward workflow for the comprehensive impurity profiling of synthetic thyroid hormones and impurities employing ultrahigh-performance liquid chromatography (UHPLC) hyphenated to high-resolution mass spectrometry (HRMS). Five different batches of synthetic thyroxin were analyzed resulting in the detection of 71 impurities within 3 min total analysis time. Structural elucidation of the compounds was accomplished via a combination of accurate mass measurements, computer based calculations of molecular formulas, multistage high-resolution mass spectrometry (HRMS(n)), and nuclear magnetic resonance spectroscopy, which enabled the identification of 71 impurities, of which 47 have been unknown so far. Thirty of the latter were structurally elucidated, including products of deiodination, aliphatic chain oxidation, as well as dimeric compounds as new class of thyroid hormone derivatives. Limits of detection for the thyroid compounds were in the 6 ng/mL range for negative electrospray ionization mass spectrometric detection in full scan mode. Within day and day-to-day repeatabilities of retention times and peak areas were below 0.5% and 3.5% R.SD. The performance characteristics of the method in terms of robustness and information content clearly show that UHPLC-HRMS is adequate for the rapid and reliable detection, identification, and semiquantitative determination of trace levels of impurities in synthetic pharmaceuticals.

Characterization of GDP-mannose dehydrogenase from the brown alga Ectocarpus siliculosus providing the precursor for the alginate polymer.

Alginate is a major cell wall polymer of brown algae. The precursor for the polymer is GDP-mannuronic acid, which is believed to be derived from a four-electron oxidation of GDP-mannose through the enzyme GDP-mannose dehydrogenase (GMD). So far no eukaryotic GMD has been biochemically characterized. We have identified a candidate gene in the Ectocarpus siliculosus genome and expressed it as a recombinant protein in Escherichia coli. The GMD from Ectocarpus differs strongly from related enzymes in bacteria and is as distant to the bacterial proteins as it is to the group of UDP-glucose dehydrogenases. It lacks the C-terminal ∼120 amino acid domain present in bacterial GMDs, which is believed to be involved in catalysis. The GMD from brown algae is highly active at alkaline pH and contains a catalytic Cys residue, sensitive to heavy metals. The product GDP-mannuronic acid was analyzed by HPLC and mass spectroscopy. The K(m) for GDP-mannose was 95 µM, and 86 µM for NAD(+). No substrate other than GDP-mannose was oxidized by the enzyme. In gel filtration experiments the enzyme behaved as a dimer. The Ectocarpus GMD is stimulated by salts even at low molar concentrations as a possible adaptation to marine life. It is rapidly inactivated at temperatures above 30 °C.

On-line solid-phase extraction high-performance liquid chromatography-tandem mass spectrometry for the quantitative analysis of tacrolimus in whole blood hemolyzate.

Tacrolimus is an immunosuppressive drug essential for preventing organ rejection after transplantation. Since tacrolimus strongly binds to erythrocytes, therapeutic monitoring requires its quantification in whole blood lyzate, representing one of the most difficult to analyze biological fluids due to its high protein load. In this communication, we report on the successful combination of whole blood hemolysis employing ionic liquids, followed by sample preparation by means of on-line solid phase extraction (SPE) using restricted access materials (RAM), which permitted the efficient removal of hemoglobin and other large biomolecules. Among six different tested RAM columns, highest hemoglobin depletion and analyte extraction efficiency was obtained with a polymer-based, glycoprotein-coated RAM stationary phase (Biotrap 500 MS) operated at an alkaline pH of 10.7. Analyte quantification was performed by high-performance liquid chromatography-selected reaction monitoring tandem mass spectrometry (HPLC-SRM-MS/MS). The ability to quantify tacrolimus in therapeutically relevant concentrations in whole blood hemolyzates was demonstrated via external calibration with lower limits of detection and quantification of 2.00 and 7.23 ng mL(-1), respectively. Moreover, the investigation of heparin-pretreated blood samples during blood sampling led to an increase in sensitivity for the analyte, while the method appeared to be more robust with ethylenediaminetetraacetic acid as anticoagulant.

Direct imaging of nanoscale field-driven domain wall oscillations in Landau structures.

Linear oscillatory motion of domain walls (DWs) in the kHz and MHz regime is crucial when realizing precise magnetic field sensors such as giant magnetoimpedance devices. Numerous magnetically active defects lead to pinning of the DWs during their motion, affecting the overall behavior. Thus, the direct monitoring of the domain wall's oscillatory behavior is an important step to comprehend the underlying micromagnetic processes and to improve the magnetoresistive performance of these devices. Here, we report an imaging approach to investigate such DW dynamics with nanoscale spatial resolution employing conventional table-top microscopy techniques. Time-averaged magnetic force microscopy and Kerr imaging methods are applied to quantify the DW oscillations in Ni81Fe19 rectangular structures with Landau domain configuration and are complemented by numeric micromagnetic simulations. We study the oscillation amplitude as a function of external magnetic field strength, frequency, magnetic structure size, thickness and anisotropy and understand the excited DW behavior as a forced damped harmonic oscillator with restoring force being influenced by the geometry, thickness, and anisotropy of the Ni81Fe19 structure. This approach offers new possibilities for the analysis of DW motion at elevated frequencies and at a spatial resolution of well below 100 nm in various branches of nanomagnetism.

An extraordinary chiral exchange-bias phenomenon: engineering the sign of the bias field in orthogonal bilayers by a magnetically switchable response mechanism.

Isothermal tuning of both the magnitude and the sign of the bias field has been achieved by exploiting a new phenomenon in a system consisting of two orthogonally coupled films: SmCo5 (out-of-plane anisotropy)-CoFeB (in-plane anisotropy). This has been achieved by using the large dipolar magnetic field of the SmCo5 layer resulting in the pinning of one of the branches of the hysteresis loop (either the ascending or the descending branch) at a fixed field value while the second one is modulated along the field axis by varying the orientation of an externally applied magnetic field. This means the possibility of controlling the sign of the bias field in a manner not reported to date. Moreover, modulation of the bias field strength is possible by varying the thickness of a spacer between the SmCo5 and CoFeB layers. This study shows that the observed phenomena find their origin in the competition between the artificially induced anisotropies in both layers, resulting in a reversible chiral bias effect that allows the selection of the initial sign of the bias field by switching (upwards/downwards) the magnetization in the SmCo5 film.

Determination of tip transfer function for quantitative MFM using frequency domain filtering and least squares method.

Magnetic force microscopy has unsurpassed capabilities in analysis of nanoscale and microscale magnetic samples and devices. Similar to other Scanning Probe Microscopy techniques, quantitative analysis remains a challenge. Despite large theoretical and practical progress in this area, present methods are seldom used due to their complexity and lack of systematic understanding of related uncertainties and recommended best practice. Use of the Tip Transfer Function (TTF) is a key concept in making Magnetic Force Microscopy measurements quantitative. We present a numerical study of several aspects of TTF reconstruction using multilayer samples with perpendicular magnetisation. We address the choice of numerical approach, impact of non-periodicity and windowing, suitable conventions for data normalisation and units, criteria for choice of regularisation parameter and experimental effects observed in real measurements. We present a simple regularisation parameter selection method based on TTF width and verify this approach via numerical experiments. Examples of TTF estimation are shown on both 2D and 3D experimental datasets. We give recommendations on best practices for robust TTF estimation, including the choice of windowing function, measurement strategy and dealing with experimental error sources. A method for synthetic MFM data generation, suitable for large scale numerical experiments is also presented.

Epitaxial hard magnetic SmCo5 MFM tips - a new approach to advanced magnetic force microscopy imaging.

Cantilever based scanning force sensors, which probe a specific tip-sample interaction through a functional tip coating, are limited by the material performance achievable in the coating process. In case of the wide spread magnetic force microscopy (MFM) technique, the magnetic performance of MFM tips, especially the response to magnetic fields and the coercivity, fall far behind the quality known from permanent magnet films prepared with optimized process conditions on appropriate substrates. We resolve this limitation by starting from an optimized thin film architecture - a highly anisotropic SmCo5 film grown epitaxially on MgO(110) substrates - from which a tip is separated by focused ion beam and is attached to a cantilever. Not compromising on resolution and sensitivity, we demonstrate an unrivaled rigidity in magnetic fields, which will largely advance quantitative microscopic investigation of magnetic materials with strong stray fields and allows MFM measurements in external magnetic fields of currently up to 0.7 T. The material optimization for a specific sample - cantilever interaction without restrictions in substrate, film architecture, film preparation conditions and tip shape, is not limited to MFM but offers new opportunities also for other scanning force microscopy modes.

Metrological large range magnetic force microscopy.

A new metrological large range magnetic force microscope (Met. LR-MFM) has been developed. In its design, the scanner motion is measured by using three laser interferometers along the x, y, and z axes. Thus, the scanner position and the lift height of the MFM can be accurately and traceably determined with subnanometer accuracy, allowing accurate and traceable MFM measurements. The Met. LR-MFM has a measurement range of 25 mm × 25 mm × 5 mm, larger than conventional MFMs by almost three orders of magnitude. It is capable of measuring samples from the nanoscale to the macroscale, and thus, it has the potential to bridge different magnetic field measurement tools having different spatially resolved scales. Three different measurement strategies referred to as Topo&MFM, MFMXY, and MFMZ have been developed. The Topo&MFM is designed for measuring topography and MFM phase images, similar to conventional MFMs. The MFMXY differs from the Topo&MFM as it does not measure the topography profile of surfaces at the second and successive lines, thus reducing tip wear and saving measurement time. The MFMZ allows the imaging of the stray field in the xz- or yz-planes. A number of measurement examples on a multilayered thin film reference sample made of [Co(0.4 nm)/Pt(0.9 nm)]100 and on a patterned magnetic multilayer [Co(0.4 nm)/Pt(0.9 nm)]10 with stripes with a 9.9 µm line width and 20 µm periodicity are demonstrated, indicating excellent measurement performance.

Calibration of multi-layered probes with low/high magnetic moments.

We present a comprehensive method for visualisation and quantification of the magnetic stray field of magnetic force microscopy (MFM) probes, applied to the particular case of custom-made multi-layered probes with controllable high/low magnetic moment states. The probes consist of two decoupled magnetic layers separated by a non-magnetic interlayer, which results in four stable magnetic states: ±ferromagnetic (FM) and ±antiferromagnetic (A-FM). Direct visualisation of the stray field surrounding the probe apex using electron holography convincingly demonstrates a striking difference in the spatial distribution and strength of the magnetic flux in FM and A-FM states. In situ MFM studies of reference samples are used to determine the probe switching fields and spatial resolution. Furthermore, quantitative values of the probe magnetic moments are obtained by determining their real space tip transfer function (RSTTF). We also map the local Hall voltage in graphene Hall nanosensors induced by the probes in different states. The measured transport properties of nanosensors and RSTTF outcomes are introduced as an input in a numerical model of Hall devices to verify the probe magnetic moments. The modelling results fully match the experimental measurements, outlining an all-inclusive method for the calibration of complex magnetic probes with a controllable low/high magnetic moment.

Magnetite Core-Shell Nanoparticles in Nondestructive Flaw Detection of Polymeric Materials.

Nondestructive flaw detection in polymeric materials is important but difficult to achieve. In this research, the application of magnetite nanoparticles (MNPs) in nondestructive flaw detection is studied and realized, to the best of our knowledge, for the first time. Superparamagnetic and highly magnetic (up to 63 emu/g) magnetite core-shell nanoparticles are prepared by grafting bromo-end-group-functionalized poly(glycidyl methacrylate) (Br-PGMA) onto surface-modified Fe3O4 NPs. These Fe3O4-PGMA NPs are blended into bisphenol A diglycidylether (BADGE)-based epoxy to form homogeneously distributed magnetic epoxy nanocomposites (MENCs) after curing. The core Fe3O4 of the Fe3O4-PGMA NPs endows the MENCs with magnetic property, which is crucial for nondestructive flaw detection of the materials, while the shell PGMA promotes colloidal stability and prevents NP aggregation during curing. The eddy current testing (ET) technique is first applied to detect flaws in the MENCs. Through the brightness contrast of the ET image, surficial and subsurficial flaws in MENCs can be detected, even for MENCs with low content of Fe3O4-PGMA NPs (1 wt %). The incorporation of Fe3O4-PGMA NPs can be easily extended to other polymer and polymer-based composite systems and opens a new and very promising pathway toward MNP-based nondestructive flaw detection in polymeric materials.

Ultrahigh-performance liquid chromatography-ultraviolet absorbance detection-high-resolution-mass spectrometry combined with automated data processing for studying the kinetics of oxidative thermal degradation of thyroxine in the solid state.

Levothyroxine as active pharmaceutical ingredient of formulations used for the treatment of hypothyroidism is distributed worldwide and taken by millions of people. An important issue in terms of compound stability is its capability to react with ambient oxygen, especially in case of long term compound storage at elevated temperature. In this study we demonstrate that ultrahigh-performance liquid chromatography coupled to UV spectrometry and high-resolution mass spectrometry (UHPLC-UV-HRMS) represent very useful approaches to investigate the influence of ambient oxygen on the degradation kinetics of levothyroxine in the solid state at enhanced degradation conditions. Moreover, the impurity pattern of oxidative degradation of levothyroxine is elucidated and classified with respect to degradation kinetics at different oxygen levels. Kinetic analysis of thyroxine bulk material at 100 °C reveals bi-phasic degradation kinetics with a distinct change in degradation phases dependent on the availability of oxygen. The results clearly show that contact of the bulk material to ambient oxygen is a key factor for fast compound degradation. Furthermore, the combination of time-resolved HRMS data and automated data processing is shown to allow insights into the kinetics and mechanism of impurity formation on individual compound basis. By comparing degradation profiles, four main classes of profiles linked to reaction pathways of thyroxine degradation were identifiable. Finally, we show the capability of automated data processing for the matching of different stressing conditions, in order to extract information about mechanistic similarities. As a result, degradation kinetics is influenced by factors like availability of oxygen, stressing time, or stressing temperature, while the degradation mechanisms appear to be conserved.