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Application of molecular SERS nanosensors: where we stand and where we are headed towards?

2020, Jahn I.J., Mühlig A., Cialla-May D.

Molecular specific and highly sensitive detection is the driving force of the surface-enhanced Raman spectroscopy (SERS) community. The technique opens the window to the undisturbed monitoring of cellular processes in situ or to the quantification of small molecular species that do not deliver Raman signals. The smart design of molecular SERS nanosensors makes it possible to indirectly but specifically detect, e.g. reactive oxygen species, carbon monoxide or potentially toxic metal ions. Detection schemes evolved over the years from simple metallic colloidal nanoparticles functionalized with sensing molecules that show uncontrolled aggregation to complex nanostructures with magnetic properties making the analysis of complex environmental samples possible. The present article gives the readership an overview of the present research advancements in the field of molecular SERS sensors, highlighting future trends. © 2020, The Author(s).

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Round robin comparison on quantitative nanometer scale magnetic field measurements by magnetic force microscopy

2020, Hu, X., Dai, G., Sievers, S., Fernández-Scarioni, A., Corte-León, H., Puttock, R., Barton, C., Kazakova, O., Ulvr, M., Klapetek, P., Havlíček, M., Nečas, D., Tang, Y., Neu, V., Schumacher, H.W.

Magnetic force microscopy (MFM) can be considered as a standard tool for nano-scale investigation of magnetic domain structures by probing the local stray magnetic field landscape of the measured sample. However, this generally provides only qualitative data. To quantify the stray magnetic fields, the MFM system must be calibrated. To that end, a transfer function (TF) approach was proposed, that, unlike point probe models, fully considers the finite extent of the MFM tip. However, albeit being comprehensive, the TF approach is not yet well established, mainly due to the ambiguities concerning the input parameters and the measurement procedure. Additionally, the calibration process represents an ill-posed problem which requires a regularization that introduces further parameters. In this paper we propose a guideline for quantitative stray field measurements by standard MFM tools in ambient conditions. All steps of the measurement and calibration procedure are detailed, including reference sample and sample under test (SUT) measurements and the data analysis. The suitability of the reference sample used in the present work for calibrated measurements on a sub-micron scale is discussed. A specific regularization approach based on a Pseudo-Wiener Filter is applied and combined with criteria for the numerical determination of a unique regularization parameter. To demonstrate the robustness of such a defined approach, a round robin comparison of magnetic field measurements was conducted by four laboratories. The guideline, the reference sample and the results of the round robin are discussed.

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Tunable charge transfer properties in metal-phthalocyanine heterojunctions

2016, Siles, P.F., Hahn, T., Salvan, G., Knupfer, M., Zhu, F., Zahn, D.R.T., Schmidt, O.G.

Organic materials such as phthalocyanine-based systems present a great potential for organic device applications due to the possibility of integrating films of different organic materials to create organic heterostructures which combine the electrical capabilities of each material. This opens the possibility to precisely engineer and tune new electrical properties. In particular, similar transition metal phthalocyanines demonstrate hybridization and charge transfer properties which could lead to interesting physical phenomena. Although, when considering device dimensions, a better understanding and control of the tuning of the transport properties still remain in the focus of research. Here, by employing conductive atomic force microscopy techniques, we provide an insight about the nanoscale electrical properties and transport mechanisms of MnPc and fluorinated phthalocyanines such as F16CuPc and F16CoPc. We report a transition from typical diode-like transport mechanisms for pure MnPc thin films to space-charge-limited current transport regime (SCLC) for Pc-based heterostructures. The controlled addition of fluorinated phthalocyanine also provides highly uniform and symmetric-polarized transport characteristics with conductance enhancements up to two orders of magnitude depending on the polarization. We present a method to spatially map the mobility of the MnPc/F16CuPc structures with a nanoscale resolution and provide theoretical calculations to support our experimental findings. This well-controlled nanoscale tuning of the electrical properties for metal transition phthalocyanine junctions stands as key step for future phthalocyanine-based electronic devices, where the low dimension charge transfer, mediated by transition metal atoms could be intrinsically linked to a transfer of magnetic moment or spin.

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Single-crystalline FeCo nanoparticle-filled carbon nanotubes: Synthesis, structural characterization and magnetic properties

2018, Ghunaim, R., Scholz, M., Damm, C., Rellinghaus, B., Klingeler, R., Büchner, B., Mertig, M., Hampel, S.

In the present work, we demonstrate different synthesis procedures for filling carbon nanotubes (CNTs) with equimolar binary nanoparticles of the type Fe-Co. The CNTs act as templates for the encapsulation of magnetic nanoparticles and provide a protective shield against oxidation as well as prevent nanoparticle agglomeration. By variation of the reaction parameters, we were able to tailor the sample purity, degree of filling, the composition and size of the filling particles, and therefore, the magnetic properties. The samples were analyzed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), superconducting quantum interference device (SQUID) and thermogravimetric analysis (TGA). The Fe-Co-filled CNTs show significant enhancement in the coercive field as compared to the corresponding bulk material, which make them excellent candidates for several applications such as magnetic storage devices.

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Imaging of buried 3D magnetic rolled-up nanomembranes

2014, Streubel, R., Han, L., Kronast, F., Ünal, A.A., Schmidt, O.G., Makarov, D.

Increasing performance and enabling novel functionalities of microelectronic devices, such as three-dimensional (3D) on-chip architectures in optics, electronics, and magnetics, calls for new approaches in both fabrication and characterization. Up to now, 3D magnetic architectures had mainly been studied by integral means without providing insight into local magnetic microstructures that determine the device performance. We prove a concept that allows for imaging magnetic domain patterns in buried 3D objects, for example, magnetic tubular architectures with multiple windings. The approach is based on utilizing the shadow contrast in transmission X-ray magnetic circular dichroism (XMCD) photoemission electron microscopy and correlating the observed 2D projection of the 3D magnetic domains with simulated XMCD patterns. That way, we are not only able to assess magnetic states but also monitor the field-driven evolution of the magnetic domain patterns in individual windings of buried magnetic rolled-up nanomembranes.

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Electrical and magnetic properties of NiTiO3 nanoparticles synthesized by the sol-gel synthesis method and microwave sintering

2019, Pavithra, C., Madhuri, W.

In this paper, we focused on microwave sintered NiTiO3 nanoparticles synthesized via sol-gel method. The crystal structure was determined by the X-ray diffraction. Vibrational bands related to Ni-O and Ti-O bands were confirmed using the Fourier transform infrared spectrum. These NiTiO3 ceramics obeyed semiconductor behavior of Arrhenius type. The activation energy was found to be 0.04 μeV. The M-H curve exhibited superparamagnetic behavior at room temperature.

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Predicting the orientation of magnetic microgel rods for soft anisotropic biomimetic hydrogels

2020, Rose, Jonas C., Fölster, Maaike, Kivilip, Lukas, Gerardo-Nava, Jose L., Jaekel, Esther E., Gehlen, David B., Rohlfs, Wilko, De Laporte, Laura

Living multicellular organisms comprise a high degree of soft anisotropic tissues but the development of controlled artificial assembly processes to mimic them remains challenging. Therefore, injectable, polymeric, magneto-responsive microgel rods are fabricated to orient within a low magnetic field. The incorporated superparamagnetic nanoparticles induce local dipole moments, resulting in a total magnetic torque that endows microgels with different structural, mechanical, and biochemical properties. In this report, a predictive macroscopic model based on an ellipsoidal element dispersed in a Newtonian fluid is adjusted using experimental data, which enables the prediction of the orientation rate and the required magnetic field strength for various microgel design parameters and fluid viscosities. The ordered microgels are fixed by crosslinking of a surrounding hydrogel, and can be employed for a wide variety of applications where anisotropic composite hydrogels play a crucial role; for instance as adaptive materials or in biomedical applications, wherein the model predictions can reduce animal experiments. © 2019 The Royal Society of Chemistry.

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Prenormative verification and validation of a protocol for measuring magnetite–maghemite ratios in magnetic nanoparticles

2021, Bogart, Lara K., Fock, Jeppe, da Costa, Geraldo M., Witte, Kerstin, Greneche, Jean-Marc, Zukrowski, Jan, Sikora, Marcin, Latta, Drew E., Scherer, Michelle M., Hansen, Mikkel Fougt, Frandsen, Cathrine, Pankhurst, Quentin A.

An important step in establishing any new metrological method is a prenormative interlaboratory study, designed to verify and validate the method against its stated aims. Here, the 57Fe Mössbauer spectrometric ‘centre of gravity’ (COG) method was tested as a means of quantifying the magnetite/maghemite (Fe3O4/γ-Fe2O3) composition ratio in biphasic magnetic nanoparticles. The study involved seven laboratories across Europe and North and South America, and six samples—a verification set of three microcrystalline mixtures of known composition, and a validation set of three nanoparticle samples of unknown composition. The spectra were analysed by each participant using in-house fitting packages, and ex post facto by a single operator using an independent package. Repeatability analysis was performed using Mandel’s h statistic and modified Youden plots. It is shown that almost all (83/84) of the Mandel h statistic values fall within the 0.5% significance level, with the one exception being borderline. Youden-based pairwise analysis indicates the dominance of random uncertainties; and in almost all cases the data analysis phase is only a minor contributor to the overall measurement uncertainty. It is concluded that the COG method is a robust and promising candidate for its intended purpose.

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Structural properties of magnetic nanoparticles determine their heating behavior - an estimation of the in vivo heating potential

2014, Ludwig, R., Stapf, M., Dutz, S., Müller, R., Teichgräber, U., Hilger, I.

Magnetically induced heating of magnetic nanoparticles (MNP) in an alternating magnetic field (AMF) is a promising minimally invasive tool for localized tumor treatment by sensitizing or killing tumor cells with the help of thermal stress. Therefore, the selection of MNP exhibiting a sufficient heating capacity (specific absorption rate, SAR) to achieve satisfactory temperatures in vivo is necessary. Up to now, the SAR of MNP is mainly determined using ferrofluidic suspensions and may distinctly differ from the SAR in vivo due to immobilization of MNP in tissues and cells. The aim of our investigations was to study the correlation between the SAR and the degree of MNP immobilization in dependence of their physicochemical features.In this study, the included MNP exhibited varying physicochemical properties and were either made up of single cores or multicores. Whereas the single core MNP exhibited a core size of approximately 15 nm, the multicore MNP consisted of multiple smaller single cores (5 to 15 nm) with 65 to 175 nm diameter in total. Furthermore, different MNP coatings, including dimercaptosuccinic acid (DMSA), polyacrylic acid (PAA), polyethylenglycol (PEG), and starch, wereinvestigated. SAR values were determined after the suspension of MNP in water. MNP immobilization in tissues was simulated with 1% agarose gels and 10% polyvinyl alcohol (PVA) hydrogels.The highest SAR values were observed in ferrofluidic suspensions, whereas a strong reduction of the SAR after the immobilization of MNP with PVA was found. Generally, PVA embedment led to a higher immobilization of MNP compared to immobilization in agarose gels. The investigated single core MNP exhibited higher SAR values than the multicore MNP of the same core size within the used magnetic field parameters. Multicore MNP manufactured via different synthesis routes (fluidMAG-D, fluidMAG/12-D) showed different SAR although they exhibited comparable core and hydrodynamic sizes. Additionally, no correlation between ζ-potential and SAR values after immobilization was observed.Our data show that immobilization of MNP, independent of their physicochemical properties, can distinctly affect their SAR. Similar processes are supposed to take place in vivo, particularly when MNP are immobilized in cells and tissues. This aspect should be adequately considered when determining the SAR of MNP for magnetic hyperthermia.

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Holographic vector field electron tomography of three-dimensional nanomagnets

2019, Wolf, D., Biziere, N., Sturm, S., Reyes, D., Wade, T., Niermann, T., Krehl, J., Warot-Fonrose, B., Büchner, B., Snoeck, E., Gatel, C., Lubk, A.

Complex 3D magnetic textures in nanomagnets exhibit rich physical properties, e.g., in their dynamic interaction with external fields and currents, and play an increasing role for current technological challenges such as energy-efficient memory devices. To study these magnetic nanostructures including their dependency on geometry, composition, and crystallinity, a 3D characterization of the magnetic field with nanometer spatial resolution is indispensable. Here we show how holographic vector field electron tomography can reconstruct all three components of magnetic induction as well as the electrostatic potential of a Co/Cu nanowire with sub 10 nm spatial resolution. We address the workflow from acquisition, via image alignment to holographic and tomographic reconstruction. Combining the obtained tomographic data with micromagnetic considerations, we derive local key magnetic characteristics, such as magnetization current or exchange stiffness, and demonstrate how magnetization configurations, such as vortex states in the Co-disks, depend on small structural variations of the as-grown nanowire.