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Organisationseinheit der BAM
Metallosupramolecular coordination polyelectrolytes (MEPEs) based on rigid and flexible ditopic bis-terpyridine ligands and Fe(II) ions are investigated by Mössbauer spectroscopy. We demonstrate the influence of mechanical stress induced by grinding on the structure of MEPE as well as the ability of MEPE to self-repair through recrystallisation.
The precursor [FeIII(L)Cl] (LH<sub2 = N,N'-bis(2'-hydroxy-benzyliden)-1,6-diamino-3-N-hexane is a high-spin (S = 5/2) complex. This precursor is combined with the bridging units [SnIV(X)4] (X = CN-, NCS-) to yield star-shaped pentanuclear clusters, [(LFeIII-X)4Sn]Cl4. For X = CN- the 57Fe-Mössbauer data show a multiple spin transition between iron(III) in the high-spin and low-spin state, while the 119mSn-Mössbauer data indicate a valence tautomerism between Sn(IV) and Sn(II). Changing the bridging unit from X = CN- to X = NCS- turns the switchability off.
Advanced peptide-based nanomaterials composed of self-assembling peptides (SAPs) are of emerging interest in pharmaceutical and biomedical applications. The introduction of fluorine into peptides, in fact, offers unique opportunities to tune their biophysical properties and intermolecular interactions. In particular, the degree of fluorination plays a crucial role in peptide engineering as it can be used to control the characteristics of fluorine-specific interactions and, thus, peptide conformation and self-assembly. Here, we designed and explored a series of amphipathic peptides by incorporating the fluorinated amino acids (2S)-4-monofluoroethylglycine (MfeGly), (2S)-4,4-difluoroethylglycine (DfeGly) and (2S)-4,4,4-trifluoroethylglycine (TfeGly) as hydrophobic components. This approach enabled studying the impact of fluorination on secondary structure formation and peptide self-assembly on a systematic basis. We show that the interplay between polarity and hydrophobicity, both induced differentially by varying degrees of side chain fluorination, does affect peptide folding significantly. A greater degree of fluorination promotes peptide fibrillation and subsequent formation of physical hydrogels in physiological conditions. Molecular simulations revealed the key role played by electrostatically driven intra-chain and inter-chain contact pairs that are modulated by side chain fluorination and give insights into the different self-organization behaviour of selected peptides. Our study provides a systematic report about the distinct features of fluorinated oligomeric peptides with potential applications as peptide-based biomaterials.
The NanoMag project brings together various leading experts in magnetic nanoparticle synthesis as well as nanoparticle analysis and characterization from research institutes, companies, universities and metrology institutes that will perform cutting-edge research and develop applications in the field of magnetic particles. This work is supported by the European Commission Framework Programme7 under the NanoMag project [grant agreement no 604448].
The mechanism of nanotriangle formation in multivesicular vesicles (MMV) is investigated by using time-dependent SAXS measurements in combination with UV−vis spectroscopy, light, and transmission electron microscopy. In the first time period 6.5 nm sized spherical gold nanoparticles are formed inside of the vesicles, which build up soft nanoparticle aggregates. In situ SAXS experiments show a linear increase of the volume and molar mass of nanotriangles in the second time period. The volume growth rate of the triangles is 16.1 nm3/min, and the growth rate in the vertical direction is only 0.02 nm/min. Therefore, flat nanotriangles with a thickness of 7 nm and a diameter of 23 nm are formed. This process can be described by a diffusionlimited Ostwald ripening growth mechanism. TEM micrographs visualize soft coral-like structures with thin nanoplatelets at the periphery of the aggregates, which disaggregate in the third time period into nanotriangles and spherical particles. The 16 times faster growth of nanotriangles in the lateral than that in the vertical direction is related to the adsorption of symmetry breaking components, i.e., AOT and the polyampholyte PalPhBisCarb, on the {111} facets of the gold nanoplatelets in combination with confinement effects of the vesicular template phase.
Resovist® originally developed as a clinical liver contrast agent for Magnetic Resonance Imaging exhibits also an outstanding performance as a tracer in Magnetic Particle Imaging (MPI). In order to study the physical mechanism of the high MPI performance of Resovist®, we applied asymmetric flow fieldflow fractionation (A4F) and static magnetic fractionation (SMF) to separate Resovist® into a set of fractions with defined size classes. As A4F based on an elution method separates MNP according to their hydrodynamic size, SMF fractionates a particle distribution by its magnetic moment. The obtained fractions of both separation techniques were then magnetically characterized by magnetorelaxometry measurements to extract the corresponding effective magnetic anisotropy and hydrodynamic size distribution parameters. Additionally, the MPI performance of each fraction was assessed using magnetic particle spectroscopy. With both separation techniques fractions (normalized to their iron amount) an MPI signal gain of a factor of two could be obtained, even though the distribution of effective anisotropy and hydrodynamic size were significantly different. Relating these findings to the results from magnetic characterization allows for a better understanding of the underlying mechanisms of MPI performance of Resovist®. This knowledge may help to improve the design of novel MPI tracers and development of separation methods.
Particle size modality in bi-modal iron oxide suspensions was resolved by exploiting complex ac-susceptibility (ACS), small angle X-ray scattering (SAXS) and photon cross-correlation spectroscopy. To explain dynamic magnetic response of bi-modal suspensions, the Debye model was expanded to a linear superposition form allowing for the contribution of both particle fractions. This modified and adopted model is able to resolve the bi-modal particle size distributions. The SAXS curves of mono- and bi-modal suspensions were fitted well using a Monte Carlo simulation scheme, allowing the detection of bi-modal particle size distributions with high precision.
Negatively charged flat gold nanotriangles, formed in a vesicular template phase and separated by an AOT-micelle-based depletion flocculation, were reloaded by adding a cationic polyelectrolyte, that is, a hyperbranched polyethylenimine (PEI). Heating the system to 100 °C in the presence of a gold chloride solution, the reduction process leads to the formation of gold nanoparticles inside the polymer shell surrounding the nanoplatelets. The gold nanoparticle formation is investigated by UV−vis spectroscopy, small-angle X-ray scattering, and dynamic light scattering measurements in combination with transmission electron microscopy. Spontaneously formed gold clusters in the hyperbranched PEI shell with an absorption maximum at 350 nm grow on the surface of the nanotriangles as hemispherical particles with diameters of ∼6 nm. High-resolution micrographs show that the hemispherical gold particles are crystallized onto the {111} facets on the bottom and top of the platelet as well as on the edges without a grain boundary. Undulated gold nanoplatelet superstructures with special properties become available, which show a significantly modified performance in SERS-detected photocatalysis regarding both reactivity and enhancement factor.
The application of appropriate analytical techniques is essential for nanomaterial (NM) characterization. In this study, we compared different analytical techniques for NM analysis. Regarding possible adverse health effects, ionic and particulate NM effects have to be taken into account. As NMs behave quite differently in physiological media, special attention was paid to techniques which are able to determine the biosolubility and complexation behavior of NMs. Representative NMs of similar size were selected: aluminum (Al0) and aluminum oxide (Al2O3), to compare the behavior of metal and metal oxides. In addition, titanium dioxide (TiO2) was investigated. Characterization techniques such as dynamic light scattering (DLS) and nanoparticle tracking analysis (NTA) were evaluated with respect to their suitability for fast characterization of nanoparticle dispersions regarding a particle's hydrodynamic diameter and size distribution. By application of inductively coupled plasma mass spectrometry in the single particle mode (SP-ICP-MS), individual nanoparticles were quantified and characterized regarding their size. SP-ICP-MS measurements were correlated with the information gained using other characterization techniques, i.e. transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). The particle surface as an important descriptor of NMs was analyzed by X-ray diffraction (XRD). NM impurities and their co-localization with biomolecules were determined by ion beam microscopy (IBM) and confocal Raman microscopy (CRM). We conclude advantages and disadvantages of the different techniques applied and suggest options for their complementation. Thus, this paper may serve as a practical guide to particle characterization techniques.
We studied the magnetic resonance imaging liver contrast agent Resovist by a variety of magnetic measurement techniques, in order to understand the physical mechanism of their high magnetic particle imaging (MPI) performance, wirh a focus on the size-dependent contributions of the MPI signal. To this end, we used asymmetric flow field-flow fractionation to separate Resovist into a set of fractions with defined hydrodynamic diameters. The individual fractions were magnetically characterized by static magnetization and magnetorelaxometry measurements to obtain the corresponding effective magnetic anisotropy and effective size distribution parameters. In addition, the MPI performance of each fraction was assessed by magnetic particle spectroscopy. We observed an MPI signal gain of about 100% with respect to their iron amount for the best fraction. Relating these finding to the results from magnetic characterization provides more insight into mechanisms of MPI performance of Resovist. This knowledge may help to improve the design of novel MPI tracers.