The chelating gadolinium-complex is routinely used as magnetic resonance imaging (MRI) -contrast enhancer. However, several safety issues have recently been reported by FDA and PRAC. There is an urgent need for the next generation of safer MRI-contrast enhancers, with improved local contrast and targeting capabilities. Cerium oxide nanoparticles (CeNPs) are designed with fractions of up to 50% gadolinium to utilize the superior MRI-contrast properties of gadolinium. CeNPs are well-tolerated in vivo and have redox properties making them suitable for biomedical applications, for example scavenging purposes on the tissue- and cellular level and during tumor treatment to reduce in vivo inflammatory processes. Our near edge X-ray absorption fine structure (NEXAFS) studies show that implementation of gadolinium changes the initial co-existence of oxidation states Ce3+ and Ce4+ of cerium, thereby affecting the scavenging properties of the nanoparticles. Based on ab initio electronic structure calculations, we describe the most prominent spectral features for the respective oxidation states. The as-prepared gadolinium-implemented CeNPs are 3–5 nm in size, have r1-relaxivities between 7–13 mM−1 s−1 and show clear antioxidative properties, all of which means they are promising theranostic agents for use in future biomedical applications.

Protein-metal ion interactions are ubiquitous in nature and can be utilized for controlling the self-assembly of complex supramolecular architectures and materials. Here, a tunable supramolecular hydrogel is described, obtained by self-assembly of a Zn2+-responsive peptide-hyaluronic acid hybrid synthesized using strain promoted click chemistry. Addition of Zn2+ triggers folding of the peptides into a helix-loop-helix motif and dimerization into four-helix bundles, resulting in hydrogelation. Removal of the Zn2+ by chelators results in rapid hydrogel disassembly. Degradation of the hydrogels can also be time-programed by encapsulation of a hydrolyzing enzyme within the gel, offering multiple possibilities for modulating materials properties and release of encapsulated species. The hydrogel further shows potential antioxidant properties when evaluated using an in vitro model for reactive oxygen species.

Combined photoemission electron microscopy (PEEM) and imaging x-ray photoelectron spectroscopy (XPS), i.e., electron spectroscopy for chemical analysis in the nanoregion, has been used for surface characterization of bio-relevant and biological samples. In the first example, the authors prepared a gold patterned silicon substrate, stepwise surface modified by self-assembled monolayers followed by quantum dot (QDot) specific linking and investigated by means of work function mapping and elemental imaging in the submicrometer range. Spatially resolved core level images of C1s, V2p, and Y3d are obtained, which verify the selective thiol adsorption on the gold squares and specific binding of europium doped yttrium vanadate QDots on the self-assembled monolayer. The second example is platelet adhesion to Immunoglobulin G modified silicon surfaces, investigated by means of laterally resolved PEEM. Images of platelets clearly show activated cells with a morphology change including an enlarged surface area and elongated pseudopodia, with a lateral resolution of 140 nm. In the last example, neutrophils were allowed to attach to plain silicon surfaces and investigated by means of PEEM and imaging XPS. Here, the cells show a round shaped morphology, as expected. Threshold imaging with work function contrast is used to localize the area of interest, followed by elemental specific mapping on cells in the submicrometer region. Chemical shifts of C1s in photoemission are used to distinguish vital parts of the cell structure. The strong C1s (C-C) signal is achieved from the region of the cell membrane, i.e., high density of phospholipids, while C1s (C-N) and C1s (C-O) signals are obtained from the core of the cell, in good agreement with the presence of cytoplasm and deoxyribonucleic acid containing cell nucleus. The combination of PEEM and imaging XPS is shown here as a tool to deliver new insight into biological samples, i.e., a rapid sample overview is obtained based on low energy secondary electrons with work function contrast, followed by detailed studies in the narrow mode for elemental compositions based on photoemission. This study illustrates the strength of combined PEEM and XPS in the imaging mode on cell studies.

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Novel pyrimidine imidazole derivatives with flexible ether chains have been synthesised and evaluated for their cell imaging performanceviaphotophysical investigations and theoretical calculations.