RESUMEN
Solid-liquid interfaces play an important role for functional devices. Hence, a detailed understanding of the interaction of soft matter objects with solid supports and of the often concomitant structural deformations is of great importance. We address this topic in a combined experimental and simulation approach. We investigated thermoresponsive poly(N-isopropylmethacrylamide) microgels (µGs) at different surfaces in an aqueous environment. As super-resolution fluorescence imaging method, three-dimensional direct stochastical optical reconstruction microscopy (dSTORM) allowed for visualizing µGs in their three-dimensional (3D) shape, for example, in a "fried-egg" conformation depending on the hydrophilicity of the surface (strength of adsorption). The 3D shape, as defined by point clouds obtained from single-molecule localizations, was analyzed. A new fitting algorithm yielded an isosurface of constant density which defines the deformation of µGs at the different surfaces. The presented methodology quantifies deformation of objects with fuzzy surfaces and allows for comparison of their structures, whereby it is completely independent from the data acquisition method. Finally, the experimental data are complemented with mesoscopic computer simulations in order to (i) rationalize the experimental results and (ii) to track the evolution of the shape with changing surface hydrophilicity; a good correlation of the shapes obtained experimentally and with computer simulations was found.
RESUMEN
The development of new contrast agents (CAs) for magnetic resonance imaging (MRI) is of high interest, especially because of the increased concerns of patient safety and quick clearance of clinically used gadolinium and iron oxide-based CAs, respectively. Here, a two-step synthesis of superparamagnetic water-soluble iron platinum (FePt) nanoparticles (NPs) with core sizes between 2 and 8 nm for use as CAs in MRI is reported. First, wet-chemical organometallic NPs are synthesized by thermal decomposition in the presence of stabilizing oleic acid and oleylamine. Second, the hydrophobic NPs are coated with an amphiphilic polymer and transferred into aqueous media. Their magnetization values and relaxation rates exceed those published for CAs already used for clinical application. Their saturation magnetization increases with the core size to approximately 82 A·m2/kgFe. For 8 nm NPs, the T2 relaxivity of approximately 221 (mM·s)-1 is 5 times larger than that for the ferumoxides, and for 6 nm NPs, the T1 relaxivity of approximately 12 (mM·s)-1 is slightly higher than that of ultrasmall gadolinium oxide NPs. The 6 nm FePt NPs are identified as excellent CAs for both T1 and T2 imaging. Most importantly, because of their coating, significantly low cytotoxicity is achieved. FePt NPs prove to be a promising alternative to gadolinium and iron oxide NPs showing high-quality CA characteristics for both T1- and T2-weighted images.
RESUMEN
Compartmentalization in soft matter is important for segregating and coordinating chemical reactions, sequestering (re)active components, and integrating multifunctionality. Advances depend crucially on quantitative 3D visualization in situ with high spatiotemporal resolution. Here, we show the direct visualization of different compartments within adaptive microgels using a combination of in situ electron and super-resolved fluorescence microscopy. We unravel new levels of structural details and address the challenge of reconstructing 3D information from 2D projections for nonuniform soft matter as opposed to monodisperse proteins. Moreover, we visualize the thermally induced shrinkage of responsive core-shell microgels live in water. This strategy opens doors for systematic in situ studies of soft matter systems and their application as smart materials.
RESUMEN
A novel DNA-microgel hybrid system with dual thermal responsiveness is introduced uitilizing covalent coupling of single stranded DNA (ssDNA) to thermoresponsive microgels (µGs). The spatial distribution of the coupling sites for the ssDNA was characterized with 3D superresolution fluorescence microscopy. The DNA-functionalized µGs remain thermoresponsive and can take up dye-labeled complementary ssDNA, which can be released again by overcoming the dehybridization temperature of the DNA independently of the volume phase transition (VPT) of the µGs. The same holds for nano-objects represented by plasmonic gold nanoparticles (AuNPs), the penetration depth of which was visualized via TEM tomography and 3D reconstruction and which show enhanced plasmonic coupling in the collapsed state of the µG and thus gets switchable. In contrast, if ssDNA was taken up just by non-specific interactions, i.e. into non-functionalized µGs, its release is temperature-independent and can only be induced by increasing the salt concentration. Thus, the incorporated ssDNA represents highly selectice binding sites determined by their base number and sequence, which makes the VPT, beeing determined by the µG composition, and the reversible uptake and release enabled through programmable DNA hybridization are independent features. The combination with the typically high biocompatibility and the retained swellability and permeability hold promise for new fundamental insights as well as for potential applications in biological environments.