Core-Shell Structure of Monodisperse Poly(ethylene glycol)-Grafted Iron Oxide Nanoparticles Studied by Small-Angle X-ray Scattering

The promising applications of core-shell nanoparticles in the biological and medical field have been well investigated in recent years. One remaining challenge is the characterization of the structure of the hydrated polymer shell. Here we use small-angle X-ray scattering (SAXS) to investigate iron oxide core-poly(ethylene glycol) brush shell nanoparticles with extremely high polymer grafting density. It is shown that the shell density profile can be described by a scaling model that takes into account the locally very high grafting density near the core. A good fit to a constant density region followed by a star-polymer-like, monotonously decaying density profile is shown, which could help explain the unique colloidal properties of such densely grafted core-shell nanoparticles. SAXS experiments probing the thermally induced dehydration of the shell and the response to dilution confirmed that the observed features are associated with the brush and not attributed to structure factors from particle aggregates. We thereby demonstrate that the structure of monodisperse core-shell nanoparticles with dense solvated shells can be well studied with SAXS and that different density models can be distinguished from each other. (Graph Presented)

Monodisperse Iron Oxide Nanoparticles by Thermal Decomposition: Elucidating Particle Formation by Second-Resolved in Situ Small-Angle X‑ray Scattering

The synthesis of iron oxide nanoparticles (NPs) by thermal decomposition of iron precursors using oleic acid as surfactant has evolved to a state-of-the-art method to produce monodisperse, spherical NPs. The principles behind such monodisperse syntheses are well-known: the key is a separation between burst nucleation and growth phase, whereas the size of the population is set by the precursor-to-surfactant ratio. Here we follow the thermal decomposition of iron pentacarbonyl in the presence of oleic acid via in situ X-ray scattering. This method allows reaction kinetics and precursor states to be followed with high time resolution and statistical significance. Our investigation demonstrates that the final particle size is directly related to a phase of inorganic cluster formation that takes place between precursor decomposition and particle nucleation. The size and concentration of clusters were shown to be dependent on precursor-to-surfactant ratio and heating rate, which in turn led to differences in the onset of nucleation and concentration of nuclei after the burst nucleation phase. This first direct observation of prenucleation formation of inorganic and micellar structures in iron oxide nanoparticle synthesis by thermal decomposition likely has implications for synthesis of other NPs by similar routes

Aligned multi-walled carbon nanotube-embodied hydrogel via low magnetic field:a strategy for engineering aligned injectable scaffolds

Abstract Injectable scaffolds are a promising strategy to restore and regenerate damaged and diseased tissues. They require minimally invasive procedure and allow the formation of an in-situ structure of any shape. However, the formation of 3D in-situ structure with aligned morphologies using a method which could be easily transferred to clinical settings remains a challenge. Herein, the rational design of an aligned injectable hydrogel-based scaffold via remote-induced alignment is reported. Carboxylated multi-walled carbon nanotubes (cMWCNT) are aligned into hydrogel via low magnetic field. The uniform dispersion and alignment of cMWCNT into the hydrogel are clearly demonstrated by small angle neutron scattering. The obtained aligned cMWCNT-embodied hydrogel is stable over 7 days at room temperature and as well at body temperature (i.e. 37 °C). As unique approach, the formation of MWCNT-hydrogel composite is investigated combining rheology with molecular dynamic and quantum mechanical calculations. The increase of MWCNT concentration into the hydrogel decreases the total energy promoting structural stabilization and increase of stiffness. The remote aligning of injectable hydrogel-based scaffold opens up horizons in the engineering of functional tissues which requires specific cell orientation

Doping Method Determines Para- or Superparamagnetic Properties of Photostable and Surface-Modifiable Quantum Dots for Multimodal Bioimaging

Semiconductor quantum dots (QDs) are widely used for optical applications and bioimaging. In comparison to organic dyes used for fluorescent labeling, QDs exhibit very high photostability and can be further surface modified. Equipping QDs with magnetic properties (mQDs) makes it possible to combine fluorescence and magnetic resonance imaging analyses. For this purpose, we have prepared water-dispersible and magnetic CdTe/ZnS mQDs, whereby ferrous ions are selectively incorporated in either their cores or their shells. This study aims at understanding the differences in optical, structural, and magnetic properties between these core- and shell-doped mQDs. Field-dependent isothermal magnetic susceptibility measurements show that shell-doped mQDs exhibit paramagnetic and their core-doped equivalents super­paramagnetic behavior near room temperature. Shell doping results in about 1.7 times higher photoluminescence quantum yields and 1.4 times higher doping efficiency than core doping. X-ray diffraction patterns reveal that core doping leads to defects in the lattice and hence to a severe decrease in crystallinity, whereas shell doping has no significant impact on the crystal structure and consequently fewer disadvantages regarding the mQD’s quantum yield. These selective doping approaches, particularly shell doping, allow for the tailored design of paramagnetic QDs having modifiable and biocompatible particle surfaces. The organic ligandsin this study <i>N</i>-acetyl-l-cysteinesufficiently prevent leakage of toxic metal ions, as shown by cytotoxicity assays with HepG2 cells. Confocal laser scanning microscopy shows that mQDs are internalized by these cells and accumulated near their nuclei. This study shows that biocompatible, fluorescent, and paramagnetic QDs are promising photostable labels for multimodal bioimaging