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.

3D mapping of crystal and nanostructure orientation shows that bone contains a mineral fraction not aligned with the nanostructure.

New 4^th-generation synchrotron sources, with their increased brilliance, promise to greatly improve the performances of coherent X-ray microscopy. This perspective is of major interest for crystal microscopy, which aims at revealing the 3D crystalline structure of matter at the nanoscale, an approach strongly limited by the available coherent flux. Our results, based on Bragg ptychography experiments performed at the first 4^th-generation synchrotron source, demonstrate the possibility of retrieving a high-quality image of the crystalline sample, with unprecedented quality. Importantly, the larger available coherent flux produces datasets with enough information to overcome experimental limitations, such as strongly deteriorated scanning conditions. We show this achievement would not be possible with 3^rd-generation sources, a limit that has inhibited the development of this otherwise powerful microscopy method, so far. Hence, the advent of next-generation synchrotron sources not only makes Bragg ptychography suitable for high throughput studies but also strongly relaxes the associated experimental constraints, making it compatible with a wider range of experimental set-ups at the new synchrotrons.

Fundamental research on nanoparticle (NP) interactions and development of next generation biomedical NP applications relies on synthesis of monodisperse, functional, core-shell nanoparticles free of residual dispersants with truly homogeneous and controlled physical properties. Still, synthesis and purification of, e.g., such superparamagnetic iron oxide nanoparticles remain a challenge. Comparing the success of different methods is marred by the sensitivity of analysis methods to the purity of the product. We synthesize monodisperse, oleic acid (OA) capped, Fe3O4 NPs in the superparamagnetic size range (3-10 nm). Ligand exchange of OA for poly(ethylene glycol) (PEG) was performed with the PEG irreversibly grafted to the NP surface by a nitrodopamine (NDA) anchor. Four different methods were investigated to remove excess ligands and residual OA: Membrane centrifugation, dialysis, size exclusion chromatography and precipitation combined with magnetic decantation. Infrared spectroscopy and thermogravimetric analysis were used to determine the purity of samples after each purification step. Importantly, only magnetic decantation yielded pure NPs at high yields with sufficient grafting densities for biomedical applications (~1 NDA-PEG(5kDa)/nm2, irrespective of size). The purified NPs withstand challenging tests such as temperature cycling in serum and long-term storage in biological buffers. Dynamic light scattering, transmission electron microscopy and small angle X-ray scattering show stability over at least 4 months also in serum. The successful synthesis and purification route is compatible with any conceivable functionalization for biomedical or biomaterial applications, such as targeted magnetic resonance imaging and drug delivery of PEGylated Fe3O4 NPs.

Bone is a complex, biological tissue made up primarily of collagen fibrils and biomineral nanoparticles. The importance of hierarchical organization in bone was realized early on, but the actual interplay between structural features and the properties on the nanostructural and crystallographic level is still a matter of intense discussion. Bone is the only mineralized tissue that can be remodeled and, at the start of the formation of new bone during this process, a structure called a cement line is formed on which regular bone grows. Here, the orientational relationship of nanostructural and crystallographic constituents as well as the structural properties of both nanostructural and crystallographic constituents around cement lines and the Haversian system in human lamellar bone are investigated. A combination of small- and wide-angle X-ray scattering tensor tomography is employed together with diffraction tomography and synchrotron computed tomography to generate a multi-modal image of the sample. This work shows that the mineral properties vary as a function of the distance to the Haversian canal and, importantly, shows that the cement line has differing mineral properties from the surrounding lamellar bone, in particular with respect to crystallite size and degree of orientation. Cement lines make up a significant portion of the bone matrix despite their small size, hence the reported findings on an altered mineral structure, together with the spatial modulation around the Haversian canal, have implications for the formation and mechanics of bone.