Defined aggregates of polymers such as polymeric micelles are of great importance in the development of pharmaceutical formulations. The amount of drug that can be formulated by a drug delivery system is an important issue, and most drug delivery systems suffer from their relatively low drug-loading capacity. However, as the loading capacities increase, i.e., promoted by good drug–polymer interactions, the drug may affect the morphology and stability of the micellar system. We investigated this effect in a prominent system with very high capacity for hydrophobic drugs and found extraordinary stability as well as a profound morphology change upon incorporation of paclitaxel into micelles of amphiphilic ABA poly(2-oxazoline) triblock copolymers. The hydrophilic blocks A comprised poly(2-methyl-2-oxazoline), while the middle blocks B were either just barely hydrophobic poly(2-n-butyl-2-oxazoline) or highly hydrophobic poly(2-n-nonyl-2-oxazoline). The aggregation behavior of both polymers and their formulations with varying paclitaxel contents were investigated by means of dynamic light scattering, atomic force microscopy, (cryogenic) transmission electron microscopy, and small-angle neutron scattering. While without drug, wormlike micelles were present, after incorporation of small amounts of drugs only spherical morphologies remained. Furthermore, the much more hydrophobic poly(2-n-nonyl-2-oxazoline)-containing triblock copolymer exhibited only half the capacity for paclitaxel than the poly(2-n-butyl-2-oxazoline)-containing copolymer along with a lower stability. In the latter, contents of paclitaxel of 8 wt % or higher resulted in a raspberry-like micellar core.

Many experimental methods are available for the characterization of nanostructures, but most of them are limited by stringent experimental conditions. When it comes to analysing nanostructures in the bulk or in their natural environment – even as ordinary as water at room temperature – small-angle scattering (SAS) of X-rays or neutrons is often the only option. The rapid worldwide development of synchrotron and neutron facilities over recent decades has opened unprecedented possibilities for using SAS in situ and in a time-resolved way. But, in spite of its huge potential in the field of nanomaterials in general, SAS is covered far less than other characterization methods in non-specialized curricula. Presented here is a rigorous discussion of small-angle scattering, at a technical level comparable to the classical undergraduate coverage of X-ray diffraction by crystals and which contains diffraction as a particular case.

The reorientation of lamellae and the dependence of the lamellar spacing, D_lam, on polymer volume fraction, ϕ_P, D_lam ∝ ϕ_P^–β, in diblock copolymer thin films during solvent vapor annealing (SVA) are examined by combining white light interferometry (WLI) and grazing-incidence small-angle X-ray scattering (GISAXS). A thin film of lamellae-forming poly(styrene-b-butadiene) prepared by spin-coating features lamellae of different orientations with the lamellar spacing depending on orientation. During annealing with ethyl acetate (EAC) vapor, it is found that perpendicular lamellae behave differently from parallel ones, which is due to the fact that their initial lamellar thicknesses differ strongly. Quantitatively, the swelling process is composed of three regimes and the drying process of two regimes. The first two regimes of swelling are associated with a significant structural rearrangement of the lamellae; i.e., the lamellae first become thicker, and then perpendicular and randomly oriented lamellae vanish, which results in a purely parallel orientation at the end of the swelling process. The rearrangement is attributed to the increase of mobility of the polymer chains imparted by the solvent and to a decrease of total free energy of the thin film. In the third regime of swelling, the scaling exponent is found to be β = −0.32. During drying, the deswelling is nonaffine which may be a consequence of the increase of nonfavorable segmental interactions as the solvent is removed.

Nanoparticles play an important role in controlling the mobility of pollutants such as arsenic (As) in the environment. In natural waters, aggregates of nanoparticles can be constituted of organic matter (OM) associated with iron (Fe). However, little is known about their network structure, especially the role of each component in the resulting aggregate morphology. This network structure can be of major importance for the metal and metalloid sorption processes. We synthesized an aggregate model of nanoparticles by varying the Fe/organic carbon (OC) ratio (R). By coupling small-angle neutron and X-ray scattering (SANS, SAXS), dynamic light scattering (DLS), transmission electron microscopy (TEM) and X-ray absorption spectroscopy (XAS), we revealed the fractal organization of Fe (i.e. primary beads forming a nanoparticle called an intermediate aggregate and then forming a secondary aggregate of nanoparticles). As the aggregate size increases with R, the As adsorption rate increases at a constant As/Fe ratio. Two hypotheses were considered: with increasing R, i) the repulsion interactions between the nanoparticles increase, inducing a structure opening, and ii) the Fe part size increases more strongly and is more ramified than the OM part, leading to a decrease of the coating by OM. Both hypotheses involve an increase in the number of available As binding sites. This study offers new perspectives on the impact of the network structure of heterogeneous nano-aggregates on their sorption capacity and could explain some metal/metalloid sorption variations observed in natural samples with variations in Fe/OC ratios.