Hollow polymeric capsules prepared from Layer-by-Layer coating of colloidal templates with polyelectrolyte multilayers are promising materials for drug delivery and release applications. Details of the wall structure arising from the core dissolution process are investigated by high resolution scanning electron microscopy (SEM), using both secondary (SE) and backscattered electron (BSE) imaging modes. Atomic force microscopy (AFM) of the capsules in liquid was used as an independent technique. BSE images of the coated templates may be used for a rough estimation of the wall thickness. A freeze-drying procedure allows for the first time the investigation of dried multilayer capsules with an intact shape by SEM. Details of the nanostructure of the capsule walls are obtained, the topography shows structures on the scale of several 10 nm, corresponding to single chains. These structures are confirmed by AFM in liquid. In addition, after core dissolution single holes with sizes above 10 nm can be identified in the capsule wall. These holes are the structural property controlling the permeation and release and are here visualized for the first time. The number of holes per capsule as well as their distribution and size are analysed and discussed in their relevance for release applications.Scheme 1 Graphical illustration of the composition of the capsules.

Cyclodextrin vesicles (CDVs) consist of a bilayer of amphiphilic cyclodextrins (CDs). CDVs exhibit CD cavities at their surface that are able to recognize and bind hydrophobic guest molecules via size-selective inclusion. In this study, the permeability of α- and β-CDVs is investigated by pulsed field gradient-stimulated echo (PFG-STE) nuclear magnetic resonance. Diffusion experiments with water and two types of water-soluble polymers, polyethylene glycol (PEG) and polypropylene glycol (PPG), revealed three main factors that influence the exchange rate and permeability of CDVs. First, the length of the hydrophobic chain of the CD amphiphile plays a crucial role. Reasonably, vesicles consisting of amphiphiles with a longer aliphatic chain are less permeable since both membrane thickness and melting temperature T(m) increase. Second, the exchange rate through the bilayer membrane depends on the molecular weight of the polymer and decreases with increasing weight of the polymer. Most interestingly, a size-selective distinction of permeation due to the embedded CDs in the bilayer membrane was found. The mechanism of permeation is shown to occur through the CD cavity, such that depending on the size of the cavity, permeation of polymers with different cross-sectional diameters takes place. Whereas PPG permeates through the membrane of β-CD vesicles, it does not permeate α-CD vesicles.