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In the field of nanometre‐sized drug‐delivery systems, a wide range of colloidal systems have been created in recent decades. All of the systems have a similar global structure, that is, an inner part and an external surface/interface. In several applications, the external interface is the support for desired properties and the basis of future developments. The engineering of the particle’s surface is an emerging step in the design of systems at the nanometre scale. This review presents and summarises the available techniques with a particular attention to recent advances. It is also a base for future works in this expanding area of research.

We have utilized para‐hexanoylcalix[4]arene nanocapsules as hosts to carry out phototransformations of cis‐ and trans‐stilbene. Single‐crystal X‐ray diffraction studies were performed to define precisely the location of encapsulated stilbenes inside the capsule and to analyze possible pathways of phototransformation. cis‐Stilbene stacks as a π–π dimer located at the center of the capsule, whereas trans‐stilbene does not form such a dimer. Irradiation of the crystalline inclusion complexes of each isomer of stilbene in the solid state leads to the appearance of the second isomer, and after prolonged photolysis, photodimerization also occurs. syn‐Tetraphenylcyclobutane is formed as the major product of dimerization and its yield depends on the time and intensity of irradiation. In most cases, the single crystals of the complexes remain intact during irradiation; hence, the nanocapsules have the potential to serve as robust nanoreactors in the solid state. The confinement in the nanocapsules is sufficient to keep the reacting molecules together, although this is less restrictive than for trans‐stilbene crystals, in which the molecules cannot achieve a favorable orientation for dimerization.

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An intercomparison exercise was led in order to study the impact of thermodynamic database (TDB) on the speciation of americium(III) in biochemical media.

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