Project description:Electronic communication between concentric macrocycles with wave functions that extend around their circumferences can lead to remarkable behavior, as illustrated by multiwalled carbon nanotubes and photosynthetic chlorophyll arrays. However, it is difficult to hold one π-conjugated molecular ring inside another. Here, we show that ring-in-ring complexes, consisting of a 6-porphyrin ring locked inside a 12-porphyrin ring, can be assembled by placing different metals in the two rings (zinc and aluminum). A bridging ligand with carboxylate and imidazole binding sites forms spokes between the two rings, resulting in a highly cooperative supramolecular self-assembly process. Excitation is transferred from the inner 6-ring to the outer 12-ring of this Russian doll complex within 40 ps. These complexes lead to a form of template-directed synthesis in which one nanoring promotes formation of a larger concentric homologous ring; here, the effective template is an eight-component noncovalent assembly. Russian doll templating provides a new approach to amplifying the size of a covalent nanostructure.
Project description:It has long been hypothesized that pretend play is beneficial to social and cognitive development. However, there is little evidence regarding the neural regions that are active while children engage in pretend play. We examined the activation of prefrontal and posterior superior temporal sulcus (pSTS) regions using near-infrared spectroscopy while 42 4- to 8-year-old children freely played with dolls or tablet games with a social partner or by themselves. Social play activated right prefrontal regions more than solo play. Children engaged the pSTS during solo doll play but not during solo tablet play, suggesting they were rehearsing social cognitive skills more with dolls. These findings suggest social play utilizes multiple neural regions and highlight how doll play can achieve similar patterns of activation, even when children play by themselves. Doll play may provide a unique opportunity for children to practice social interactions important for developing social-emotional skills, such as empathy.