Adult-born granule cells modulate CA2 network activity during retrieval of developmental memories of the mother.

Adult-born granule cells (abGCs) project to the CA2 region of the hippocampus, but it remains unknown how this circuit affects behavioral function. Here, we show that abGC input to the CA2 of adult mice is involved in the retrieval of remote developmental memories of the mother. Ablation of abGCs impaired the ability to discriminate between a caregiving mother and a novel mother, and this ability returned after abGCs were regenerated. Chemogenetic inhibition of projections from abGCs to the CA2 also temporarily prevented the retrieval of remote mother memories. These findings were observed when abGCs were inhibited at 4-6 weeks old, but not when they were inhibited at 10-12 weeks old. We also found that abGCs are necessary for differentiating features of CA2 network activity, including theta-gamma coupling and sharp wave ripples, in response to novel versus familiar social stimuli. Taken together, these findings suggest that abGCs are necessary for neuronal oscillations associated with discriminating between social stimuli, thus enabling retrieval of remote developmental memories of the mother by their adult offspring.

Inner and outer beauty.

Symmetry and pattern are precious forms of beauty that can be appreciated on both the macroscopic and molecular scales. Crystallographers have long appreciated the intimate connections between symmetry and molecular structure, reflected in their appreciation for the artwork of Escher. This admiration has been applied in the design of highly symmetrical coordination compounds. Two classes of materials are discussed: extended coordination arrays and discrete supramolecular assemblies. Extended coordination polymers have been implemented in gas separation and storage due to the remarkably porosity of these materials, aided by the ability to design ever-larger inner spaces within these frameworks. In the case of discrete symmetrical structures, defined inner and outer space present a unique aesthetic and chemical environment. The consequent host-guest chemistry and applications in catalysis are discussed.

Hydroalkoxylation catalyzed by a gold(I) complex encapsulated in a supramolecular host.

Gold(I)-phosphine complexes are readily encapsulated by a tetrahedral supramolecular host (Ga(4)L(6)). We have investigated the catalytic activity of the resulting complexes for the intramolecular hydroalkoxylation of allenes. The catalytic activity of Me(3)PAuBr was increased 8-fold by encapsulation, as determined by initial rate kinetics, and we observed up to 67 catalytic turnovers by Me(3)PAu(+) encapsulated in Ga(4)L(6).

High-turnover supramolecular catalysis by a protected ruthenium(II) complex in aqueous solution.

The design of a supramolecular catalyst capable of high-turnover catalysis is reported. A ruthenium(II) catalyst is incorporated into a water-soluble supramolecular assembly, imparting the ability to catalyze allyl alcohol isomerization. The catalyst is protected from decomposition by sequestration inside the host but retains its catalytic activity with scope governed by confinement within the host. This host-guest complex is a uniquely active supramolecular catalyst, capable of >1000 turnovers.

Enantioselective catalysis of the aza-Cope rearrangement by a chiral supramolecular assembly.

The chiral supramolecular catalyst Ga(4)L(6) [L = 1,5-bis(2,3-dihydroxybenzoylamino)naphthalene] is a molecular tetrahedron that catalyzes the 3-aza-Cope rearrangement of allyl enammonium cations. This catalysis is accomplished by preorganizing the substrate in a reactive conformation within the host. This work demonstrates that through the use of enantiopure assembly, its chiral cavity is capable of catalyzing the 3-aza-Cope rearrangement enantioselectively, with yields of 21-74% and enantiomeric excesses from 6 to 64% at 50 degrees C. At lower temperatures, the enantioselectivity improved, reaching 78% ee at 5 degrees C. This is the highest enantioselectivity to date induced by the chiral cavity of a supramolecular assembly.