Conspectus Fullerene carbon cages can encapsulate a wide variety of atoms, ions, clusters, or small molecules inside, resulting in stable compounds with unusual structures and electronic properties. These compounds are collectively defined as endohedral fullerenes. The most studied endohedral fullerenes are those containing metal atoms or ions inside, and these are referred to as endohedral metallofullerenes (EMFs). For EMFs, the inner isolated space of the fullerene cages can lead to the stabilization of unique clusters, which are otherwise not synthetically accessible. This offers an excellent environment and opportunity for investigating the nature of previously unobserved metal–metal, metal–non-metal, and metal–fullerene interactions, which are of fundamental interest and importance. Up until now, most of the work in this field has been mainly focused on the rare-earth metals and related elements (groups II, III, and IV). The encapsulation of other elements of the periodic table could potentially lead to totally new structures and bonding motifs and to material properties beyond those of the existing EMFs. Actinides were originally explored as encapsulated elements in fullerenes when Smalley et al. (Science19922571661) reported mass spectral evidence of actinide endohedral fullerenes back in 1992. However, the full characterization of these actinide endohedral fullerenes, including single crystal X-ray diffractometric analyses, was not reported until very recently, in 2017. In this Account, we highlight some recent advances made in the field of EMF compounds, focusing primarily on the molecular and electronic structures of novel actinide-based EMFs, new evidence for the formation mechanisms of EMFs, and the influence of the entrapped species on the reactivity and regiochemistry of EMF compounds. We recently reported that some monometallic actinide EMFs represent the first examples of tetravalent metals encapsulated inside fullerenes that exhibit considerably stronger host–guest interactions when compared to those observed for the lanthanide EMFs. These unusually strong metal–cage interactions, along with very high mobilities of the actinides inside the fullerene cages at high temperatures, result in the stabilization of unexpected non-IPR (isolated pentagon rule) fullerene cages encapsulating only one metal ion. Strikingly, such covalent stabilization factors had never been previously observed, although Sm@C 2v (19138)-C76 was the first reported mono-EMF with a non-IPR cage, see details below. In addition, we showed that a long sought-after actinide–actinide bond was obtained upon encapsulation of U2 inside an I h (7)-C80 fullerene cage. More interestingly, we demonstrated that actinide multiple bonds, which are very difficult to prepare by conventional synthetic methods, are stabilized when trapped inside fullerene cages. A totally unexpected and previously unreported uranium carbide cluster, UCU, was fully characterized inside an EMF, U2C@I h (7)-C80, which, for the first time, clearly exhibits two unsu...
Increased (18)F-florbetapir binding values were found in patients with late-life major depression relative to comparison subjects in specific brain regions, despite no differences in age, sex, education, Mini Mental Status Examination score, vascular risk factor score, homocysteine and ApoE ε4 genotype between the two groups. A longitudinal follow-up study with a large sample size would be worthwhile.
BackgroundAs elegant structures designed for neural communication, synapses are the building bricks of our mental functions. Recently, many studies have pointed out that synaptic protein-associated mutations may lead to dysfunctions of social cognition. Dlgap2, which encodes one of the main components of scaffold proteins in postsynaptic density (PSD), has been addressed as a candidate gene in autism spectrum disorders. To elucidate the disturbance of synaptic balance arising from Dlgap2 loss-of-function in vivo, we thus generated Dlgap2 −/− mice to investigate their phenotypes of synaptic function and social behaviors.MethodsThe creation of Dlgap2 −/− mice was facilitated by the recombineering-based method, Cre-loxP system and serial backcross. Reversal learning in a water T-maze was used to determine repetitive behaviors. The three-chamber approach task, resident–intruder test and tube task were performed to characterize the social behaviors of mutant mice. Cortical synaptosomal fraction, Golgi-Cox staining, whole-cell patch electrophysiology and transmission electron microscopy were all applied to investigate the function and structure of synapses in the orbitofrontal cortex (OFC) of Dlgap2 −/− mice.ResultsDlgap2 −/− mice displayed exacerbated aggressive behaviors in the resident–intruder task, and elevated social dominance in the tube test. In addition, Dlgap2 −/− mice exhibited a clear reduction of receptors and scaffold proteins in cortical synapses. Dlgap2 −/− mice also demonstrated lower spine density, decreased peak amplitude of miniature excitatory postsynaptic current and ultra-structural deficits of PSD in the OFC.ConclusionsOur findings clearly demonstrate that Dlgap2 plays a vital role in social behaviors and proper synaptic functions of the OFC. Moreover, these results may provide valuable insights into the neuropathology of autism.
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