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In all metallofullerenes known before this work, metal atoms form single highly polar bonds with non-metal atoms in endohedral cluster. This is rather surprising for titanium taking into account the diversity of organotitanium compounds. Here we show that the arc-discharge synthesis of mixed titanium-lutetium metallofullerenes in the presence of ammonia, melamine or methane unexpectedly results in the formation of TiLu 2 C@ I h -C 80 with an icosahedral I h (7) carbon cage. Single-crystal X-ray diffraction and spectroscopic studies of the compound reveal an unprecedented endohedral cluster with a μ 3 -carbido ligand and Ti-C double bond. The Ti(IV) in TiLu 2 C@ I h -C 80 can be reversibly reduced to the Ti(III) state. The Ti=C bonding and Ti-localized lowest unoccupied molecular orbital in TiLu 2 C@ I h -C 80 bear a certain resemblance to titanium alkylidenes. TiLu 2 C@ I h -C 80 is the first metallofullerene with a multiple bond between a metal and the central, non-metal atom of the endohedral cluster. Metallofullerenes typically have polar single bonds between metals and non-metals. Here, through arc-discharge experiments, the authors observe the formation of an endohedral fullerene with an encapsulated tri-coordinate μ 3 -carbon centre and a stable titanium-carbon double bond.

In all metallofullerenes known before this work, metal atoms form single highly polar bonds with non-metal atoms in endohedral cluster. This is rather surprising for titanium taking into account the diversity of organotitanium compounds. Here we show that the arc-discharge synthesis of mixed titanium-lutetium metallofullerenes in the presence of ammonia, melamine or methane unexpectedly results in the formation of TiLu2 C@Ih -C80 with an icosahedral Ih (7) carbon cage. Single-crystal X-ray diffraction and spectroscopic studies of the compound reveal an unprecedented endohedral cluster with a μ3 -carbido ligand and Ti-C double bond. The Ti(IV) in TiLu2 C@Ih -C80 can be reversibly reduced to the Ti(III) state. The Ti=C bonding and Ti-localized lowest unoccupied molecular orbital in TiLu2 C@Ih -C80 bear a certain resemblance to titanium alkylidenes. TiLu2 C@Ih -C80 is the first metallofullerene with a multiple bond between a metal and the central, non-metal atom of the endohedral cluster.

Background Concerns exist regarding the impact of widely used clinical drugs on brain development. This study investigates long-term neurocognitive functioning in relation to frequently used drug exposure at the Pediatric Intensive Care Unit (PICU). Methods This study compared children aged 6–12 years with previous PICU admission (age ≤1 year) for bronchiolitis requiring mechanical ventilation (patient group, n  = 65) to a demographically comparable control group ( n  = 76) on a broad range of neurocognitive outcomes. The patient group was selected because bronchiolitis seldom manifests neurologically and is therefore not expected to affect neurocognitive functioning in itself. The relation between exposure to sedatives, analgesics and anesthetics and neurocognitive outcomes was assessed by regression analyses. Results The patient group had lower intelligence than the control group ( p  < 0.001, d  = −0.59) and poorer performance in neurocognitive functions; i.e., speed and attention ( p  = 0.03, d  = −0.41) and verbal memory ( p  < 0.001, d  = −0.60). Exposure to sedatives, analgesics and anesthetics was not related to neurocognitive outcomes. Conclusions Children with PICU admission for bronchiolitis requiring mechanical ventilation are at risk of adverse neurocognitive outcomes. This study found no evidence for a role of exposure to sedatives, analgesics or anesthetics. Findings underline the importance of long-term follow-up after PICU admission, even in the absence of disease with neurological manifestation. Impact Animal studies have indicated that exposing the maturing brain to clinical drugs may cause neurodegeneration. Clinical studies show mixed evidence regarding the association between clinical drugs and neurocognitive outcomes. This study provides evidence for considerably lower neurocognitive functioning among children with a history of PICU admission for bronchiolitis compared to healthy peers. Bronchiolitis seldom manifests neurologically and is therefore not expected to affect neurocognitive functioning in itself. We found no evidence supporting a relation between drug exposure (i.e., sedatives, analgesics and anesthetics) and long-term neurocognitive outcomes. Findings underline the importance of structured follow-up after PICU admission.