Multiple Hydrogen-Bond Modification of [1,2,5]Oxadiazolo[3,4-b]pyridine 1-Oxide Framework Enables Access to Low-Sensitivity High-Energy Materials.

In this work, a fused-ring [1,2,5]oxadiazolo[3,4-b]pyridine 1-oxide framework with multiple modifiable sites was utilized to develop novel energetic materials with multiple hydrogen bonds. The prepared materials were characterized, and their energetic properties were extensively investigated. Among those studied, compound 3 exhibited high densities of 1.925 g cm-3 at 295 K and 1.964 g cm-3 at 170 K, with high detonation performances (Dv: 8793 m s-1 and P: 32.8 GPa), low sensitivities (IS: 20 J, FS: 288 N), and good thermal stability (Td: 223 °C). N-Oxide compound 4 had higher-energy explosive (Dv: 8854 m s-1 and P: 34.4 GPa) and low sensitivities (IS: 15 J and FS: 240 N). Compound 7 with a high enthalpy group (tetrazole) was determined as a high-energy explosive (Dv: 8851 m s-1, P: 32.4 GPa). Notably, the detonation properties of compounds 3, 4, and 7 were similar to high-energy explosive RDX (Dv: 8801 m s-1 and P: 33.6 GPa). The results indicated that compounds 3 and 4 were potential low-sensitivity high-energy materials.

Prehabilitative resistance exercise reduces neuroinflammation and improves mitochondrial health in aged mice with perioperative neurocognitive disorders.

BACKGROUND: Postoperative neurocognitive dysfunction remains a significant problem in vulnerable groups such as the elderly. While experimental data regarding its possible pathogenic mechanisms accumulate, therapeutic options for this disorder are limited. In this study, we evaluated the neuroprotective effect of a period of preconditioning resistant training on aged mice undergoing abdominal surgery. Further, we examined the underlying mechanisms from the perspective of neuroinflammatory state and synaptic plasticity in the hippocampus. METHODS: 18-month-old C57BL/6N mice were trained for 5 weeks using a ladder-climbing protocol with progressively increasing weight loading. Preoperative baseline body parameters, cognitive performance and neuroinflammatory states were assessed and compared between sedentary and trained groups of 9-month-old and 18-month-old mice. To access the neuroprotective effect of resistance training on postoperative aged mice, both sedentary and trained mice were subjected to a laparotomy under 3% sevoflurane anesthesia. Cognitive performance on postoperative day 14, hippocampal neuroinflammation, mitochondrial dysfunction and synaptic plasticity were examined and compared during groups. RESULTS: 18-month-old mice have increased body weight, higher peripheral and central inflammatory status, reduction in muscle strength and cognitive performance compared with middle-aged 9-month-old mice, which were improved by resistance exercise. In the laparotomy group, prehabilitative resistant exercise improved cognitive performance and synaptic plasticity, reduced inflammatory factors and glial cells activation after surgery. Furthermore, resistance exercise activated hippocampal PGC-1α/BDNF/Akt/GSK-3ß signaling and improved mitochondrial biogenesis, as well as ameliorated mitochondrial dynamics in postoperative-aged mice. CONCLUSIONS: Resistance exercise reduced risk factors for perioperative neurocognitive disorders such as increased body weight, elevated inflammatory markers, and pre-existing cognitive impairment. Accordantly, preoperative resistance exercise improved surgery-induced adverse effects including cognitive impairment, synaptic deficit and neuroinflammation, possibly by facilitate mitochondrial health through the PGC1-a/BDNF pathway.

Dearomatizing [4+1] Spiroannulation of Naphthols: Discovery of Thermally Activated Delayed Fluorescent Materials.

Disclosed here is a palladium-catalyzed direct [4+1] spiroannulation of ortho-C-H bonds of naphthols with cyclic diaryliodonium salts to construct spirofluorenyl naphthalenones (SFNP) under mild reaction conditions. This spiroannulation directly transforms the hydroxy group into a carbonyl group, and also tolerates reactive functional groups such as the halo groups, which provide an opportunity to rapidly assemble structurally new thermally activated delayed fluorescent (TADF) materials that feature a carbonyl group with an adjacent spirofluorenyl unit as the acceptor. As an illustrated example, the OLED device utilizing the assembled DMAC-SFNP as the host material exhibits a low turn-on voltage of 2.5 V and an ultra-high external quantum efficiency of 32.2 %. This work provides inspiration for structurally new TADF materials, and also displays the potential of C-H activation as a synthetic strategy for the innovation of optoelectronic materials.

Molecular design of thermally activated delayed fluorescent emitters for narrowband orange-red OLEDs boosted by a cyano-functionalization strategy.

The establishment of a simple molecular design strategy to realize red-shifted emission while maintaining good color purity for multi-resonance induced thermally activated delayed fluorescent (MR-TADF) materials remains an appealing yet challenging task. Herein, we demonstrate that the attachment of a cyano (CN) functionality at the lowest unoccupied molecular orbital location of the MR-TADF skeleton can promote attractive red-shifted emission due to the exceptional electron-withdrawing capacity of the CN group, which represents the first example of orange-red MR-TADF emitters. Meanwhile, the linear CN group adopts a coplanar conformation with the MR-framework to restrict structure relaxation associated with rotation, which is beneficial to maintain a small full-width at half-maximum and thus a good color purity. The CNCz-BNCz-based OLED device, which utilizes a TADF sensitized mechanism to accelerate the up-conversion process of triplet excitons in the emitting layer, exhibits an outstanding external quantum efficiency (EQE) as high as 33.7%, representing the state-of-the-art performance for orange-red TADF-OLEDs.

Mechanically induced single-molecule white-light emission of excited-state intramolecular proton transfer (ESIPT) materials.

Described herein is the first example of mechanically induced single-molecule white-light emission based on excited-state intramolecular proton transfer (ESIPT) materials. The mechanism of mechanochromism is clearly disclosed by powder and single crystal X-ray diffraction (XRD) data, infrared spectroscopy, and fluorescence up-conversion measurement, etc. 2-(2'-Hydroxyphenyl)oxazole (6b) with a herringbone packing motif exhibits a predominant keto-form emission, giving off yellowish-green fluorescence. Mechanical grinding transforms the herringbone packing motif into a brickwork packing motif, decreases the intermolecular distances, which results in an enhanced intermolecular charge-transfer interaction, and therefore changes the ESIPT dynamics, leading to an enhanced enol-form emission and white fluorescence. Herringbone-packing 6b is thermodynamically more stable than brickwork-packing 6b. Thus, the latter can convert to the former by solvent fuming or thermal annealing.

A methyl-shield strategy enables efficient blue thermally activated delayed fluorescence hosts for high-performance fluorescent OLEDs.

Here, we report a novel methyl-shield strategy to design ideal TADF hosts for the improvement of the performance of TSF-OLEDs. The methyl group on the xanthone acceptor acts like a shield to protect the luminance center from close intermolecular hydrogen bonding with adjacent molecules, thus alleviating exciton quenching, and meanwhile the small size of the methyl group almost does not disturb the π-π stacking between acceptors, thus maintaining fast electron-transport pathways. dMeACRXTO having two methyl shields is exploited as the host to achieve a record-high EQE of 32.3%, which represents the first report of an EQE above 30% in TSF-OLEDs.