Unraveling non-radiative decay channels of exciplexes to construct efficient red emitters for organic light-emitting diodes.

Exciplex emitters naturally have thermally activated delayed fluorescence characteristics due to their spatially separated molecular orbitals. However, the intermolecular charge transfer potentially induces diverse non-radiative decay channels, severely hindering the construction of efficient red exciplexes. Thus, a thorough comprehension of this energy loss is of paramount importance. Herein, different factors, including molecular rigidity, donor-acceptor interactions and donor-donor/acceptor-acceptor interactions, that impact the non-radiative decay were systematically investigated using contrasting exciplex emitters. The exciplex with rigid components and intermolecular hydrogen bonds showed a photoluminescence quantum yield of 84.1% and a singlet non-radiative decay rate of 1.98 × 106 s-1 at an optimized mixing ratio, respectively, achieving a 3.3-fold increase and a 70% decrease compared to the comparison group. In the electroluminescent device, a maximum external quantum efficiency of 23.8% was achieved with an emission peak of 608 nm, which represents the state-of-the-art organic light-emitting diodes using exciplex emitters. Accordingly, a new strategy is finally proposed, exploiting system rigidification to construct efficient red exciplex emitters that suppress non-radiative decay.

A high-performance dual-functional organic upconversion device with detectivity approaching 1013 Jones and photon-to-photon efficiency over 20.

Organic upconversion devices (UCDs) are a cutting-edge technology and hot topic because of their advantages of low cost and convenience in the important applications of near-infrared (NIR) detection and imaging. However, to realize utilization of triplet excitons (T1), previous UCDs have the drawback of heavily relying on toxic and costly heavy-metal-doped emitters. More importantly, due to poor performance of the detecting unit and/or emitting unit, improving their detectivity (D*) and photon-to-photon conversion efficiency (ηp-p) is still a challenge for real applications. Here, we report a high-performance dual-functional purely organic UCD that has an outstanding D* approaching 1013 Jones and a high ηp-p of 20.1% in the NIR region, which are some of the highest values among those reported for UCDs. The high performance is credited to the excellent D* of the detecting unit, exceeding 1014 Jones, and is also attributed to efficient T1 utilization via a dual reverse intersystem crossing channel and high optical out coupling achieved via a high horizontal dipole ratio in the emitting unit. The high D* and ηp-p enable the UCD to detect 850 nm light at as little as 0.29 µW cm-2 and with a high display contrast of over 70 000 : 1, significantly improving the potential of practical applications of UCDs in NIR detection and imaging. Furthermore, a fast rise time and fall time of 8.9 and 14.8 µs are also achieved. Benefiting from the high performance, consequent applications of low-power pulse-state monitoring and fine-structure bio-imaging are successfully realized with high quality results by using our organic UCDs. These results demonstrate that our design not only eliminates dependence of UCDs on heavy-metal emitters, but also takes their performance and applications to a high level.

A novel orange-red thermally activated delayed fluorescence emitter with high molecular rigidity and planarity realizing 32.5% external quantum efficiency in organic light-emitting diodes.

Simultaneous optimization of photoluminescence quantum yield (ΦPL) and horizontally oriented dipoles (Θ‖) is considerably challenging for orange and red thermally activated delayed fluorescence (TADF) emitters, due to the conflicts between enhancing molecular rigidity and improving molecular planarity. Herein, a novel orange-red TADF emitter 10-(dipyrido[3,2-a:2',3'-c]phenazin-11-yl)-10H-spiro[acridine-9,9'-fluorene] (SAF-2NP) was constructed with a donor-acceptor structure. The highly rigid donor and acceptor segments ensure the overall rigidity of the emitter. More importantly, the quasi-coplanar structure between the acceptor and the fluorene moiety in the donor unit enlarges the molecular plane without weakening rigidity. Consequently, SAF-2NP exhibited extremely high ΦPL and Θ‖ of 99% and 85%, respectively. The optimal organic light-emitting diode using SAF-2NP as the emitter and 4,4'-di(9H-carbazol-9-yl)-1,1'-biphenyl (CBP) as the host demonstrated an unparalleled external quantum efficiency of 32.5% and a power efficiency of 85.2 lm W-1 without any extra light extraction structure. This work provides a feasible strategy to establish efficient orange and red TADF emitters with both high rigidity and planarity.

Nuclear Receptor NR1D1 Regulates Abdominal Aortic Aneurysm Development by Targeting the Mitochondrial Tricarboxylic Acid Cycle Enzyme Aconitase-2.

BACKGROUND: Metabolic disorder increases the risk of abdominal aortic aneurysm (AAA). NRs (nuclear receptors) have been increasingly recognized as important regulators of cell metabolism. However, the role of NRs in AAA development remains largely unknown. METHODS: We analyzed the expression profile of the NR superfamily in AAA tissues and identified NR1D1 (NR subfamily 1 group D member 1) as the most highly upregulated NR in AAA tissues. To examine the role of NR1D1 in AAA formation, we used vascular smooth muscle cell (VSMC)-specific, endothelial cell-specific, and myeloid cell-specific conditional Nr1d1 knockout mice in both AngII (angiotensin II)- and CaPO4-induced AAA models. RESULTS: Nr1d1 gene expression exhibited the highest fold change among all 49 NRs in AAA tissues, and NR1D1 protein was upregulated in both human and murine VSMCs from AAA tissues. The knockout of Nr1d1 in VSMCs but not endothelial cells and myeloid cells inhibited AAA formation in both AngII- and CaPO4-induced AAA models. Mechanistic studies identified ACO2 (aconitase-2), a key enzyme of the mitochondrial tricarboxylic acid cycle, as a direct target trans-repressed by NR1D1 that mediated the regulatory effects of NR1D1 on mitochondrial metabolism. NR1D1 deficiency restored the ACO2 dysregulation and mitochondrial dysfunction at the early stage of AngII infusion before AAA formation. Supplementation with αKG (α-ketoglutarate, a downstream metabolite of ACO2) was beneficial in preventing and treating AAA in mice in a manner that required NR1D1 in VSMCs. CONCLUSIONS: Our data define a previously unrecognized role of nuclear receptor NR1D1 in AAA pathogenesis and an undescribed NR1D1-ACO2 axis involved in regulating mitochondrial metabolism in VSMCs. It is important that our findings suggest αKG supplementation as an effective therapeutic approach for AAA treatment.

Design, Synthesis and Antibacterial Evaluation of 3-Substituted Ocotillol-Type Derivatives.

Antibiotic resistance has become a serious global problem that threatens public health. In our previous work, we found that ocotillol-type triterpenoid saponin showed good antibacterial activity. Based on preliminary structure-activity relationship, novel serious C-3 substituted ocotillol-type derivatives 7⁻26 were designed and synthesized. The in vitro antibacterial activity was tested on five bacterial strains (B. subtilis 168, S. aureus RN4220, E. coli DH5α, A. baum ATCC19606 and MRSA USA300) and compared with the tests on contrast. Among these derivatives, C-3 position free hydroxyl substituted compounds 7⁻14, showed good antibacterial activity against Gram-positive bacteria. Furthermore, compound 22 exhibited excellent antibacterial activity with minimum inhibitory concentrations (MIC) values of 2 µg/mL against MRSA USA300 and 4 µg/mL against B. subtilis. The structure-activity relationships of all current ocotillol-type derivatives our team synthesised were summarized. In addition, the prediction of absorption, distribution, metabolism, and excretion (ADME) properties and the study of pharmacophores were also conducted. These results can provide a guide to further design and synthesis works.

Synthesis and Antibacterial Evaluation of Novel 3-Substituted Ocotillol-Type Derivatives as Leads.

Due to the rapidly growing bacterial antibiotic-resistance and the scarcity of novel agents in development, bacterial infection is still a global problem. Therefore, new types of antibacterial agents, which are effective both alone and in combination with traditional antibiotics, are urgently needed. In this paper, a series of antibacterial ocotillol-type C-24 epimers modified from natural 20(S)-protopanaxadiol were synthesized and evaluated for their antibacterial activity. According to the screening results of Gram-positive bacteria (B. subtilis 168 and MRSA USA300) and Gram-negative bacteria (P. aer PAO1 and A. baum ATCC19606) in vitro, the derivatives exhibited good antibacterial activity, particularly against Gram-positive bacteria with an minimum inhibitory concentrations (MIC) value of 2-16 µg/mL. The subsequent synergistic antibacterial assay showed that derivatives 5c and 6c enhanced the susceptibility of B. subtilis 168 and MRSA USA300 to chloramphenicol (CHL) and kanamycin (KAN) (FICI < 0.5). Our data showed that ocotillol-type derivatives with long-chain amino acid substituents at C-3 were good leads against antibiotic-resistant pathogens MRSA USA300, which could improve the ability of KAN and CHL to exhibit antibacterial activity at much lower concentrations with reduced toxicity.

Design and synthesis of 28-hydroxy protopanaxadiol as a novel probe template.

To explore the antitumour mechanism of 20(S)-protopanaxadiol (PPD) while maintaining its uncovered pharmacological active site 3-hydroxyl, 28-hydroxy protopanaxadiol (17), a small molecular probe template of PPD was first designed and synthesised based on the Baldwin's reaction. Thus, 28-hydroxyl of 17 was built successfully as a derivatized site of molecular probe's functional and report groups. The important intermediates and final product were confirmed by ESI-MS and nuclear magnetic resonance spectra with good yield. These studies provided a valuable basis for probe research of PPD.

Anti-neutrophil cytoplasmic antibodies in cholesterol embolism: A case report and literature review.

Cholesterol embolism is a multisystemic disorder with clinical manifestations that resemble vasculitis. Anti-neutrophil cytoplasmic antibodies (ANCA) are a defining feature of ANCA-associated vasculitis, and the presence of ANCA in cholesterol embolism complicates its differential diagnosis and treatment. At present, the role of ANCA in cholesterol embolism remains unclear and no effective treatment is currently available. The present study reports the case of an Asian male who presented with spontaneous cholesterol embolism with proteinase 3 (PR3)-specific ANCA, subacute interstitial nephritis and late-developing skin lesions. The 69-year-old patient was admitted to The First Affiliated Hospital of Xiamen University (Xiamen, China) complaining of chest tightness, fatigue, progressive renal failure and refractory hypertension. In addition, transient eosinophilia was detected. Following immunosuppressive therapy with steroids and cyclophosphamide for 6 months, hemodialysis treatment was initiated. Skin lesions appeared at >1 month following hemodialysis initiation; however, they were gradually improved following treatment with atorvastatin and anti-platelet aggregation therapy for 5 months. The patient was maintained on hemodialysis for ~2 years and exhibited general good health at the most recent follow-up. In addition, 11 cases of cholesterol embolism associated with ANCA reported in the literature were discussed in the present study.