Thermally activated delayed fluorescence (TADF) emitters induced by the multiple resonance (MR) effect have garnered considerable attention. However, it is difficult to develop MR‐TADF emitters that ...maintain high color purities in the red region. In this work, the importance of excited state alignments of MR‐based donor‐acceptor (D‐A) molecules in determining their preferring characteristics is clarified. By using the newly designed molecule mBDPA‐TOAT whose apparent excited states show hybridization of MR and intersegmental charge‐transfer features as an emitter in an organic light‐emitting diode (OLED), a high external quantum efficiency of 17.3% is achieved with a full width at half‐maximum of 45 nm (154 meV) and Commission Internationale de L'Éclairage coordinate of (0.61, 0.39). This work demonstrates when introducing D‐A typed structures, features, and alignments of molecular excited states determine ultimate material properties. This could help to develop high efficiency and high color purity TADF emitters toward long wavelength range.
Two molecules mBDPA‐TOAT and pBDPA‐TOAT that show hybridization of multiple resonance and intersegmental charge‐transfer features in their apparent excited states are obtained by considering their excited state alignment. The mBDPA‐TOAT‐based organic light‐emitting diode exhibits an external quantum efficiency of 17.3% with a full width at half maximum of 45 nm and Commission Internationale de l'Eclairage coordinate of (0.61, 0.39).
•Our results suggested that compared with participants who do not experience persistent musculoskeletal pain, those with persistent musculoskeletal pain, pain (pain sites≧5), persistent neck pain, ...back pain, waist pain, shoulder pain, wrist pain, and knee pain had higher dementia risk scores and lower cognitive function scores.•Age, gender, C-reactive protein (CRP), pain intensity, sleep duration, and participation in social activities may be the potential influencing factors of musculoskeletal pain and dementia risk.
Recent studies have confirmed an association between pain and dementia. Whether musculoskeletal pain in the spine, upper limbs, and lower limbs is associated with dementia risk remains unclear. The longitudinal effect of musculoskeletal pain on dementia risk also remains unclear.
This work aimed to investigate the association between musculoskeletal pain and dementia risk score.
We conducted cross-sectional and longitudinal analyses using data from the China Health and Retirement Longitudinal Study. Participants aged 45 years or older were recruited in 2011. A total of 10,759 participants with complete pain information at baseline were eligible for the cross-sectional analysis, and 5,855 were eligible for the longitudinal analyses. We utilized the Rotterdam Study Basic Dementia Risk Model (BDRM) to assess dementia risk. Generalized estimating equations were used to investigate the associations.
Compared with participants without persistent musculoskeletal pain, those with persistent musculoskeletal pain (standardized, β = 0.83; 95 % CI: 0.06, 1.61, p = 0.036), multisite pain (sites≧5; β = 1.52; 95 % CI: 0.13, 2.91, p = 0.032), neck pain (β = 2.33; 95 % CI: 0.41, 4.25, p = 0.018), back pain (β = 2.12; 95 % CI: 0.43, 3.82, p = 0.014), waist pain (β = 1.09; 95 % CI: 0.07, 2.11, p = 0.037), shoulder pain (β = 1.74; 95 % CI: 0.46, 3.02, p = 0.008), wrist pain (β = 2.72; 95 % CI: 0.42, 5.02, p = 0.021), and knee pain (β = 1.91; 95 % CI: 0.70, 3.13, p = 0.002) had a higher BDRM score during 4 years of follow-up.
Promoting the management of musculoskeletal pain may be beneficial in reducing the dementia risk score.
Estrogen‐induced premature closing of the growth plate in the long bones is a major cause of short stature after premature puberty. Recent studies have found that chondrocytes can directly ...trans‐differentiate into osteoblasts in the process of endochondral bone formation, which indicates that cartilage formation and osteogenesis may be a continuous biological process. However, whether estrogen promotes the direct trans‐differentiation of chondrocytes into osteoblasts remains largely unknown. Chondrocytes were treated with different concentrations of 17β‐estradiol, and Alizarin Red staining and alkaline phosphatase activity assay were used to detected osteogenesis. Specific short hairpin RNA and tamoxifen were used to block the estrogen receptor (ER) pathway and osteogenic marker genes and downstream gene expression were detected using real‐time quantitative polymerase chain reaction, western blot, and immunohistochemistry staining. The findings showed that 17β‐estradiol promoted the chondrocyte osteogenesis in vitro, even at high concentrations. In addition, blocking of the ERα/β pathway inhibited the trans‐differentiation of chondrocytes into osteogenic cells. Furthermore, we found that dentin matrix protein 1 (DMP1), which is a direct downstream molecular of ER, was involved in 17β‐estradiol/ER pathway‐regulated osteogenesis. As well, glycogen synthase kinase‐3 beta (GSK‐3β)/β‐catenin signal pathway also participates in ERα/β/DMP1‐regulated chondrocyte osteogenesis. The GSK‐3β/β‐catenin signal pathway was involved in ERα/β/DMP1‐regulated chondrocyte osteogenesis. These findings suggest that ER/DMP1/GSK‐3β/β‐catenin plays a vital role in estrogen regulation of chondrocyte osteogenesis and provide a therapeutic target for short stature caused by epiphyseal fusion.
Here, we demonstrate that 17β‐estradiol promotes the chondrocyte osteogenesis in vitro and obstruction of the estrogen receptor (ER)α/β pathway inhibits the trans‐differentiation of chondrocytes into osteogenic cells. Dentin matrix protein 1 (DMP1), which is a direct downstream molecular of ER, was involved in 17β‐estradiol/ER pathway‐regulated osteogenesis. The glycogen synthase kinase‐3 beta (GSK‐3β)/β‐catenin signal pathway also participates in osteogenesis regulated by ERα/β/DMP1 chondrocytes.
This report describes palladium-catalyzed C–H glycosylation and retro Diels–Alder tandem reaction via structurally modified norbornadienes (smNBDs). smNBDs were proposed to regulate the reactivity of ...the aryl-norbornadiene-palladacycle (ANP), including its high chemoselectivity and regioselectivity, which were the key to constructing C2 and C3 unsubstituted C4-glycosidic indoles. The scope of this substrate is extensive; the halogenated six-membered and five-membered glycosides were applied to the reaction smoothly, and N -alkyl (primary, secondary and tertiary) C4-glycosidic indoles can also be obtained by this method. In terms of mechanism, the key ANP intermediates characterized by X-ray single-crystal diffraction and further controlled experiments proved that the migration-insertion of smNBDs with phenylpalladium intermediate endows them with high chemo- and regioselectivity. Finally, density functional theory (DFT) calculation further verified the rationality of the mechanism.
In this study, we aimed to identify an immune-related signature for predicting prognosis in cutaneous melanoma (CM). Sample data from The Cancer Genome Atlas (TCGA; n = 460) were used to develop a ...prognostic signature with 23 immune-related gene pairs (23 IRGPs) for CM. Patients were divided into high- and low-risk groups using the TCGA and validation datasets GSE65904 (n = 214), GSE59455 (n = 141), and GSE22153 (n = 79). The ability of the 23-IRGP signature to predict CM was precise, with the stratified high-risk groups showing a poor prognosis, and it had a significant predictive power when used for immune microenvironment and biological analyses. We subsequently established a novel promising prognostic model in CM to determine the association between the immune microenvironment and CM patient results. This approach may be used to discover signatures in other diseases while avoiding the technical biases associated with other platforms.
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•CuCo-Ni3S2/NF has many merits for oxygen evolution reaction.•The 1:1 of molar ratio of copper to cobalt demonstrates superior OER activity.•The intrinsic activity of CuCo-Ni3S2/NF ...may be determined by cobalt and nickel sulfide.
Multi metal-based elctrocatalyst may provide the more active sties, optimal synergistic effect and unique nanostructure for efficient oxygen evolution reaction (OER). Here, we report the efficient OER performance of copper and cobalt co-doped Ni3S2 supported on nickle foam (CuCo-Ni3S2/NF). The nanoparticles of Ni3S2 grown on NF are synthesized by simple hydrothermal method and liquid phase vulcanization method. Direct hydrothermal growth results in a strong bonding between CuCo-Ni3S2 and the substrate, which has strong electrical conductivity and long-term stability. The different ratio of copper to cobalt doping has been investigated. The optimized CuCo-Ni3S2/NF (1:1 of molar ratio of copper to cobalt) demonstrates superior catalytic activity to OER in 1.0 M KOH with the lowest overpotential of 400 mV at a current density of 100 mA cm−2. CuCo-Ni3S2/NF has the largest electrochemically active surface area (ECSA) of 513 cm2 and excellent conductivity. The enhanced mechanisms may be ascribed to the incorporation of copper and the strong electron interaction among copper, cobalt and nickel element. The intrinsic activity of CuCo-Ni3S2/NF may be determined by cobalt and nickel sulfide. This low-cost and efficient electrocatalyst can be used as a promising electrode material for the oxygen evolution reaction.
Multicomponent reactions can efficiently construct complex molecular structures from simple precursors. Herein, a novel ruthenium-catalyzed three-component highly selective remote C-H ...functionalization of 8-aminoquinoline amides has been described. The reaction tolerates a wide range of functional groups, producing arylation/difluoroalkylation products of olefins with potential biological activity and pharmaceutical value. Radical scavenging and radical clock experiments show that a free radical process is involved and a H/D exchange experiment suggests that the reaction might involve
ortho
-C-H activation of the aromatic ring. A possible mechanism is proposed.
Multicomponent reactions can efficiently construct complex molecular structures from simple precursors.
C-oligosaccharides are found in natural products and drug molecules. Despite the considerable progress made during the last decades, modular and stereoselective synthesis of C-oligosaccharides ...continues to be challenging and underdeveloped compared to the synthesis technology of O-oligosaccharides. Herein, we design a distinct strategy for the stereoselective and efficient synthesis of C-oligosaccharides via palladium-catalyzed nondirected C1-H glycosylation/C2-alkenylation, cyanation, and alkynylation of 2-iodoglycals with glycosyl chloride donors while realizing the difunctionalization of 2-iodoglycals. The catalysis approach tolerates various functional groups, including derivatives of marketed drugs and natural products. Notably, the obtained C-oligosaccharides can be further transformed into various C-glycosides while fully conserving the stereochemistry. The results of density functional theory (DFT) calculations support oxidative addition mechanism of alkenyl-norbornyl-palladacycle (ANP) intermediate with α-mannofuranose chloride and the high stereoselectivity of glycosylation is due to steric hindrance.
The benzotriazole and GO co-modified zinc phosphate (ZP/BTA/GO) pigments with chemically oriented laminated structure are synthesized massively by in situ self-heating method for the first time. The ...heat released from the formation of ZP increases the solubility of BTA achieving the self-sufficiency of system energy in one step. After modification by BTA, the anticorrosive blind region of ZP pigments in the initial corrosion stage is repaired. With the co-modification by BTA and GO, the strong interaction among ZP, BTA and GO makes the compact laminated structure of ZP/BTA/GO pigments more stable, exerting bidirectional shielding effect on the penetration of corrosive medium. Meanwhile, the electrochemical impedance spectroscopy (EIS) and polarization curve tests reveal that the anticorrosion performance of ZP/BTA/GO pigments is increased by 366.1% compared to ZP pigments. The remarkable improvement of corrosion inhibition is attributed to the synergistic complementary anticorrosion mechanism containing the extension of electrons transport path, the deviation of electrons transfer and the formation of diversified passive films. The formation of zinc phosphate-based laminated pigments with full-covered anticorrosion time and excellent corrosion inhibition performance promotes the industrial production and development of anticorrosion materials.
The zinc phosphate pigments co-modified by BTA and GO (ZP/BTA/GO) are prepared massively by in situ self-heating method, of which early anticorrosive blind regions are repaired and the stability is enhanced. The triple-effect synergistic complementary anticorrosion mechanism containing bidirectional shielding effect, deflection of corrosion charge transfer and formation of diversified passivating films contribute the impedance of ZP pigments to improving by 366.1%. Display omitted
•Synchronous co-modification for ZP pigments is achieved by self-heating method.•Triple-effect synergy makes anticorrosion performance of ZP enhance by 366.1%.•Early anticorrosion blind area of inorganic pigments is repaired.•Novel laminated and complementary anticorrosion pigments are obtained firstly.•Formation of ZnN and ZnO bonds enhances the stability of ZP/BTA/GO pigments.
Adipose‐derived stem cells (ADSCs) have emerged as a cell source for regeneration medicine. ADSCs possess the capacity to differentiate into endothelial cells and serve an essential role in vascular ...development and function. LncRNA taurine upregulated gene 1 (TUG1) has recently been linked with angiogenesis in hepatoblastoma. However, the roles of TUG1 in endothelial differentiation of ADSCs remain unidentified. Human adipose‐derived stem cells (hADSCs) were obtained and characterized by flow cytometry, Oil red O and Alizarin Red staining. HADSCs were maintained in the endothelial differentiation medium and the expressions of TUG1, miR‐143, and FGF1 were examined by qRT‐PCR. To assess endothelial differentiation, the expressions of CD31, von Willebrand factor (vWF), VE‐cadherin were examined by Western blot analysis, qRT‐PCR, and immunofluorescence. Tube formation in Matrigel was examined. The interactions between TUG1 and miR‐143, miR‐143 and FGF1 were validated by luciferase assays. During the endothelial differentiation process, TUG1 and FGF1 were upregulated, whereas miR‐143 was downregulated. TUG1 overexpression downregulated miR‐143, upregulated FGF1, CD31, vWF, and VE‐cadherin, and enhanced capillary tube formation. Luciferase assays showed that TUG1 interacted with miR‐143, and FGF1 was a direct target of miR‐143. Furthermore, the enhancement of endothelial differentiation induced by TUG1 overexpression was abolished by miR‐143 overexpression. Our findings implicated that lncRNA TUG1 promoted endothelial differentiation of ADSCs by regulating the miR‐143/FGF1 axis.
1) LncRNA taurine upregulated gene 1 (TUG1) and FGF1 were upregulated whereas miR‐143 was downregulated during the endothelial differentiation process of adipose‐deprived stem cells (ADSCs).
2) LncRNA TUG1 overexpression promoted endothelial differentiation of ADSCs.
3) LncRNA TUG1 acted as a sponge of miR‐143 and FGF1 was a direct target of miR‐143.
4) miR‐143 overexpression abolished the enhancement of endothelial differentiation induced by TUG1 overexpression.
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