Kincaidbendix5684
tal-to-ligand charge transfer (3LC/3MLCT) character) to trimer excimers (i.e., of triplet metal-metal-to-ligand charge transfer (3MMLCT) character). The EDA reveals that the total interaction energy on trimer excimers is subtly controlled by the electrostatic and dispersion terms.The NiII literature complex cis-[Ni(C6F5)2(THF)2] is a synthon of cis-Ni(C6F5)2 that allows us to establish a protocol to measure and compare the ligand effect on the NiII → Ni0 reductive elimination step (coupling), often critical in catalytic processes. Several ligands of different types were submitted to this Ni-meter comparison bipyridines, chelating diphosphines, monodentate phosphines, PR2(biaryl) phosphines, and PEWO ligands (phosphines with one potentially chelate electron-withdrawing olefin). Extremely different C6F5-C6F5 coupling rates, ranging from totally inactive (producing stable complexes at room temperature) to those inducing almost instantaneous coupling at 25 °C, were found for the different ligands tested. The PR2(biaryl) ligands, very efficient for coupling in Pd, are slow and inefficient in Ni, and the reason for this difference is examined. In contrast, PEWO type ligands are amazingly efficient and provide the lowest coupling barriers ever observed for NiII complexes; they yield up to 96% C6F5-C6F5 coupling in 5 min at 25 °C (the rest is C6F5H) and 100% coupling with no hydrolysis in 8 h at -22 to -53 °C.Osteoarthritis (OA) is a degenerative articular cartilage pathogenic process that is accompanied by excessive chondrocyte apoptosis. The occurrence of chondrocyte death and OA is related to decreased autophagy. Tetrahedral framework nucleic acid (TFNA), a potent bioactive DNA nanomaterial, exerts antiapoptotic and antioxidative effects in various diseases, resulting in autophagy promotion and inhibition of the Wnt/β-catenin-signaling pathway. Here, we aimed to elucidate the therapeutic effects of TFNA on OA and its potential molecular mechanism of action. TFNA was synthesized and characterized by established methods. An interleukin (IL)-1β stimulated OA cell model was established and treated with TFNA. Cellular uptake of TFNA and intracellular reactive oxygen species levels were examined via immunofluorescence and flow cytometry. Apoptotic cell death was documented by the Cell Counting Kit-8 (CCK8) assay and flow cytometry. Transmission electron microscopy was applied to view the autophagosomes. The expression of BCL2, BAX, caspase-3, Nrf2, HO-1, LC3-II, Beclin1, Atg7, β-catenin, Lef-1, and CyclinD1 was detected by immunofluorescence and western blotting. TFNA was successfully synthesized and effectively entered chondrocytes in the absence or presence of IL-1β without the help of transfection agents. TFNA treatment in IL-1β-induced chondrocytes reduced apoptosis by activating the BCL2/BAX/caspase-3 pathway, inhibited oxidative stress by regulating the Nrf2/HO-1-signaling pathway, and enhanced autophagy through upregulated LC3-II, Beclin1, and Atg7. Moreover, TFNA showed chondroprotective effects by regulating the Wnt/β-catenin-signaling pathway. Overall, TFNA may have utility as a therapeutic nanomedicine for OA.The stability of organic solar cells (OSCs) is an urgent problem for commercialization. In this work, a novel asymmetric molecule TB-4Cl was designed and synthesized. Quantum chemical computations revealed that TB-4Cl has a larger dipole moment of 1.98 Debye than that of Y6, which can induce a stronger intermolecular interaction. Without thermal annealing, devices based on PM6TB-4Cl achieved a higher efficiency of 14.67%. Impressively, all of the devices showed a negligible difference in power conversion efficiency (PCE) before and after thermal-annealing treatment. Compared to the unencapsulated PM6Y6-based devices, PM6TB-4Cl-based devices exhibited improved thermal and air stability, evidenced by retaining around 75% (TB-4Cl) and 60% (Y6) after being heated at 100 °C in nitrogen for 110 h and 65% (TB-4Cl) and 50% (Y6) in air for 92 h. This work indicates that an A-D1A'D2-A asymmetric molecule can be a promising candidate for achieving stable OSCs with high efficiency.Perovskite quantum dots (PQDs) have expanded the scalability of perovskite materials by their high crystallinity, band-gap tunability, and surface ligand-driven functionalities in the colloidal state across optoelectronics as well as photovoltaics. To improve PQD performance in applications, however, defect control has emerged as a major challenge given the increased PQD surface area. Herein, we have developed a heterostructured PQD solar cell by combining CsPbI3 and FAPbI3 (FA, formamidinium) PQD layers to introduce a multinary PQD layer based on a solid-state A-site cation-exchange strategy. A heterostructure, including the solid-state diffusion-driven multinary PQD layer, creates an internally graded heterojunction for more efficient charge extraction. The best PQD cell achieves a power conversion efficiency (PCE) of 16.07% with negligible hysteresis. Furthermore, this architecture offers significantly enhanced stability with reduction of trap-assisted recombination as compared to cells of a monocompositional PQD layer. 2,3-Butanedione-2-monoxime inhibitor The unencapsulated device retains a 96% PCE after 1000 h in ambient storage.The development of intelligent and multifunctional hydrogels having photothermal properties, good mechanical properties, sustained drug release abilities with low burst release, antibacterial properties, and biocompatibility is highly desirable in the biomaterial field. Herein, mesoporous polydopamine (MPDA) nanoparticles wrapped with graphene oxide (GO) were physically cross-linked in cellulose nanofibril (CNF) hydrogel to obtain a novel MPDA@GO/CNF composite hydrogel for controllable drug release. MPDA nanoparticles exhibited a high drug loading ratio (up to 35 wt %) for tetracycline hydrochloride (TH). GO was used to encapsulate MPDA nanoparticles for extending the drug release time and reinforcing the physical strength of the obtained hydrogel. The mechanical strength of the as-fabricated MPDA@GO/CNF composite hydrogel was five times greater compared to that of the pure CNF hydrogel. Drug release experiments demonstrated that burst release behavior was significantly reduced by adding MPDA@GO. The drug release time of the MPDA@GO/CNF composite hydrogel was 3 times and 7.