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Deep‐red and near‐infrared emitters with twisted donor–acceptor (D–A) structures often exhibit suboptimal performance in organic light‐emitting diodes (OLEDs) due to constraints imposed by the energy gap law. In this work, a pure hydrogen carbon (PHC) host material named SBF‐DTP is purposefully tailored for deep‐red OLEDs. The excellent capacity of SBF‐DTP to support D–A type DR emitters effectively arises from its distinctive attributes: localized excitation states, 3D configuration, and low polarity. When employing SBF‐DTP as the host for the fluorescence emitter DCPA‐TPA and the thermally activated delayed fluorescence emitter APDC‐DTPA, doped films exhibit substantially enhanced photoluminescence quantum yields. This improvement leads to high‐efficiency OLEDs with external quantum efficiencies of 5.47% for DCPA‐TPA and 20.03% for APDC‐DTPA, respectively, which is about twice as high as the initial reports. This findings underscore the paramount significance of developing efficient host materials in the pursuit of high‐performance deep red and even near‐infrared OLEDs. [ABSTRACT FROM AUTHOR]

An asymmetric decarboxylative Mannich reaction of phosphonate sultam‐ketimines with malonic acid half esters is developed enabled by saccharide‐derived bifunctional amino thiourea catalysis. This protocol provides access to a broad range of α‐amino‐β‐carboxylic phosphonates featuring the N,P‐containing tetrasubstituted stereocenters with 78–99% ee. Further synthetic derivatizations could allow the introduction of amide, alcohol, and azetidine scaffolds to the core structures. [ABSTRACT FROM AUTHOR]

Compared with red and green perovskite light‐emitting diodes (PeLEDs), blue PeLEDs are still unable to well control spectral stability due to the issues of ion migration and phase separation under external operating conditions. Herein, a strategy using organometallic ligands is reported to achieve spectrally stable PeLEDs. The obtained perovskite film exhibits stable photoluminescence spectra under UV excitation (365nm) and continuous heating of 70 °C. The device delivers an external quantum efficiency (EQE) of 6.7% with 50% lifetime (T50) of 21.6 min. Under high driving voltage (from 2 to 7.5 V), no obvious spectral shift has occurred for the electroluminescence spectrum at 481 nm. This work confirms the positive effect of organometallic ligands in quasi‐2D perovskite and provides a new idea for proposing effective ligands to act on the perovskite luminescence layer in the future. [ABSTRACT FROM AUTHOR]

Genistein, a soy derived isoflavanoid compound, exerts anticancer effects in various cancers. Nasopharyngeal cancer stem cells (NCSCs) are a small subpopulation of cancer cells which are responsible for initiation, progression, metastasis, and recurrence of nasopharyngeal cancer. The present study aimed to investigate the suppressive effects of genistein on NCSCs and its underlying mechanism. NCSCs were enriched from human nasopharyngeal cancer cell lines CNE2 and HONE1 through tumorsphere-forming assay. It was shown that genistein inhibited the tumorsphere formation capacity, decreased the number of EpCAM+ cells, downregulated the expression of NCSCs markers, suppressed cell proliferation, and induced apoptosis of NCSCs. Genistein suppressed the activity of Sonic hedgehog (SHH) signaling, which was important for the maintenance of NCSCs, while activation of SHH signaling by purmorphamine diminished the inhibitory effects of genistein on NCSCs. Our data suggested that genistein inhibited NCSCs through the suppression of SHH signaling. These findings support the use of genistein for targeting NCSCs. [ABSTRACT FROM AUTHOR]

Cancer stem cells (CSCs) are considered to play essential roles in the process of origination, proliferation, migration, and invasion of cancer, and their properties are regulated by Wnt/β-catenin pathway. Phenethyl isothiocyanate (PEITC) is a natural product obtained from cruciferous vegetables with anticancer activities. The present study aimed to investigate the inhibitory effect and the underlying mechanisms of PEITC on colorectal CSCs. In this study, we found that PEITC can significantly reduce the size and number of colorectal cancer cell spheroids in serum-free medium. With increasing PEITC concentrations (10-40 μM), the number of spheroids was reduced to about 10% of the control group, and the percentage of CD133+ cells was decreased by about 3-16 folds. PEITC also decreased the expression of CSC markers. Meanwhile, inhibition of proliferation as well as induction of apoptosis of colorectal CSCs was observed after PEITC treatment. Furthermore, through activating Wnt/β-catenin pathway with LiCl, the inhibitory effects of PEITC on colorectal CSCs were diminished. Our data suggested that PEITC can be an effective inhibitor of colorectal CSCs by targeting Wnt/β-catenin pathway. [ABSTRACT FROM AUTHOR]

Multi‐layer π‐stacked emitters based on spatially confined donor/acceptor/donor (D/A/D) patterns have been developed to achieve high‐efficiency thermally activated delayed fluorescence (TADF). In this case, dual donor moieties and a single acceptor moiety are introduced to form two three‐dimensional (3D) emitters, DM‐BD1 and DM‐BD2, which rely on spatial charge transfer (CT). Owing to the enforced face‐to‐face D/A/D pattern, effective CT interactions are realized, which lead to high photoluminescence quantum yields (PLQYs) of 94.2 % and 92.8 % for the two molecules, respectively. The resulting emitters exhibit small singlet–triplet energy splitting (ΔEST) and fast reverse intersystem crossing (RISC) processes. Maximum external quantum efficiencies (EQEs) of 28.0 % and 26.6 % were realized for devices based on DM‐BD1 and DM‐BD2, respectively, which are higher than those of their D/A‐type analogues. [ABSTRACT FROM AUTHOR]

Remote functionalization reactions have the power to transform a C−H (or C−C) bond at a distant position from a functional group. This Review summarizes recent advances and key breakthroughs in remote fluorination, trifluoromethylation, difluoromethylation, trifluoromethylthiolation, and fluoroalkenylation reactions. Several powerful strategies have emerged to control the reactivity and distal selectivity such as the undirected radical approach, the 1,5‐hydrogen atom transfer, the metal migration, the use of distant directing groups, and the ring‐opening reactions. These unconventional and predictable C−H (and C−C) functionalization transformations should allow for the preparation of a wide range of otherwise‐difficult‐to‐access alkyl, aromatic, heteroaromatic, and structurally complex fluorides. [ABSTRACT FROM AUTHOR]

With the inherent organic–metal system property, phosphorescent organic light‐emitting diodes (PhOLEDs) are capable of exhibiting high performance. However, the existence of unintended triplet–triplet annihilation (TTA), which is mainly originated from high triplet exciton density leading to inferior device performance, is a current predicament. For mitigating the TTA in devices, reported herein is an effective host system with the role of precisely controlling the triplet excitons via the multichannel processes, in which a bipolar host material, a hole‐transporting material, and an electron‐transporting material are mixed to manage the triplet exciton transfer. The mixed‐host with so‐called "triplet excitons harvesting" strategy exhibits two concomitant reverse intersystem crossing (RISC) processes that simultaneously occur in the bipolar host material:electron‐transporting material and the host‐transporting material:electron‐transporting material exciplexes, respectively. Highly efficient green and red PhOLEDs are demonstrated by these multichannel processes, in which phosphorescent emitters bis(2‐phenylpyridine) (acetylacetonate) iridium(III) (Ir(ppy)2(acac)) and bis(2‐methyldibenzo[f,h]‐quinoxaline) (acetylacetonate) iridium(III) (Ir(MDQ)2(acac)) are doped into the mixed‐host, respectively. The green and red PhOLEDs realize nearly 30% of maximum external quantum efficiencies of 29.4% and 29.2%, respectively, and also maintain 29.1% and 28.3% at 1000 cd m−2. These excellent efficiencies and low roll‐offs confirm that the concomitant RISC processes effectively manage and utilize triplet excitons. [ABSTRACT FROM AUTHOR]

Keywords: 1,5-hydrogen atom transfer; fluorination; fluoroalkyl(thiol)ation; metal migration; remote functionalization EN 1,5-hydrogen atom transfer fluorination fluoroalkyl(thiol)ation metal migration remote functionalization 1 1 1 12/03/20 20201201 NES 201201 B Remote functionalization reactions b have the power to transform a C-H (or C-C) bond at a distant position from a functional group. 1,5-hydrogen atom transfer, fluorination, fluoroalkyl(thiol)ation, metal migration, remote functionalization. [Extracted from the article]

Outcomes for metastatic Ewing sarcoma and osteosarcoma are dismal and have not changed for decades. Oxidative stress attenuates melanoma metastasis, and melanoma cells must reduce oxidative stress to metastasize. We explored this in sarcomas by screening for oxidative stress sensitizers, which identified the class I HDAC inhibitor MS‐275 as enhancing vulnerability to reactive oxygen species (ROS) in sarcoma cells. Mechanistically, MS‐275 inhibits YB‐1 deacetylation, decreasing its binding to 5′‐UTRs of NFE2L2 encoding the antioxidant factor NRF2, thereby reducing NFE2L2 translation and synthesis of NRF2 to increase cellular ROS. By global acetylomics, MS‐275 promotes rapid acetylation of the YB‐1 RNA‐binding protein at lysine‐81, blocking binding and translational activation of NFE2L2, as well as known YB‐1 mRNA targets, HIF1A, and the stress granule nucleator, G3BP1. MS‐275 dramatically reduces sarcoma metastasis in vivo, but an MS‐275‐resistant YB‐1K81‐to‐alanine mutant restores metastatic capacity and NRF2, HIF1α, and G3BP1 synthesis in MS‐275‐treated mice. These studies describe a novel function for MS‐275 through enhanced YB‐1 acetylation, thus inhibiting YB‐1 translational control of key cytoprotective factors and its pro‐metastatic activity. Synopsis: Class 1 HDAC inhibitors including MS‐275 inhibit the RNA binding protein YB‐1 by enhancing its acetylation. This reduces its affinity to mRNA targets under cellular stress, and decreases tumor cell fitness and metastatic capacity. YB‐1 translationally activates NRF2 synthesis under oxidative stress.MS‐275‐mediated YB‐1 acetylation reduces translation of multiple YB‐1 translational targets.MS‐275 blocks metastasis of childhood sarcoma cell lines and PDX tumors in pre‐clinical models. [ABSTRACT FROM AUTHOR]