Determination for KIR genotype and allele copy number via real-time quantitative PCR method.

Killer cell immunoglobulin-like receptor (KIR) and human leukocyte antigen (HLA) play crucial roles in regulating NK cell activity. Here, we report a real-time quantitative PCR (qPCR) to genotype all KIR genes and their copy numbers simultaneously. With 18 pairs of locus-specific primers, we identified KIR genes by Ct values and determined KIR copy number using the 2-∆Ct method. Haplotypes were assigned based on KIR gene copy numbers. The real-time qPCR results were consistent with the NGS method, except for one sample with KIR2DL5 discrepancy. qPCR is a multiplex method that can identify KIR copy number, which helps obtain a relatively accurate haplotype structure, facilitating increased KIR research in laboratories where NGS or other high-resolution methods are not available.

STAT3 phosphorylation inhibitor Bt354 exhibits anti-neoplastic activity in glioblastoma multiforme cells.

The high mortality rate of glioblastoma multiforme (GBM), a lethal primary brain tumor, is attributable to postsurgical recurrence. STAT3, an oncogenic protein, is a signal transducer and transcription activator encourages cancer cell migration and proliferation, which results in resistance to therapy. STAT3 inhibition reduces cancer metastasis and improves patient prognosis. Bt354, a small molecule STAT inhibitor, exhibits significant cytotoxic and anti-proliferative activities against certain cancer types. Here, we demonstrated that exposure of GBM cells (U87 MG) to Bt354 had a significant, concentration-dependent growth suppression. Bt354 also induced apoptosis and downregulated the expression of the epithelial-mesenchymal transition genes. Therefore, this study suggests the potential of Bt354 for treating GBM owing to its ability to induce cytotoxicity.

Tetraborated Intrinsically Axial Chiral Multi-resonance Thermally Activated Delayed Fluorescence Materials.

Chiral multi-resonance thermally activated delayed fluorescence (CP-MR-TADF) materials hold promise for circularly polarized organic light-emitting diodes (CP-OLEDs) and 3D displays. Herein, we present two pairs of tetraborated intrinsically axial CP-MR-TADF materials, R/S-BDBF-BOH and R/S-BDBT-BOH, with conjugation-extended bidibenzo[b,d]furan and bidibenzo[b,d]thiophene as chiral sources, which effectively participate in the distribution of the frontier molecular orbitals. Due to the heavy-atom effect, sulfur atoms are introduced to accelerate the reverse intersystem crossing process and increase the efficiency of molecules. R/S-BDBF-BOH and R/S-BDBT-BOH manifest ultra-pure blue emission with a maximum at 458/459 nm with a full width at half maximum of 27 nm, photoluminescence quantum yields of 90 %/91 %, and dissymmetry factors (|gPL|) of 6.8×10-4/8.5×10-4, respectively. Correspondingly, the CP-OLEDs exhibit good performances with an external quantum efficiency of 30.1 % and |gEL| factors of 1.2×10-3.

Significant CircRNAs in liver cancer stem cell exosomes: mediator of malignant propagation in liver cancer?

Hepatocellular carcinoma (HCC), one of the most prevalent forms of cancer worldwide, presents a significant global healthcare challenge. Cancer stem cells (CSCs), which can influence neighboring non-CSCs, are believed to play a crucial role in tumor growth and resistance to treatment, but the specific mechanisms and mediators are not fully understood. Regulation of the CSC state is considered an ideal therapeutic strategy both in the early stages of tumor formation and within established tumors. Exosomes have emerged as key players in intercellular communication, similar to classical hormone signaling, and are essential for facilitating communication between cells in liver cancer. Here, by coupling immunomagnetic bead sorting and exosomal sequencing, we found that exosome-derived circRNAs enriched in liver cancer CSCs were the key subsets with stemness characteristics and ultimately promoted HCC development. Of interest, we found that circ-ZEB1 and circ-AFAP1 are strongly correlated with liver cancer stemness and a poor prognosis, and can regulate the epithelial-mesenchymal transition (EMT) process. Our novel exosome-derived circRNAs play a vital role as key components of various intercellular crosstalk and communication systems in malignant transmission. This finding not only provides valuable support for utilizing plasma exosomal circRNAs as clinical prognostic indicators for HCC patients but also highlights a new research direction in exploring the signaling between liver CSCs and the messenger molecules contained within exosomes.

Association of GAB1 gene with asthma susceptibility and the efficacy of inhaled corticosteroids in children.

Asthma is a polygenic disease that may onset during childhood. Inhaled corticosteroids (ICS) are the main therapy in asthma, although their efficacy varies among individuals. Nuclear factor κB (NF-κB) is an important target of ICS treatment of asthma. Recent research has reported that GRB2 associated binding protein 1 (GAB1) gene may participate in the pathogenesis of asthma by regulating the NF-κB pathway. Therefore, we used the technique of an improved multiplex ligation detection reaction to sequence GAB1 gene and investigated the involvement of Single-nucleotide variants (SNVs) in GAB1 gene in asthma and ICS efficacy in asthmatic children. We found no differences between asthma cases and controls in allele or genotype frequencies of GAB1. Haplotype analysis showed an increased tendency for AGGAGC frequency in asthma patients compared with controls (OR = 2.69, p = 0.018). The percentage of EOS and genotype distribution of rs1397527 were associated (p = 0.007). The EOS percentage was higher in GT genotype when compared to the GG genotype (5.50 vs 3.00, Bonferroni adjusted p = 0.005). After 12-weeks ICS treatment, GAB1 rs1397527 TT and GT genotype carriers had a smaller change in forced expiratory volume in 1 second/forced vital capacity (FEV1/FVC) than GG carriers (p = 0.009), and rs3805236 GG and AG genotype carriers also had a smaller change in FEV1/FVC than AA carriers (p = 0.025). For ICS response, the frequency of GG genotype of rs1397527 was significantly higher in good responders (p = 0.038). The generalized multifactor dimensionality reduction (GMDR) analysis showed a best significant four-order model (rs1397527, allergen exposure, environmental tobacco smoke exposure, and pet exposure) involving gene-environment interactions (p = 0.001). In summary, we found that GAB1 SNVs were not associated with asthma susceptibility. Haplotype AGGAGC was a risk factor for asthma. GAB1 variants were associated with eosinophils and ICS response in asthmatics. Furthermore, gene-environment interaction was observed.

A Configurationally Confined Thermally Activated Delayed Fluorescent Two-Coordinate CuI Complex for Efficient Blue Electroluminescence.

Thermally activated delayed fluorescence (TADF) from linear two-coordinate coinage metal complexes is sensitive to the geometric arrangement of the ligands. Herein we realize the tuning of configuration from coplanar to orthogonal gradually by variation of substituents. In a complex with confined twist configuration, its blue emission peaking at 458 nm presents a high ΦPL of 0.74 and a short τTADF of 1.9 µs, which indicates a fast enough kr,TADF of 3.9×105  s-1 and a depressed knr of 1.4×105  s-1 . Such outstanding luminescent properties are attributed to the proper overlap of HOMO and LUMO on CuI d orbitals that guarantees not only small ΔEST but also sufficient transition oscillator strength for fast k r , S 1 ${{k}_{{\rm r},{{\rm S}}_{1}}}$ . Vacuum-deposited blue OLEDs with either doped or host-free emissive layer present external quantum efficiencies over 20 % and 10 %, respectively, demonstrating the practicality of the configurationally confined strategy for efficient linear CuI TADF emitters.

Planar Chiral Multiple Resonance Thermally Activated Delayed Fluorescence Materials for Efficient Circularly Polarized Electroluminescence.

Chiral boron/nitrogen doped multiple resonance thermally activated delayed fluorescence (MR-TADF) emitters are promising for highly efficient and color-pure circularly polarized organic light-emitting diodes (CP-OLEDs). Herein, we report two pairs of MR-TADF materials (Czp-tBuCzB, Czp-POAB) based on planar chiral paracyclophane with photoluminescence quantum yields of up to 98 %. The enantiomers showed symmetric circularly polarized photoluminescence spectra with dissymmetry factors |gPL | of up to 1.6×10-3 in doped films. Meanwhile, the sky-blue CP-OLEDs with (R/S)-Czp-tBuCzB showed an external quantum efficiency of 32.1 % with the narrowest full-width at half-maximum of 24 nm among the reported CP-OLEDs, while the devices with (R/S)-Czp-POAB displayed the first nearly pure green CP electroluminescence with |gEL | factors at the 10-3 level. These results demonstrate the incorporation of planar chirality into MR-TADF emitter is a reliable strategy for constructing of efficient CP-OLEDs.

Helical ß-isoindigo-Based Chromophores with B-O-B Bridge: Facile Synthesis and Tunable Near-Infrared Circularly Polarized Luminescence.

It is essential to create organic compounds that exhibit circularly polarized luminescence (CPL) in the near-infrared (NIR) range. Helicene-type emitters possess appealing chiroptical features, however, such NIR molecules are scarce due to a paucity of synthetic strategies. Herein, we developed a series of helical ß-isoindigo-based B-O-B bridged aza-BODIPY analogs that were synthesized conveniently. The reaction of diimino-ß-isoindigo with a heteroaromatic amine produced a restricted ligand cavity, which triggered off the generation of a B-O-B bridge. The B-O-B bridge led to distorted conformations that satisfy the helical requirements, resulting in excellent spectroscopic and chiroptical properties. Tunable CPL with the highest luminescence dissymmetry factor (glum ) of 1.3×10-3 and a CPL brightness (BCPL =11.5 M-1 cm-1 ) in the NIR region was achieved. This synthetic approach is expected to offer a new opportunity to chiral chemistry and increase flexibility for chiroptical tuning.

Tough, Reprocessable, and Recyclable Dynamic Covalent Polymers with Ultrastable Long-Lived Room-Temperature Phosphorescence.

Room-temperature phosphorescence (RTP) polymers, whose emission can persist for a long period after photoexcitation, are of great importance for practical applications. Herein, dynamic covalent boronic ester linkages with internal B-N coordination are incorporated into a commercial epoxy matrix. The reversible dissociation of B-N bonds upon loading provides an efficient energy dissipation pathway for the epoxy network, while the rigid epoxy matrix can inhibit the quenching of triplet excitons in boronic esters. The obtained polymers exhibit enhanced mechanical toughness (12.26 MJ m-3 ), ultralong RTP (τ=540.4 ms), and shape memory behavior. Notably, there is no apparent decrease in the RTP property upon prolonged immersion in various solvents because the networks are robust. Moreover, the dynamic bonds endow the polymers with superior reprocessablity and recyclability. These novel properties have led to their potential application for information encryption and anti-counterfeiting.

Circularly Polarized White Organic Light-Emitting Diodes Based on Spiro-Type Thermally Activated Delayed Fluorescence Materials.

In this study, we report the first circularly polarized white organic light-emitting diodes (CP-WOLEDs) based on all thermally activated delayed fluorescence (TADF) materials. Two pairs of spiro-type TADF enantiomers, (R/S)-SPOCN (5,5'-((2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-7,7'-diyl)bis(oxy))bis(4-(10H-phenoxazin-10-yl)phthalonitrile)) and (R/S)-OSFSO (2'-(trifluoromethyl)-spiro[quinolino[3,2,1-kl]phenoxazine-9,9'-thioxanthene]-10',10'-dioxide), serve as emitters with complementary emission. The CP-OLEDs exhibit warm white emission with a CIE coordinate of (0.35, 0.46). Besides, decent device performances are observed with an external quantum efficiency of up to 21.6 % at maximum and 11.8 % at 1000 cd m-2 . Obvious circularly polarized electroluminescence signals are detected with a dissymmetry factor |gEL | of around 3.0×10-3 . This is the first report of CP-WOLEDs that can harvest both singlet and triplet excitons, which provides a feasible strategy for the development of CP-WOLEDs with remarkable device performances.

Multiple-Resonance-Induced Thermally Activated Delayed Fluorescence Materials Based on Indolo[3,2,1-jk]carbazole with an Efficient Narrowband Pure-Green Electroluminescence.

Herein, we report two multiple-resonance thermally activated delayed fluorescence emitters (VTCzBN and TCz-VTCzBN) based on indolo[3,2,1-jk]carbazole unit and boron-nitrogen skeletons, whose emissions peaking at 496 and 521 nm with full width at half maximum of 34 and 29 nm, respectively. Meanwhile, fast rate constants of reverse intersystem crossing of above 106  s-1 are obtained due to small singlet-triplet energy gaps and large spin-orbital coupling values. Notably, planar molecular structures along the transition dipole moment direction endow them with high horizontal emitting dipole ratios of up to 94 %. Consequently, the corresponding organic light-emitting diodes (OLEDs) show the maximum external quantum efficiencies of 31.7 % and 32.2 %, respectively. Particularly, OLED with TCz-VTCzBN display ultra-pure green emission with Commission Internationale de l'Eclairage coordinates of (0.22, 0.71), consistent with the green display standard of the National Television System Committee.

Chiral-at-Cage Carboranes for Circularly Polarized Luminescence and Aggregation-Induced Electrochemiluminescence.

Herein, we report the structures of chiral-at-cage carborane derivatives bearing carbazole chromophores that emit circularly polarized luminescence (CPL) and aggregation-induced electrochemiluminescence (AIECL). By adjusting the substituent positions on the carborane derivatives, two chiral luminescent molecules, Cb1 and Cb2, with different properties were obtained. The photoluminescence dissymmetry factors |gPL | of both (R/S)-Cb1 and (R/S)-Cb2 enantiomers in neat films were as high as 6.24×10-3 and 7.38×10-3 , respectively. Cb1 showed a deep blue emission peak at 434 nm in n-pentane. Interestingly, distinct fluorescence and CPL spectra were observed in solvents of different polarities due to the twisted intramolecular charge transfer effect, suggesting its potential use in solvent recognition. Meanwhile, Cb2 exhibited good AIECL property, excellent ECL stability and could be used for determining dopamine concentrations, suggesting its potential applications in biology and diagnosis.

Circularly Polarized Organic Room Temperature Phosphorescence from Amorphous Copolymers.

Organic optoelectronic functional materials featuring circularly polarized emission and persistent luminescence represent a novel research frontier and show promising applications in data encryption, displays, biological imaging, and so on. Herein, we present a simple and universal approach to achieve circularly polarized organic phosphorescence (CPP) from amorphous copolymers by the incorporation of axial chiral chromophores into polymer chains via radical cross-linked polymerization. Our experimental data reveal that copolymers (R/S)-PBNA exhibit a maximum CPP efficiency of 30.6% and the largest dissymmetric factor of 9.4 × 10-3 and copolymers (R/S)-PNA show the longest lifetime of 0.68 s under ambient conditions. Given the CPP property of these copolymers, their potential applications in multiple information encryption and displays are demonstrated, respectively. These findings not only lay the foundation for the development of amorphous polymers with superior CPP but also expand the outlook of room-temperature phosphorescent materials.

Simple Synthesis of Red Iridium(III) Complexes with Sulfur-Contained Four-Membered Ancillary Ligands for OLEDs.

Phosphorescent iridium(III) complexes have been widely researched for the fabrication of efficient organic light-emitting diodes (OLEDs). In this work, three red Ir(III) complexes named Ir-1, Ir-2, and Ir-3, with Ir-S-C-S four-membered framework rings, were synthesized efficiently at room temperature within 5 min using sulfur-containing ancillary ligands with electron-donating groups of 9,10-dihydro-9,9-dimethylacridine, phenoxazine, and phenothiazine, respectively. Due to the same main ligand of 4-(4-(trifluoromethyl)phenyl)quinazoline, all Ir(III) complexes showed similar photoluminescence emissions at 622, 619, and 622 nm with phosphorescence quantum yields of 35.4%, 50.4%, and 52.8%, respectively. OLEDs employing these complexes as emitters with the structure of ITO (indium tin oxide)/HAT-CN (dipyra-zino[2,3-f,2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile, 5 nm)/TAPC (4,4'-cyclohexylidenebis[N,N-bis-(4-methylphenyl)aniline], 40 nm)/TCTA (4,4″,4″-tris(carbazol-9-yl)triphenylamine, 10 nm)/Ir(III) complex (10 wt%): 2,6DCzPPy (2,6-bis-(3-(carbazol-9-yl)phenyl)pyridine, 10 nm)/TmPyPB (1,3,5-tri(mpyrid-3-yl-phenyl)benzene, 50 nm)/LiF (1 nm)/Al (100 nm) achieved good performance. In particular, the device based on complex Ir-3 with the phenothiazine unit showed the best performance with a maximum brightness of 22,480 cd m-2, a maximum current efficiency of 23.71 cd A-1, and a maximum external quantum efficiency of 18.1%. The research results suggest the Ir(III) complexes with a four-membered ring Ir-S-C-S backbone provide ideas for the rapid preparation of Ir(III) complexes for OLEDs.

Two-Photon Ionization Induced Stable White Organic Long Persistent Luminescence.

Organic long persistent luminescence (OLPL) materials with afterglow duration in the scale of minutes or even hours are still rare. Most OLPL systems are based on exciplexes, which require complicated multi-component system in order to realize white afterglow but with slightly compromised duration and color stability. In this work, OLPLs lasting from 20 to 40 minutes are realized in a simple binary system based on two-photon ionization mechanism, which can simultaneously harvest excitons from both singlet and triplet excited states, making it potentially one of the most promising candidates to achieve stable white OLPL. Through modulation and optimization of dopant molecules in dibenzo[b,d]thiophen-2-yldiphenyl phosphine oxide host, the emission profiles of afterglow can be readily tuned from cyan (0.19, 0.22), cold white (0.31, 0.35), standard white (0.33, 0.33) to warm white (0.31, 0.46), with excellent color consistency.

Organic Long Persistent Luminescence Through In Situ Generation of Cuprous(I) Ion Pairs in Ionic Solids.

Recent development of most organic long persistent luminescence (OLPL) systems employed binary or tertiary doping. However, the design strategies towards OLPL materials with hour-long afterglow duration are still quite limited. Here, we propose a novel OLPL system through melt-casting method with 0.1 mol % of CuI complexes: 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl BINAP-CuX (X=Cl, Br and I) doped into the triphenylphosphine (TPP) host. The charge separation was initiated prior to excitation through host coordination with CuI complexes, resulting in semi-free halogen ions and in situ generated CuI cations, which forms TPP + BINAP-CuX ionic pairs and subsequently ionic solids. The OLPL lifetime can be readily modulated by different halogen atoms and the afterglow can last up to more than 3 hours perceivable to human eyes. This is a rare example of OLPL initiated through host-guest coordination that could potentially expand the definition of OLPL systems and design strategies.

Chiral Spiro-Axis Induced Blue Thermally Activated Delayed Fluorescence Material for Efficient Circularly Polarized OLEDs with Low Efficiency Roll-Off.

A spiro-axis skeleton not only introduces circularly polarized luminescence (CPL) into thermally activated delayed fluorescence (TADF) molecules but also enhances the intramolecular through space charge transfer (TSCT) process. Spiral distributed phenoxazine and 2-(trifluoromethyl)-9H-thioxanthen-9-one-10,10-dioxide act as donor and acceptor units, respectively. The resulting TADF enantiomers, (rac)-OSFSO, display emission maxima at 470 nm, small singlet-triplet energy gap (ΔEST ) of 0.022 eV and high photoluminescence quantum yield (PLQY) of 81.2 % in co-doped film. The circularly polarized OLEDs (CP-OLEDs) based on (R)-OSFSO and (S)-OSFSO display obvious circularly polarized electroluminescence (CPEL) signals with dissymmetry factor up to 3.0×10-3 and maximum external quantum efficiency (EQEmax ) of 20.0 %. Moreover, the devices show remarkably low efficiency roll-off with an EQE of 19.3 % at 1000 cd m-2 (roll-off ca. 3.5 %), which are among the top results of CP-OLEDs.

Enantiomorphic Perovskite Ferroelectrics with Circularly Polarized Luminescence.

Materials with circularly polarized luminescence (CPL) activity have immense potential applications in molecular switches, optical sensors, information storage, asymmetric photosynthesis, 3D optical displays, biological probe, and spintronic devices. However, the achiral architectures of most of the luminophores severely limit their practical needs. Within this context, molecular ferroelectrics with striking chemical variability and structure-property flexibility bring light to the assembly of CPL-active ferroelectric materials. Herein, we report organic-inorganic perovskite enantiomorphic ferroelectrics, (R)- and (S)-3-(fluoropyrrolidinium)MnBr3, undergoing a 222F2-type ferroelectric phase transition at 273 K. Their mirror relationships are verified by both single-crystal X-ray diffraction and vibrational circular dichroism (VCD). Furthermore, the corresponding Cotton effect for two chiral crystals was captured by mirror CPL activity. This may be assigned to the inducing interaction between the achiral luminescent perovskite framework and chiral organic components. As far as we know, this is the first molecular ferroelectric with CPL activity. Accordingly, this will inspire intriguing research in molecular ferroelectrics with CPL activity and holds great potential for the development of new optoelectronic devices.

Circularly Polarized Thermally Activated Delayed Fluorescence Emitters in Through-Space Charge Transfer on Asymmetric Spiro Skeletons.

This work describes a strategy to produce circularly polarized thermally activated delayed fluorescence (CP-TADF). A set of two structurally similar organic emitters SFST and SFOT are constructed, whose spiro architectures containing asymmetric donors result in chirality. Upon grafting within the spiro frameworks, the donor and acceptor are fixed proximally in a face-to-face manner. This orientation allows intramolecular through-space charge transfer (TSCT) to occur in both emitters, leading to TADF properties. The donor units in SFST and SFOT have a sulfur and oxygen atom, respectively; such a subtle difference has great impacts on their photophysical, chiroptical, and electroluminescence (EL) properties. SFOT exhibits greatly enhanced EL performance in doped organic light-emitting diodes, with external quantum efficiency (EQE) up to 23.1%, owing to the concurrent manipulation of highly photoluminescent quantum efficiency (PLQY, ∼90%) and high exciton utilization. As a comparison, the relatively larger sulfur atom in SFST introduces heavy atom effects and leads to distortion of the molecular backbone that lengthens the donor-acceptor distance. SFST thus has lower PLQY and faster nonradiative decay rate. The collective consequence is that the EQE value of SFST, i.e., 12.5%, is much lower than that of SFOT. The chirality of these two spiro emitters results in circularly polarized luminescence. Because SFST has a more distorted molecular architecture than SFOT, the luminescence dissymmetry factor (|glum|) of circularly polarized luminescence of one enantiomer of the former, namely, either (S)-SFST or (R)-SFST, is almost twice that of (S)-SFOT/(R)-SFOT. Moreover, the CP organic light-emitting diodes (CP-OLEDs) show obvious circularly polarized electroluminescence (CPEL) signals with gEL of 1.30 × 10-3 and 1.0 × 10-3 for (S)-SFST and (S)-SFOT, respectively.

Visible-Light-Mediated Click Chemistry for Highly Regioselective Azide-Alkyne Cycloaddition by a Photoredox Electron-Transfer Strategy.

Click chemistry focuses on the development of highly selective reactions using simple precursors for the exquisite synthesis of molecules. Undisputedly, the CuI -catalyzed azide-alkyne cycloaddition (CuAAC) is one of the most valuable examples of click chemistry, but it suffers from some limitations as it requires additional reducing agents and ligands as well as cytotoxic copper. Here, we demonstrate a novel strategy for the azide-alkyne cycloaddition reaction that involves a photoredox electron-transfer radical mechanism instead of the traditional metal-catalyzed coordination process. This newly developed photocatalyzed azide-alkyne cycloaddition reaction can be performed under mild conditions at room temperature in the presence of air and visible light and shows good functional group tolerance, excellent atom economy, high yields of up to 99 %, and absolute regioselectivity, affording a variety of 1,4-disubstituted 1,2,3-triazole derivatives, including bioactive molecules and pharmaceuticals. The use of a recyclable photocatalyst, solar energy, and water as solvent makes this photocatalytic system sustainable and environmentally friendly. Moreover, the azide-alkyne cycloaddition reaction could be photocatalyzed in the presence of a metal-free catalyst with excellent regioselectivity, which represents an important development for click chemistry and should find versatile applications in organic synthesis, chemical biology, and materials science.