A star-shaped 1,3,5-triazine/cyano hybrid molecule CN-T2T was designed and synthesized as a new electron acceptor for efficient exciplex-based OLED emitter by mixing with a suitable electron donor ...(Tris-PCz). The CN-T2T/Tris-PCz exciplex emission shows a high ΦPL of 0.53 and a small ΔE T‑S = −0.59 kcal/mol, affording intrinsically efficient fluorescence and highly efficient exciton up-conversion. The large energy level offsets between Tris-PCz and CN-T2T and the balanced hole and electron mobility of Tris-PCz and CN-T2T, respectively, ensuring sufficient carrier density accumulated in the interface for efficient generation of exciplex excitons. Employing a facile device structure composed as ITO/4% ReO3:Tris-PCz (60 nm)/Tris-PCz (15 nm)/Tris-PCz:CN-T2T(1:1) (25 nm)/CN-T2T (50 nm)/Liq (0.5 nm)/Al (100 nm), in which the electron–hole capture is efficient without additional carrier injection barrier from donor (or acceptor) molecule and carriers mobilities are balanced in the emitting layer, leads to a highly efficient green exciplex OLED with external quantum efficiency (EQE) of 11.9%. The obtained EQE is 18% higher than that of a comparison device using an exciplex exhibiting a comparable ΦPL (0.50), in which TCTA shows similar energy levels but higher hole mobility as compared with Tris-PCz. Our results clearly indicate the significance of mobility balance in governing the efficiency of exciplex-based OLED. Exploiting the Tris-PCz:CN-T2T exciplex as the host, we further demonstrated highly efficient yellow and red fluorescent OLEDs by doping 1 wt % Rubrene and DCJTB as emitter, achieving high EQE of 6.9 and 9.7%, respectively.
The lack of structural information impeded the access of efficient luminescence for the exciplex type thermally activated delayed fluorescence (TADF). We report here the pump-probe Step-Scan Fourier ...transform infrared spectra of exciplex composed of a carbazole-based electron donor (CN-Cz2) and 1,3,5-triazine-based electron acceptor (PO-T2T) codeposited as the solid film that gives intermolecular charge transfer (CT), TADF, and record-high exciplex type cyan organic light emitting diodes (external quantum efficiency: 16%). The transient infrared spectral assignment to the CT state is unambiguous due to its distinction from the local excited state of either the donor or the acceptor chromophore. Importantly, a broad absorption band centered at ~2060 cm
was observed and assigned to a polaron-pair absorption. Time-resolved kinetics lead us to conclude that CT excited states relax to a ground-state intermediate with a time constant of ~3 µs, followed by a structural relaxation to the original CN-Cz2:PO-T2T configuration within ~14 µs.
Liquid crystals have great potential for developing photonic devices that control the optical behaviors of liquid crystals in smart devices with external stimulation. In this study, we have ...demonstrated a series of bistable cholesteric liquid crystal devices using the dual-frequency nematic liquid crystal HEF951 assisted by a predesigned chiral ferroelectric liquid crystal. The synthesized chiral ferroelectric liquid crystal was used to induce the formation of the cholesteric liquid crystal phase and decrease the driving voltages and response times of the fabricated bistable liquid crystal devices. The fabricated ferroelectric liquid crystal-assisted bistable cholesteric liquid crystal devices showed a stable opaque focal conic state and stable transparent planar state without any energy consumption once they were turned "from focal-conic to planar" and "from planar to focal-conic". To enhance the reliability, the fabricated bistable cholesteric liquid crystal devices were further stabilized by polymer matrixes. Switching of the bistable liquid crystal cells from one state to another was achieved by a one-step voltage bias with various frequencies. Furthermore, the response time of the sample cell was calculated as 1.7 ms. These results suggest that fabricated ferroelectric liquid crystal-assisted bistable cholesteric liquid crystal devices can be applied to produce energy-saving green liquid crystal displays and other related smart devices.
Fabricated polymer-stabilized bistable cholesteric liquid crystal devices show a stable opaque focal conic state and a stable transparent planar state without any energy consumption once they are turned.
The development of high-performance near-infrared organic light-emitting diodes is hindered by strong non-radiative processes as governed by the energy gap law. Here, we show that exciton ...delocalization, which serves to decouple the exciton band from highly vibrational ladders in the S0 ground state, can bring substantial enhancements in the photoluminescence quantum yield of emitters, bypassing the energy gap law. Experimental proof is provided by the design and synthesis of a series of new Pt(ii) complexes with a delocalization length of 5–9 molecules that emit at 866–960 nm with a photoluminescence quantum yield of 5–12% in solid films. The corresponding near-infrared organic light-emitting diodes emit light with a 930 nm peak wavelength and a high external quantum efficiency up to 2.14% and a radiance of 41.6 W sr−1 m−2. Both theoretical and experimental results confirm the exciton–vibration decoupling strategy, which should be broadly applicable to other well-aligned molecular solids.Pt(ii) complexes allow the fabrication of efficient near-infrared organic light-emitting diodes that operate beyond the 900 nm region.
Through the incorporation of various halogen‐substituted chiral organic cations, the effects of chiral molecules on the chiroptical properties of hybrid organic–inorganic perovskites (HOIPs) are ...investigated. Among them, the HOIP having a Cl‐substituted chiral cation exhibits the highest circular dichroism (CD) and circular polarized luminescence (CPL) intensities, indicating the existence of the largest rotatory strength, whereas the F‐substituted HIOP shows the weakest intensities. The observed modulation can be correlated to the varied magnetic transition dipole of HOIPs, which is sensitive to the d‐spacing between inorganic layers and the halogen–halogen interaction between organic cations and the inorganic sheets. These counteracting effects meet the optimal CD and CPL intensity with chlorine substitution, rendering the rotatory strength of HOIPs arranged in the order of (ClMBA)2PbI4>(BrMBA)2PbI4>(IMBA)2PbI4>(MBA)2PbI4>(FMBA)2PbI4.
Through the incorporation of Cl‐substituted chiral organic cations, the chiroptical properties of 2D chiral perovskites can be significantly enhanced. The observed circular dichroism and circular polarized luminescence intensities are found to be associated with the d‐spacing of hybrid organic–inorganic perovskites and the strength of the halogen–halogen interaction within the system.
Multidrug resistance (MDR) resulting from the overexpression of drug transporters such as P‐glycoprotein (Pgp) increases the efflux of drugs and thereby limits the effectiveness of chemotherapy. To ...address this issue, this work develops an injectable hollow microsphere (HM) system that carries the anticancer agent irinotecan (CPT‐11) and a NO‐releasing donor (NONOate). Upon injection of this system into acidic tumor tissue, environmental protons infiltrate the shell of the HMs and react with their encapsulated NONOate to form NO bubbles that trigger localized drug release and serve as a Pgp‐mediated MDR reversal agent. The site‐specific drug release and the NO‐reduced Pgp‐mediated transport can cause the intracellular accumulation of the drug at a concentration that exceeds the cell‐killing threshold, eventually inducing its antitumor activity. These results reveal that this pH‐responsive HM carrier system provides a potentially effective method for treating cancers that develop MDR.
Two is better than one: A carrier system is developed that can generate NO bubbles in the acidic environment of tumor tissues to trigger localized drug release (specifically irinotecan, denoted CPT‐11) and to reverse Pgp‐mediated multidrug resistance (Pgp=P‐glycoprotein). The combined system enhances intracellular drug accumulation in cancer cells so that the concentration exceeds the therapeutic threshold, eventually leading to antitumor activity.
We introduce a self-supervised speech pre-training method called TERA, which stands for Transformer Encoder Representations from Alteration. Recent approaches often learn by using a single auxiliary ...task like contrastive prediction, autoregressive prediction, or masked reconstruction. Unlike previous methods, we use alteration along three orthogonal axes to pre-train Transformer Encoders on a large amount of unlabeled speech. The model learns through the reconstruction of acoustic frames from their altered counterpart, where we use a stochastic policy to alter along various dimensions: time, frequency, and magnitude. TERA can be used for speech representations extraction or fine-tuning with downstream models. We evaluate TERA on several downstream tasks, including phoneme classification, keyword spotting, speaker recognition, and speech recognition. We present a large-scale comparison of various self-supervised models. TERA achieves strong performance in the comparison by improving upon surface features and outperforming previous models. In our experiments, we study the effect of applying different alteration techniques, pre-training on more data, and pre-training on various features. We analyze different model sizes and find that smaller models are strong representation learners than larger models, while larger models are more effective for downstream fine-tuning than smaller models. Furthermore, we show the proposed method is transferable to downstream datasets not used in pre-training.
Major depressive disorder (MDD) has become a leading contributor to the global burden of disease; however, there are currently no reliable biological markers or physiological measurements for ...efficiently and effectively dissecting the heterogeneity of MDD. Here we propose a novel method based on scalp electroencephalography (EEG) signals and a robust spectral-spatial EEG feature extractor called kernel eigen-filter-bank common spatial pattern (KEFB-CSP). The KEFB-CSP first filters the multi-channel raw EEG signals into a set of frequency sub-bands covering the range from theta to gamma bands, then spatially transforms the EEG signals of each sub-band from the original sensor space to a new space where the new signals (i.e., CSPs) are optimal for the classification between MDD and healthy controls, and finally applies the kernel principal component analysis (kernel PCA) to transform the vector containing the CSPs from all frequency sub-bands to a lower-dimensional feature vector called KEFB-CSP. Twelve patients with MDD and twelve healthy controls participated in this study, and from each participant we collected 54 resting-state EEGs of 6 s length (5 min and 24 s in total). Our results show that the proposed KEFB-CSP outperforms other EEG features including the powers of EEG frequency bands, and fractal dimension, which had been widely applied in previous EEG-based depression detection studies. The results also reveal that the 8 electrodes from the temporal areas gave higher accuracies than other scalp areas. The KEFB-CSP was able to achieve an average EEG classification accuracy of 81.23% in single-trial analysis when only the 8-electrode EEGs of the temporal area and a support vector machine (SVM) classifier were used. We also designed a voting-based leave-one-participant-out procedure to test the participant-independent individual classification accuracy. The voting-based results show that the mean classification accuracy of about 80% can be achieved by the KEFP-CSP feature and the SVM classifier with only several trials, and this level of accuracy seems to become stable as more trials (i.e., <7 trials) are used. These findings therefore suggest that the proposed method has a great potential for developing an efficient (required only a few 6-s EEG signals from the 8 electrodes over the temporal) and effective (~80% classification accuracy) EEG-based brain-computer interface (BCI) system which may, in the future, help psychiatrists provide individualized and effective treatments for MDD patients.
Research into organic light emitters employing multiple resonance-induced thermally activated delayed fluorescence (MR-TADF) materials is presently attracting a great deal of attention due to the ...potential for efficient deep-blue emission. However, the origins and mechanisms of successful TADF are unclear, as many MR-TADF materials do not show TADF behaviour in solution, but only as particular pure solids. Here, an investigation into a well-known MR-TADF material, DABNA-1, together with other new MR materials (9H-quinolino3,2,1-klphenothiazin-9-one (QPO) and 9H-quinolino-3,2,1-kl-phenothiazin-9-one 5,5-dioxide (QP3O)), yields new insights regarding the origin of TADF. Although a material system may support the concept of MR, inefficiency in both forward and reverse intersystem crossings forbids TADF unless a suitable host material allows an exciplex-like host–emitter interaction that boosts TADF. This boosted-TADF mechanism can be generalized to any fluorescence dye that lacks TADF in the photoluminescence measurement but has a thermally accessible S1–T1 energy gap, opening the way to high-performance organic light-emitting diodes.This study reveals the importance of host–guest interactions for effective multiple-resonance thermally activated delayed fluorescence in organic light emitters.
The tumor microenvironment (TME) governs all aspects of cancer progression and in vitro 3D cell culture platforms are increasingly developed to emulate the interactions between components of the ...stromal tissues and cancer cells. However, conventional cell culture platforms are inadequate in recapitulating the TME, which has complex compositions and dynamically changing matrix mechanics. In this study, we developed a dynamic gelatin-hyaluronic acid hybrid hydrogel system through integrating modular thiol-norbornene photopolymerization and enzyme-triggered on-demand matrix stiffening. In particular, gelatin was dually modified with norbornene and 4-hydroxyphenylacetic acid to render this bioactive protein photo-crosslinkable (through thiol-norbornene gelation) and responsive to tyrosinase-triggered on-demand stiffening (through HPA dimerization). In addition to the modified gelatin that provides basic cell adhesive motifs and protease cleavable sequences, hyaluronic acid (HA), an essential tumor matrix, was modularly and covalently incorporated into the cell-laden gel network. We systematically characterized macromer modification, gel crosslinking, as well as enzyme-triggered stiffening and degradation. We also evaluated the influence of matrix composition and dynamic stiffening on pancreatic ductal adenocarcinoma (PDAC) cell fate in 3D. We found that either HA-containing matrix or a dynamically stiffened microenvironment inhibited PDAC cell growth. Interestingly, these two factors synergistically induced cell phenotypic changes that resembled cell migration and/or invasion in 3D. Additional mRNA expression array analyses revealed changes unique to the presence of HA, to a stiffened microenvironment, or to the combination of both. Finally, we presented immunostaining and mRNA expression data to demonstrate that these irregular PDAC cell phenotypes were a result of matrix-induced epithelial-mesenchymal transition (EMT).
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