Switching from Thermally Activated Delayed Fluorescence in Single Crystals for Low-Threshold Laser to Room-temperature Phosphorescence in Amorphous-Film for Highly Efficient OLEDs.

Metal-organic phosphorescent complexes containing Ir or Pt are work horse in organic light-emitting diode (OLED) technology, which can harvest both singlet and triplet excitons in electroluminescence (EL) owing to strong heavy-atom effect. Recently, organic room-temperature phosphorescence (ORTP) have achieved high photoluminescence quantum yield (PLQY) in rigid crystalline state, which, however, is unsuitable for OLED fabrication, therefore leading to an EL efficiency far low behind those of metal-organic phosphorescent complexes. Here, we reported a luminescence mechanism switch from thermally activated delayed fluorescence (TADF) in single crystal microwires to ORTP in amorphous thin-films, based on a tert-butylcarbazole difluoroboron ß-diketonate derivative of DtCzBF2. Tightly packed and well-faceted single-crystal microwires exhibit aggregation induced emission (AIE), enabling TADF microlasers at 473 nm with an optical gain coefficient as high as 852 cm-1 . In contrast, loosely packed dimers of DtCzBF2 formed in guest-host amorphous thin-films decrease the oscillator strength of fluorescence transition but stabilize triplets for ORTP with a PLQY up to 61 %, leading to solution-processed OLEDs with EQE approaching 20 %. This study opens possibilities of low-cost ORTP emitters for high performance OLEDs and future low-threshold electrically injected organic semiconductor lasers (OSLs).

Host Surface-Induced Excitation Wavelength-Dependent Organic Afterglow.

The design and construction of organic afterglow materials is an attractive but formidably challenging task due to the low intersystem crossing efficiency and nonradiative decay. Here, we developed a host surface-induced strategy to achieve excitation wavelength-dependent (Ex-De) afterglow emission through a facile dropping process. The prepared PCz@dimethyl terephthalate (DTT)@paper system exhibits a room-temperature phosphorescence afterglow, with the lifetime up to 1077.1 ± 15 ms and duration time exceeding 6 s under ambient conditions. Furthermore, we can switch the afterglow emission on and off by adjusting the excitation wavelength below or above 300 nm, showing a remarkable Ex-De behavior. Spectral analysis demonstrated that the afterglow originates from the phosphorescence of PCz@DTT assemblies. The stepwise preparation process and detailed experiments (XRD, 1H NMR, and FT-IR analysis) proved the presence of strong intermolecular interactions between the carbonyl groups on the surface of DTT and the entire frame of PCz, which can inhibit the nonradiative processes of PCz to achieve afterglow emission. Theoretical calculations further manifested that DTT geometry alteration under different excitation beams is the main reason for the Ex-De afterglow. This work discloses an effective strategy for constructing smart Ex-De afterglow systems that can be fully exploited in a range of fields.

Dynamic Evolving Exothermicity Steers Ultrafast Formation of a Correlated Triplet Pair State.

Singlet fission (SF) presents an attractive solution to overcome the Shockley-Queisser limit of single-junction solar cells. The conversion from an initial singlet state to final triplet is mediated by the correlated triplet pair state 1(T1T1). Despite significant advancement on 1(T1T1) properties and its role in SF, a comprehensive understanding of the energetic landscape during SF is still unclear. Here, we study an unconventional SF system with excited-state aromaticity, i.e., cyano-substituted dipyrrolonaphtheridinedione derivative (DPND-CN), using time-resolved spectroscopy as a function of the temperature. We demonstrate that the population transfer from S1 to 1(T1T1) is driven by a time-dependent exothermicity resulting from the coherent coupling between electronic and spin degrees of freedom. This is followed by thermal-activated dissociation of 1(T1T1) to yield free triplets. Our results provide some new insight into the SF mechanism, which may guide the development of new efficient and stable SF materials for practical applications.

Amplified Spontaneous Emission from Organic Phosphorescence Emitters.

Organic gain materials (OGMs) currently used in organic lasers and optical amplifiers are focused on singlet-fluorescence materials, while triplet-phosphorescence-based OGMs have hardly been developed yet. Herein, we report a novel pure organic phosphorescence gain molecule (SBP) for optical amplification by stimulated emission from triplet states. The introduction of the benzophenone carbonyl group and sulfur atoms increases the spin orbit coupling constant of SBP, which accelerates the intersystem crossing (ISC) and phosphorescence processes. Experimental and theoretical results verify that the formation of the H-type dimer aggregate decreases the fluorescence radiation rate while accelerating the ISC rate, also enhancing the phosphorescence emission of SBP. Doping SBP molecules into a PMMA matrix can stabilize triplet excitons, yielding the maximum phosphorescence quantum yield of 18.9%. We realized triplet phosphorescent amplified spontaneous emission (ASE) at 557 nm from 30.0 wt % SBP@PMMA samples. Our results provide a novel strategy to develop triplet phosphor OGMs.

Excitation-Wavelength-Dependent Organic Long-Persistent Luminescence Originating from Excited-State Long-Range Proton Transfer.

Stimuli-responsive functional luminescent materials with tunable color and long-persistent emission have emerged as a powerful tool in information encryption, anticounterfeiting, and bioelectronics. Herein, we prove a novel strategy for manipulating the proton transfer pathways in the salicylaldehyde derivative EQCN solutions/powder to produce excitation wavelength-dependent (Ex-De) performances with switchable emissions (blue-sky, green, and orange). The experiments and theoretical results demonstrated that the different luminous colors are originated from enol (E) form (blue-sky), Keto-1 (K1) form (orange) through the excited-state intramolecular proton transfer (ESIPT) process, and Keto-2 (K2) form (green) through the excited-state long-range proton transfer (ESLRPT) process. We leverage synergistic effects between the dopant and matrix (dimethyl terephthalate, DTT) to manipulate the excited-state proton transfer pathway in EQCN@DTT mixture powders to generate Ex-De long-persistent luminescence (Ex-De-LPL), which can be well applied in multilevel information encryption. This strategy not only paves an intriguing way for the construction and preparation of pure organic Ex-De materials but also offers a guideline for developing LPL materials based on ESLRPT processes.

IL-7 and CCL19-secreting CAR-T cell therapy for tumors with positive glypican-3 or mesothelin.

Although chimeric antigen receptor (CAR)-engineered T cells have shown great success in the treatment of B cell malignancies, this strategy has limited efficacy in patients with solid tumors. In mouse CAR-T cells, IL-7 and CCL19 expression have been demonstrated to improve T cell infiltration and CAR-T cell survival in mouse tumors. Therefore, in the current study, we engineered human CAR-T cells to secrete human IL-7 and CCL19 (7 × 19) and found that these 7 × 19 CAR-T cells showed enhanced capacities of expansion and migration in vitro. Furthermore, 7 × 19 CAR-T cells showed superior tumor suppression ability compared to conventional CAR-T cells in xenografts of hepatocellular carcinoma (HCC) cell lines, primary HCC tissue samples and pancreatic carcinoma (PC) cell lines. We then initiated a phase 1 clinical trial in advanced HCC/PC/ovarian carcinoma (OC) patients with glypican-3 (GPC3) or mesothelin (MSLN) expression. In a patient with advanced HCC, anti-GPC3-7 × 19 CAR-T treatment resulted in complete tumor disappearance 30 days post intratumor injection. In a patient with advanced PC, anti-MSLN-7 × 19 CAR-T treatment resulted in almost complete tumor disappearance 240 days post-intravenous infusion. Our results demonstrated that the incorporation of 7 × 19 into CAR-T cells significantly enhanced the antitumor activity against human solid tumor. Trial registration: NCT03198546. Registered 26 June 2017, https://clinicaltrials.gov/ct2/show/NCT03198546?term=NCT03198546&draw=2&rank=1.

Prdx2 Upregulation Promotes the Growth and Survival of Gastric Cancer Cells.

Peroxiredoxins (Prdxs) play important roles in cell proliferation, differentiation, and the mediation of intracellular signalling pathways. Prdx2 is an important member of the peroxiredoxin family and is upregulated in many cancers. Until now, the biological functions of Prdx2 in gastric cancer have not been completely understood, and the underlying mechanisms remain elusive. The aim of this study was to identify the role of Prdx2 on the growth of gastric cancer cells and the underlying mechanisms. We demonstrated that Prdx2 was highly expressed in gastric cancer tissues and cell lines and that the over-expression of Prdx2 correlated with the progression of gastric cancer. Further, Prdx2 was silenced with a specific, lentiviral vector-mediated shRNA, and this suppressed the proliferation of gastric cancer cells and promoted the apoptosis of gastric cancer cells. Finally, the knockdown of Prdx2 contributed to the attenuated gastric cancer growth in BALB/c nude mice. In conclusion, these findings demonstrate that Prdx2 may participate in the carcinogenesis and development of gastric cancer.

[Intervention effect of Tibetan patent medicine Ruyi Zhenbao pills in acute ischemic stroke in rats].

Ischemic stroke is a primary cause of death and long-term disability all over the world. This disease is resulted from ischemia and hypoxia in brain tissues because of insufficient blood supply and causes a series of physiochemical metabolism disorders and physiological dysfunction. Its high disability ratio has bright huge burdens to society, governments and families. However, there is not efficacious medicine to treat it. In this study, a right middle cerebral artery occlusion was established in rats to observe the multi-path and multi-aspect intervention effects of Tibetan patent medicine Ruyi Zhenbao pills in reducing injuries to Nissl bodies, cerebral edema and inflammatory reactions and preventing cellular apoptosis, in order to lay a foundation for defining its therapeutic mechanism in acute ischemic stroke.