Rational Design of Coumarin-Based Hybridized Local and Charge-Transfer Blue Emitters for Solution-Processed Organic Light-Emitting Diodes.

Hybridized local and charge-transfer (HLCT) with the utilization of both singlet and triplet excitons through the "hot excitons" channel have great application potential in highly efficient blue organic light-emitting diodes (OLEDs). The proportion of charge-transfer (CT) and locally excited (LE) components in the relevant singlet and triplet states makes a big difference for the high-lying reverse intersystem crossing process. Herein, three novel donor (D)-acceptor (A) type HLCT materials, 7-([1,1'-biphenyl]-4-yl(9,9-dimethyl-9H-fluoren-2-yl)amino)-3-phenyl-1H-isochromen-1-one (pPh-7P), 7-([1,1'-biphenyl]-4-yl(9,9-dimethyl-9H-fluoren-2-yl)amino)-3-methyl-1H-isochromen-1-one (pPh-7M), and 6-([1,1'-biphenyl]-4-yl(9,9-dimethyl-9H-fluoren-2-yl)amino)-3-methyl-1H-isochromen-1-one (pPh-6M), were rationally designed and synthesized with diphenylamine derivative as donor and oxygen heterocyclic coumarin moiety as acceptors. The proportions of CT and LE components were fine controlled by changing the connection site of diphenylamine derivative at C6/C7-position and the substituent at C3-position of coumarin moiety. The HLCT characteristics of pPh-7P, pPh-7M, and pPh-6M were systematically demonstrated through photophysical properties and density functional theory calculations. The solution-processed doped OLEDs based on pPh-6M exhibited deep-blue electroluminescence with the maximum emission wavelength of 446 nm, maximum luminance of 8755 cd m-2, maximum current efficiency of 5.83 cd A-1, and maximum external quantum efficiency of 6.54 %. The results reveal that pPh-6M with dominant 1LE and 3CT components has better OLED performance.

Correlation of oxidative stress and vascular endothelial dysfunction with hippocampal perfusion in atrial fibrillation patients with cognitive impairment.

Objectives: To evaluate the correlation of oxidative stress and vascular endothelial dysfunction with hippocampal perfusion in patients with atrial fibrillation and cognitive impairment. Methods: In total, 41 atrial fibrillation patients with cognitive impairment were compared to 45 atrial fibrillation patients without cognitive impairment. Oxidative stress, vascular endothelial dysfunction, hippocampal perfusion, and cognitive function were measured. Results: Serum level of oxidized low-density lipoprotein was significantly higher in the atrial fibrillation + cognitive impairment group than in the atrial fibrillation group. Serum levels of intercellular adhesion molecule-1 and vascular cell adhesion molecule-1 were significantly higher, and nitric oxide was lower, in the atrial fibrillation + cognitive impairment group than in the atrial fibrillation group. The regional cerebral blood volume, mean transit time, and time to peak were significantly higher in the atrial fibrillation + cognitive impairment group than in the atrial fibrillation group. Moreover, regional cerebral blood flow was significantly lower in the atrial fibrillation + cognitive impairment group than in the atrial fibrillation group. Age, left atrial diameter, and regional cerebral blood volume were negatively correlated with the cognitive function score in the atrial fibrillation + cognitive impairment group. Serum levels of oxidized low-density lipoprotein, regional cerebral blood volume, regional cerebral blood flow, mean transit time, and time to peak were significantly correlated with cognitive impairment in atrial fibrillation patients after multivariate logistic regression analysis. Conclusion: Hippocampal perfusion and oxidative stress were significantly correlated with cognitive impairment in atrial fibrillation patients.

Preventing lead leakage in perovskite solar cells and modules with a low-cost and stable chemisorption coating.

Despite the promising commercial prospects of perovskite solar cells, the issue of lead toxicity continues to hinder their future industrial applications. Here, we report a low-cost and rapidly degraded sulfosuccinic acid-modified polyvinyl alcohol (SMP) coating that prevents lead leakage and enhances device stability without compromising device performance. Even under different strict conditions (simulated heavy rain, acid rain, high temperatures, and competing ions), the coatings effectively prevent lead leakage by over 99%. After 75 days of outdoor exposure, the coating still demonstrates similar lead sequestration efficiency (SQE). In addition, it can be applied to different device structures (n-i-p and p-i-n) and modules, with over 99% SQE, making it a general method for preventing lead leakage.

Clinical management of a patient following a granulocyte transfusion from a donor positive for COVID-19.

Granulocyte transfusions are indicated for patients with severe neutropenia and evidence of bacterial or fungal infection who are unresponsive to standard antimicrobial therapy. With a limited expiration time of 24 hours after collection, granulocytes are often transfused before results of infectious-disease screening tests are available, and before a transfusion service can perform a risk assessment if postdonation information is provided after the collection. The case we describe herein demonstrates a clinical scenario meeting indications for granulocyte transfusion, coupled with the clinical management undertaken after the granulocyte donor disclosed a positive result for a COVID-19 self-test taken 1 day after donation. In this case, the patient did not develop new COVID-19 symptoms and tested negative for COVID-19 after transfusion of the implicated unit. These findings add to the body of evidence in the literature that COVID-19 is not transmitted via blood transfusion.

Lack of RBC transfusion independence by Day 30 following allogeneic hematopoietic stem cell transplant strongly predicts inferior survival and high non-relapse mortality in acute myeloid leukemia patients.

BACKGROUND: Studies have suggested that acute myeloid leukemia (AML) patients with incomplete hematologic recovery undergoing allogeneic stem cell transplantation (allo-HSCT) had inferior overall survival (OS). STUDY DESIGN AND METHODS: This single-center, retrospective study of AML patients evaluated the relationship between red blood cell (RBC) and platelet (PLT) transfusion requirements during the first 30 days and long-term outcomes after allo-HSCT through multivariate analyses. RESULTS: A total of 692 AML patients received peripheral blood stem cells (89.2%), marrow (5.6%), or umbilical cord (5.2%) from matched related (37.4%), unrelated (49.1%), or haploidentical (8.2%) donors in 2011-2017. Transfusion requirements during the first 30 days for RBC (89.5% transfused, median 3, range 1-18 units) or PLT (98.2% transfused, median 6, range 1-144 units) were variable. By Day 30, 56.7% (95% confidence interval [CI]: 52.8-60.3%) and 86.1% (95% CI: 83.2-88.5%) had achieved RBC and PLT transfusion independence, respectively. Median follow-up among survivors (n = 307) was 7.1 years (range: 2.7-11.8). Lack of RBC transfusion independence by Day 30 was strongly and independently associated with worse 5-year OS (39.2% vs. 59.6%, adjusted hazard ratio [HR] 1.83, 95% CI: 1.49-2.25), leukemia-free survival (35.8% vs. 55.5%, HR = 1.75, 95% CI: 1.43-2.14), and NRM (29.7% vs. 13.7%, HR = 2.05, 95% CI: 1.45-2.89) (p < .001). There was no difference in relapse rates among patients who achieved or did not achieve RBC (p = .34) or PLT (p = .64) transfusion independence. CONCLUSION: Prolonged RBC dependence predicted worse survival and NRM rates, but not increased relapse. Posttransplant surveillance of such patients should be adjusted with more attention to non-relapse complications.

Microencapsulated Perovskite Crystals via In Situ Permeation Growth from Polymer Microencapsulation-Expansion-Contraction Strategy: Advancing a Record Long-Term Stability beyond 10 000 h for Perovskite Solar Cells.

Organic metal halide perovskite solar cells (PSCs) bearing both high efficiency and durability are predominantly challenged by inadequate crystallinity of perovskite. Herein, a polymer microencapsulation-expansion-contraction strategy is proposed for the first time to optimize the crystallization behavior of perovskite, typically by adeptly harnessing the swelling and deswelling characteristics of poly(4-acryloylmorpholine) (poly(4-AcM)) network on PbI2 surface. It can effectively retard the crystallization rate of perovskite, permitting meliorative crystallinity featured by increased grain size from 0.74 to 1.32 µm and reduced trap density from 1.12 × 1016 to 2.56 × 1015 cm-3. Moreover, profiting from the protection of poly(4-AcM) microencapsulation layer, the degradation of the perovskite is markedly suppressed. Resultant PSCs gain a robust power conversion efficiency (PCE) of 24.04%. Typically, they maintain 91% of their initial PCE for 13 008 h in a desiccated ambient environment and retain 92% PCE after storage for 4000 h with a relative humidity of 50 ± 10%, which is the state-of-the-art long-term stability among the reported contributions.

Tailoring Phase Distribution of Quasi-2D Perovskites via Taurine-Assistance Enables Efficient Blue Light-Emitting Diodes.

Quasi-2D (Q-2D) perovskites with typical varied n-phase structures deserve promising candidates in pursuing high-performance perovskite light-emitting diodes (PeLEDs). Whereas their weakness in precise n-phase distribution control disables the optical property of PeLEDs since the n = 1 phase is dominated by severe nonradiative recombination. Here, an effective phase distribution tailoring strategy is developed for pure blue PeLEDs by introducing taurine (TAU) into mixed halide Q-2D perovskites. The sulfonic acid group in TAU can coordinate with Pb2+ to suppress the formation of the n = 1 phase while promoting the growth of Q-2D perovskites into domains with the graded distribution of n = 2 and 3. The amino group in TAU forms hydrogen bonds with electronegative halide ions, suppressing the formation of halide vacancies and reducing the defect density in the Q-2D perovskite films. As a result, optimized blue Q-2D perovskite films boosted PLQY to 92%. Target blue PeLED  was endowed with a peak EQE of 14.82% (average 12.6%) at 475 nm and a maximum luminance of 1937 cd m-2 , which is among the reported high-level pure blue PeLEDs. This work demonstrates a feasible approach to regulate the phase distribution of Q-2D perovskites for high-performance blue PeLEDs.

Crosstalk between Gut Sensory Ghrelin Signaling and Adipose Tissue Sympathetic Outflow Regulates Metabolic Homeostasis.

The stomach-derived orexigenic hormone ghrelin is a key regulator of energy homeostasis and metabolism in humans. The ghrelin receptor, growth hormone secretagogue receptor 1a (GHSR), is widely expressed in the brain and gastrointestinal vagal sensory neurons, and neuronal GHSR knockout results in a profoundly beneficial metabolic profile and protects against diet-induced obesity (DIO) and insulin resistance. Here we show that in addition to the well characterized vagal GHSR, GHSR is robustly expressed in gastrointestinal sensory neurons emanating from spinal dorsal root ganglia. Remarkably, sensory neuron GHSR deletion attenuates DIO through increased energy expenditure and sympathetic outflow to adipose tissue independent of food intake. In addition, neuronal viral tract tracing reveals prominent crosstalk between gut non-vagal sensory afferents and adipose sympathetic outflow. Hence, these findings demonstrate a novel gut sensory ghrelin signaling pathway critical for maintaining energy homeostasis.

Improving XYG3-type doubly hybrid approximation using self-interaction corrected SCAN density and orbitals via the PZ-SIC framework: The xDH@SCAN(SIC) approach.

XYG3-type doubly hybrid (xDH) approximations have gained widespread recognition for their accuracy in describing a diverse range of chemical and physical interactions. However, a recent study [Song et al., J. Phys. Chem. Lett. 12, 800-807 (2021)] has highlighted the limitation of xDH methods in calculating the dissociation of NaCl molecules. This issue has been related to the density and orbitals used for evaluating the energy in xDH methods, which are obtained from lower-rung hybrid density functional approximations (DFAs) and display substantial density errors in the dissociation limit. In this work, we systematically investigate the influence of density on several challenging datasets and find that xDH methods are less sensitive to density errors compared to semi-local and hybrid DFAs. Furthermore, we demonstrate that the self-interaction corrected SCAN density approach offers superior accuracy compared to the self-consistent SCAN density and Hartree-Fock density approaches, as evidenced by performing charge analysis on the dissociation of heterodimers, such as NaCl and LiF. Building on these insights, we propose a five-parameter xDH method using the SCAN density and orbitals corrected by the PZ-SIC scheme. This new xDH@SCAN(SIC) method provides a balanced and accurate description across a wide range of challenging systems.

The Correlation of Inflammation, Oxidative Stress, and Hippocampal Perfusion in Patients with Atrial Fibrillation.

Atrial fibrillation (AF) is closely related to abnormal cerebral blood flow. Inflammation and oxidative stress have always been important factors in the pathophysiology of AF. It remains unknown whether inflammation and oxidative stress are correlated to hippocampal perfusion in patients with AF.Sixty-three patients with AF with normal hippocampal blood perfusion (NHBP) were compared to 71 patients with AF with abnormal hippocampal blood perfusion (AHBP) using a case-control study design. The serum levels of inflammation and oxidative stress were measured. The hippocampal perfusion was detected. (1) The serum levels of high-sensitivity C-reactive protein (hs-CRP), interleukin 6 (IL-6), and oxidized low-density lipoprotein (ox-LDL) were statistically higher in the AHBP group than in the NHBP group. In the AHBP subgroup analysis, the serum levels of hs-CRP and IL-6 were statistically higher in patients with persistent AF than those with paroxysmal AF. (2) The relative cerebral blood volume (rCBV), mean transit time (MTT), and the time-to-peak (TTP) were statistically higher in the AHBP group than in the NHBP group. Moreover, cerebral blood flow (rCBF) was statistically lower in the AHBP group than in the NHBP group. (3) relative cerebral blood volume (rCBV), rCBF, MTT, and TTP were passively associated with serum hs-CRP and IL-6; rCBV, rCBF, and MTT were positively associated with ox-LDL. The serum levels of hs-CRP, IL-6, and ox-LDL were associated with AHBP in patients with AF after multivariate logistic regression analysis.Oxidative stress and inflammatory biomarkers were increased in patients with AF with AHBP, in which the serum levels of hs-CRP and IL-6 in the persistent AF group were statistically higher than those in the paroxysmal AF group. The serum levels of hs-CRP, IL-6, and ox-LDL were associated with AHBP in patients with AF.

Neural Decoding for Intracortical Brain-Computer Interfaces.

Brain-computer interfaces have revolutionized the field of neuroscience by providing a solution for paralyzed patients to control external devices and improve the quality of daily life. To accurately and stably control effectors, it is important for decoders to recognize an individual's motor intention from neural activity either by noninvasive or intracortical neural recording. Intracortical recording is an invasive way of measuring neural electrical activity with high temporal and spatial resolution. Herein, we review recent developments in neural signal decoding methods for intracortical brain-computer interfaces. These methods have achieved good performance in analyzing neural activity and controlling robots and prostheses in nonhuman primates and humans. For more complex paradigms in motor rehabilitation or other clinical applications, there remains more space for further improvements of decoders.

A Breakthrough in Solution-Processed Ultra-Deep-Blue HLCT OLEDs: A Record External Quantum Efficiency Exceeding 10% Based on Novel V-Shaped Emitters.

It is always a great challenge to achieve high-efficiency solution-processed ultra-deep-blue organic light-emitting diodes (OLEDs) with the Commission Internationale de l'Eclairage (CIE) 1931 chromaticity coordinates matching the blue primary of Rec. International Telecommunication Union-Radiocommunication BT.2100, which specifies high dynamic range television image parameters. Inspired by hybrid local and charge transfer (HLCT) excited state emitters improving exciton utilization through high-lying reverse intersystem crossing, here, a series of high-performance blue emitters by a V-shaped symmetric donor (D)-π-acceptor (A)-π-D design strategy are developed. Here, the large torsions and unstable bonds of D-A structures can be improved through π bridges, and also the conjugation length and donor groups can be easily adjusted. The obtained emitters merit excellent photophysical and electrochemical properties, thermal stability, solution processibility, and HLCT excited state excellence. Results suggest that the OLEDs based on the obtained blue emitters all achieve high maximum external quantum efficiency (EQEmax ) of more than 8% with very low efficiency roll-off. In particular, the device based on 4',5'-bis(4-(9H-carbazol-9-yl)phenyl)spiro[fluorene-9,2'-imidazole] exhibits a satisfactory ultra-deep-blue emission (CIEx , y = 0.1579, 0.0387) and a record-high EQEmax (10.40%) among solution-processed HLCT OLEDs, which is very close to the record EQEmax of devices by vacuum vapor deposition technology.

Solvent Effects on the 1 H-NMR Chemical Shifts of Imidazolium-Based Ionic Liquids.

The 1 H nuclear magnetic resonance (1 H-NMR) spectrum is a useful tool for characterizing the hydrogen bonding (H-bonding) interactions in ionic liquids (ILs). As the main hydrogen bond (H-bond) donor of imidazolium-based ILs, the chemical shift (δH2 ) of the proton in the 2-position of the imidazolium ring (H2) exhibits significant and complex solvents, concentrations and anions dependence. In the present work, based on the dielectric constants (ϵ) and Kamlet-Taft (KT) parameters of solvents, we identified that the δH2 are dominated by the solvents polarity and the competitive H-bonding interactions between cations and anions or solvents. Besides, the solvents effects on δH2 are understood by the structure of ILs in solvents: 1) In diluted solutions of inoizable solvents, ILs exist as free ions and the cations will form H-bond with solvents, resulting in δH2 being independent with anions but positively correlated with ßS . 2) In diluted solutions of non-ionzable solvents, ILs exist as contact ion-pairs (CIPs) and H2 will form H-bond with anions. Since non-ionizable solvents hardly influence the H-bonding interactions between H2 and anions, the δH2 are not related to ßS but positively correlated with ßIL .

Epigenetic Regulation of Hepatic Lipid Metabolism by DNA Methylation.

While extensive investigations have been devoted to the study of genetic pathways related to fatty liver diseases, much less is known about epigenetic mechanisms underlying these disorders. DNA methylation is an epigenetic link between environmental factors (e.g., diets) and complex diseases (e.g., non-alcoholic fatty liver disease). Here, it is aimed to study the role of DNA methylation in the regulation of hepatic lipid metabolism. A dynamic change in the DNA methylome in the liver of high-fat diet (HFD)-fed mice is discovered, including a marked increase in DNA methylation at the promoter of Beta-klotho (Klb), a co-receptor for the biological functions of fibroblast growth factor (FGF)15/19 and FGF21. DNA methyltransferases (DNMT) 1 and 3A mediate HFD-induced methylation at the Klb promoter. Notably, HFD enhances DNMT1 protein stability via a ubiquitination-mediated mechanism. Liver-specific deletion of Dnmt1 or 3a increases Klb expression and ameliorates HFD-induced hepatic steatosis. Single-nucleus RNA sequencing analysis reveals pathways involved in fatty acid oxidation in Dnmt1-deficient hepatocytes. Targeted demethylation at the Klb promoter increases Klb expression and fatty acid oxidation, resulting in decreased hepatic lipid accumulation. Up-regulation of methyltransferases by HFD may induce hypermethylation of the Klb promoter and subsequent down-regulation of Klb expression, resulting in the development of hepatic steatosis.

High-Performance Planar Self-Driven Visible and Near-Infrared Photodetector Based on Pb-Sn Perovskite Single Crystals.

MAPbI3 single crystals (SCs) are promising candidates for self-driven photodetectors due to their spontaneous polarization properties. However, their absorption cutoff wavelength, which is limited to 850 nm, severely hinders their further application in near-infrared photodetectors. In this work, a series of high-quality (MAPbI3)x(FASnI3)1-x (x = 0.8, 0.5 and 0.2) SCs with low defect density and wide absorption range were obtained by employing 1,4-pentanolactone as the solvent at low temperature. Typically, (MAPbI3)0.2(FASnI3)0.8 SCs grown at 32 °C realize absorption in the UV-vis-NIR range from 200 to 1120 nm, which is superior among the absorption wavelengths reported for Pb-Sn perovskite SCs. Resultantly, by merit of the spontaneously polarized built-in electric field, for (MAPbI3)0.2(FASnI3)0.8 SCs based self-driven photodetectors with planar symmetric electrodes exhibiting significant responsivities at 405-1064 nm, the device achieved a maximum responsiveness and detection of 0.247 A/W and 1.17 × 1012 Jones, respectively.

Mixed Cations Enabled Combined Bulk and Interfacial Passivation for Efficient and Stable Perovskite Solar Cells.

Here, we report a mixed GAI and MAI (MGM) treatment method by forming a 2D alternating-cation-interlayer (ACI) phase (n = 2) perovskite layer on the 3D perovskite, modulating the bulk and interfacial defects in the perovskite films simultaneously, leading to the suppressed nonradiative recombination, longer lifetime, higher mobility, and reduced trap density. Consequently, the devices' performance is enhanced to 24.5% and 18.7% for 0.12 and 64 cm2, respectively. In addition, the MGM treatment can be applied to a wide range of perovskite compositions, including MA-, FA-, MAFA-, and CsFAMA-based lead halide perovskites, making it a general method for preparing efficient perovskite solar cells. Without encapsulation, the treated devices show improved stabilities.

Effects of UBE3A on Cell and Liver Metabolism through the Ubiquitination of PDHA1 and ACAT1.

Nonalcoholic fatty liver disease (NAFLD) is substantiated by the reprogramming of liver metabolic pathways that disrupts the homeostasis of lipid and glucose metabolism and thus promotes the progression of the disease. The metabolic pathways associated with NAFLD are regulated at different levels from gene transcription to various post-translational modifications including ubiquitination. Here, we used a novel orthogonal ubiquitin transfer platform to identify pyruvate dehydrogenase A1 (PDHA1) and acetyl-CoA acetyltransferase 1 (ACAT1), two important enzymes that regulate glycolysis and ketogenesis, as substrates of E3 ubiquitin ligase UBE3A/E6AP. We found that overexpression of UBE3A accelerated the degradation of PDHA1 and promoted glycolytic activities in HEK293 cells. Furthermore, a high-fat diet suppressed the expression of UBE3A in the mouse liver, which was associated with increased ACAT1 protein levels, while forced expression of UBE3A in the mouse liver resulted in decreased ACAT1 protein contents. As a result, the mice with forced expression of UBE3A in the liver exhibited enhanced accumulation of triglycerides, cholesterol, and ketone bodies. These results reveal the role of UBE3A in NAFLD development by inducing the degradation of ACAT1 in the liver and promoting lipid storage. Overall, our work uncovers an important mechanism underlying the regulation of glycolysis and lipid metabolism through UBE3A-mediated ubiquitination of PDHA1 and ACAT1 to regulate their stabilities and enzymatic activities in the cell.

Seeding Agents in Metal Halide Perovskite Solar Cells: From Material to Mechanism.

Metal halide perovskite solar cells (PSCs) have been showing up in the commercial field, with an inspiring power conversion efficiency (PCE) of over 26 % in the laboratory. The quality of perovskite films is still a bottleneck due to the random and fast crystallization of ionic perovskite materials. Seeding agent-mediated crystallization has consistently been recognized as an efficient method for preparing bulk single crystals and high-quality films. Herein, we summarized the seeding mechanism, characterization techniques, and seeding agents working in different locations during PSC device fabrication. This Review could further facilitate researchers with a deeper understanding of seeding agents and enhance more choices for seeding crystallization to improve the performance further and the device's large-scale fabrication toward commercialization.

Bioresorbable thin-film silicon diodes for the optoelectronic excitation and inhibition of neural activities.

Neural activities can be modulated by leveraging light-responsive nanomaterials as interfaces for exerting photothermal, photoelectrochemical or photocapacitive effects on neurons or neural tissues. Here we show that bioresorbable thin-film monocrystalline silicon pn diodes can be used to optoelectronically excite or inhibit neural activities by establishing polarity-dependent positive or negative photovoltages at the semiconductor/solution interface. Under laser illumination, the silicon-diode optoelectronic interfaces allowed for the deterministic depolarization or hyperpolarization of cultured neurons as well as the upregulated or downregulated intracellular calcium dynamics. The optoelectronic interfaces can also be mounted on nerve tissue to activate or silence neural activities in peripheral and central nervous tissues, as we show in mice with exposed sciatic nerves and somatosensory cortices. Bioresorbable silicon-based optoelectronic thin films that selectively excite or inhibit neural tissue may find advantageous biomedical applicability.