High-efficiency stretchable light-emitting polymers from thermally activated delayed fluorescence.

Stretchable light-emitting materials are the key components for realizing skin-like displays and optical biostimulation. All the stretchable emitters reported to date, to the best of our knowledge, have been based on electroluminescent polymers that only harness singlet excitons, limiting their theoretical quantum yield to 25%. Here we present a design concept for imparting stretchability onto electroluminescent polymers that can harness all the excitons through thermally activated delayed fluorescence, thereby reaching a near-unity theoretical quantum yield. We show that our design strategy of inserting flexible, linear units into a polymer backbone can substantially increase the mechanical stretchability without affecting the underlying electroluminescent processes. As a result, our synthesized polymer achieves a stretchability of 125%, with an external quantum efficiency of 10%. Furthermore, we demonstrate a fully stretchable organic light-emitting diode, confirming that the proposed stretchable thermally activated delayed fluorescence polymers provide a path towards simultaneously achieving desirable electroluminescent and mechanical characteristics, including high efficiency, brightness, switching speed and stretchability as well as low driving voltage.

Enhanced Electron Transport in Nonconjugated Radical Oligomers Occurs by Tunneling.

Incorporating temperature- and air-stable organic radical species into molecular designs is a potentially advantageous means of controlling the properties of electronic materials. However, we still lack a complete understanding of the structure-property relationships of organic radical species at the molecular level. In this work, the charge transport properties of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) radical-containing nonconjugated molecules are studied using single-molecule charge transport experiments and molecular modeling. Importantly, the TEMPO pendant groups promote temperature-independent molecular charge transport in the tunneling region relative to the quenched and closed-shell phenyl pendant groups. Results from molecular modeling show that the TEMPO radicals interact with the gold metal electrodes near the interface to facilitate a high-conductance conformation. Overall, the large enhancement of charge transport by incorporation of open-shell species into a single nonconjugated molecular component opens exciting avenues for implementing molecular engineering in the development of next-generation electronic devices based on novel nonconjugated radical materials.

Influence of Regional Nerve Block in Addition to General Anesthesia on Postoperative Delirium, Pain, and In-hospital Stay in Patients Undergoing Cardiothoracic Surgery: A Meta-analysis.

ABSTRACT: This study aims to investigate whether venous injection of sedative agent or regional nerve block in alliance with major anesthesia could decrease the risk of postoperative delirium occurrence in patients receiving cardiothoracic surgery. Electronic academic databases were retrieved for related publications, and statistical software was used for data pooling and analysis. Forest plot was used to show the pooled sensitivity, specificity, and diagnostic odds ratio. Combined receiver operating characteristic curve was used to show the area under the curve of complex data. Seven studies were included for analysis. The risk of occurrence of delirium still showed no difference (risk rate = 0.93, 95% CI, 0.85-1.03) between the intervention group and placebo group. Postoperative pain feeling was more alleviated in patients with prophylactic application of regional nerve block. In addition, prophylactic application of regional nerve block could decrease the risk of postoperative in-hospital stay (risk rate = 0.28, 95% CI, 0.02-0.54). Our study demonstrated that, in elderly patients or pediatric patients undergoing cardiac surgery, prophylactic application of regional nerve block failed to decrease the incidence of postoperative delirium. However, the option of regional nerve block could decrease the duration of in-hospitalization stay and alleviate the acute pain during the postoperative period after open-heart surgery.

Efficient Intermolecular Charge Transport in π-Stacked Pyridinium Dimers Using Cucurbit[8]uril Supramolecular Complexes.

Intermolecular charge transport through π-conjugated molecules plays an essential role in biochemical redox processes and energy storage applications. In this work, we observe highly efficient intermolecular charge transport upon dimerization of pyridinium molecules in the cavity of a synthetic host (cucurbit[8]uril, CB[8]). Stable, homoternary complexes are formed between pyridinium molecules and CB[8] with high binding affinity, resulting in an offset stacked geometry of two pyridiniums inside the host cavity. The charge transport properties of free and dimerized pyridiniums are characterized using a scanning tunneling microscope-break junction (STM-BJ) technique. Our results show that π-stacked pyridinium dimers exhibit comparable molecular conductance to isolated, single pyridinium molecules, despite a longer transport pathway and a switch from intra- to intermolecular charge transport. Control experiments using a CB[8] homologue (cucurbit[7]uril, CB[7]) show that the synthetic host primarily serves to facilitate dimer formation and plays a minimal role on molecular conductance. Molecular modeling using density functional theory (DFT) reveals that pyridinium molecules are planarized upon dimerization inside the host cavity, which facilitates charge transport. In addition, the π-stacked pyridinium dimers possess large intermolecular LUMO-LUMO couplings, leading to enhanced intermolecular charge transport. Overall, this work demonstrates that supramolecular assembly can be used to control intermolecular charge transport in π-stacked molecules.

GmAOC4 modulates seed germination by regulating JA biosynthesis in soybean.

KEY MESSAGE: An allene oxide cyclase 4, GmAOC4, was determined by GWAS and RT-PCR to be significantly associated with seed germination in soybean, and regulates seed germination by promoting more JA accumulation. The seed germination phase is a critical component of the plant lifecycle, and a better understanding of the mechanism behind seed germination in soybeans is needed. We used a genome-wide association study (GWAS) to detect a GWAS signal on chromosome 18. In this GWAS signal, SNP S18_56189166 was located within the 3'untranslated region of Glyma.18G280900, which encodes allene oxide cyclase 4 (named GmAOC4). Analysis of real-time PCR demonstrated that expression levels of GmAOC4 in the low-germination variety (KF, carrying SNP S18_56189166-T) were higher than in the high-germination variety (NN, carrying SNP S18_56189166-C). In these two varieties, KF showed a higher JA concentration than NN at 0 and 24 h after imbibition. Moreover, the overexpression of GmAOC4 led to an increase in the concentration of jasmonic acid (JA) in soybean hairy roots and Arabidopsis thaliana. Furthermore, it was found that GmAOC4-OE lines showed less seed germination than the wild type (WT) under normal conditions in Arabidopsis. After 7 days of ABA treatment, transgenic lines exhibited lower seed germination and higher expression levels of AtABI5 compared with WT, indicating that the overexpression of GmAOC4 resulted in hypersensitivity to ABA. Our findings demonstrate that GmAOC4, which promotes more JA accumulation, helps to regulate seed germination in soybeans.

Transition between Nonresonant and Resonant Charge Transport in Molecular Junctions.

Efficient long-range charge transport is required for high-performance molecular electronic devices. Resonant transport is thought to occur in single molecule junctions when molecular frontier orbital energy levels align with electrode Fermi levels, thereby enabling efficient transport without molecular or environmental relaxation. Despite recent progress, we lack a systematic understanding of the transition between nonresonant and resonant transport for molecular junctions with different chemical compositions. In this work, we show that molecular junctions undergo a reversible transition from nonresonant tunneling to resonant transport as a function of applied bias. Transient bias-switching experiments show that the nonresonant to resonant transition is reversible with the applied bias. We determine a general quantitative relationship that describes the transition voltage as a function of the molecular frontier orbital energies and electrode Fermi levels. Overall, this work highlights the importance of frontier orbital energy alignment in achieving efficient charge transport in molecular devices.

Comparative selective signature analysis and high-resolution GWAS reveal a new candidate gene controlling seed weight in soybean.

KEY MESSAGE: We detected a QTL qHSW-16 undergone strong selection associated with seed weight and identified a novel candidate gene controlling seed weight candidate gene for this major QTL by qRT-PCT. Soybean [Glycine max (L.) Merr.] provides more than half of the world's oilseed production. To expand its germplasm resources useful for breeding increased yield and oil quality cultivars, it is necessary to resolve the diversity and evolutionary history of this crop. In this work, we resequenced 283 soybean accessions from China and obtained a large number of high-quality SNPs for investigation of the population genetics that underpin variation in seed weight and other agronomic traits. Selective signature analysis detected 78 (~ 25.0 Mb) and 39 (~ 22.60 Mb) novel putative selective signals that were selected during soybean domestication and improvement, respectively. Genome-wide association study (GWAS) identified five loci associated with seed weight. Among these QTLs, qHSW-16, overlapped with the improvement-selective region on chromosome 16, suggesting that this QTL may be underwent strong selection during soybean improvement. Of the 18 candidate genes in qHSW-16, only SoyZH13_16G122400 showed higher expression levels in a large seed variety compared to a small seed variety during seed development. These results identify SoyZH13_16G122400 as a novel candidate gene controlling seed weight and provide foundational insights into the molecular targets for breeding improvement of seed weight and potential seed yield in soybean.

Covalent Ag-C Bonding Contacts from Unprotected Terminal Acetylenes for Molecular Junctions.

Robust molecule-metal linkages are essential for developing high-performance and air-stable devices for molecular and organic electronics. In this work, we report a facile method for forming robust and covalent bonding contacts between unprotected terminal acetylenes and metal (Ag) interfaces. Using this approach, we study the charge transport properties of conjugated oligophenylenes with covalent metal-carbon contacts to silver electrodes formed from unprotected terminal acetylene anchors. We performed single molecule charge transport experiments and molecular simulations on a series of arylacetylenes using gold and silver electrodes. Our results show that molecular junctions on silver electrodes spontaneously form silver-carbynyl carbon (Ag-C) contacts, resulting in a nearly 10-fold increase in conductance compared to the same molecules on gold electrodes. Overall, this work presents a simple, new electrode-anchor pair that reliably forms molecular junctions with stable and robust contacts for molecular electronics.

Charge Transport in Sequence-Defined Conjugated Oligomers.

A major challenge in synthetic polymers lies in understanding how primary monomer sequence affects materials properties. In this work, we show that charge transport in single molecule junctions of conjugated oligomers critically depends on the primary sequence of monomers. A series of sequence-defined oligomers ranging from two to seven units was synthesized by an iterative approach based on the van Leusen reaction, providing conjugated oligomers with backbones consisting of para-linked phenylenes connected to oxazole, imidazole, or nitro-substituted pyrrole. The charge transport properties of these materials were characterized using a scanning tunneling microscope-break junction (STM-BJ) technique, thereby enabling direct measurement of molecular conductance for sequence-defined dimers, trimers, pentamers, and a heptamer. Our results show that oligomers with specific monomer sequences exhibit unexpected and distinct charge transport pathways that enhance molecular conductance more than 10-fold. A systematic analysis using monomer substitution patterns established that sequence-defined pentamers containing imidazole or pyrrole groups in specific locations provide molecular attachment points on the backbone to the gold electrodes, thereby giving rise to multiple conductance pathways. These findings reveal the subtle but important role of molecular structure including steric hindrance and directionality of heterocycles in determining charge transport in these molecular junctions. This work brings new understanding for designing molecular electronic components.

Charge Transport and Quantum Interference Effects in Oxazole-Terminated Conjugated Oligomers.

Charge transport in single molecule junctions critically depends on the chemical identity of anchor groups used to connect molecular wires to electrodes. In this work, we report the charge transport properties of conjugated oligomers with oxazole anchors, focusing on the role of the heteroatom substitution position in terminal oxazole groups. Our results show that oxazole serves as an efficient anchor group to form stable gold-molecule-gold junctions. We further observe quantum interference (QI) effects in oxazole-terminated phenylene molecular junctions, including destructive QI in meta-substituted phenyl rings and constructive QI in para-substituted phenyl rings containing terminal oxazole groups with the same chemical constitution on both termini (i.e., O5O5 (5-oxazolyl) or O4O4 (4-oxazolyl) linkages on both termini). Surprisingly, meta-substituted phenyl rings with nonequivalent constitutions (i.e., O4O5 oxazole terminal linkages) show unexpectedly higher conductance as compared to para-substituted analogues. These results suggest that charge transport in oxazole-terminated molecules is determined by the heteroatom substitution position of the oxazole anchor in addition to the aryl substitution pattern of the π-conjugated core. Our results further show that conjugated molecules with homogeneous oxazole linkages obey a quantum circuit rule such that GO4-p-O4/GO4-m-O4 = GO5-p-O5/GO5-m-O5, where G is molecular conductance. Overall, our work provides key insight into the development of new chemistries for molecular circuitry in the rapidly advancing field of single molecule electronics.

Interleukin-6 (IL-6) Receptor Antagonist Protects Against Rheumatoid Arthritis.

BACKGROUND The aim of this study was to investigate the protective effect of interleukin-6 (IL-6) receptor antagonist tocilizumab (TCZ) on rheumatoid arthritis (RA) and its related mechanism. MATERIAL AND METHODS Thirty RA patients receiving long-term methotrexate therapy at moderate and severe active stages were selected and treated with TCZ 8 mg/kg/time iv gtt intravenously guttae every 4 weeks. Peripheral blood was extracted before and 24 weeks after TCZ treatment. Peripheral blood mononuclear cells (PBMC) were collected by density gradient centrifugation. Flow cytometry was used to detect the ratio of CD4 naïve T cells and CD4 memory T cells, Th17 cells, and Treg cells in PBMC. DAS28 score, CRP, RF, and CCP levels in patients were evaluated. RESULTS Compared with before treatment, IL-6 receptor antagonist TCZ significantly improved patients' condition, including DAS28 score, CRP, RF, and CCP levels (P<0.01). Furthermore, TCZ obviously upregulated CD4 naïve T cells proportion and decreased CD4 memory T cells ratio (P<0.01). TCZ also markedly reduced the proportion of Th17 cells and increased the proportion of Treg cells (P<0.01). CONCLUSIONS TCZ can treat RA patients through regulating the ratio of CD4 naïve T cells, CD4 memory T cells, Th17 cells, and Treg cells in PBMC.

bHLH122 is important for drought and osmotic stress resistance in Arabidopsis and in the repression of ABA catabolism.

• Although proteins in the basic helix-loop-helix (bHLH) family are universal transcription factors in eukaryotes, the biological roles of most bHLH family members are not well understood in plants. • The Arabidopsis thaliana bHLH122 transcripts were strongly induced by drought, NaCl and osmotic stresses, but not by ABA treatment. Promoter::GUS analysis showed that bHLH122 was highly expressed in vascular tissues and guard cells. Compared with wild-type (WT) plants, transgenic plants overexpressing bHLH122 displayed greater resistance to drought, NaCl and osmotic stresses. In contrast, the bhlh122 loss-of-function mutant was more sensitive to NaCl and osmotic stresses than were WT plants. • Microarray analysis indicated that bHLH122 was important for the expression of a number of abiotic stress-responsive genes. In electrophoretic mobility shift assay and chromatin immunoprecipitation assays, bHLH122 could bind directly to the G-box/E-box cis-elements in the CYP707A3 promoter, and repress its expression. Further, up-regulation of bHLH122 substantially increased cellular ABA levels. • These results suggest that bHLH122 functions as a positive regulator of drought, NaCl and osmotic signaling.

Sodium chloride salinity reduces Cd uptake by edible amaranth (Amaranthus mangostanus L.) via competition for Ca channels.

Soil salinity is known to enhance cadmium (Cd) accumulation in crops. However, the mechanism by which this occurs independent of the surrounding soil remains unclear. In this study, root adsorption and uptake of salt cations and Cd by edible amaranth under NaCl salinity stress were investigated in hydroponic cultures with 0, 40, 80, 120, and 160mM of NaCl and 27nM Cd. The dominant Cd species in the nutrient solution changed from free Cd(2+) to Cd chlorocomplexes as NaCl salinity increased. High salinity significantly reduced K, Ca, and Cd root adsorption and K, Ca, Mg, and Cd uptake. High salinity decreased root adsorption of Cd by 43 and 58 percent and Cd uptake by 32 and 36 percent in salt-tolerant and salt-sensitive cultivars, respectively. Transformation of Cd from free ion to chlorocomplexes is unlikely to have significantly affected Cd uptake by the plant because of the very low Cd concentrations involved. Application of Ca ion channel blocker significantly reduced Na, K, Ca, Mg, and Cd uptake by the roots, while blocking K ion channels significantly reduced Na and K uptake but not Ca, Mg, and Cd uptake. These results suggest that Na was absorbed by the roots through both Ca and K ion channels, while Cd was absorbed by the roots mainly through Ca ion channels and not K ion channels. Salinity caused a greater degree of reduction in Cd adsorption and uptake in the salt-sensitive cultivar than in the salt-tolerant cultivar. Thus, competition between Na and Cd for Ca ion channels can reduce Cd uptake at very low Cd concentrations in the nutrient solution.

Spectral analysis of the bounded linear operator in the reproducing kernel space W2(m)(D).

We first introduce some related definitions of the bounded linear operator L in the reproducing kernel space W(2)(m)(D). Then we show spectral analysis of L and derive several property theorems.

Modified response evaluation criteria in solid tumors: A better response evaluation criteria for patients with non-squamous non-small cell lung cancer after bevacizumab treatment.

AIM: Cavitation of lesions is common in non-squamous non-small cell lung cancer (non-squamous-NSCLC) patients treated with vascular endothelial growth factor receptor tyrosine kinase inhibitors (VEGFRIs). However, traditional response evaluation criteria in solid tumors (RECIST) do not take cavitation into consideration and may no longer be accurate for potentially reflecting the real clinical efficacy of anti-vessel growth therapy. Here, we aimed to optimize the traditional RECIST version 1.1 by adding cavitation into the evaluation criteria. METHODS: We performed a post-hoc radiologic review of 517 patients in a phase III clinical trial of bevacizumab biosimilar (SIBP04) combined with chemotherapy for the treatment of non-squamous NSCLC. Tumor responses were assessed by RECIST1.1 and mRECIST criteria (modified RECIST, a novel alternate method where the longest diameter of the cavity was subtracted from the overall longest diameter of that lesion to measure target lesions), respectively, and correlated with clinical outcomes. RESULTS: Cavitations of pulmonary lesions were seen in nine (2%) patients at baseline, and 97 (19%) during treatment. The use of mRECIST resulted in an alteration of the response category. For patients with post-therapy cavitation, the objective response rate was 56% using RECIST1.1 and 67% by mRECIST. In addition, the survival rates between partial response, stable disease, and progressive disease when the mRECIST was applied were significantly different (p < 0.05), while RECIST1.1 failed to show survival differences (p = 0.218). CONCLUSION: For patients with post-therapy cavitation, mRECIST exhibited higher predictability of survival than RECIST1.1. Response assessment might be improved by incorporating cavitation into assessment, potentially altering outcomes of key clinical efficacy parameters.

Top management team career experience heterogeneity, digital transformation, and the corporate green innovation: a moderated mediation analysis.

Introduction: Drawing upon upper echelon theory and the resource-based view, this study employs a moderated mediation model to investigate the moderating role and underlying mechanisms of digital transformation in the influence of top management teams (TMT) on corporate green innovation. Methods: Our analysis of panel data from 19,155 Chinese A-share listed companies (2011-2020) demonstrates that TMT career experience heterogeneity has a positive effect on green innovation, a relationship that is further strengthened by digital transformation. Results: This study shows the role of digital transformation in amplifying the effects of TMT diversity on green innovation and the crucial role of industry-academia-research collaboration as a mediator. Heterogeneity analysis highlights that non-state-owned enterprises (non-SOEs) show more agility than state-owned enterprises (SOEs) in leveraging heterogeneous TMT to drive green innovation. Conversely, green innovation in SOEs benefits more from digital transformation, which includes both its direct and indirect effects of digital transformation. Enterprises located in non-Yangtze River Economic Belt regions benefit more from digital transformation, demonstrating the importance of a balanced distribution of digital resources. Discussion: This study provides novel insights into leveraging inclusive leadership and digital capabilities to enhance ecological sustainability. This study underscores the potential of diversified TMTs and digitalization technology integration to catalyze green innovation, which is critical for environmentally responsible transformation.

Aluminum surface defect detection method based on a lightweight YOLOv4 network.

Deep learning is currently being used to automate surface defect detection in aluminum. The common target detection models based on neural networks often have a large number of parameters and a slow detection speed, which is not conducive to real-time detection. Therefore, this paper proposes a lightweight aluminum surface defect detection model, M2-BL-YOLOv4, based on the YOLOv4 algorithm. First, in the YOLOv4 model, the complex CSPDarkNet53 backbone network was modified into an inverted residual structure, which greatly reduced the number of parameters in the model and increased the detection speed. Second, a new feature fusion network, BiFPN-Lite, is designed to improve the fusion ability of the network and further improve its detection accuracy. The final results show that the mean average precision of the improved lightweight YOLOv4 algorithm in the aluminum surface defect test set reaches 93.5%, the number of model parameters is reduced to 60% of the original, and the number of frames per second (FPS) detected is 52.99, which increases the detection speed by 30%. The efficient detection of aluminum surface defects is realized.

Outcome benefits of bevacizumab biosimilar (SIBP04) combined with carboplatin and paclitaxel in advanced non-squamous non-small-cell lung cancer patients with EGFR mutation: subgroup analysis of a prospective, randomized phase III clinical trial.

PURPOSE: SIBP04 is a bevacizumab biosimilar, and bevacizumab combined with carboplatin and paclitaxel in advanced non-squamous non-small-cell lung cancer (nsqNSCLC) has been recommended as the first-line treatment choice. However, the efforts of bevacizumab combined with carboplatin and paclitaxel for nsqNSCLC patients with EGFR mutation remained unclear. Here we report an EGFR mutation subgroup analysis of a prospective, randomized phase III clinical trial (NCT05318443). METHODS: In this randomized, double-blind, multi-center, parallel controlled, phase III clinical trial, locally advanced, metastatic NSCLC patients were enrolled, and EGFR expression was examined and considered as a stratification factor. All patients received 4 to 6 cycles of paclitaxel and carboplatin plus SIBP04 or bevacizumab 15 mg/kg intravenously followed by SIBP04 15 mg/kg maintenance until intolerable toxicity, disease progression or death. Patients with EGFR mutation and wild-type were assessed for progression-free survival (PFS) and overall survival (OS). RESULTS: EGFR expression was examined in 398 NSCLC patients (142 with EGFR mutation, 256 with EGFR wild type). PFS in EGFR mutation patients was significantly longer than EGFR wild-type patients (10.91 vs. 7.82 months; HR = 0.692, 95% CI 0.519-0.921, P = 0.011). The median OS in patients with EGFR mutation was not reached while that of EGFR wild-type group was 17.54 months (HR = 0.398, 95% CI 0.275-0.575, P < 0.001). However, there were no significant differences in objective response rate (61.97% vs. 55.86%, P = 0.237) or disease control rate (90.14% vs. 89.84%, P = 0.925). CONCLUSION: Bevacizumab combined with chemotherapy significantly prolonged the PFS and OS of advanced nsqNSCLC patients with EGFR mutation.

Bioadhesive polymer semiconductors and transistors for intimate biointerfaces.

The use of bioelectronic devices relies on direct contact with soft biotissues. For transistor-type bioelectronic devices, the semiconductors that need to have direct interfacing with biotissues for effective signal transduction do not adhere well with wet tissues, thereby limiting the stability and conformability at the interface. We report a bioadhesive polymer semiconductor through a double-network structure formed by a bioadhesive brush polymer and a redox-active semiconducting polymer. The resulting semiconducting film can form rapid and strong adhesion with wet tissue surfaces together with high charge-carrier mobility of ~1 square centimeter per volt per second, high stretchability, and good biocompatibility. Further fabrication of a fully bioadhesive transistor sensor enabled us to produce high-quality and stable electrophysiological recordings on an isolated rat heart and in vivo rat muscles.